AspenPolymersUnitOpsV8 - 4-Usr PDF

Aspen Polymers
Unit Operations and Reaction Models

Version Number: V8.4 November 2013
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Contents
Introducing Aspen Polymers ...................................................................................1
About This Documentation Set...........................................................................1 Related
Documentation.....................................................................................2 Technical Support
............................................................................................3
1 Polymer Manufacturing Process Overview...........................................................5
About Aspen Polymers ......................................................................................5 Overview of
Polymerization Processes.................................................................6 Polymer Manufacturing Process
Steps .......................................................6 Issues of Concern in Polymer Process
Modeling....................................................7 Monomer Synthesis and Purification
.........................................................8
Polymerization.......................................................................................8 Recovery / Separation
............................................................................9 Polymer Processing
................................................................................9
Summary..............................................................................................9 Aspen Polymers Tools
.......................................................................................9 Component
Characterization.................................................................. 10 Polymer Physical Properties
................................................................... 10 Polymerization Kinetics
......................................................................... 10 Modeling
Data...................................................................................... 11 Process
Flowsheeting............................................................................ 11 Defining a Model in Aspen Polymers
.................................................................12 References
.................................................................................................... 14
2 Polymer Structural Characterization .................................................................15
Polymer Structure .......................................................................................... 15 Polymer Structural
Properties .......................................................................... 19 Characterization
Approach............................................................................... 19 Component
Attributes........................................................................... 20 References
.................................................................................................... 20
3 Component Classification ..................................................................................21
Component Categories.................................................................................... 21 Conventional
Components ..................................................................... 22
Polymers.............................................................................................22 Oligomers
........................................................................................... 23
Segments............................................................................................ 24 Site-Based
.......................................................................................... 24 Component
Databanks.................................................................................... 25 Pure Component Databank
.................................................................... 25 PC-SAFT Databank
............................................................................... 26 POLYPCSF Databank
............................................................................. 26
Contents iii
INITIATO Databank .............................................................................. 26 Segment
Databank............................................................................... 26 Polymer Databank
................................................................................ 27 Segment Methodology
.................................................................................... 27 Specifying
Components................................................................................... 28 Selecting Databanks
............................................................................. 28 Defining Component Names and Types
................................................... 28 Specifying Segments ............................................................................
29 Specifying Polymers ............................................................................. 29 Specifying Oligomers
............................................................................ 30 Specifying Site-Based
Components......................................................... 30 References
.................................................................................................... 31
4 Polymer Structural Properties...........................................................................33
Structural Properties as Component Attributes...................................................33 Component Attribute
Classes ........................................................................... 34 Component Attribute Categories
...................................................................... 35 Polymer Component
Attributes............................................................... 35 Site-Based Species Attributes
................................................................ 44 User Attributes
.................................................................................... 45 Component Attribute Initialization
.................................................................... 46 Attribute Initialization Scheme
............................................................... 47 Component Attribute Scale
Factors................................................................... 50 Specifying Component Attributes
..................................................................... 51 Specifying Polymer Component Attributes
............................................... 51 Specifying Site-Based Component Attributes ...........................................
51 Specifying Conventional Component Attributes ........................................ 52 Initializing Component
Attributes in Streams or Blocks..............................52 Specifying Component Attribute Scaling
Factors.......................................53 References
.................................................................................................... 53
5 Structural Property Distributions ......................................................................55
Property Distribution Types ............................................................................. 55 Distribution Functions
..................................................................................... 56 Schulz-Flory Most Probable
Distribution................................................... 56 Stockmayer Bivariate Distribution
.......................................................... 58 Distributions in Process Models
........................................................................ 58 Average Properties and Moments
........................................................... 58 Method of Instantaneous
Properties........................................................60 Copolymerization
................................................................................. 64 Mechanism for Tracking
Distributions................................................................ 65 Distributions in Kinetic Reactors
............................................................. 65 Distributions in Process Streams
............................................................ 67 Verifying the Accuracy of Distribution
Calculations....................................68 Requesting Distribution Calculations
................................................................. 69 Selecting Distribution Characteristics
...................................................... 69 Displaying Distribution Data for a Reactor
............................................... 70 Displaying Distribution Data for Streams .................................................
70 References .................................................................................................... 71
iv Contents
6 End-Use Properties............................................................................................73
Polymer Properties ......................................................................................... 73 Prop-Set Properties
........................................................................................ 73 End-Use
Properties......................................................................................... 74 Relationship to Molecular Structure
........................................................ 75 Method for Calculating End-Use Properties
........................................................76 Intrinsic Viscosity
................................................................................. 77 Zero-Shear Viscosity
............................................................................ 77 Density of Copolymer
........................................................................... 78 Melt
Index........................................................................................... 78 Melt Index
Ratio................................................................................... 79 Calculating End-Use Properties
........................................................................ 79 Selecting an End-Use
Property............................................................... 79 Adding an End-Use Property Prop-
Set.....................................................79 References
.................................................................................................... 79
7 Polymerization Reactions..................................................................................81
Polymerization Reaction Categories .................................................................. 81 Step-Growth
Polymerization .................................................................. 83 Chain-Growth
Polymerization................................................................. 83 Polymerization Process Types
.......................................................................... 84 Aspen Polymers Reaction
Models...................................................................... 85 Built-in
Models..................................................................................... 85 User
Models......................................................................................... 86 References
.................................................................................................... 86
8 Step-Growth Polymerization Model ...................................................................89
Summary of Applications................................................................................. 89 Step-Growth Processes
................................................................................... 90 Polyesters
........................................................................................... 90 Nylon-
6............................................................................................... 96 Nylon-
6,6............................................................................................98 Polycarbonate
.................................................................................... 100 Reaction Kinetic Scheme
............................................................................... 101 Nucleophilic Reactions
........................................................................ 101 Polyester Reaction
Kinetics.................................................................. 105 Nylon-6 Reaction
Kinetics.................................................................... 111 Nylon-6,6 Reaction Kinetics
................................................................. 115 Melt Polycarbonate Reaction Kinetics
.................................................... 122 Model Features and Assumptions
................................................................... 124 Model Predictions
............................................................................... 124 Phase Equilibria
................................................................................. 126 Reaction Mechanism
........................................................................... 126 Model Structure
........................................................................................... 127 Reacting Groups and
Species............................................................... 127 Reaction Stoichiometry
Generation....................................................... 132 Model-Generated Reactions
................................................................. 133 User
Reactions................................................................................... 138 User Subroutines
............................................................................... 140 Specifying Step-Growth Polymerization Kinetics
............................................... 155 Accessing the Step-Growth Model.........................................................
155
Contents v
Specifying the Step-Growth Model........................................................ 156 Specifying Reacting
Components.......................................................... 156 Listing Built-In
Reactions..................................................................... 157 Specifying Built-In Reaction Rate
Constants........................................... 157 Assigning Rate Constants to
Reactions.................................................. 158 Including User
Reactions..................................................................... 158 Adding or Editing User
Reactions.......................................................... 159 Specifying Rate Constants for User Reactions
........................................ 159 Assigning Rate Constants to User Reactions...........................................
159 Selecting Report Options..................................................................... 160 Selecting the Reacting
Phase ............................................................... 160 Specifying Units of Measurement for Pre-Exponential
Factors................... 160 Including a User Kinetic Subroutine ...................................................... 161
Including a User Rate Constant Subroutine............................................ 161 Including a User Basis
Subroutine ........................................................ 161 References
.................................................................................................. 161
9 Free-Radical Bulk Polymerization Model..........................................................163
Summary of Applications............................................................................... 163 Free-Radical
Bulk/Solution Processes.............................................................. 164 Reaction Kinetic Scheme
............................................................................... 165 Initiation
........................................................................................... 171 Propagation
....................................................................................... 176 Chain Transfer to Small Molecules
........................................................ 178
Termination....................................................................................... 179 Long Chain Branching
......................................................................... 181 Short Chain Branching
........................................................................ 182 Beta-
Scission..................................................................................... 183 Reactions Involving Diene
Monomers.................................................... 183 Model Features and Assumptions
................................................................... 185 Calculation Method
............................................................................. 185 Quasi-Steady-State Approximation (QSSA)
........................................... 188 Phase Equilibrium............................................................................... 188
Gel Effect .......................................................................................... 188 Polymer Properties
Calculated........................................................................ 190 Specifying Free-Radical Polymerization
Kinetics................................................ 193 Accessing the Free-Radical Model
......................................................... 193 Specifying the Free-Radical Model
........................................................ 193 Specifying Reacting
Species................................................................. 194 Listing Reactions
................................................................................ 194 Adding Reactions
............................................................................... 194 Editing Reactions
............................................................................... 195 Assigning Rate Constants to
Reactions.................................................. 195 Adding Gel-Effect
............................................................................... 196 Selecting Calculation
Options............................................................... 196 Specifying User
Profiles....................................................................... 197 References
.................................................................................................. 197
10 Emulsion Polymerization Model.....................................................................199
Summary of Applications............................................................................... 199 Emulsion Polymerization
Processes................................................................. 200 Reaction Kinetic Scheme
............................................................................... 200
vi Contents
Micellar Nucleation ............................................................................. 201 Homogeneous Nucleation
.................................................................... 204 Particle Growth
.................................................................................. 206 Radical
Balance.................................................................................. 207 Kinetics of Emulsion
Polymerization...................................................... 211 Model Features and Assumptions
................................................................... 215 Model
Assumptions............................................................................. 215 Thermodynamics of Monomer
Partitioning ............................................. 215 Polymer Particle Size Distribution
......................................................... 216 Polymer Particle Properties Calculated
............................................................ 218 User Profiles
...................................................................................... 218 Specifying Emulsion Polymerization Kinetics
.................................................... 219 Accessing the Emulsion
Model.............................................................. 219 Specifying the Emulsion
Model............................................................. 219 Specifying Reacting
Reactions.................................................. 221 Selecting Calculation
Options............................................................... 222 Adding Gel-Effect
............................................................................... 222 Specifying Phase Partitioning
............................................................... 222 Specifying Particle Growth
Parameters.................................................. 223 References
.................................................................................................. 223
11 Ziegler-Natta Polymerization Model ..............................................................225
Summary of Applications............................................................................... 225 Ziegler-Natta Processes
................................................................................ 226 Catalyst Types
................................................................................... 226 Ethylene Process
Types....................................................................... 227 Propylene Process Types
..................................................................... 228 Reaction Kinetic Scheme
............................................................................... 230 Catalyst Pre-
Activation........................................................................ 237 Catalyst Site Activation
....................................................................... 237 Chain Initiation
.................................................................................. 237 Propagation
....................................................................................... 238 Chain Transfer to Small Molecules
........................................................ 239 Site
Deactivation................................................................................ 239 Site
Inhibition.................................................................................... 240 Cocatalyst
Poisoning........................................................................... 240 Terminal Double Bond Polymerization
................................................... 240 Model Features and Assumptions
................................................................... 243 Phase Equilibria
................................................................................. 243 Rate Calculations
............................................................................... 243 Polymer Properties
Calculated........................................................................ 243 Specifying Ziegler-Natta Polymerization
Kinetics .............................................. 244 Accessing the Ziegler-Natta
Model........................................................ 244 Specifying the Ziegler-Natta Model
....................................................... 244 Specifying Reacting
............................................................................... 246
Contents vii
Assigning Rate Constants to Reactions.................................................. 246 References
.................................................................................................. 247
12 Ionic Polymerization Model...........................................................................249
Summary of Applications............................................................................... 249 Ionic Processes
............................................................................................ 250 Reaction Kinetic Scheme
............................................................................... 250 Formation of Active
Species................................................................. 254 Chain Initiation
.................................................................................. 255 Propagation
....................................................................................... 255 Association or Aggregation
.................................................................. 256 Exchange
.......................................................................................... 256 Equilibrium with Counter-Ion
............................................................... 256 Chain Transfer
................................................................................... 257 Chain Termination
.............................................................................. 257 Coupling
........................................................................................... 258 Model Features and Assumptions
................................................................... 258 Phase Equilibria
................................................................................. 258 Rate Calculations
............................................................................... 258 Polymer Properties
Calculated........................................................................ 259 Specifying Ionic Polymerization Kinetics
.......................................................... 260 Accessing the Ionic Model
................................................................... 260 Specifying the Ionic
Model................................................................... 260 Specifying Reacting
Reactions.................................................. 262 References
.................................................................................................. 262
13 Segment-Based Reaction Model ....................................................................265
Summary of Applications............................................................................... 265 Step-Growth Addition
Processes........................................................... 266 Polymer Modification Processes
............................................................ 266 Segment-Based Model Allowed Reactions
........................................................ 267 Conventional
Species.......................................................................... 268 Side Group or Backbone
Modifications................................................... 269 Chain Scission
................................................................................... 269 Depolymerization
............................................................................... 269 Propagation
....................................................................................... 270 Combination
...................................................................................... 270 Branch
Formation............................................................................... 270 Cross
Linking..................................................................................... 270 Kinetic Rate
Expression....................................................................... 270 Model Features and Assumptions
................................................................... 272 Polymer Properties
Calculated........................................................................ 273 User Subroutines
............................................................................... 274 Specifying Segment-Based Kinetics
................................................................ 285 Accessing the Segment-Based Model
.................................................... 285 Specifying the Segment-Based Model
................................................... 285 Specifying Reaction
Settings................................................................ 285 Building A Reaction Scheme
................................................................ 287
viii Contents
Adding or Editing Reactions ................................................................. 287 Specifying Reaction Rate
Constants ...................................................... 288 Assigning Rate Constants to
Reactions.................................................. 288 Including a User Rate Constant
Subroutine............................................ 289 Including a User Basis Subroutine
........................................................ 289 References
.................................................................................................. 289
14 Steady-State Flowsheeting............................................................................291
Polymer Manufacturing Flowsheets ................................................................. 291 Monomer Synthesis
............................................................................ 292 Polymerization
................................................................................... 293 Recovery /
Separations....................................................................... 293 Polymer Processing
............................................................................ 293 Modeling Polymer Process Flowsheets
............................................................. 293 Steady-State Modeling
Features..................................................................... 294 Unit Operations Modeling Features
....................................................... 294 Plant Data Fitting Features
.................................................................. 294 Process Model Application Tools
........................................................... 294 References
.................................................................................................. 294
15 Steady-State Unit Operation Models..............................................................295
Summary of Aspen Plus Unit Operation Models ................................................ 295 Dupl
................................................................................................. 296
Flash2............................................................................................... 298
Flash3............................................................................................... 298
FSplit................................................................................................ 299 Heater
.............................................................................................. 299 Mixer
................................................................................................ 299
Mult.................................................................................................. 299
Pump................................................................................................ 300
Pipe.................................................................................................. 300 Sep
.................................................................................................. 301 Sep2
................................................................................................ 301 Distillation Models
........................................................................................ 301 RadFrac
............................................................................................ 301 Reactor Models
............................................................................................ 302 Mass-Balance Reactor Models
........................................................................ 302
RStoic............................................................................................... 302 RYield
............................................................................................... 303 Equilibrium Reactor
Models............................................................................ 304 REquil
............................................................................................... 304
RGibbs.............................................................................................. 304 Kinetic Reactor
Models.................................................................................. 304 RCSTR
.............................................................................................. 304
RPlug................................................................................................ 317
RBatch.............................................................................................. 327 Treatment of Component
Attributes in Unit Operation Models ............................ 335 References
.................................................................................................. 338
16 Plant Data Fitting ..........................................................................................339
Data Fitting Applications ............................................................................... 339
Contents ix
Data Fitting For Polymer Models..................................................................... 340 Data Collection and
Verification............................................................ 341 Literature Review
............................................................................... 341 Preliminary Parameter
Fitting............................................................... 342 Preliminary Model Development
........................................................... 343 Trend Analysis
................................................................................... 343 Model Refinement
.............................................................................. 344 Steps for Using the Data Regression Tool
........................................................ 345 Identifying Flowsheet
Variables............................................................ 346 Manipulating Variables
Indirectly.......................................................... 347 Entering Point Data
............................................................................ 349 Entering Profile
Data........................................................................... 350 Entering Standard Deviations
.............................................................. 351 Defining Data Regression Cases
........................................................... 352 Sequencing Data Regression Cases
...................................................... 352 Interpreting Data Regression
Results.................................................... 352 Troubleshooting Convergence Problems
................................................ 353
17 User Models...................................................................................................359
User Unit Operation Models ........................................................................... 359 User Unit Operation
Models Structure ................................................... 359 User Unit Operation Model
Calculations................................................. 360 User Unit Operation Report
Writing....................................................... 365 User Kinetic Models
...................................................................................... 365 User Physical Property
Models........................................................................ 370 References
.................................................................................................. 373
18 Application Tools...........................................................................................375
Example Applications for a Simulation Model ................................................... 375 Application Tools
Available in Aspen Polymers.................................................. 376 CALCULATOR
..................................................................................... 376 DESIGN-SPEC
.................................................................................... 377 SENSITIVITY
..................................................................................... 377 OPTIMIZATION
.................................................................................. 377 Model Variable Accessing
.............................................................................. 378 References
.................................................................................................. 380
19 Run-Time Environment..................................................................................381
Aspen Polymers Architecture ......................................................................... 381 Installation Issues
........................................................................................ 382 Hardware
Requirements...................................................................... 382 Installation Procedure
......................................................................... 382 Configuration Tips
........................................................................................ 382 Startup
Files...................................................................................... 382 Simulation Templates
......................................................................... 382 User Fortran
................................................................................................ 383 User Fortran
Templates....................................................................... 383 User Fortran Linking
........................................................................... 383 Troubleshooting Guide
.................................................................................. 383 User Interface
Problems...................................................................... 383 Simulation Engine Run-Time
Problems................................................. 385
x Contents
References .................................................................................................. 386
A Component Databanks ....................................................................................387
Pure Component Databank............................................................................ 387 POLYMER Databank
...................................................................................... 387 POLYMER Property
Parameters............................................................. 387 POLYMER Databank
Components.......................................................... 388 SEGMENT Databank
..................................................................................... 391 SEGMENT Property Parameters
............................................................ 391 SEGMENT Databank Components
......................................................... 392
B Kinetic Rate Constant Parameters...................................................................431
Initiator Decomposition Rate Parameters......................................................... 431 Solvent Dependency
........................................................................... 431 Concentration
Dependency.................................................................. 432 Temperature Dependency
................................................................... 432 Pressure Dependency
......................................................................... 433 References
.................................................................................................. 444
C Fortran Utilities...............................................................................................445
D Input Language Reference..............................................................................447
Specifying Components................................................................................. 447 Naming Components
.......................................................................... 447 Specifying Component Characterization
Inputs........................................ 448 Specifying Component Attributes
................................................................... 451 Specifying Characterization
Attributes................................................... 451 Specifying Conventional Component Attributes
...................................... 451 Initializing Attributes in Streams .......................................................... 451
Specifying Attribute Scaling Factors................................................................ 453 Specifying Component
Attribute Scale Factors ....................................... 453 Requesting Distribution Calculations
............................................................... 454 Calculating End Use
Properties....................................................................... 454 Specifying Physical Property Inputs
................................................................ 456 Specifying Property
Methods................................................................ 456 Specifying Property
Data..................................................................... 458 Estimating Property Parameters
........................................................... 459 Specifying Step-Growth Polymerization Kinetics
............................................... 460 Specifying Free-Radical Polymerization
Kinetics................................................ 467 Specifying Emulsion Polymerization Kinetics
.................................................... 477 Specifying Ziegler-Natta Polymerization Kinetics
.............................................. 484 Specifying Ionic Polymerization Kinetics
.......................................................... 494 Specifying Segment-Based Polymer Modification
Reactions................................ 501 References
.................................................................................................. 505
Index ..................................................................................................................507
Contents xi
xii Contents
Introducing Aspen Polymers
Aspen Polymers (formerly known as Aspen Polymers Plus) is a general- purpose process modeling
system for the simulation of polymer manufacturing processes. The modeling system includes modules
for the estimation of thermophysical properties, and for performing polymerization kinetic calculations and
associated mass and energy balances.
Also included in Aspen Polymers are modules for:
Characterizing polymer molecular structure
Calculating rheological and mechanical properties
Tracking these properties throughout a flowsheet
There are also many additional features that permit the simulation of the entire manufacturing processes.
About This Documentation Set

The Aspen Polymers User Guide is divided into two volumes. Each volume documents features unique to
Aspen Polymers. This User Guide assumes prior knowledge of basic Aspen Plus capabilities or user
access to the Aspen Plus documentation set. If you are using Aspen Polymers with Aspen Dynamics,
please refer to the Aspen Dynamics documentation set.
Volume 1 provides an introduction to the use of modeling for polymer processes and discusses specific
Aspen Polymers capabilities. Topics include:
Polymer manufacturing process overview - describes the basics of polymer process modeling and the
steps involved in defining a model in Aspen Polymers.
Polymer structural characterization - describes the methods used for characterizing components.
Included are the methodologies for calculating distributions and features for tracking end-use properties.
Polymerization reactions - describes the polymerization kinetic models, including: step-growth, free-
radical, emulsion, Ziegler-Natta, ionic, and segment based. An overview of the various categories of
polymerization kinetic schemes is given.
Steady-state flowsheeting - provides an overview of capabilities used in constructing a polymer process
flowsheet model. For example, the unit
Introducing Aspen Polymers 1
operation models, data fitting tools, and analysis tools, such as sensitivity studies.
Run-time environment - covers issues concerning the run-time environment including configuration and
troubleshooting tips.
Volume 2 describes methodologies for tracking chemical component properties, physical properties, and
phase equilibria. It covers the physical property methods and models available in Aspen Polymers. Topics
include:
Thermodynamic properties of polymer systems describes polymer thermodynamic properties, their
importance to process modeling, and available property methods and models.
Equation-of-state (EOS) models provides an overview of the properties calculated from EOS models
and describes available models, including: Sanchez-Lacombe, polymer SRK, SAFT, and PC-SAFT.
Activity coefficient models provides an overview of the properties calculated from activity coefficient
models and describes available models, including: Flory-Huggins, polymer NRTL, electrolyte-polymer
NRTL, polymer UNIFAC.
Thermophysical properties of polymers provides and overview of the thermophysical properties
exhibited by polymers and describes available models, including: Aspen ideal gas, Tait liquid molar
volume, pure component liquid enthalpy, and Van Krevelen liquid and solid, melt and glass transition
temperature correlations, and group contribution methods.
Polymer viscosity models describes polymer viscosity model implementation and available models,
including: modified Mark- Houwink/van Krevelen, Aspen polymer mixture, and van Krevelen polymer
solution.
Polymer thermal conductivity models - describes thermal conductivity model implementation and
available models, including: modified van Krevelen and Aspen polymer mixture.
Related Documentation
A volume devoted to simulation and application examples for Aspen Polymers is provided as a
complement to this User Guide. These examples are designed to give you an overall understanding of
the steps involved in using Aspen Polymers to model specific systems. In addition to this document, a
number of other documents are provided to help you learn and use Aspen Polymers, Aspen Plus, and
Aspen Dynamics applications. The documentation set consists of the following:
Installation Guides
Aspen Engineering Suite Installation Guide
Aspen Polymers Guides

Aspen Polymers User Guide, Volume 1
2 Introducing Aspen Polymers
Aspen Polymers User Guide, Volume 2 (Physical Property Methods & Models)
Aspen Polymers Examples & Applications Case Book
Aspen Plus Guides

Aspen Plus User Guide
Aspen Plus Getting Started Guides
Aspen Physical Property System Guides
Aspen Physical Property System Physical Property Methods and Models
Aspen Physical Property System Physical Property Data
Aspen Dynamics Guides

Aspen Dynamics Examples
Aspen Dynamics User Guide
Aspen Dynamics Reference Guide
Help
Aspen Polymers has a complete system of online help and context-sensitive prompts. The help system
contains both context-sensitive help and reference information. For more information about using Aspen
Polymers help, see the Aspen Plus User Guide.
Third-Party
More detailed examples are available in Step-Growth Polymerization Process Modeling and Product
Design by Kevin Seavey and Y. A. Liu, ISBN: 978-0- 470-23823-3, Wiley, 2008.
Technical Support
AspenTech customers with a valid license and software maintenance agreement can register to access
the online AspenTech Support Center at:
http://support.aspentech.com
This Web support site allows you to:
Access current product documentation
Search for tech tips, solutions and frequently asked questions (FAQs)
Search for and download application examples
Search for and download service packs and product updates
Submit and track technical issues
Send suggestions
Report product defects
Introducing Aspen Polymers 3
Review lists of known deficiencies and defects
Registered users can also subscribe to our Technical Support e-Bulletins. These e-Bulletins are used to
alert users to important technical support information such as:
Technical advisories
Product updates and releases
Customer support is also available by phone, fax, and email. The most up-to- date contact information is
available at the AspenTech Support Center at http://support.aspentech.com.
4 Introducing Aspen Polymers
1 Polymer Manufacturing Process
Overview
This chapter provides an overview of the issues related to polymer manufacturing process modeling and
their handling in Aspen Polymers (formerly known as Aspen Polymers Plus).
Topics covered include:
About Aspen Polymers, 5
Overview of Polymerization Processes, 6
Issues of Concern in Polymer Process Modeling, 7
Aspen Polymers Tools, 9
Defining a Model in Aspen Polymers, 12
About Aspen Polymers

Aspen Polymers is a general-purpose process modeling system for the simulation of polymer
manufacturing processes. The modeling system includes modules for the estimation of thermophysical
properties, and for performing polymerization kinetic calculations and associated mass and energy
balances.
Also included in Aspen Polymers are modules for:
Characterizing polymer molecular structure
Calculating rheological and mechanical properties
Tracking these properties throughout a flowsheet
There are also many additional features that permit the simulation of the entire manufacturing processes.
1 Polymer Manufacturing Process Overview 5
Overview of Polymerization Processes
Polymer Definition
A polymer is a macromolecule made up of many smaller repeating units providing linear and branched
chain structures. Although a wide variety of polymers are produced naturally, synthetic or man-made
polymers can be tailored to satisfy specific needs in the market place, and affect our daily lives at an
ever-increasing rate. The worldwide production of synthetic polymers, estimated at approximately 100
million tons annually, provides products such as plastics, rubber, fibers, paints, and adhesives used in the
manufacture of construction and packaging materials, tires, clothing, and decorative and protective
products.
Polymer Molecular Bonds

Polymer molecules involve the same chemical bonds and intermolecular forces as other smaller chemical
species. However, the interactions are magnified due to the molecular size of the polymers. Also
important in polymer production are production rate optimization, waste minimization and compliance to
environmental constraints, yield increases and product quality. In addition to these considerations, end-
product processing characteristics and properties must be taken into account in the production of
polymers (Dotson, 1996).
Polymer Manufacturing Process Steps

Polymer manufacturing processes are usually divided into the following major steps: 1 Monomer
Synthesis and Purification 2 Polymerization 3 Recovery / Separation 4 Polymer Processing
The four steps may be carried out by the same manufacturer within a single integrated plant, or specific
companies may focus on one or more of these steps (Grulke, 1994).
The four steps may be carried out by the same manufacturer within a single integrated plant, or specific
companies may focus on one or more of these steps (Grulke, 1994).
The following figure illustrates the important stages for each of the four polymer production steps. The
main issues of concern for each of these steps are described next.
6 1 Polymer Manufacturing Process Overview
Issues of Concern in Polymer Process
Modeling
There are modeling issues associated with each step in the production of polymers. The following table
summarizes these issues along with the required tools:
Step Modeling Issues/Concerns Tools Required
Monomer synthesis and purification
Feedstock purity Monomer degradation Emissions Waste disposal
Unit operations: separators Reaction kinetics Phase equilibria
Polymerization Temperature control
Molecular weight control, polymer specifications Conversion yield Reaction medium viscosity Residence time Reactor
stability Waste minimization
Characterization Reaction kinetics Phase equilibria Heat transfer Unit operations: reactors Transport phenomena
Process dynamics Process control Recovery / Separation Solvent removal
Monomer recovery
Unit operations: separators Phase equilibria Heat and mass transfer Polymer processing Solvent removal
Solids handling
Heat and mass transfer Unit operations: separators
Monomer Synthesis and Purification

During monomer synthesis and purification, the engineer is concerned with purity. This is because the
presence of contaminants, such as water or dissolved gases for example, may adversely affect the
subsequent polymerization stage by:
Poisoning catalysts
Depleting initiators
Causing undesirable chain transfer or branching reactions
Another concern of this step is the prevention of monomer degradation through proper handling or the
addition of stabilizers. Control of emissions, and waste disposal are also important factors in this step.
Polymerization
The polymerization step is usually the most important step in terms of the economic viability of the
manufacturing process. The desired outcome for this step is a polymer product with specified properties
such as:
Molecular weight distribution
Melt index
Composition
Crystallinity/density
Viscosity
The obstacles that must be overcome to reach this goal depend on both the mechanism of polymer
synthesis (chain growth or step growth), and on the polymerization process used.
Polymerization processes may be batch, semi-batch or continuous. In addition, they may be carried out in
bulk, solution, slurry, gas-phase, suspension or emulsion. Batch and semi-batch processes are preferred
for specialty grade polymers. Continuous processes are usually used to manufacture large volume
commodity polymers. Productivity depends on heat removal rates and monomer conversion levels
achieved. Viscosity of polymer solutions, and polymer particle suspensions and mixing are important
considerations. These factors influence the choice of, for example, bulk versus solution versus slurry
polymerization. Another example is the choice of emulsion polymerization that is often dictated by the
form of the end-use product, water-based coating or adhesive. Other important considerations may
include health, safety and environmental impact.
Most polymerizations are highly exothermic, some involve monomers that are known carcinogens and
others may have to deal with contaminated water.
In summary, for the polymerization step, the reactions which occur usually cause dramatic changes in the
reaction medium (e.g. significant viscosity increases may occur), which in turn make high conversion
kinetics, residence- time distribution, agitation and heat transfer the most important issues for the majority
of process types.
Recovery / Separation
The recovery/separation step can be considered the step where the desired polymer produced is further
purified or isolated from by-products or residual reactants. In this step, monomers and solvents are
separated and purified for recycle or resale. The important concerns for this step are heat and mass
transfer.
Polymer Processing
The last step, polymer processing, can also be considered a recovery step. In this step, the polymer slurry
is turned into solid pellets or chips. Heat of vaporization is an important factor in this step (Grulke, 1994).
Summary
In summary, production rate optimization, waste minimization and compliance to environmental
constraints, yield increase, and product quality are also important issues in the production of polymers. In
addition, process dynamics and stability constitute important factors primarily for reactors.
Aspen Polymers Tools

Aspen Polymers provides the tools that allow polymer manufacturers to capture the benefits of process
modeling.
Aspen Polymers can be used to build models for representing processes in two modes: with Aspen Plus
for steady-state models, and with Aspen Dynamics or Aspen Custom ModelerTM for dynamic models. In
both cases, the tools used specifically for representing polymer systems fall into four categories:
Polymer characterization
Physical properties
Reaction kinetics
Data
Through Aspen Plus, Aspen Dynamics and Aspen Custom Modeler, Aspen Polymers provides robust and
efficient algorithms for handling:
Flowsheet convergence and optimization
Complex separation and reaction problems
User customization through an open architecture
Component Characterization
Characterization of a polymer component poses some unique challenges. For example, the polymer
component is not a single species but a mixture of many species. Properties such as molecular weight
and copolymer composition are not necessarily constant and may vary throughout the flowsheet and with
time. Aspen Polymers provides a flexible methodology for characterizing polymer components (U.S.
Patent No. 5,687,090).
Each polymer is considered to be made up of a series of segments. Segments have a fixed structure. The
changing nature of the polymer is accounted for by the specification of the number and type of segments
it contains at a given processing step.
Each polymer component has associated attributes used to store information on molecular structure and
distributions, product properties, and particle size when necessary. The polymer attributes are
solved/integrated together with the material and energy balances in the unit operation models.
Polymer Physical Properties

Correlative and predictive models are available in Aspen Polymers for representing the thermophysical
properties of a polymer system, the phase equilibrium, and the transport phenomena. Several physical
property methods combining these models are available. In addition to the built-in thermodynamic
models, the open architecture design allows users to override the existing models with their own in-house
models.
Polymerization Kinetics
The polymerization step represents the most important stage in polymer processes. In this step, kinetics
play a crucial role. Aspen Polymers provides built-in kinetic mechanisms for several chain-growth and
step-growth type polymerization processes. The mechanisms are based on well-established sources from
the open literature, and have been extensively used and
validated against data during modeling projects of industrial polymerization reactors.
There are also models for representing polymer modification reactions, and for modeling standard
chemical kinetics. In addition to the built-in kinetic mechanisms, the open-architecture design allows users
to specify additional reactions, or to override the built-in mechanisms.
Modeling Data
A key factor in the development of a successful simulation model is the use of accurate thermodynamic
data for representing the physical properties of the system, and of kinetic rate constant data which
provide a good match against observed trends.
In order to provide the physical property models with the parameters necessary for property calculations,
Aspen Polymers has property parameter databanks available. These include:
Polymer databank containing parameters independent of chain length
Segment databank containing parameters to which composition and chain length are applied for
polymer property calculations
Functional group databank containing parameters for models using a group contribution approach is
also included
This User Guide contains several tabulated parameters which may be used as starting values for specific
property models. Property data packages are also being compiled for some polymerization processes
and will be made available in future versions.
In addition to physical property data, Aspen Polymers provides users with ways of estimating missing
reaction rate constant data. For example, the data regression tool can be used to fit rate constants
against molecular weight data.
Process Flowsheeting
Aspen Polymers provides unit operation models, flowsheeting options, and analysis tools for a complete
representation of a process.
Models for batch, semi-batch and continuous reactors with mixing extremes of plug flow to backmix are
available. In addition, other unit operation models essential for flowsheet modeling are available such as:
Mixers
Flow splitters
Flash tanks
Devolatilization units
Flowsheet connectivity and sequencing is handled in a straightforward manner.
Several analysis tools are available for applying the simulation models developed. These include tools
for:
Process optimization
Examining process alternatives
Analyzing the sensitivities of key process variables on polymer product properties
Fitting process variables to meet design specifications
Defining a Model in Aspen Polymers

In order to build a model of a polymer process you must already be familiar with Aspen Plus. Therefore,
only the steps specific to polymer systems will be described in detail later in this User Guide. The steps
for defining a model in Aspen Polymers are as follows:
Step 1. Specifying Global Simulation Options
The first step in defining the model is the specification of:
Global simulation options, i.e. simulation type
Units to be used for simulation inputs and results
Basis for flowrates
Maximum simulation times
Diagnostic options
Step 2. Defining the Flowsheet
For a full flowsheet model, the next step is the flowsheet definition. Here you would specify the unit
operation models contained in the flowsheet and define their connectivity.
Chapter 4 describes the unit operation models available for building a flowsheet.
Step 3. Defining Components
Most simulation types require a definition of the component system. You must correctly identify polymers,
polymer segments, and oligomers as such. All other components are considered conventional by default.
Chapter 2 provides information on defining components.
Step 4. Characterizing Components
Conventional components in the system are categorized by type. Additional characterization information
is required for other than conventional components. You must specify the:
Component attributes to be tracked for polymers
Type of segments present
Structure of oligomers
Type and activity of catalysts
In addition, you may wish to request tracking of molecular weight distribution.
Component characterization is discussed in Chapter 2.
Step 5. Specifying Property Models
You must select the models to be used to represent the physical properties of your system.
The Aspen Polymers User Guide, Volume 2, Aspen Polymers Physical Property Methods and Models,
describes the options available for specifying physical property models.
Step 6. Defining Polymerization Kinetics
Once you have made selections out of the built-in polymerization kinetic models to represent your
reaction system, you need to choose specific reactions from the sets available and enter rate constant
parameters for these reactions.
Chapter 3 describes the models available and provides descriptions of the input options.
Step 7. Defining Feed Streams
For flowsheet simulations, you must enter the conditions of the process feed streams. If the feed streams
contain polymers, you must initialize the polymer attributes.
Polymer attribute definition in streams is discussed in a separate section of Chapter 2.
Step 8. Specifying UOS Model Operating Conditions
You must specify the configuration and operating condition for unit operation models contained in the
flowsheet. In the case of reactors, you have the option of assigning kinetic models defined in step 6 to
specific reactors.
Chapter 4 provides some general information regarding the use of unit operation models.
Step 9. Specifying Additional Simulation Options
For a basic simulation the input information you are required to enter in steps 1-8 is sufficient. However,
there are many more advanced simulation options you may wish to add in order to refine or apply your
model. These include setting up the model for plant data fitting, sensitivity analyses, etc.
Many of these options are described in a separate section of Chapter 4.
Information for building dynamic models is given in the Aspen Dynamics and Aspen Custom Modeler
documentation sets. Note that for building dynamic models, users must first build a steady-state model
containing:
Definition of the polymer system in terms of components present
Physical property models
Polymerization kinetic models
Note: Aspen Polymers setup and configuration instructions are given in Chapter 5.
References
Dotson, N. A., Galvn, R., Laurence, R. L., & Tirrell, M. (1996). Polymerization Process Modeling. New
York: VCH Publishers.
Grulke, E. A. (1994). Polymer Process Engineering. Englewood Cliffs, NJ: Prentice Hall.
Odian, George. (1991). Principles of Polymerization (3rd Ed.). New York: John Wiley and Sons.
2 Polymer Structural
Characterization
One of the fundamental aspects of modeling polymer systems is the handling of the molecular structure
information of polymers. This chapter discusses the approaches used to address this issue in Aspen
Polymers (formerly known as Aspen Polymers Plus).
Polymer Structure, 15
Polymer Structural Properties, 19
Characterization Approach, 19
Included in this manual are several sections devoted to the specification of polymer structural
characterization information.
3 Component Classification, 21
Polymer Structural Properties, 33
Structural Property Distributions, 55
End-Use Properties, 73
Polymer Structure
Polymers can be defined as large molecules or macromolecules where a smaller constituting structure
repeats itself along a chain. For this reason, polymers tend to exhibit different physical behavior than
small molecules also called monomers. Synthetic polymers are produced when monomers bond together
through polymerization and become the repeating structure or segment within a chain. When two or more
monomers bond together, a polymer is formed. Small polymer chains containing 20 or less repeating
units are usually called oligomers.
The fact that identifiable segments are found repeatedly along a polymer chain, provides convenient ways
to categorize polymers. Polymers can be classified based on segment composition or sequence:
Homopolymers - containing one type of repeating unit which can be mapped into one segment
2 Polymer Structural Characterization 15
Copolymers - which have two or more repeating units. Copolymers can be in a random, alternating,
block, or graft configuration
If we consider the arrangement of a given chain, another classification arises. Polymers may be:
Linear
Branched (with short or long chains)
Star
Ladder
Network
Another classification that results from polymer structure has to do with physical state. A solid polymer
may be:
Amorphous - when the chains are not arranged in a particular pattern
Crystalline - when the chains are arranged in a regular pattern
A related classification divides polymers by thermal and mechanical properties into:
Thermoplastics (may go from solid to melt and vice versa)
Thermosets (remain solid through heating)
Elastomers (which have elastic properties)
Finally, polymers can be categorized based on the form they are manufactured into: plastics, fibers, film,
coatings, adhesives, foams, and composites.
Polymer Types by Physical Structure

The following figure illustrates the various polymer types based on chain structure:
16 2 Polymer Structural Characterization
Polymer Types by Property
The following table illustrates the various polymer types based on properties:
Classification Type Physical Property
Thermal / Mechanical properties
Thermoplastics Thermosets Elastomers
Can melt and solidify again Remain solid through heating Have elastic properties Fabrication Plastics
Fibers Coatings Adhesives Foams Composites Elastomers
Very versatile in terms of application Most commonly used as textiles Used for both decorative and protective
purposes Used for their bonding properties Used as packaging, upholstery, insulation, etc. Can be tailored to many
applications Used for their elastic properties
In addition to these classifications, polymers can be categorized based on the type of constituting atoms
on the chains.
Homochains produced through chain-growth polymerization have only carbon atoms on the polymer
backbone.
Heterochains produced through step-growth polymerization have other types of atom incorporated into
the polymer backbone.
Polymer Categories by Chemical Structure
The following table lists various homochain and heterochain polymers based on the type of atoms on the
polymer backbone or the substituted side groups:
Polymer Category Description Examples
Polymers with carbon-carbon backbone
Polyacrylics Ethylene backbone with one acrylic
acid (or derivative) as side group per ethylene
Polyacrylic acid, polymethyl methacrylate, polyacrylonitrile, polyacrylamide Polydienes One double bond per repeat
unit Polybutadiene Polyhalogen hydrocarbons
Fluorine or chlorine side group per ethylene
Polyvinyl fluoride, polyvinylidene fluoride, polyvinylchloride, Polyolefins Alphatic or aromatic substituents
Polyethylene, polypropylene, polyisobutylene, polystyrene Polyvinyls From vinyl monomers Polyvinyl acetate,
polyvinyl alcohol
Polymers with carbon-nitrogen backbone
Polyamides Amide group on backbone Nylon 6, nylon 6,6 Polyurethanes Urethane group on backbone Polyurethane
foams Polyureas Urea group on backbone Polyurea resins
Polymer Category Description Examples
Polymers with carbon-oxygen backbone
Polyacetals Acetal group on backbone Polyacetate Polyethers Ether group on backbone Polyethylene oxide,
polyphenylene
oxide Polyesters Ester group on backbone Polycarbonate polyethylene
therephthalate, polybutylene therephthalate polylactide
Polymers with carbon-sulfur backbone
Polysulfides Sulfide group on backbone Polysulfide fibers
Polymer Structural Properties

All the methods of categorizing polymers point to certain key characteristics that must be taken into
account in order to fully define polymer molecules. Typical information needed to capture the structure
and behavior of polymers includes:
Chemical structure of segments: segment type, and configuration
Chain size for the mixture of polymer chains
Crystallinity
Additional structural, thermal, and mechanical characteristics
Characterization Approach
Aspen Polymers allows for the different types of chemical species that may be found in a polymer system:
Monomers
Solvents
Catalysts
Oligomers
Polymers
Polymer segments are introduced to identify the chemical structure of the polymer or oligomer repeat unit.
In addition, they are used as building blocks within polymerization reactions, and in the determination of
thermodynamic properties.
More than the chemical structure of the segments is needed in order to define a polymer. Also needed is
the segment composition of the chains. In addition, properties related to size are needed: degree of
polymerization or number of segments.
Component Attributes
Within Aspen Polymers, component attributes are used to define these structural characteristics.
Component attributes are available to track segment composition, degree of polymerization, molecular
weight, etc. Because the polymer is a mixture of chains, there is normally a distribution of these structural
characteristics. The component attributes are used to track the averages.
There are additional attributes used to track information about the distribution of chain sizes. These are
the moments of chain length distribution. For detailed information about component attributes, see
Polymer Structural Properties on page 33.
In addition to the component attributes, users have the option within Aspen Polymers to examine polymer
molecular weight distribution. This feature is based on a method of instantaneous properties. For more
information, see Method of Instantaneous Properties on page 60.
References
Munk, P. (1989). Introduction to Macromolecular Science. New York: John Wiley and Sons.
Odian, G. (1991). Principles of Polymerization (3rd Ed.). New York: John Wiley and Sons.
Rudin, A. (1982). The Elements of Polymer Science and Engineering. Orlando: Academic Press.
3 Component Classification
This section discusses the specification of components in a simulation model.
Component Categories, 21
Component Databanks, 25
Segment Methodology, 27
Specifying Components, 28
Component Categories
When developing a simulation model in Aspen Polymers (formerly known as Aspen Polymers Plus), users
must assign components present in process flow streams to one of the following categories:
Conventional
Polymer
Oligomer
Segment
Site-based
The following figure illustrates the different categories of components and their input requirements:
3 Component Classification 21
Conventional Components
Standard conventional components are molecular components such as water. These components have a
fixed molecular structure and participate in phase equilibrium. Components falling into this category
include:
Monomers
Initiators
Chain transfer agents
Solvents
Catalysts
In order to fully specify conventional components, you need only specify pure component data required
for the phase equilibrium calculations. This data may be entered or retrieved from component databanks.
Note: Ziegler-Natta catalysts and ionic initiators require additional characterization information.
Polymers
In Aspen Polymers, polymer components represent a distribution of polymeric species. The average size
and composition of the molecules in this distribution
22 3 Component Classification
can change throughout the simulation. Each polymer molecule is considered to be made up of repeating
units or segments. Typically, the segments correspond to the monomers that are used to grow the
polymer.
The structure of polymers depends on the number and type of segments they contain and the
arrangement of segments in linear, branched, or cross-linked forms.
Component attributes are used to track polymer structural properties (U.S. Patent No. 5,687,090) such
as:
Segment composition
Copolymer composition and average sequence length
Degree of polymerization
Molecular weight
Branching
Moments of molecular weight distribution
Molecular architecture (physical arrangement of segments within the polymer molecule)
Segments are specified independently from polymers. For each polymer, you must select the types of
component attributes to be included in the simulation model. If the polymer is present in the process feed
streams, you must provide its properties by initializing the component attributes while specifying input
data for these feed streams.
For more information on component attribute specification, see Polymer Structural Properties on page 33.
Oligomers
By convention, oligomers are defined as components with two or more segments and a fixed molecular
structure. They can be defined as volatile or non-volatile. Typically, the oligomer feature is used to allow
users to track the loss of volatile short-chain polymers.
In order to specify oligomers, you must specify their composition in terms of the number and type of
segments they contain. Oligomers do not require component attributes. For this reason, you may treat a
polymer as an oligomer in cases where you want to process the polymer within a unit operation model
which cannot handle polymer component attribute data.
When using oligomer components, you may specify addition properties through the following unary
property parameters:
Parameter Definition Default
POLDP Number-average chain
length
Calculated *
POLPDI Polydispersity index 1 ** POLCRY Mass fraction crystallinity
* Calculated from the number of segments in the oligomer as specified in the
Polymers form Oligomers subform. ** Used to calculate DPW and MWW.
Note: Not all kinetic models track oligomers as separate components. If a model does not provide fields
for specifying oligomers on its input forms, then these components are not tracked.
Segments
Segments are the structural units of a polymer or oligomer and are specified independently from these
components. Their structure is fixed throughout a simulation. Segments typically correspond to the
monomers used to grow the polymer. They are divided into types depending on their location on the
polymer chain:
Repeat units
End groups
Branch point (attached to three or four branches)
Site-Based
Site-based components pertain to multisite reaction kinetic models (Ziegler- Natta and Ionic). Site-based
components include Ziegler-Natta catalysts and ionic initiators.
Ziegler-Natta Catalysts
Ziegler-Natta catalysts are often used to initiate polymer chain formation in chain-growth polymerization
reactions. Catalysts can be treated as standard conventional components. Ziegler-Natta catalysts or
metallocene catalysts involve one or more polymerization site types which may be in an activated or
deactivated state.
In order to use Ziegler-Natta catalysts, you must specify the number of site types and the catalyst
properties to be tracked, that is, the site activity.
Catalyst properties are defined as component attributes. You must initialize the catalyst properties while
specifying input data for the streams containing the catalysts.
For more information on component attribute specification, see Polymer Structural Properties on page 33.
Ionic Initiators
Ionic initiators are used in anionic and cationic polymerization. The ionic initiators can be treated as
standard conventional components. The propagating species in ionic polymerization can be:
Free-ions
Ion-pairs
Dormant esters
In Aspen Polymers, these different species are modeled as different sites of an ionic initiator. Three
different site-based attributes are tracked for an ionic initiator. For more information, see Ionic Initiator
Attributes on page 45.
Component Databanks
The thermodynamic and transport property models needed to perform the physical property and phase
equilibrium calculations during a simulation require pure component property data. These include:
Molecular weight
Heat capacity
Heat of formation
Heat of vaporization
Vapor pressure
Density
Enter that information while selecting and specifying physical property models. Normally, you would make
use of the pure component databanks and retrieve data from them for each of the components present in
the simulation model:
Data for conventional components are retrieved from the Pure Component databank
Data for free-radical initiators are retrieved from the INITIATOR databank
Data for polymers are retrieved from the POLYMER databank
Data for oligomers are retrieved either from the pure component databank or from the POLYMER
databank
Data for segments are retrieved from the SEGMENT databank
Data for PC-SAFT are retrieved from the PC-SAFT databank
Data for POLYPCSF are retrieved from the POLYPCSF databank
Descriptions of the databanks, and the parameters they contain are given in Appendix A.
Pure Component Databank

In the Pure Component databank, components are named using a nomenclature developed for Aspen
Plus. Each component is given an alias summarizing the number of each type of atom: C, H, O, N, P, S,
CL, F, etc. (e.g. C2H4 for ethylene). For cases where the same alias matches several components, a
counter is added to make the distinction (e.g. C2H4O2-1 for acetic acid).
Note: Catalysts are often solid components and may not be found in the PURE11 databank. Normally,
you do not need a rigorous representation of these components.
An acceptable approach is to assign a monomer alias to the catalyst and then provide the correct
molecular weight and certain parameters which will prevent the catalyst from vaporizing. If an activity
coefficient model is being used for phase equilibrium representation, the catalysts can be assumed to be
non-volatile by specifying -40 as the first Antoine parameter (PLXANT(1) = - 40).
PC-SAFT Databank
The PC-SAFT databank contains pure and binary parameters used with the PC-SAFT property method.
The parameters are taken from the literature, including many normal compounds, polar compounds and
associating compounds.
POLYPCSF Databank
The POLYPCSF databank contains pure and binary parameters used with the POLYPCSF property
method. The parameters are taken from the literature, including many normal compounds, but excluding
polar compounds and associating compounds.
INITIATO Databank
The INITIATO databank contains data for initiator components. Rate constants in this databank are
derived from half-life data in vendor datasheets published on public web sites. These datasheets
generally contain data at several temperatures, allowing the activation energy and prefactor to be
determined. These rate constants depend on the reaction environment, and may vary between polar and
non-polar solvents. Where multiple sets of data were available, the data from monomer or organic
solvents were used in preference to data from aqueous solutions.
Molecular weight and other parameters are calculated from structure using estimation methods from
Aspen Plus, except in those few cases where vapor pressure data was provided in the datasheets.
In the INITIATO databank, components are named using industry-standard acronyms. Each component
is given an alias summarizing the number of each type of atom: C, H, O, N, P, S, CL, F, etc. For cases
where the same alias matches several components, a counter is added to make the distinction (e.g. 1,-
2, etc).
Segment Databank
In the Segment Databank, a segment name comes from the name of the monomer from which it
originates. Therefore, in this databank component names and aliases follow the same conventions as
those for the Pure Component Databank.
A label is added to the monomer name to identify the segment as either a repeat unit,-R, an end group,-
E, or a branch point, -B (e.g. for butadiene segments: C4H6-R-1or BUTADIENE-R-1 corresponding to the
repeat unit
CH
2
CH=CHCH
2
, C4H5-E-1 or BUTADIENE-E-1 corresponding to the end group CH=CHCH=CH
2
and C4H5-B or BUTADIENE-B corresponding to the branch segment CH
2
CH CH CH ).
Polymer Databank
The Polymer Databank does not follow the conventional nomenclature. The polymer aliases are the
typical acronyms used in industry or academia, and the polymer names consist of the repeat unit name
enclosed in parentheses and preceded by the prefix Poly (e.g. PS or POLY(STYRENE) for polystyrene).
Note: The MW property parameter used to store molecular weights in the component databanks is the
true molecular weight for all component types except polymers. For polymers, the true polymer molecular
weight is normally tracked as a component attribute only. The molecular weight stored in the databank is
the apparent molecular weight calculated as the average segment molecular weight (See Appendix A).
Segment Methodology
The segment approach to characterizing components is a fundamental methodology which affects almost
every functionality within Aspen Polymers. Segments are used as the building blocks for polymers. Once
you have specified the types of segments in the polymer, the segment composition and degree of
polymerization defined as component attributes may be used to define the size and composition of the
polymer.
For oligomers, although component attributes are not used, the number of each segment must be
specified directly.
Most of the Aspen Polymers physical property models calculate polymer and oligomer properties from
segment properties. This is done by taking into account the degree of polymerization and the segment
composition. The calculated properties should be the same for both oligomers and polymers, assuming
that the oligomer structure and molecular weight were specified correctly. Note that this is true for mass-
based properties only. Mole-based properties will be different between polymer and oligomer if their
apparent molecular weights are different.
Within the polymerization reaction models, segments also play a key role. As polymerization progresses,
the models map the reacting monomers into the corresponding segments and return rates of change for
the segment composition.
Specifying Components
To specify components within your model you need to know the following:
Item For
Component types All the species in your system Property parameter databank selections
The species in the system
IUPAC names All conventional components or you need their
physical properties (molecular weight, boiling point, Antoine constants, etc.) Segment structure All polymers and
oligomers (define whether you want
to include any end groups or branch points) Polymer properties to be tracked
All polymers, that is, degree of polymerization, segment composition Additional characteristics All additional
characteristics for catalysts, or ionic
initiators
Selecting Databanks
For an Aspen Polymers simulation, you generally retrieve physical property data from the following
databanks:
Pure component databank (PURE12)
Polymer databank (POLYMER)
Polymer segment databank (SEGMENT)
Initiator databank (INITIATOR)
You can also use other Aspen Plus databanks, user databanks, or in-house databanks. Appendix A
provides descriptions of the polymer and segment databanks and the parameters they contain.
If you selected a polymer template to start your simulation, the correct databanks are already specified.
If you did not select a polymer template, or if you want to modify the databank selection: 1 From the Data
Browser, click Components. 2 From the Components folder, click Specifications. 3 On the Selection
sheet, click the Databanks tab to open the databank
selection form.
Defining Component Names and Types

You must specify a:
Name and a type for each component in the simulation
Component name or identifier
Databank name or alias that sets the pure component properties for the component
Component type that sets the category to which the component belongs and determines the treatment
of that component
To access the components specifications input sheet: 1 From the Data Browser, click Components. 2
From the Components folder, click Specifications. 3 On the Selection sheet, click the Databanks tab to
set the databanks to
be searched for pure component properties.
To define component names and types: 1 On the Selection sheet, in the Component ID field, specify an
ID for
each component. This ID is used to refer to the component in all subsequent input, and is also used to
identify the component in the simulation report. 2 For polymers, oligomers, and segments, specify the
component type in
the Type field. By default, all components are assumed to be standard conventional components. For
Aspen Polymers simulation you must correctly identify the component types:
Use For
Conventional Standard conventional components Polymer Homo and copolymers Oligomer Short chain polymer
molecules Segment Polymer or oligomer repeat units
3 If component property data is being retrieved from databanks, you must
also supply either the databank alias in the Alias field, or the databank name in the Component name
field.
Specifying Segments
The Type of each polymer or oligomer segment must be specified on the Polymer Characterization
Segments sheet. Segments can be repeat units, end groups or branch points attached to three or four
branches.
To access the segments definition input form: 1 From the Data Browser, click Components. 2 From the
Components folder, click Polymers. 3 From the Polymers folder, click Characterization.
To define segments:
On the Segments sheet, assign a type to the segments from the Type field.
Specifying Polymers
For each polymer you must define the component attributes to be tracked. All components specified
Polymer in the Components Specifications folder require component attributes.
To access the polymer input specifications: 1 From the Data Browser, click Components. 2 From the
Components folder, click Polymers. 3 From the Polymers folder, click Characterization. 4 From the
Characterization form, click the Polymers tab.
To specify component attributes for the polymers in your simulation: 1 In the Polymer ID field, select the
polymer. 2 If you want to retrieve a predefined set of component attributes, in Built- in attribute group
select a grouping. The attribute summary table is filled in. For a complete discussion of Aspen Polymers
component attributes, see Polymer Structural Properties on page 33. - or - If you do not want to use a
predefined set of attributes, or if you want to change the attribute selection for a given group, click the
attribute table or click Edit to open the attribute list. 3 Click specific attributes to add or remove them from
the list. Repeat these steps for each polymer.
Specifying Oligomers
For each oligomer you must specify an ID and a structure in terms of number and name of contained
segments.
To access the oligomers definition input form: 1 From the Data Browser, click Components. 2 From the
Components folder, click Polymers. 3 From the Polymers folder, click Characterization. 4 From the
Characterization form, click the Oligomers tab.
To define oligomers: 1 In the Oligomer field, select the oligomer. 2 In the Segment field, enter the name of
a segment contained in the
oligomer. 3 Repeat these steps for each oligomer.
You can define as many segments as needed for an oligomer.
Specifying Site-Based Components

Specify the structure and activity of site-based catalytic species such as Ziegler-Natta catalysts and ionic
initiators.
To access the site-based species definition form: 1 From the Data Browser, click Components. 2 From
the Components folder, click Polymers. 3 From the Polymers folder, click Characterization. 4 From the
Characterization form, click the Site-Based Species tab.
To specify site-based species characteristics: 1 Select the component type: Ziegler-Natta catalyst, ionic
initiator, etc. 2 In the Comp ID field, specify the component name. 3 Specify the number of site types in
Number of sites for the component.
For Ziegler-Natta catalysts, you must also specify the moles of sites per gram of catalyst. 4 Select the list
of properties or component attributes to be tracked for that
component. Click the attribute list table or Edit to open the attribute list. 5 Click specific attributes to
add or remove them from the list for the
component.
References
Bailey, J., & Ollis, D. F. (1986) Biochemical Engineering Fundamentals (2nd Ed.). New York: McGraw-
Hill.
Brandrup, J., & Immergut, E. H. (Eds.). (1989). Polymer Handbook (3rd Ed.). New York: John Wiley &
Sons.
Danner R. P., & High, M. S. (1992). Handbook of Polymer Solution Thermodynamics. New York:
American Institute of Chemical Engineers.
Kroschwitz, J. (Ed.). (1990). Concise Encyclopedia of Polymer Science and Engineering. New York: John
Wiley and Sons.
4 Polymer Structural Properties
This section discusses the use of component attributes for tracking polymer structural properties in a
simulation model.
Structural Properties as Component Attributes, 33
Component Attribute Classes, 34
Component Attribute Categories, 35
Component Attribute Initialization, 46
Component Attribute Scale Factors, 50
Specifying Component Attributes, 51
Structural Properties as Component

Attributes
Component attributes provide a convenient framework to associate structural characterization data to
components in a flow stream. They are carried throughout the flowsheet along with state and composition
information, and effectively extend the stream structure.
Aspen Polymers (formerly known as Aspen Polymers Plus) uses component attributes as a vehicle for
tracking important modeling information for polymers, ionic initiators and Ziegler-Natta catalysts (U.S.
Patent No. 5,687,090). For example, there are component attributes to store:
Segment composition (segment fraction or segment flow)
Copolymer composition and average sequence length
Degree of polymerization (number, weight, and z-average)
Molecular weight (number, weight, and z-average)
Degree of branching (long and short)
Degree of cross-linking (cross-link density)
Molecular architecture (physical arrangement of segments within the polymer molecule)
4 Polymer Structural Properties 33
Live polymer properties
Aggregate polymer properties
In the case of multi-site-type Ziegler-Natta catalyst polymerization, the attributes provide the structure to
store the properties by site. Examples of catalyst attributes include the fraction of dead and potential
sites. The catalyst attributes are used to track catalyst activity. There are also component attributes
available to track user defined data.
The complete list of available attributes is given in the Polymer Component Attributes, Site-Based
Species Attributes, and User Attributes sections of this chapter (pages 35 through 45).
Component Attribute Classes

Component attributes are divided into classes to reflect the nature of various structural properties carried
in process streams:
Class 0 component attributes are derived quantities from other attributes. They are therefore
recalculated from these attributes after they are updated. For example, number average degree of
polymerization is a Class 0 component attribute. It is computed from the zeroth and the first moments of
chain length distribution.
Class 1 component attributes are structural properties per unit mass. They are not used for polymers.
Class 2 component attributes are structural properties per unit time. Examples are zeroth and first
moments of chain length distribution
The following table lists the differences between the Aspen Polymers component attribute classes:
Class Conserved
Quantity
Convergence Treatment
Unit of Measurement Examples
0 N/A Recalculated Varies Degree of
polymerization 1
Attribute
component mass
Direct substitution Attribute / component
mass
None for polymers
2 Attribute Accelerated
convergence
Attribute / time Segment flows,
moments of chain length distribution
For a typical polymer process simulation, Class 0 and Class 2 component attributes are used. Since
Class 0 component attributes are calculated from Class 2 attributes, users have the option of entering
either of the two types for simulation models where polymer is present in the process feed streams. For
this reason, an attribute initialization scheme has been designed. For more information, see Component
Attribute Initialization on page 46.
34 4 Polymer Structural Properties
Component Attribute Categories
The main categories of component attributes available are:
Polymer attributes
Ziegler-Natta catalyst attributes
Ionic initiator attributes
User attributes
Polymer Component Attributes

The polymer properties tracked as component attributes include:
Segment fraction
Segment flow
Flow and fraction of segment dyads (pairs)
Number-average degree of polymerization and molecular weight
Weight-average degree of polymerization and molecular weight
Z-average degree of polymerization and molecular weight
Zeroth through third moment of chain length distribution
Number of long and short chain branches
Long and short chain branching frequency
Number and frequency of cross-links
Number-average block length (sequence length)
Several aspects of molecular architecture, including tacticity, head-to- head insertions (orienticity)
Flow and fraction of terminal double bonds
Flow and fraction of cis-, trans-, and vinyl- isomers associated with diene segments (internal and
pendent double bonds)
There are component attributes available to track most of these properties for dead polymer, live polymer,
and aggregate polymer. You may want to track information for live polymers for cases of free-radical
polymerization where the quasi-steady-state approximation (QSSA) is not used. Site based component
attributes are also available to accommodate multi-site type Ziegler-Natta catalyst polymerization.
Composite attributes are summed over all site types. They represent the average properties of the
polymer.
Polymer Attribute Sets
In summary, there are six sets of polymer component attributes.
Composite Polymer Set contains the basic attributes that may be used for any type of polymerization,
including the minimum required set for all simulation models.
Composite Live Polymer Set contains the attributes required to track the characteristics of live polymer
chains in chain growth polymerization.
Composite Aggregate Polymer Set contains the attributes required to track the characteristics of
aggregate polymer chain in ionic polymerization.
Site-Based Polymer Set contains attributes corresponding to the composite set, but structured to track
information for each catalyst site type.
Site-Based Live Polymer Set contains attributes corresponding to the composite live polymer set,
structured to track information by catalyst site type.
Site-Based Aggregate Polymer Set contains attributes corresponding to the composite aggregate
polymer set, structured to track information by ionic site type.
The tables that follow list the component attributes available in each set. Attributes must be associated
from these sets to each of your polymer components when building a simulation model. To simplify this,
the attributes in the tables were grouped by model usage, or polymerization reaction type (for example,
physical property simulation model, free-radical polymerization model). Select a grouping and all the
attributes needed are retrieved automatically. A table of the minimum required attributes by model usage
is also provided. Attribute Definitions Composite Polymer Attribute Set
Name Symbol Description Equation Class Dimension Units
DPN DP
n
DP n
=1/
0
0 1 Unitless
DPW DP
w
Number-average degree of polymerization
DP
w
=2/
1
0 1 Unitless
DPZ DP z
Weight-average degree of polymerization Z-average degree of polymerization
DP z
=3/
2
0 1 Unitless
PDI PDI Polydispersity index PDI= DP w /DP
n
0 1 Unitless
MWN M
n
Number-average molecular weight
= 0 1 Unitless
MWW M
w
M n DP n
M
seg
Weight-average molecular weight
0 1 Unitless
MWZ M
z
Mw=
DP w
M
seg
Z-average molecular weight
0 1 Unitless
MWSEG M
seg
Mz=
DP z
M
seg
( ) 0 1 Unitless
ZMOM
0
Average segment molecular weight
M seg =
FpiM
i
Zeroth moment of chain
length distribution
---- 2 1 Mole
flow
FMOM
1
First moment of chain length distribution
( )i 0 1 Mole flow SMOM

2
1=
1
Second moment of
chain length distribution
---- 2 1 Mole
flow
TMOM
3
Third moment of chain length distribution
---- 2 1 Mole
flow
SFLOW
1
( i ) Mole flow of segments
of type i
---- 2 NSEG Mole
flow
Attribute Definitions - Composite Polymer Attribute Set (continued)
SFRAC F p
(i
) Mole fraction of
segments of type i
Fp
(i)=1(i
)/
1
0 NSEG Unitless
EFRAC F e
(i
) Fraction of chain end
segments of type i
1
0 NEND Unitless
DYADFLOW
ji,
Fe
() i =
()/ i () i
ends Molar flow rate of
dyads composed of ( type I and j segments
---- 2
NN + )
Mole 2
flow
DYADFRAC
ji,
2 seg seg Fraction of dyads
composed of type I ( and j segments
ji
= ji / 0
NN + )
Unitless 2
BLOCKN
i
2,
, 1 seg seg Bn Number-average block
length for segment i
ii
0 NSEG Unitless
Attributes Related to Branching and Terminal Double Bonds
LCB LCB Number of long chain
branches
i Bn
i
=
1i
1 - ---- 2 1 Mole flow SCB SCB Number of short chain

branches
---- 2 1 Mole
flow
FLCB FLCB Long chain branching
0 1 Unitless frequency FLCB
FSCB FSCB Short chain branching
frequency FSLB
=
103
LCB
1
0 1 Unitless
TBDFLOW = 0
(i)
=
103
SCB
1
Mole flow of terminal
double bond segments of type i
---- 2 NSEG Mole
flow
TBDFRAC )(iF
p
=
Mole fraction of terminal double bond
iF p = /)()( =
=0
i 1 0 NSEG Unitless
segments of type i
Attributes Related to Molecular Architecture (Tacticity and Orienticity)
ATACFLOW 1
atactic
Apparent mole flow of atactic polymer
---- 2 1 Mole
flow
ATACFRAC F atactic Mass fraction of atactic polymer
F atactic = atactic / 0 1 Unitless
HTHFLOW HTH
ii
1 1 Mole flow rate of i-I
dyads with head-to- head orientation
---- 2 NSEG Mole
flow
HTHFRAC ii
HTH
Fraction of i-I dyads with head-to-head orientation
ii
HTH
= ii
HTH
/ ii
0 NSEG Unitless
Attribute Definitions - Composite Polymer Attribute Set (continued)
Attributes Related to Reactions with Diene Monomers
XFLOW XFLOW Number of cross links ---- 2 NSEG* Mole
flow
XDENSITY
XL
Cross-linking density
=
XLFLOW
0
0 NSEG* Kmol/kg
CIS-FLOW cisi,
1
XL M
n
Flow rate of diene

segment i in cis configuration
---- 2 NSEG* Mole
flow
TRANSFLO 1
transi,
Flow rate of diene segment i in trans configuration
---- 2 NSEG* Mole
flow
VINYLFLO 1
vinyli,
Flow rate of diene segment i in vinyl configuration
---- 2 NSEG* Mole
flow
CIS-FRAC f i
cis
Fraction of diene segment i in cis configuration
= / 0 NSEG* Unitless
TRANSFRA Fraction of diene
segment i in trans configuration
f
i
cis
cisi , 1
i1
fi
trans
0 NSEG* Unitless
VINYLFRA Fraction of diene
segment i in vinyl configuration
trans i
=
1
transi , / i vinyl i
f
1
ff
i
vinyl
=
1
vinyli ,
/ 1
i 0 NSEG* Unitless
Attributes Related to Particle Size (Emulsion Polymerization)
PDV PD
v
Polydispersity for PSD (volume)
VV
0 1 Unitless
PSDZMOM
0
PD
v
=
n
v ---- 2 1 #/s
PSDFMOM
1
Zeroth moment of the particle size distribution (volume)
1
= Mass /
0 1 m 3 /s PSDSMOM
2
First moment of the PSD (volume) Second moment of the PSD (volume)
---- 2 1
m 6 /s
PSDTMOM
3
Third moment of the PSD (volume)
---- 2 1 m 9 /s VOLN V
n
Number average volume of the particles
0 1 m3
VOLV V
v
V
n
=
1
0
Volume average volume of the particles
01
m3
VOLZ V
z
V
v
=
2
1
Z-average volume of
the particles
01
m3
DIAV D
v
V
z
=
3
2
Volume average diameter D
v
=3
6
1
0
01

i = Segment index
Moments of the chain length distribution are defined as
=
Qn m
n
Where: m
= 0-3 n
= Chain length Q
n
= Number of moles of polymer of length n.
Equation for recalculating class 0 attributes only. Class 2 attributes are integrated. * Although the dimension is
NSEG, these attributes only apply to diene segments, other elements
will be set to zero.
Attribute Definitions Composite Live Polymer Attribute Set
LDPN DP n
L Number average DP
of live polymer
/ 0 1 Unitless
LDPW DP
w
DP n
L=1
0
L Weight average DP of
live polymer
/ 0 1 Unitless
LPDI PDI L Polydispersity index
of live polymer
DP
w
L=2
1
= / L 0 1 Unitless
LMWN M
n
PDI L
DP w L
DP n
L Number average MW
of live polymer
= L 0 1 Unitless
LMWW M
w
MnL
DP n
L
M
seg
L Weight average MW
of live polymer
= L 0 1 Unitless
LMWSEG M
seg
MwL
DP w L
M
seg
L Average segment
molecular weight of
()
live polymer
0 1 Unitless
LZMOM
0
M seg
L
=
LF p i M
i
Zeroth moment of live polymer
( )i
0 1 Mole flow
LFMOM
1
0=
0
First moment of live polymer
( )i
0 1 Mole flow
LSMOM
2
1=
1
Second moment of live polymer
---- 2 1 Mole flow
LSFLOW
1
( )i Segment flow rates in live polymer
---- 2 NSEG Mole flow
LSFRAC LF p
(i
) Segment mole fraction in live polymer
LF p
(i)=1(i
)/
1
0 NSEG Unitless
LEFLOW
0
( )i End segment flow
rates in live polymer
---- 2 NSEG Mole flow
LEFRAC LF e
(i
) End segment mole
fractions in live polymer
LF e
(i)=0(i
)/
0
0 NSEG Unitless
LPFRAC F
lp
Fraction of polymer that is live
F
lp
0
0
0 1 Mole
fraction
i = Segment index Equation for recalculating class 0 attributes only. Class 2 attributes are integrated.
Attribute Definitions Composite Aggregate Polymer Attribute Set
ADPN DP n
A Number average DP of
aggregate polymer
/ 0 1 Unitless
ADPW DP
w
DP n
A=1
0
A Weight average DP of
aggregate polymer
/ 0 1 Unitless
APDI PDI A Polydispersity index of
aggregate polymer
DP
w
A=2
1
= / A 0 1 Unitless
AMWN M
n
PDI A
DP w
A
DP n
A Number average MW of
aggregate polymer
= A 0 1 Unitless
AMWW M
w
MnA
DP n
A
M
seg
A Weight average MW of
aggregate polymer
= A 0 1 Unitless
AMWSEG M
seg
MwA
DP w
A
M
seg
A Average segment
molecular weight of
()
aggregate polymer
0 1 Unitless
AZMOM
0
M seg
A
=
AF p i M i
( )i 0 1 Mole flow AFMOM

1
Zeroth moment of aggregate polymer
0=
0
( )i 0 1 Mole flow ASMOM
2
First moment of aggregate polymer
1=
1
( )i 0 1 Mole flow ASFLOW
1
Second moment of aggregate polymer
2=
2
( )i Segment flow rates in
aggregate polymer
0 NSEG Mole flow ASFRAC AF p
i
1 () i =
1 (, i j ) ( ) Segment mole fraction in

aggregate polymer
AF p
(i)=1(i
)/
1
0 NSEG Unitless
AEFLOW
0
( )i End segment flow rates
in aggregate polymer
0 NSEG Mole flow AEFRAC End segment mole
fractions in aggregate polymer
0 () i =
0 (, i j ) AF e
(i
)
F
ap
AF e
(i)=0(i
)/
0
0 NSEG Unitless
APFRAC Fraction of polymer that
is aggregate

0 1 Mole
fraction
i = Segment index Equation for recalculating class 0 attributes only. Class 2 attributes are integrated.
Attribute Definitions Site-Based Polymer Attribute Set
SDPN DP n
j
F
ap
=
0
0
( ) Number average degree of polymerization at site j
DP n
( j ) = 1 ( j )/
0
(j
) 0 NSITE Unitless
SDPW DP w
(j
) Weight average degree
of polymerization at site j
DP w
( j ) = 2 ( j )/
1
(j
) 0 NSITE Unitless
SDPZ DP z
(j
) Z-average degree of
polymerization at site j
DP z
( j ) = 3 ( j )/
2
(j
) 0 NSITE Unitless
SPDI PDI ( j ) Polydispersity index at
site j
PDI ( j ) = DP w ( j )/ DP n
(j
) 0 NSITE Unitless
SMWN M n
(j
) Number-average
molecular weight at site j
( ) = ( ) ( ) 0 NSITE Unitless
SMWW M w
j
M n j DP n j M seg
j
( ) Weight-average
SMWZ M z
j
M w j DP w j M seg
j
( ) Z-average molecular
weight at site j
SMWSEG M seg
j
M z j DP z j M seg
j
0 NSITE Unitless
SZMOM
0
( ) Average segment
M seg ( j ) =
F p (, i j ) M
i
( )j Zeroth moment of chain
length distribution at site j
---- 2 NSITE Mole
flow
SFMOM
1
( )j First moment of chain
length distribution at
0 NSITE Mole flow site j SSMOM
2
1(j)=
1 (, i j ) ( )j Second moment of chain

---- 2 NSITE Mole
flow
STMOM
3
( )j Third moment of chain
---- 2 NSITE Mole
flow
SSFLOW
1
(, i j ) Mole flow of segments
of type I at site j
---- 2 NSEG, NSITE
Mole flow SSFRAC F p
(, i j
) Mole fraction of
segments of type I at site j
Fp
(, i j ) = 1 (, i j )/
1
(j
) 0 NSEG; NSITE
Unitless
SEFRAC F e
(, i j
) Fraction of chain end segments of type i at
1
site j
0 NEND, NSITE
Unitless
SLCB LCB ( j ) Number of long chain
branches at site j
Fe
(, i j ) =
(, i j )/ (, i j ends
---- 2 NSITE Mole
flow
SSCB SCB ( j )
Number of short chain
---- 2 NSITE Mole branches at site j
flow
SFLCB FLCB ( j )
Long chain branching frequency at site j
FLCB j
0 NSITE Unitless
SFSCB Short chain branching
frequency at site j
()
=
103
LCB 1 ( j
)(j
)
FSCB ( j )
FSLB j
0 NSITE Unitless
SPFRAC Mass fraction of
composite polymers at that site
103
1 FSP ( j )
()
=
SCB ( j
)(j
)
0 NSITE Unitless
i = Segment index
j = Site number Equation for recalculating class 0 attributes only. Class 2 attributes are integrated.
Attribute Definitions Site-Based Live Polymer Attribute Set
LSDPN DP n
L( j
) Number average
DP of live polymer
( ) 0 NSITE Unitless
LSDPW DP w
j
DP n
L( j ) = 1 ( j )/
0
j
L( ) Weight average
DP of live polymer
LSPDI PDI L( j ) Polydispersity
index of live polymer
DP w
L( j ) = 2 ( j )/
1
j
( ) = ( )/ L ( ) 0 NSITE Unitless
LSMWN M n
j
PDI L
j DP w L
j DP n j L( ) Number average
MW of live polymer
( ) = ( ) L ( ) 0 NSITE Unitless
LSMWW M w
j
MnL
j DP n
L
j M seg
j
L( ) Weight average
MW of live polymer
( ) = ( ) L ( ) 0 NSITE Unitless
LSMWSEG M seg
j
MwL
j DP w L
j M seg
j
0 NSITE Unitless
LSZMOM
0
L ( ) Average segment molecular weight of live polymer
M seg
L
(j)=
LF p (, i j ) M
i
0 NSITE Mole flow LSFMOM
1
( )j Zeroth moment
of live polymer
0(j)=
0 (, i j ) ( )j First moment of
live polymer
0 NSITE Mole flow LSSMOM
2
1(j)=
1 (, i j ) ( )j Second moment
of live polymer
---- 2 NSITE Mole
flow
LSSFLOW
1
(, i j ) Segment flow
---- 2 NSEG, NSITE
Mole flow
LSSFRAC LF p
(i
) Segment mole fraction in live polymer
LF p
(, i j ) = 1 (, i j )/
1
(j
) 0 NSEG, NSITE
Unitless
LSEFLOW
0
(, i j ) End segment flow
---- 2 NSEG, NSITE
Mole flow
LSEFRAC LF e
(, i j
) End segment
mole fractions in live polymer
LF e
(, i j ) = 0 (, i j )/
0
(j
) 0 NSEG, NSITE
Unitless
LSPFRAC F lp
(j
) Fraction of
polymer that is live
F(j
)
=
(j
0
(j
))
0 NSITE Mole lp
fraction
i = Segment index
Attribute Definitions Site-Based Aggregate Polymer Attribute Set
ASDPN DP n
A( j
) Number average DP
of aggregate polymer
ASDPW DP w
j
DP n
A( j ) = 1 ( j )/
0
j
A( ) Weight average DP of
aggregate polymer
ASPDI PDI A( j ) Polydispersity index
DP w
A( j ) = 2 ( j )/
1
j
( ) = ( )/ A ( ) 0 NSITE Unitless
ASMWN M n
j
PDI A
j DP w
A
j DP n j A( ) Number average MW
( ) = ( ) A ( ) 0 NSITE Unitless
ASMWW M w
j
MnA
j DP n
A
j M seg
j
A( ) Weight average MW
( ) = ( ) A ( ) 0 NSITE Unitless
ASMWSEG M seg
j
MwA
j DP w
A
j M seg
j
0 NSITE Unitless
ASZMOM
0
A ( ) Average segment
molecular weight of aggregate polymer
M seg
A
(j)=
AF p (, i j ) M i
0 NSITE Mole flow ASFMOM
1
( )j Zeroth moment of
aggregate polymer
0(j)=
0 (, i j ) ( )j First moment of
aggregate polymer
0 NSITE Mole flow ASSMOM
2
1(j)=
1 (, i j ) ( )j Second moment of
aggregate polymer
---- 2 NSITE Mole
flo
w ASSFLOW
1
(, i j ) Segment flow rates
in aggregate polymer
---- 2 NSEG, NSITE
Mole flow
ASSFRAC AF p
(i
) Segment mole
fraction in aggregate polymer
AF p
(, i j ) = 1 (, i j )/
1
(j
) 0 NSEG, NSITE
Unitless
ASEFLOW
0
(, i j ) End segment flow rates in aggregate polymer
---- 2 NSEG, NSITE
Mole flow
ASEFRAC AF e
(, i j
) End segment mole
fractions in aggregate polymer
AF e
(, i j ) = 0 (, i j )/
0
(j
) 0 NSEG, NSITE
Unitless
ASPFRAC F ap
(j
) Fraction of polymer
that is aggregate
ap
(j
)
(j)
0 NSITE Mole
fraction
DSEFLOW
0
F(j
)
=
0
0 (, i j ) End segment flow
rates in dissociated (from aggregate) polymer
---- 2 NSEG, NSITE
---
DSSFLOW
1
(, i j ) Segment polymer
flow rates in dissociated (from aggregate) polymer
---- 2 NSEG, NSITE
---
DSSMOM
2
( )j Second moment of
dissociated (from aggregate) polymer
---- 2 NSITE ---
i = Segment index
The following table lists the minimum required component attributes by model:
Model Attributes
Property Models
MWN, DPN or both ZMOM and FMOM SFRAC or SFLOW Emulsion MWN, DPN or both ZMOM and FMOM
SFRAC or SFLOW DIAV or both PSDZMOM and PSDFMOM Other polymer particle attributes (optional) Free-
Radical MWN, DPN or both ZMOM and FMOM
SFRAC or SFLOW Other composite attributes (optional) Composite live attributes (optional) Step-Growth MWN, DPN
or both ZMOM and FMOM
SFRAC or SFLOW Ziegler-Natta MWN, DPN or both ZMOM and FMOM
SFRAC or SFLOW Other composite attributes (optional) Composite live attributes (optional) Site based component
attributes (optional) Site based live component attributes (optional) Ionic SZMOM, LSEFLOW
ASEFLOW, DSEFLOW (if association reaction present) LSSFLOW, SSFLOW ASSFLOW, DSSFLOW (if association
reaction present)
Site-Based Species Attributes

There are two types of site-based species attributes:
Zielger-Natta catalyst attributes
Ionic initiator attributes
Zielger-Natta Catalyst attributes

Component attributes are used to track multi-site Ziegler-Natta catalyst site activity, in terms of mole flow
and fraction of potential, inhibited, vacant, and dead sites. The occupied sites are not tracked since that
information may be obtained from the live polymer zeroth moment of chain length distribution. The site
types are defined as follows:
Potential Sites - these are sites not yet activated.
Vacant Site - these are activated sites without a growing polymer attached.
Inhibited Sites - these are activated sites temporarily in an inactive state.
Dead Sites - these are sites having permanently lost their catalytic activity.
Occupied Sites - these are activated sites with a growing polymer attached.
The following table lists the catalyst component attributes:
Attribute Description Class Dimension
CPSFLOW Mole flow of potential sites 2 NSITE CPSFRAC Mole fraction of potential sites 0 NSITE CVSFLOW Mole
flow of vacant sites of type k 2 NSITE CVSFRAC Mole fraction of vacant sites of type
k
0 NSITE
CISFLOW Mole flow of inhibited sites of type k 2 NSITE CISFRAC Mole fraction of inhibited sites of
type k
0 NSITE
CDSFLOW Mole flow of dead sites 2 NSITE CDSFRAC Mole fraction of dead sites 0 NSITE CMSFLOW Mole flow of
metal hydride 2 NSITE CMSFRAC Mole fraction of metal hydride 0 NSITE
Ionic Initiator Attributes

The component attributes are used to track various states of ionic initiator (free ions, ion pairs, dormant
esters) using a multi-site model.
The following table lists the three ionic component attributes:
Attribute Description Class Dimension
P0FLOW Mole flow of
P0
2 NSITE
PT0FLOW Mole flow of
P
T0
2 NSITE
CIONFLOW Mole flow of counter-ion
C
I
2 NSITE
For more information on ionic attributes, see Ionic Polymerization Model in Chapter 3.
User Attributes
Generic component attributes are available for tracking user-specified data. These may be used to track
additional properties not available through the pre-defined attributes.
User component attributes are available as Class 0 through Class 2 attributes. You must supply a Fortran
subroutine to return rates of change for Class 2 attributes and recalculate Class 0 attributes. This would
typically be a user kinetic routine.
User attributes DPSDN and DPSDW are designed to hold data related to particle size distributions of
solid polymers or monomers. The number flow rates (DPSDN) have units of inverse time. Since particle
flow rates are often very high the user may wish to apply appropriate scaling to define this attribute on a
relative basis (for example use this attribute to track flow rates in trillions of particles/sec). The DPSDW
attribute tracks the mass flow rate of each element of the distribution. User subroutines are required to
use this advanced feature.
The following table lists the available user component attributes:
Attribute Description Unit Type Dimension
CACLASS0 Class 0 user attribute Unitless 10 CAUSR1...5 Class 1 user attributes Unitless 10 CAUSRA...E Class 2
user attributes Mole flow 10 DPSDN Discrete particle size
distribution, particle number flow rates. Class 2.
Inverse time 50
DPSDW Discrete particle size
distribution, particle mass flow rates. Class 2.
Mass flow 50
Component Attribute Initialization

In cases where polymer is present in the process feed streams, values for the polymer component
attributes must be specified. Enter this information while specifying the feed stream conditions.
Within Aspen Polymers, material streams are made up of substreams that carry the flow of material of
different types:
Conventional vapor/liquid flow goes into the Mixed substream type
Solid polymer and other solid components which do not participate in phase equilibrium go into the
Cisolid substream type
Most simulations only make use of the Mixed substream. In this substream, you would enter the
conditions, such as temperature and pressure, the number of phases (2 if both vapor and liquid are
present), and the composition in terms of component flows or fractions (along with the total stream flow).
If one of the components for which you enter composition data is a polymer or a catalyst, you must
specify its component attributes. Because users are allowed to specify either Class 0 or Class 2
component attributes, an initialization mechanism had to be defined to calculate the corresponding Class
2. Remember that the Class 2 attributes are the ones which are converged upon during simulation.
Attribute Initialization Scheme
The attribute initialization scheme performs several important functions. In addition to calculating the
needed Class 2 attributes, it automatically calculates an expanded component attribute set from the
minimum required and specified by the user. The minimum required attributes are:
Segment flow rates (SFLOW), or segment fractions (SFRAC)
Number average degree of polymerization (DPN), or both
Zeroth and first moment of chain length distribution (ZMOM and FMOM)
From this set, several other attributes can be calculated using the definitions given in the attribute
definition tables provided earlier in this chapter. The scheme uses priority rules to decide how to calculate
each attribute.
The following table describes the calculation methods and order of priority. The initialization scheme is
also used for recalculating Class 0 attributes during flowsheet convergence. Finally, it can be considered
as a method of ensuring consistency between interrelated attributes.
The Aspen Polymers component attribute initialization methodology is:
Attribute Calculated from Priority
Composite Bulk Polymer Attribute Set
SFRAC SFRAC
SFLOW / SUM (SFLOW) 1 / NSEG
1 2 3 ZMOM ZMOM
FMOM / DPN FMOM*MWSEG / MWN PDI*FMOM*FMOM / SMOM
1 2 3 4 FMOM SUM (SFLOW)
PMASS / MWSEG
1 2 SMOM SMOM
FMOM*DPW FMOM*MWW / MWSEG FMOM*FMOM*PDI / ZMOM ZMOM
1 2 3 4 5 TMOM TMOM
SMOM*DPZ SMOM*MWZ / MWSEG
1 2 3 LCB LCB
FMOM*FLCB / 1.E3
1 2 SCB SCB
FMOM*FSCB / 1.E3
1 2 PSDZMOM PSDZMOM 1 PSDFMOM PSDFMOM
PMASS / PDENS
1 2 PSDSMOM PSDSMOM 1 PSDTMOM PSDTMOM 1
VOLN VOLN
PSDFMOM / PSDZMOM 0.0
1 2 3 VOLV VOLV
PSDSMOM / PSDSMOM / PSDFMOM 0.0
1 2 3 VOLZ VOLZ
PSDTMOM / PSDSMOM 0.0
1 2 3 DIAV DIAV
(6.0*PSDFMOM / / PSDZMOM) 0.0
1 2 3 PDV PDV
(PSDZMOM*PSDSMOM) / (PSDFMOM) 0.0
123
Composite Live Polymer Attribute Set
LSFRAC LSFRAC
LSFLOW / SUM (LSFLOW) 1 / NSEG
1 2 3 LZMOM LZMOM
LPFRA*ZMOM LFMOM / LDPN LFMOM*LMWSEG / LMWN LPDI*LFMOM*LFMOM / LSMOM
1 2 3 4 5 LFMOM SUM (LSFLOW)
LZMOM*LDPN LZMOM*LMWN / LMWSEG LZMOM*LSMOM / LPDI
1 2 3 4 LSMOM LSMOM
LFMOM*LDPW LFMOM*LMWW / LMWSEG LFMOM*LFMOM*LPDI / LZMOM
1234
Composite Aggregate Polymer Attribute Set
ASFRAC ASFRAC
ASFLOW / SUM (ASFLOW) 1 / NSEG
123
AZMOM AZMOM
APFRA*ZMOM AFMOM / ADPN AFMOM*AMWSEG / AMWN APDI*AFMOM*AFMOM / ASMOM
1 2 3 4 5 AFMOM SUM (ASFLOW)
AZMOM*ADPN AZMOM*AMWN / AMWSEG AZMOM*ASMOM / APDI
1 2 3 4 ASMOM ASMOM
AFMOM*ADPW AFMOM*AMWW / AMWSEG AFMOM*AFMOM*APDI / AZMOM
1234
Site Based Bulk Polymer Attribute Set
SSFRAC SSFRAC
SSFLOW / SUM (SSFLOW) 1 / NSEG
1 2 3 SZMOM SZMOM
SFMOM / SDPN SFMOM*SMWSEG / SMWN SPDI*SFMOM*SFMOM / SSMOM
1 2 3 4 SFMOM SUM(SSFLOW)
SPFRAC*PMASS / SMWSEG
1 2 SSMOM SSMOM
SFMOM*SDPW SFMOM*SMWW / SMWSEG SFMOM*SFMOM*SPDI / SZMOM SZMOM
1 2 3 4 5 STMOM STMOM
SSMOM*SDPZ SSMOM*SMWZ / SMWSEG
1 2 3 SLCB SLCB
SFMOM*SFLCB / 1.E3
1 2 SSCB SSCB
SFMOM*SFLCB / 1.E3
12
Site Based Live Polymer Attribute Set
LSSFRAC LSSFRAC
LSSFLOW / SUM (LSSFLOW) 1 / NSEG
123
LSZMOM LSZMOM
LSPFRA*SZMOM LFSMOM / SLDPN LSFMOM*LSMWSEG / SLMWN LSPDI*LSFMOM*LSFMOM / LSSMOM
1 2 3 4 5 LSFMOM SUM (LSSFLOW) LSZMOM*LSDPN LSZMOM*LSMWN / LSMWSEG DSQRT
(LSZMOM*LSSMOM / LSPDI)
1 2 3 4 LSSMOM LSSMOM
LSFMOM*LSDPW LSFMOM*LSMWW / LSMWSEG LSFMOM*LSFMOM*LSPDI / LSZMOM
1234
Site Based Aggregate Polymer Attribute Set
ASSFRAC ASSFRAC
ASSFLOW / SUM (ASSFLOW) 1 / NSEG
1 2 3 ASZMOM ASZMOM
ASPFRA*SZMOM AFSMOM / SADPN ASFMOM*ASMWSEG / SAMWN ASPDI*ASFMOM*ASFMOM / ASSMOM
1 2 3 4 5 ASFMOM SUM (ASSFLOW) ASZMOM*ASDPN ASZMOM*ASMWN / ASMWSEG DSQRT
(ASZMOM*ASSMOM / ASPDI)
1 2 3 4 ASSMOM ASSMOM
ASFMOM*ASDPW ASFMOM*ASMWW / ASMWSEG ASFMOM*ASFMOM*ASPDI / ASZMOM
1234
PMASS is polymer mass, PDENS is polymer density
Component Attribute Scale Factors

Aspen Plus uses numerical solvers to resolve flowsheet recycle streams and to solve the conservation
equations in each of the kinetic reactor models (RCSTR, RPLUG, and RBATCH). The solver algorithms
use scaled variables. Typically, the ideal scale factors for each type of variable should be on the same
order of magnitude as the variable itself. In other words, the solvers work best when the scaled variables
are all close to unity.
In Aspen Polymers, default scaling factors are defined for each type of component attribute variable.
These defaults are designed to address a wide range of problems, however they may not be ideal for any
particular problem. The Scaling form lets you view and change the default scaling factors for each type of
component attribute.
Under some circumstances, you may be able to improve the reactor and/or flowsheet recycle stream
convergence by optimizing the attribute scaling factors. For example, in a Ziegler-Natta polymerization
process the live end flow rate (LEFLOW) and the related attributes LZMOM and LSZMOM are sensitive to
the catalyst activity. Highly active catalysts result in very low live end flow rates. Further, the number of
vacant and potential sites (CVSFLOW and CPSFLOW) may be very low for the catalyst.
The Scaling form can be used to specify more accurate scaling factors for the component attributes for
polymers, catalysts, and other types of attributed components.
Reducing the scaling factors on this form tightens the tolerance on the selected variables. If the scaling
factors are set too low, the tolerance will be unreasonably tight, leading to convergence problems or
excessive CPU time. If the scaling factors are set too high, the problem may be loosely converged and
the simulation accuracy may suffer.
The reactor models and flowsheet recycle convergence algorithms currently ignore the attribute upper
bound limits that appear on this form.
Specifying Component Attributes

There are several categories of components for which you can specify component attributes:
Polymers
Site-based components
Conventional components
Specifying Polymer Component Attributes

See Specifying Polymers on page 29.
Specifying Site-Based Component Attributes

See Specifying Site-Based Components on page 30.
Specifying Conventional Component Attributes
You can associate attributes to conventional components by selecting user attributes. Typically, you do
this if you have a user subroutine to return values for these attributes.
To access the user component attribute selection form: 1 From the Data Browser, click Components. 2
From the Components folder, click Component Attributes.
To associate user attributes to conventional components: 1 On the Selection sheet, specify the
component name in the Component
field. 2 In the Attribute field, specify the attribute name. 3 Continue adding as many attributes as
needed.
Initializing Component Attributes in Streams or Blocks

If you have an attributed component present in a feed stream, you must specify component attribute
values for that component.
To access the component attribute input form for a stream: 1 From the Process Flowsheet window, use
the right mouse button to click
the feed stream. 2 Click Input. 3 From the stream input specifications sheet, click the Component Attr.
tab. 4 On the Component Attr. sheet, select the Component ID. 5 For each attribute, select the
Attribute ID and enter the values for the
attributes.
If you have an attributed component produced within a reactor, you can specify attribute values (product
values or product value estimates) for that component. This is not available for all reactors.
For a description of the treatment of component attributes in reactors, see Steady-State Unit Operation
Models in Chapter 4.
To access the component attribute input form for a reactor: 1 From the Process Flowsheet window, use
the reactor. 2 Click Input. 3 From the reactor input specifications sheet, click the Component Attr.
tab. 4 On the Component Attr. sheet, select the Component ID. 5 For each attribute, select the
Attribute ID and enter the values for the
attributes.
Specifying Component Attribute Scaling Factors
You can override default component attribute convergence parameters for polymer or catalyst
components. Adjusting the scaling factor helps you improve flowsheet convergence and internal
convergence in reactor models. Typically, the scaling factor should be the same order as the expected
value of the variable.
To access the component attribute scaling form: 1 From the Data Browser, click Components. 2 From the
Components folder, click Scaling.
To adjust the default scaling factor and upper bound of defined attributes: 1 On the Input tab, specify the
component name in the Component ID
field. 2 In the Attribute field, specify the attribute name. 3 Continue adding as many attributes as
needed. 4 Adjust the Scaling factor and/or Upper bound as needed.
References
Aspen Plus User Guide. Burlington, MA: Aspen Technology, Inc.
5 Structural Property Distributions
This section discusses the mechanism available in Aspen Polymers (formerly known as Aspen Polymers
Plus) for tracking structural property distributions, in particular chain size distribution, for chain-growth
polymerization processes (U.S. Patent No. 6,093,211).
Property Distribution Types, 55
Distribution Functions, 56
Distributions in Process Models, 58
Mechanism for Tracking Distributions, 65
Requesting Distribution Calculations, 69
Property Distribution Types

The common polymer structural properties for which distributions are typically considered include:
Chain size - molecular weight or chain length
Copolymer composition
Degree of branching
Polymer particle size
In order to accurately characterize a polymer component, and maintain control of polymer product
properties, engineers must concern themselves with these distributions.
From a modeling standpoint, many theoretical and empirical functions have been developed to represent
distributions. These functions tend to fall into categories derived from their formulation, or from their
graphical representation.
For example, distributions that consider two dependent parameters simultaneously (for example, chain
size and copolymer composition) are termed bivariate distributions.
5 Structural Property Distributions 55
Distributions that mimic the normal bell-shaped graphical representation are called unimodal distributions.
This is in contrast with distributions that reveal several peaks and are called bimodal or multimodal
distributions. The following figure shows examples of unimodal and bimodal distributions:
Distribution Functions
In the majority of cases, the distribution functions proposed in the literature are based on a statistical
approach and use one of three types of mathematical functions: binomial, Poisson or Gaussian.
The parameters in these distribution functions can easily be calculated from the polymer average
properties (degree of polymerization, polydispersity index, etc.). The following are the common
distribution functions that have been applied to the calculation of polymer property distributions:
Schulz-Flory Most Probable (Flory, 1936, 1953; Schulz, 1935, 1939)
Schulz (Schulz, 1935, 1939)
Weibull-Tung Generalized Exponential (Tung, 1956; Weibull, 1951)
Normal (Biesenberger & Sebastian, 1983)
Wesslau Logarithmic Normal (Wesslau, 1956)
Lansing Logarithmic Normal (Lansing, 1935)
Poisson (Biesenberger & Sebastian, 1983)
Zimm (Zimm, 1948)
Stockmayer Bivariate (Stockmayer, 1945)
In addition to these distribution functions, a method using the moments of distributions is also available
(Tompa, 1976). Of these functions, two have greater importance for Aspen Polymers.
Schulz-Flory Most Probable Distribution

Schulz and Flory developed a one-parameter equation to represent the distribution of polymers falling into
one of the following categories:
56 5 Structural Property Distributions
Addition polymers - formed by a constant rate of initiation, with invariant monomer concentration, with
termination by disproportionation only, and with no chain transfer to monomer
Linear condensation polymers - obeying the assumption of equal reactivities of chain ends or linear
condensation polymers formed by random interchange of units
Low molecular weight polymer - formed from a high molecular weight polymer by random scission
The Schulz-Flory distribution is also known as the Most-Probable distribution since it is dictated by the
probability of random events, such as the location of a scission reaction on a long-chain molecule. The
number or mole-fraction distribution and the weight fraction distribution are given by:
Mole-Fraction Distribution
F ( r ) = p r -1 ( 1 - p ) (number distribution)
Weight-Fraction Distribution
W ( r ) = rp r -1 ( 1 - p ) 2 (weight distribution)
Where:
p = Extent of reaction
r = Size of the molecule or number of segments
For addition polymerizations p is the probability that a growing live polymer molecule will propagate. For
step-growth reactions, p is the fractional conversion of monomer end groups.
From these distributions, the number, weight, and z-average degree of polymerization are:
DP
1( n =
1-
p
)
DP
=
((11
p+-
p
)w
)
F ( r ) = p r -1 ( 1 - p ) PDI = +1 p To generate the distribution, p can be calculated from degree of
polymerization as:
p
= -1
1 DP n
Note that the polydispersity approaches two as p unity.
Stockmayer Bivariate Distribution
There are cases where two polymer property distributions must be considered simultaneously, which are
called bivariate. Stockmayer developed a distribution function to consider both chain size and
composition distribution for example (Stockmayer, 1945).
This model may be extended to other combinations of polymer properties such as chain size and long
chain branching distribution for the case of copolymers.
Distributions in Process Models

There is a great demand to know the full molecular weight distribution, particularly for complex
distributions that may have a shoulder, or are even bimodal. This information is needed for optimization of
rheological and mechanical properties of the final polymer product.
Within Aspen Polymers a dual approach for determining polymer properties is used:
Method of moments continues to be the preferred approach for calculating average properties.
Method of instantaneous properties is used to calculate distributions. This method addresses the issue
of data storage and computational complexity in tracking distributions.
Under special circumstances, the most general form of the instantaneous distribution function reduces to
Florys most probable distribution. The instantaneous distribution functions are unimodal. However, the
distribution functions for polymer accumulated in a multi-reactor system may be multimodal.
Average Properties and Moments

It is convenient to examine polymer molecular properties in terms of averages instead of considering the
complete distribution. Average properties must be determined from the actual distributions either through
distribution moments or through instantaneous properties.
The average properties tracked for polymers were described in the Polymer Component Attributes
section on page 35. These properties are calculated using the method of moments within kinetic models.
For a given property s, the property distribution may be described by a frequency function f
s
when the property is a discrete variable, and by a

density function when the property s is continuous. Therefore, f
s
f s( )
and f s( ) represent the portion (for example, number, weight, volume, fraction) of the
population whose property is exactly s (discrete) or whose property lies between s and s + ds.
The frequency and density distribution functions are respectively:
Frequency Function
FS=
S
f
ss
0
and
Density Function
F(S)=s
S
0
f ( s ) ds
Where:
s
0
= Initial value of s
S = Arbitrary higher value (Biesenberger & Sebastian,
1983)
Distribution moments may be defined from the origin of the average property, i.e. property is equal to 0, or
from the mean value of that property. The moments employed in Aspen Polymers use the first approach.
In this case, the generalized form of the relationship between distribution moment and distribution
function is shown below:
Where:
= Moment
k = Moment order (e.g. 0-3 for zeroth through third
moment)
s = Property value (e.g. chain length, molecular weight,
particle size, etc.) f
s
k
all s
sf
s
for the frequency function
all s
sk
f(s)
ds
for the density function
= Frequency function
f s( ) = Density function
Average Properties
The average properties can be calculated as ratios of the moments. Number average is the ratio of first to
zeroth moment, 1 /
0
. Weight or Volume average is the ratio of

second to first moment, 2 /
1
. Z-average is the ratio of third to second

moment, 3 /
2
.
For the case of chain length distribution the moment frequency distribution is given by:
nm
Qn
Where:
= Moment
m = Moment order
n = Chain length or degree of polymerization Q
n
= Number of moles of polymer of length n

The average chain length properties are then: DPn = 1 /
0 DPw = 2 /
1 DPz = 3 /
PDI = 2 0 /
21
A similar definition of moments for the frequency distribution can be applied to molecular weight.
Typically, in Aspen Polymers it is applied to chain length. Then the average molecular weight values are
determined using the average degree of polymerization and average segment molecular weight.
Method of Instantaneous Properties

Applying the method of moments for the calculation of property distributions has several drawbacks. In
addition to CPU requirements and computational complexity, a larger number of moments than currently
calculated would be required. Knowledge of leading moments of a distribution does not permit one to
unambiguously construct a complex distribution. One must therefore look beyond the method of moments
for a more powerful method to predict these complex distributions.
A better approach for generating molecular weight distributions consists of storing reaction rate data
throughout the kinetic calculations, and later using them to construct the full distribution of polymer
accumulated in the reactor system. Such an approach was developed by Hamielec (Hamielec, 1992).
Note: The method of instantaneous properties assumes that polymer molecules grow and deactivate
quickly as the growing center terminates or moves to another molecule of monomer, solvent, or chain
transfer agent. The method assumes that the polymer molecules are conserved once they are formed.
These assumptions limit the method of instantaneous properties to addition polymerization (ionic
polymerization and step-growth condensation reactions are specifically excluded because these reaction
schemes are reversible).
Further, the assumption that polymer molecules are conserved once they are formed can be invalid in the
presence of certain side reactions, including random (thermal) scission, which destroys polymer
molecules, and chain transfer to polymer, which causes inactive polymer molecules to become active
again, leading to long-chain branch formation and significantly increasing the weight-average molecular
weight and PDI. The molecular weight distribution charts display the MWW and PDI calculated by the
method of moments and the method of instantaneous properties. If the predicted values for the PDI are
not in reasonable agreement with each other, it is most likely due to these types of side reactions.
In the simplest case, linear polymerization in a single CSTR reactor, the ratios of termination and chain
transfer reaction rates to propagation reaction rates are stored. The instantaneous chain length
distribution is expressed as a function of these ratios and chain length.
For the case of two CSTRs in series, at steady-state, the outlet polymer distribution function is the
weighted average of the distribution function in each CSTR taken separately. The case of a plug flow
reactor can be approximated using multiple CSTRs, and similarly for a batch reactor.
By looking at the treatment of such reactor configurations, it can be deduced that the final polymer
distribution is a result of the entire system of reactors. For this reason, the MWD implementation in Aspen
Polymers needs to consider the proper data structure to track distribution parameters at every point in the
flowsheet. Users should be able to request MWD from any point in the flowsheet, and from this point the
Aspen Plus flowsheet connectivity information can be used to track polymerization history.
The calculation of chain length distribution for a batch reactor from reaction rate parameters for linear
addition polymerization was described by Hamielec (Hamielec, 1992).
Consider the equations for the generation and consumption of free radicals. A similar approach may be
used for other active centers (Ziegler-Natta, metallocene, etc.):
Radical Generation and Consumption Rates [ R

o
l
]
=
RKKTKMKMK
p
][
o
o ][ ][ ( ) ][ RTKRMKR
I
+
fm ]][[
+ fT ]][[ +
fm + fT + tc + td o
[R
o
r
]
=
RKKTKMKMK
p
][
o ][ ][ ( )
][ p +
fm RMK
][[
1 ] + fT tc td r
-
++o
Where: [ R I ]
=2Kd
f[I
] = Initiation rate
Instantaneous Distribution Parameters

Introducing two dimensionless parameters and .
o R td +
R
fR
p
=
K [ R ] + K fm [ M ] + K fT K p
[M
]=
td
[T
]
=R
tc R
p
=
K tc
[R
o
]Kp
[M
]
Where:
Rp=Kp
[ R o ][ M
] = Propagation rate
R td = K td
[R
o ]2 = Rate of termination by disproportionation
R tc = K tc
[R
o ]2 = Rate of termination by combination
R f = K fm
[Ro
][ M ] + K fT
[ R o ][ T
] = Total rate of chain transfer to
small molecules (not polymers)
If we assume that the stationary-state hypothesis holds, then the initiation rate is equal to the sum of the
termination rates, R I = R td + R
tc
.
The equations for the rate of generation and consumption of radicals can be written as follows:
[Rol
]=
1
++
+
[Ro]
[Ro
r
]=
1
+1
+
[Ro
r
-
1
]
Therefore: [ R o
r
] = [ R o ]( + )
r Where:
=
1+1
+

The rate of production of polymer molecules of chain length r , R Fp
(r
) is
given by:
R FP
(r
)=V
1 dV ( [ P r
] ) dt
= ( K fm [ M ] + K fT [ T ] + K td
[ R o ] )[ R o
r
]+
12
K tc
r
s
-
1
[ ][ ] =
1
Ro
s
R
o
r-
s
Substituting [ R
of
] gives:
R FP ( r ) = K p
[ R o ][ M ]( + )
+2
(+
)( r
-
1)
r
Instantaneous Weight Chain Length Distribution
Therefore, the instantaneous weight chain length distribution can be calculated from production rate of
polymer molecules as follows:
()
()
Wr
( ( ) = FP
=
) ( )( r + +
)
r
r ( ) ( )( r ) r r FP r
rR + + + -
1 rR r
r
1
2
In other words, W(r) is the weight chain length distribution of dead polymer chains produced in a small
time interval t to t+dt, in a batch reactor. W(r) is also the weight chain length distribution of dead polymer
chains produced in a CSTR operating at steady-state. If << , which is the case when the polymer
chains are formed by chain transfer or by termination by disproportionation, this equation reduces to:
Wrrr
r
2
=+
++-
1
+
1
1
()=
2
+
1
1+1
r
-
1
1
Where: 1 1/( + ) = Probability of growth for a polymer radical

/1+ = Probability that a polymer radical stops growing
Chain Length distribution equation

Since r is usually large, W(r) in the original equation on page 63 can be approximated as a continuous
function with small error:
W(r)(+)

+2
( + )( r -
1
)
r .exp { - ( +
)r}
For most free-radical polymerizations
( + )
<<1 and is of the order
10 - 6 - 10 - 2 .
The weight-average chain length for polymer produced instantaneously is given by:
Pw
rW ( r
)
=(2+r=
1
+)+(3++
)(+
)2
2+
3(+
)
2
The instantaneous number-average chain length distribution is given by:

Pn
=

Wr
r
(r11
++
)()
1
21
-
The polydispersity index for polymer produced instantaneously is given by:

PDI
=PwPn
Copolymerization
The chain length distribution equation on page 63 applies to both homo- and co-polymerization with two
or more monomer types. When chain growth polymerizations are done with active center types other than
radicals (Ziegler-Natta, metallocene, etc.) = 0 in the equation, and the instantaneous chain length
distribution becomes a single parameter distribution, which is Florys most probable distribution with a
polydispersity index of 2.0.
This equation is the main expression used in Aspen Polymers to generate chain length distribution. Within
the context of a polymerization reactor, this expression is valid for the case of linear chains of a
homopolymer produced in a single CSTR at steady-state.
CSTR in Series
For the case of two CSTRs in series, the end product polymer distribution is a composite that is a
weighted average of the distributions of polymer produced in the first and the second reactor:
Wr
(2+(3
+)
)
+
2
out
()=mm1
*W1
(r
)+mm2
*W2
( r ) Where:
m=m1+
m2
= Total mass of polymer produced in the first and second reactor per unit time
The distribution function in each reactor is given by the chain length distribution equation on page 63 with
the and , varying from reactor 1 to reactor 2, and independent of time under steady-state operation.
Plug Flow & Batch Reactors

A plug flow reactor can be divided into several volume elements and treated as a series of CSTRs. The ,
, and polymer mass values are stored for each volume element and later used for the calculation of the
composite chain length distribution function. A batch reactor is handled using a similar approach. In this
case, the , , and polymer mass values are stored for each time element.
For linear chains of a copolymer, the difference from the homopolymer case can be factored into the
calculation of the reaction rates for propagation, termination, and transfer reactions, R p , R tc , R
td
, and R
fm
.
Mechanism for Tracking Distributions
The method of instantaneous properties is used to generate chain length distributions in Aspen Polymers.
This method is applied at two levels:
Reactor level for determining the distribution of polymer newly produced within the vessel (local
distribution), and
Flowstream level for determining the distribution of polymer produced up to that point in the flowsheet
(cumulative distribution)
Distributions in Kinetic Reactors

Within kinetic reactors, the method of instantaneous properties is used to determine the distribution of
newly produced polymer. The reaction models calculate the instantaneous properties and using the
respective equations on page 62. In addition, the polymer mass corresponding to these values is saved.
Calculating Distribution Increments

The distribution increments are spaced in logarithmic steps between unity and the specified upper limit
(Upper) using the following formula:
ri
=
alog,max
i
i
log
N
10
point
( upper )
Where i varies between one and the specified number of points N

point
, and upper is the user-

specified upper bound of the distribution. This spacing provides good resolution over the entire spectrum
of molecular weights, with emphasis on the low molecular weight species that are more likely to be lost in
fractionation steps. To ensure accuracy, the upper bound should be set at least five times higher than the
observed weight-average degree of polymerization.
Calculating Local Distributions
For CSTR reactors, the values of and are stored during simulation. For multi-site kinetics (such as
Ziegler-Natta kinetics), values of and and polymer mass generation are stored for each site j. These
parameters are used to calculate the local distribution for the CSTR reactor.
For single-site kinetics (free radical and emulsion):
Wr
local
=r(+)
+2
(
+ )( r - exp1
)
[-
r(+)]
For multi-site kinetics (Ziegler-Natta):
W jr
local ,
=r(j
+j)
j+j2
(
j
+ j )( r - exp1
)
[-
r(j+j)]
W
r
local
=
Wm
j

j
local jr , m
For plug-flow reactors, the values of and are calculated at each axial step during the numerical
integration. The local distribution for the reactor is calculated by summing the instantaneous distributions
(from either equations for
j
j
Wr
local
given previously) at each step over all the steps from the reactor inlet (z = 0) to the reactor
outlet (z = L).
For single-site kinetics:
rW zr
,
=(z+z) z+
z2
(
z
+ z )( r - exp1
)
[-
r(z+z)]
L
Wm
z
zr W
r
local
=
z
L
mz
=
0
,=
0
z
For multi-site kinetics:

W
zjr ,,
=
r ( zj , + zj , ) zj , +
( zj
+ zj )( - )
[ ( zj zj ) ] - +
zj , 2
, r exp1 r , , L
Wm
zj ,
zjr ,, W
jr
local ,
=
z
=
0
L
mz
=
0
The local composite distribution is calculated using the equation given previously for
zj ,
Wr
local
for multi-site kinetics.

The local site-based and composite distributions are stored in the reactor results form and can be viewed
from the Reactor folder Results subfolder, Distributions sheet and plotted using the Aspen Plot Wizard.
Calculating Cumulative Distributions

For a reactor with multiple feeds, the feed distribution is calculated as shown below:
N feeds
Wm
k
kr W
r
feed
=
k
N feeds
mk
=
1
,=
1
k
The cumulative composite distribution is calculated by adding the feed distribution to the local composite
distribution:
feed local W
r composite
=
Wm
feed
feed r m
local + Wm local r + m The composite cumulative distribution is stored in the outlet stream of the reactor
and can be viewed through the stream results form.
GPC Distributions
If the user selects the GPC Distribution format, the distribution is calculated as
rW r
.
Distributions in Process Streams

The polymer distribution calculated within kinetic reactors is transferred into the outlet stream. This allows
flowsheeting of the cumulative distribution data, i.e. the data follows the polymer component throughout
the flowsheet. The cumulative distribution is stored within the stream.
Aspen Plus provides several different vehicles for associating data with process streams. These include:
Basic stream vector, which contains composition and state information
Component attributes, which are a fundamental tool in Aspen Polymers
Prop-Sets, which allow users to request additional properties for streams
Other non-accessible storage space
The first two categories are processed during convergence calculations while the last two are not.
The information used for calculating the distributions is derived from converged quantities. There is no
need for applying convergence calculations to the distribution data itself. Therefore, the polymer
distribution data is carried in non-accessible storage space.
The following figure illustrates the procedure followed to generate the distribution:
Verifying the Accuracy of Distribution Calculations
The molecular weight distributions calculations involve round-off error associated with the discretization
into a finite number of elements and truncation error due to the upper bound imposed on the distribution.
The following expressions can be used to verify the accuracy of the distribution. These expressions
calculate the area under the distribution curve and the number- and weight-average molecular weight of
the polymer in the distribution.
For non-GPC curves:
rrw
i
=(i+
1
-i)
WW
i
+
1
2
+
i
For GPC curves (distribution stores
rW i
):
w
i=
( Wrr
i
+
1
-2
i)
i+1r
i
+
1
+
Wiri
Where:
Wi
= Y-axis value of distribution element i

ri
= X-axis value of distribution element i

wi
= Mass-fraction of polymer in the size range between

ri
and r
1+i
The total mass fraction of all elements in the distribution should sum to unity:
N
points
0.1
=i
1
wi
If the calculated area is below unity, the specified upper bound of the distribution may be too low. If the
calculated area is greater than one, the number of points in the distribution may need to be increased to
improve the accuracy of the distribution calculations.
For chain-length distributions, the value r refers to the molecular size. The number average and weight
average degree of polymerization can be calculated as:
P
n
=
N
points
i=12
( rr
i
+w1i
+
i)
-
1
P
=
11
w
2
N
points
rrw ii ( + 1 + i ) i =
1
For molecular-weight distributions, the term r refers to the molecular weight of each increment. The
number and weight average molecular weights of the distributions are calculated as:
M
n
=
(1
)N

points
i=12
wi
+
1+
-
N
rr
ii1
M
w
=
12
points
rrw ii ( + 1 + i ) i =
1
The area under the distribution curve and the number- and weight-average properties of the distribution
can be generated by the plot wizard and displayed on the distribution plots.
For unit operation blocks, the number- and weight-average properties of the distribution may be verified
against the local polymer results, displayed on the Polymer Results sheet for each reactor.
For streams, the number- and weight-average properties of the distribution may be verified against the
polymer component attributes shown in the stream table.
Requesting Distribution Calculations

In order to track distributions in your simulation, you must select the distribution characteristics. After the
simulation is complete you must retrieve the distribution data for plotting. You can display and plot the
distribution data for the polymerization reactor, or you can display a distribution table for a stream or for
the entire flowsheet.
Selecting Distribution Characteristics

To access the polymer distribution specifications: 1 From the Data Browser, click Components. 2 From
the Components folder, click Polymers. 3 From the Polymers folder, click Distributions.
The Selection sheet appears.
To request tracking of distributions, from the Selection sheet:
1 In the Polymer ID field, select the polymer for which you would like
distributions tracked. 2 In the Distribution type frame, select the type of distribution. 3 Select the
distribution plot characteristics: number of points for plot
resolution, maximum for x-axis. 4 For a GPC distribution, select Perform GPC Distribution
Calculations.
The distribution is calculated as rW(r) vs. r where r is number-average degree of polymerization.
Displaying Distribution Data for a Reactor

Once simulation calculations are complete, you can display and plot the distribution data for the
polymerization reactor (RCSTR, RPLUG, or RBATCH) .
To display the distribution data for a polymerization reactor: 1 From the Process Flowsheet window, use
the reactor. 2 Click Results. 3 From the reactor Results form, click the Distributions tab. 4 On the
Distributions sheet, select the distribution to view.
To plot the distribution data: 1 From the Plot menu, select Plot Wizard. 2 Click Next. 3 Click a distribution
plot sample, then click Next. 4 Change the plot settings as needed, then click Next or Finish to display
the plot. 5 Click the plot graphics to change the plot configuration: reconfigure axes, legends, or
change titles. If you requested the GPC distribution format, you must set the x-axis to a log scale for the
plot to display properly.
Displaying Distribution Data for Streams

To display a distribution data table for a stream: 1 From the Process Flowsheet window, use the right
mouse button to click
the feed stream. 2 Click Results. 3 From the Results form, click the Poly. Curves tab. 4 On the Poly.
Curves sheet, select the distribution to view.
To display a distribution data table for the flowsheet: 1 From the Data Browser, click Results Summary. 2
From the Results Summary folder, click Streams. 3 From the Streams form, click the Poly. Curves tab. 4
On the Poly. Curves sheet, select the distribution to view.
To plot the distribution data: 1 From the Plot menu, select Plot Wizard.
2 Click Next. 3 Click a distribution plot sample, then click Next. 4 Change the plot settings as needed,
then click Next or Finish to display
the plot. 5 Click the plot graphics to change the plot configuration: reconfigure axes,
legends, or change titles.
References
Biesenberger, J. A., & Sebastian, D. H. (1983). Principles of Polymerization Engineering. New York:
Wiley-Interscience.
Billmeyer, F. W. (1971). Textbook of Polymer Science. New York: Wiley- Interscience.
Flory, P. J. (1936). Molecular Size Distribution in Linear Condensation Polymers. J. Am. Chem. Soc., 58,
1877.
Flory, P. J. (1953). Principles of Polymer Chemistry. Ithaca, NY: Cornell University Press.
Hamielec, A. E. (1992). Polymerization Processes. In B. Elvers, S. Hawkins, & G. Schulz (Eds.),
Ullmanns Encyclopedia of Industrial Chemistry (5th Ed.) A21, (pp. 324-330). New York: VCH.
Lansing, W. D., & Kramer, E.O. (1935). Molecular Weight Analysis of Mixtures by Sedimentation
Equilibrium in the Svedberg Ultracentrifuge. J. Am. Chem. Soc., 57, 1369.
Peebles, L. H., Jr. (1971). Molecular Weight Distribution in Polymers. New York: Wiley-Interscience.
Rodriguez, F. (1989). Principles of Polymer Systems. New York: Hemisphere Publishing.
Schulz, G. V. (1935). Uber die Beziehung zwischen Reaktionsgeschwindigkeit und Zusammensetzung
des Reaktionsproduktes bei Makropolymerisationsvorgngen., Z. Physik. Chem., B30, 379.
Schulz, G. V. (1939). Uber die Kinetik der kettenpolymerisationen. V. Der Einfluss verschiedener
Reaktionsarten auf die Polymolekularitt. Z. Physik. Chem., B43, 25.
Stockmayer, W. H. (1945). J. Chem. Phys., 13, 199.
Tompa, H. (1976). The Calculation of Mole-Weight Distributions from Kinetic Schemes. In C.H. Bamford &
C.F.H. Tipper (Eds.), Comprehensive Chemical Kinetics, 14A. New York: American Elsevier.
Tung, L. H. (1956). Fractionation of Polyethylene. J. Polymer Sci., 20, 495.
Weibull, W. (1951). A Statistical Distribution Function of Wide Applicability. J. Appl. Mech., 18, 293.
Wesslau, H. (1956). Die Molekulargewichtsverteilung einiger Niederdruckpolythelene. Makromol. Chem.,
20, 111.
Zimm, B. H. (1948). Apparatus and Methods for Measurement and Interpretation of the Angular Variation
of Light Scattering; Preliminary Results on Polystyrene Solutions. J. Chem. Phys., 16, 1099.
6 End-Use Properties
This section describes polymer end-use properties. First, an overview of the properties of interest for
polymers is given, followed by methods available in Aspen Polymers (formerly known as Aspen Polymers
Plus) for calculating these properties.
Polymer Properties, 73
Prop-Set Properties, 73
End-Use Properties, 74
Method for Calculating End-Use Properties, 76
Calculating End-Use Properties, 79
Polymer Properties
Polymer properties fall into many categories:
Structural properties
Thermophysical properties - which provide an indication of the thermodynamic behavior of polymers
Thermochemical properties - which provide information on thermal stability
Transport properties
Processing and end-use properties - which provide information about processability and performance
during end-use
Polymer structural properties do not provide a direct measure of the performance of the polymer product
during processing or during its end use.
However, there is a relationship between polymer structural properties and the end use properties. For
this reason, it is important to account for such properties within polymer process simulation models.
Prop-Set Properties
A property set is a collection of thermodynamic, transport, and other properties that you can use in:
6 End-Use Properties 73
Stream reports
Physical property tables and Analysis
Unit operation model heating/cooling curve reports
Distillation column stage property reports and performance specifications
Reactor profiles
Design specifications and constraints
Calculator and sensitivity blocks
Optimization and Data-Fit blocks
Aspen Plus has several built-in property sets that are sufficient for many applications. The list of built-in
property sets is determined by the Template you choose when creating a new run.
You can use a built-in property set and modify it to fit your needs, or you can create your own property
sets. To see the built-in sets available or to select one, use the drop-down list on any property set list box.
The list prompts describe the contents of each built-in property set.
For information on defining a property set, see the Aspen Plus User Guide.
The following table summarizes key property sets for the major thermophysical and transport properties of
interest in polymer process simulations:
Property Set Name
Description
Valid Qualifiers
Phase Comps. Temp. Pres.
CP Pure component heat capacity X X X X CPMX Mixture heat capacity X X X K Pure component thermal
conductivity
XXXX
KMX Mixture thermal conductivity X X X KINVISC Mixture kinematic viscosity X X X MU Pure component viscosity
(zero
shear)
XXXX
MUMX Mixture viscosity (at zero shear) X X X RHO Pure component density X X X X RHOMX Mixture density X X X
TG Component glass transition
temp.
XX
TM Component melt transition temp. X X TRUEFLOW Component true mole flow rate X X TRUEFRAC Component
true mole fraction X X TRUEMW Component true molecular
weight
X
End-Use Properties
The end-use or processing properties of interest for polymers include properties that describe their
performance in the last stage of the polymer
74 6 End-Use Properties
manufacturing process. Also of interest are properties relating to their performance when they reach the
consumer.
The following table summarizes some end-use properties:
Category Property Availability in
Aspen Polymers
Processing Melt index
Melt index ratio (I10/I2) Moldability index Zero-shear viscosity Density of copolymer
Yes No No Yes Yes Polymer product
Deformation Toughness/hardness Flammability
No No No
Relationship to Molecular Structure

The end-use properties such as rheological and mechanical properties are functions of the polymer
structural properties and processing history. For example, long chain branching raises low shear
viscosity, increases shear thinning, delays melt fracture, and increases extrudate swell.
For example, one could relate end-use properties of polyethylene to density, molecular weight, or melt
index (Foster, 1993). See the following table:
Properties Molecular
Weight
Melt
Density Index
Molecular weight --- Melt Index --- Impact strength Stress crack resistance Elongation --- Tensile
strength Melt strength --- Orientation --- Elasticity --- Parision sag resistance --- Distortion
resistance --- Weatherability Stiffness --- --- Heat Resistance --- --- Hardness --- --- Permeation
resistance --- -- Shrinkage --- --- Creep resistance --- --- Transparency --- ---
Density Properties Molecular
Weight
Flexibility --- ---
The basic structure-property relationship has attracted much research activity as the relationship is critical
for product performance control. We recommended you follow the recent developments in structure-
property relationship (Bicerano, 1996; Foster, 1993).
Method for Calculating End-Use Properties

Few end-use properties of interest for polymers are currently available in Aspen Polymers. However, the
method used for implementing the ones available is a good mechanism for users to incorporate additional
ones if they have the necessary correlations to molecular structure and/or thermophysical properties.
Within Aspen Polymers, end-use properties are available as property sets (Prop-Set). A Prop-Set
provides a method for calculating properties for components within process flowstreams or vessel
contents.
A number of built-in Prop-Sets are available (See your Aspen Plus User Guide documentation). In
addition, Prop-Sets allow the specification of a property set with add-on user correlations. When doing
this, a Fortran subroutine is required to perform the calculations.
End-use polymer properties are available as user property sets. This is because the correlations available
to calculate these properties are highly empirical and are often dependent on the type of polymer for
which they are used.
User property sets can easily be modified. Users can directly change the property correlation in the
associated Fortran subroutine.
User Property Sets

The following table summarizes the Prop-Set name and Fortran subroutine name for the built-in user
property sets:
Property Prop-Set Name Fortran Subroutine
Melt index MI-KAR, MI-SIN USRPRP Intrinsic viscosity IV USRPRP Zero-shear viscosity ZVIS USRPRP Density of
copolymer DENS USRPRP
Melt Index
Intrinsic Viscosity
The intrinsic viscosity is given as:
= K M w + JM
w
Where:
= Intrinsic viscosity
M
w
= Weight-average molecular weight

J and K = Correlation constants
Zero-Shear Viscosity
For some ethyl branched paraffinic monodisperse polymers, Arnett and Thomas reported an empirical
correlation for zero-shear viscosity as a function of molecular weight, number of branched sites per 1000
carbon atoms, and temperature (Arnett & Thomas, 1980):
ln
0
= a ln M
+
d(1
+T
cn
)
3
bn + ( ) Where:
0
w
eBn
=Zero shear viscosity in Poise
M
w
=Molecular weight
n =Number of branched sites per 1000 carbon
atoms
a =3.41
d =3523
c =0.832
b =2.368
B(n) =Function of number of branches with:
B(0) =-35.78
B(0.02) =-37.04
B(0.069) =-38.11
B(0.13) =-40.88
B(0.183) =-43.54
Density of Copolymer
Randall and Ruff presented an empirical correlation for semicrystalline copolymer density (Randall & Ruff,
1988):
-
ac-
Where:
= Actual density
c
=a+b(1
-
)
2
n
i
i
i
=
1
= Crystalline density
a
= Amorphous density
a and b = Correlation constants
n = Minimum crystallization run length of monomer
= Reaction probability that monomer is followed by
similar monomer
Melt Index
Karol and colleagues suggested a Quackenbos equation for high density polyethylene prepared with
chromocene-based catalysts (Karol et al., 1973; Quackenbos, 1969):
MI = a ( bM w +
cM
n
)
d
Where:
MI = Melt index
a = 10 . 1018 b = 0.2
c = 0.8
d = -3.9
M
w
= Weight-average molecular weight

M
n
= Number-average molecular weight

Sinclair suggested a simpler correlation (Sinclair, 1983):
MI
1
Ma
w
Where:
a = 111,525
b = 0.288
b
Melt Index Ratio
The Quackenbos equation can also be used to correlate melt index ratio.
Calculating End-Use Properties

End-use properties are calculated as Prop-Sets. You must first select which end-use property to include
in the simulation, then you must define this property as a Prop-Set.
Selecting an End-Use Property

To access end-use property Prop-Sets: 1 From the Data Browser, click Properties. 2 From the Properties
folder, click Advanced. 3 From the Advanced folder, click User Properties. 4 From the User Properties
object manager, click New. 5 If necessary, change the default ID for the user-property and click OK. 6
From the User Properties Specifications sheet, choose the standard
property as the type (default), then provide the subroutine name.
Create one User-Property for each end-use property.
Adding an End-Use Property Prop-Set

To access Prop-Sets: 1 From the Data Browser, click Properties. 2 From the Properties folder, click Prop-
Sets. 3 From the Prop-Sets object manager, click New. 4 If necessary, change the default ID for the Prop-
set and click OK. 5 From the Prop-Set Properties sheet, in the Physical Properties field,
select the ID for the end-use property User-Property. You can have as many User-Properties as needed.
References
Arnett, R. L. & Thomas, C. P. (1980). Zero-Shear Viscosity of Some Ethyl Branched Paraffinic Model
Polymers. J. Phys. Chem., 84, 649-652.
Bicerano, J. (1996). Prediction of Polymer Properties. New York: Marcel Dekker.
Foster, G.N. (1993). Short Course: Polymer Reaction Engineering. Ontario, Canada: McMaster Institute
for Polymer Production Technology.
Hamielec, A. E. (1996), Polymer Reactor Modeling Technology (Course Notes). Cambridge, MA: Aspen
Technology, Inc.
Karol, F. J., Brown, G. L., & Davison, J. M. (1973) Chromocene-Based Catalysts for Ethylene
Polymerization: Kinetic Parameters. J. of Polymer Science: Polymer Chemistry Edition, 11, 413-424.
Quackenbos, H. M. (1969). Practical Use of Intrinsic Viscosity for Polyethylenes. J. of Applied Polymer
Science, 13, 341-351.
Randall, J. C. & Ruff, C. J. (1988). A New Look at the 'Run Number' Concept in Copolymer
Characterization. Macromolecules, 21, 3446-3454.
Rudin, A. (1982). The Elements of Polymer Science and Engineering. New York: Academic Press Inc.,
Harcourt Brace Jovanovich.
Sinclair, K. B. (1983). Characteristics of Linear LPPE and Description of UCC Gas Phase Process,
Process Economics Report. Menlo Park, CA: SRI International.
7 Polymerization Reactions
This chapter discusses polymerization mechanisms and kinetics. Topics discussed in the introductory
section include:
Polymerization Reaction Categories, 81
Polymerization Process Types, 84
Aspen Polymers Reaction Models, 85
Following an introduction that provides background information of the subject, a separate section is
devoted to each of the polymerization kinetic models available in Aspen Polymers (formerly known as
Aspen Polymers Plus).
Step-Growth Polymerization Model, 89
Free-Radical Bulk Polymerization Model,
Emulsion Polymerization Model,
Ziegler-Natta Polymerization Model,
Ionic Polymerization Model,
Segment-Based Reaction Model,
Polymerization Reaction Categories

Over the years, many classifications have been developed for polymerization reactions. One classification
divides them into condensation and addition polymerization.
Condensation Polymerization
Condensation polymerization results in the elimination of a smaller molecule, water for example, through
the reaction of bi- or polyfunctional monomers.
Addition Polymerization
Addition polymerization, on the other hand, does not produce small molecule byproducts. The repeating
units within the polymer have the same structure as the monomers from which they originated.
7 Polymerization Reactions 81
The problem with this classification is that while it describes differences in the molecular structure of the
resulting polymer, it does not fully capture the differences in the reaction mechanism. Furthermore, a
given polymer can be made by more then one pathway, one which would result in an addition polymer,
and one which would result in a condensation polymer, by this classification.
For example, Nylon-6 can be made through a caprolactam, and therefore be labeled an addition polymer,
or through an -aminohexanoic acid, and in this case be labeled a condensation polymer.
Step Growth and Chain Growth Polymerization

A classification that is more useful for capturing the difference in the mechanisms through which polymers
are produced divides polymerization reactions into step-growth and chain-growth polymerization. The
differences between step-growth and chain-growth polymerization are summarized in the following tables:
Step Growth Polymerization
Chain Growth Polymerization
Monomer type Bi-, polyfunctional No functionality Reaction categories
Single intermolecular reaction
Several consecutive reactions for initiation, growth, and termination Reacting species Any combination of
monomers, oligomers, polymer chains
Monomers and active centers (free-radical, ion, polymer, catalyst end) Elimination product
Small molecule elimination product for condensation polymerization only
None
Polymer growth rate
Slow, chain lifetime of the order of hours
Rapid, chain lifetime of the order of seconds Polymer size High molecular weight at
high conversion
High molecular weight at all conversion levels
Reaction Type Active Center Initiation Growth Reaction
Step Growth
Condensation Bi-, polyfunctional
end groups
None Nucleophilic substitution
Pseudo condensation
Bi-, polyfunctional end groups
None Nucleophilic addition
Ring Scission Bi-, polyfunctional
end groups
Yes for ring opening
Nucleophilic addition or substitution
Chain Growth
Free-radical Free radical Chemical,
thermal, radiative
Monomers add on to radical
Coordination Metal complex Catalyst activation Monomers insert into metal
complex carbon bond Ionic Anion or cation
Dissociation Monomers add on at ion pair
82 7 Polymerization Reactions
Step-Growth Polymerization
Step-growth polymerization retains the definition given for condensation polymers for the majority of
cases. That is, monomers react with each other to eliminate small molecules. Step-growth polymers are
formed through the same reaction type occurring between functional groups located on any combination
of monomers, oligomers, or polymer chains. The polymer chains continue to grow from both ends as
polymerization progresses. The reactions occur at a relatively slow rate and chains grow slowly.
Some examples of step-growth polymers include polyamides, polyesters, polycarbonates, and
polyurethanes (See Polymer Structure in Chapter 2 for a discussion of polymer types based on molecular
structure).
Step Growth Polymer Categories

Step-growth polymerization can be sub-categorized as condensation, pseudocondensation, and ring-
opening or ring-scission depending on the chemical pathways through which the reactions occur. The
following table lists typical commercial step-growth polymers:
Polymer (Trade Name)
Monomers Repeat Unit Reaction
Type
Applications (Similar Polymers)
Polyamide (Nylon 6,6)
Adipic acid Hexamethylene diamine
Dicarboxylic acid + diamines
Fiber, plastics (Lycra, Nylon 6)
Polyester (PET)
O O NH (CH
2
)
6
NHC(CH
2
)
4
C
Terephthalic acid Ethylene glycol
C
O Dicarboxylic onhydride + glycols
Fiber (PBT, Dacron, Nylon)
Polycarbonate (Lexan)
O
C O CH
2
CH
2
O
Bisphenol-A Phosgene
OC
CH
3
Dihydroxy reactant + Phosgene
Lenses, packaging (Merlon)
Polyurethane Toluene
diisoyamate polyether diol
CH
3
O
OC
R NH CO O R
1
Diisocyanate
Foam, + dialcohol
packaging
Chain-Growth Polymerization
Chain growth polymers are formed through the addition of monomers to an active center (free-radical,
ion, or polymer-catalyst bond), in a chain reaction, at a very fast rate. Furthermore, several different
types of reaction occur to initiate, propagate, and terminate polymer growth. Examples of chain growth
polymers include various polyolefins, polyvinyls, and several copolymers (styrenic copolymers, for
example).
Chain Growth Polymer Categories
Chain-growth polymerization can be categorized as free-radical, coordination complex, or ionic,
depending on the type and method of formation of the active center. The following table lists typical
commercial chain-growth polymers:
Polymer Monomers Repeat Unit Reaction Types Applications
Polyethylene Ethylene Bulk/solution (free-
radical) Coordination complex (Ziegler-Natta)
Film, CH
2
CH
2
packaging
Polystyrene Styrene Bulk/solution/
CH
2
suspension (free- radical)
Containers, CH
packaging, insulation
Polypropylene Propylene Coordination complex
CH
2
(Ziegler-Natta)
Films, packaging, autoparts, sealants Polyisobutylene Isobutylene Ionic Films, plastic
tubing
Polyvinyl chloride Vinyl
chloride
CH
CH
3
CH
3C
CH
2 CH
3
CH
2
Bulk/solution/ suspension (free- radical)
Floor coverings, pipes Polymethalmethacryl ate
CH
Cl
Methyl Methacrylat e
CH
2
Bulk/solution (free- radical)
Lenses, plastics
Styrene butadiene rubber
CH
3
CH
2
C
COOCH
3
Styrene Butadiene
Emulsion (free-radical) Tires, belting, CH CH
2
CH CH CH
2
shoe soles
Polymerization Process Types

Step Growth Reaction Sub-classes
In addition to chemical pathways, the environment or process conditions in which the polymerization
reactions occur introduce more sub-classes of polymers. For example, step-growth reactions may take
place as melt phase, solid-state, solution, or interfacial polymerization:
Melt-phase processes are carried out above the melting point of the polymer
Solid-state processes are carried out below the melting point of the polymer
Solution processes are carried out in the presence of an inert solvent
Interfacial processes are carried out in the interface between an organic phase and an aqueous phase
Chain Growth Reaction Sub-classes
Chain-growth polymerization may take place in bulk phase, solution, precipitation, suspension, or
emulsion:
Bulk polymerization is carried out in the bulk monomer phase without a solvent
Solution polymerization is carried out in the presence of an inert solvent in which monomers and
polymer are dissolved
Precipitation polymerization is carried out using a solvent to precipitate out the polymer
Suspension polymerization involves monomers suspended as droplets in a continuous phase (usually
water) to which an oil-soluble initiator is added
Emulsion polymerization involves monomers and micelles dispersed in a continuous water phase using
surfactants. Initiator is added to the emulsion of partially water soluble monomers in the surfactant
solution
There are additional process related classifications that have to do with reactor geometry. These are
discussed in sections covering unit operation modeling later in this User Guide.
Aspen Polymers Reaction Models

There are two types of reaction models available in Aspen Polymers:
Built-in models
User models
Built-in Models
The polymerization reaction models available in Aspen Polymers are summarized in the following table:
Model Name Chemistry Processes Polymers
Step-growth
STEP-GROWTH Step-growth condensation Melt phase,
solution, interfacial
PC, PBT, PET, Nylons
SEGMENT-BAS Step-growth addition Melt phase,
solution, interfacial
Polyurethanes, polyimides, PPO, engineering plastics
Chain-growth
FREE-RAD Free-radical Bulk, solution PS, PVAC, SAN, PMMA EMULSION Free-radical Emulsion SBR, SBA
ZIEGLER-NAT Ziegler-Natta / metallocene
coordination complex
Bulk, solution HDPE, PP, LLDPE
IONIC Anionic/Cationic group
transfer
Solution PIB, SBR, PEO
Model Name Chemistry Processes Polymers
Generic
SEGMENT-BAS Segment-based power-law
reaction model
N/A PVA from PVAC
In addition to models for the chemistries and process types listed, there is one model available for generic
polymer modification reactions. This model follows a standard power-law scheme and is used to
represent reactions involving modifications to segments of polymers made through one of the
conventional reaction schemes. One of the standard Aspen Plus reaction models can also be used in
conjunction with the polymerization reaction models. The standard Aspen Plus reaction models are:
Model Name Description
LHHW Langmuir-Hinshelwood-Hougen-Watson reaction rate expressions POWERLAW Power-law reaction rate
expressions USER Kinetic rate expressions supplied by user, kinetic rate computed in
user supplied subroutine
For more information about these models, consult the Aspen Plus User Guide and Aspen Plus User
Models.
User Models
There are cases where the built-in models do not provide the features necessary to model specific
polymerization kinetics. Some of the polymerization reaction models provide capabilities to incorporate
user reactions. In addition, the USER reaction model provides the capabilities for defining user kinetic
schemes.
The USER reaction model is structured to allow the specification of the reaction stoichiometry. In addition,
there are vectors for entering user real and integer parameters. This input information along with the
reaction vessel contents, in the form of the stream structure, is made available to a user supplied Fortran
subroutine during calculations.
Note that component attributes are part of the stream structure. There is an update and initialization
scheme to automatically process these attributes. The user supplied Fortran subroutine can return rates
for components and component attributes.
From the subroutine, Aspen Plus utilities including physical property routines, math utilities, and stream
handling utilities can be accessed. Some of these utilities are documented in Chapter 4 of Aspen Plus
User Models.
References
Aspen Plus User Models. Burlington, MA: Aspen Technology, Inc.
Dotson, N. A, Galvn, R., Laurence, R. L., & Tirrell, M. (1996). Polymerization Process Modeling. New
Hamielec, A. E. (1992). Polymerization Processes. In B. Elvers, S. Hawkins, & G. Schulz (Eds.),
Ullmanns Encyclopedia of Industrial Chemistry (5th Ed.) A21, (pp. 324-330). New York: VCH.
Odian, G. (1991). Principles of Polymerization, 3rd Ed. New York: John Wiley & Sons.
Rudin, A. P. (1982). The Elements of Polymer Science and Engineering. Orlando, FL: Academic Press.
Sun, S. F. (1994). Physical Chemistry of Macromolecules. New York: John Wiley & Sons.
8 Step-Growth Polymerization
Model
This section covers the step-growth polymerization model available in Aspen Polymers (formerly known
as Aspen Polymers Plus). It begins with general background information on step-growth polymerization
and covers some of the terms associated with these kinetics. Several industrial polymerization processes
are examined in detail. A discussion of the model features and usage is also included.
Summary of Applications, 89
Step-Growth Processes, 90
Reaction Kinetic Scheme, 101
Model Features and Assumptions, 124
Model Structure, 127
Specifying Step-Growth Polymerization Kinetics, 155
The Aspen Polymers Examples & Applications Case Book illustrates how to use the step-growth model to
simulate nylon-6 polymerization from caprolactam.
More detailed examples are available in Step-Growth Polymerization Process Modeling and Product
Design by Kevin Seavey and Y. A. Liu, ISBN: 978-0- 470-23823-3, Wiley, 2008.
Summary of Applications
Step-growth polymerization can be used to model various polycondensation and specialty plastic
processes. Some of the applicable polymers are described below:
Aliphatic polycarbonates - Transesterification of diols with lower dialkyl carbonates, dioxolanones, or
diphenyl carbonate in the presence of catalysts such as alkali metal, tin, and titanium compounds.
Aromatic polycarbonates - Reaction product of bisphenols with carbonic acid derivatives. May be
prepared by transesterification, solution polymerization, and, most often by interfacial polymerization.
8 Step-Growth Polymerization Model 89
Polyesters - Produced commercially in two steps: monomer formation by ester interchange of diesters
with diols or esterification of diacids with diols, followed by polycondensation by removing excess diols to
promote chain extension. This is accomplished commercially on a simple two-vessel batch process or on
large-scale multi-vessel continuous-polymerization process.
Polyamides - Produced via direct amidation, reaction of acid chlorides with amines, ring-opening
polymerization, reaction of diacids and diisocyanates, etc. Commercially prepared by melt
polycondensation, ring- opening polymerization, and low temperature solution polymerization.
Polyurethanes - Polyurethane isocyanates are usually produced commercially by the phosgenation of
amines. Polyester polyols are prepared by step-growth polymerization.
Step-Growth Processes
Several commodity polymers, including polyesters, nylons, and polycarbonate, are manufactured through
step-growth polymerization processes. This section examines some of the major processes that can be
represented using the step-growth polymerization kinetics model.
Polyesters
Continuous Polyethylene-Terephthalate Processes
Polyethylene-terephthalate (PET) is produced by the step-growth polymerization of ethylene glycol, a diol,
and either terephthalic acid, a diacid, or dimethyl terephthalate, a diester. Most processes are continuous
although many older process lines operate in batch or semi-batch mode.
Direct Esterification
The direct esterification process involves the reaction of ethylene glycol with terephthalic acid. The
terephthalic acid is mixed with excess ethylene glycol to form a solid-liquid paste. In the continuous
process, the monomer paste is typically fed to a well-mixed reactor, the primary esterifier, which operates
at temperatures of 250-290 C and pressures ranging from one to several atmospheres. Typical
residence times range from one to four hours in this stage of the process.
A solid at room temperature, terephthalic acid has limited solubility in the polymer solution, even at the
relatively high process temperatures. Further, the dissolution rate of TPA may be limited by the solid-
liquid mass transfer rate, especially if the average particle size is large, or when the reactor operates at
high temperatures and pressures.
The following figure illustrates a continuous direct esterification process for PET:
90 8 Step-Growth Polymerization Model
Secondary Esterification
In most continuous plants, the primary esterifier is followed by secondary and, occasionally, a tertiary
esterifier. These reactors range from single-tank CSTRs to a variety of multiple-stage CSTRs composed
of vertical or horizontal vessels divided into two or more chambers by partitions. Secondary esterification
reactors typically have residence times on the order of an hour, with temperatures similar to or slightly
higher than the primary esterifier. The secondary esterification reactor is often run under atmospheric
conditions, although slight positive pressure or vacuum pressures are also used in some processes.
Vapor from the esterification reactors flows to one or more distillation columns which separate ethylene
glycol from the reaction by-products which include water and acetaldehyde. In some processes, spray-
condenser loops are used to wash entrained TPA and vaporized low-molecular weight oligomers from
the vapor stream to prevent oligomer build-up in the distillation columns.
Glycol Recovery
The ethylene glycol from the esterification distillation columns can be recycled directly to the esterification
reactors, to the paste mixing tank, or, in the case of high-quality products, it can be collected for further
processing to remove contaminants. The companies which license PET technology use a wide variety of
glycol recovery and recycling schemes. All of these recycling schemes can be simulated using
conventional distillation, flash, and heat exchanger models available in Aspen Plus.
Esterification Results
The product of the esterification reactors is composed of short-chain oligomers with some residual
monomers. The main oligomer in the product is
bis-hydroxyethyl-terephthalate (BHET), which is slightly volatile under typical operating conditions. The
step-growth model includes an oligomer feature which can be used to account for evaporative loss of
linear oligomers such as BHET.
Transesterification Process
In the transesterification process, dimethyl terephthalate (DMT) is used instead of terephthalic acid (TPA).
One advantage of this process is the relatively high solubility of DMT, which eliminates the solid-liquid
mass transfer problem in the first stage of the process. A second advantage is the low acidity of DMT,
which reduces several of the side reaction rates and results in a higher quality polymer. The limitations of
the transesterification process include increased monomer cost, production of methanol as a by- product
(instead of water), and reduced reactivity in the finishing stages.
The transesterification process produces methanol as a reaction by-product. The methanol is distilled
from ethylene glycol through distillation columns. Recovered glycol may be recycled to the reactor, the
paste mixing tank, or accumulated for additional processing.
It is desirable to minimize the concentration of methylester ends in the feed to the polymerization section.
Obtaining high conversions is very important in the DMT process because the reverse reaction of
methanol with PET is more highly favored than the reaction of water and PET. A wide variety of
proprietary reactors are used to effect high end-group conversion during the transesterification process.
Continuous Polymerization
The continuous polymerization process is the same for the direct esterification and transesterification
processes. Typically, the polymerization section consists of one or more CSTR reactors (pre-
polymerization reactors) followed by one or more horizontal finishing reactors (polymerization reactors).
These reactors consist of a series of rotating blades or disks which lift polymer from a pool at the bottom
of the reactor into a vapor space over the pool. The design criteria of these reactors are to maximize
surface area generation while minimizing back-mixing. In polyester processes, the finishing reactors are
almost always limited by the liquid-vapor mass transfer rates. In some cases, the pre-polymerization
reactors are also limited by mass transfer.
The reactors in the polymerization section operate at increasingly higher temperatures and lower
pressures to enhance the devolatilization of excess glycol and reaction byproducts such as water,
methanol, and acetaldehyde. Reactor residence times range from thirty minutes to four hours depending
on the number and type of reactors in the polymerization section.
Vapor from the polymerization section is scrubbed by spray-condenser loops composed of a contacting
vessel, accumulation tank, pump, and heat exchanger. In most plants, vacuum is generated through
venturi jets operated by steam or vaporized glycol. In some process configurations, the condensed glycol
and water mixture is recycled to the esterification columns. Otherwise, the condensate is accumulated
and processed to recover glycol.
Operating Conditions
The esterification and transesterification sections of PET processes frequently operate below the melting
point of the polymer. Under these operating conditions, the process can be considered solution
polymerization. The polymerization reactors operate above the melting point of the polymer in a true melt-
phase polymerization. The step-growth reaction model may be used for both modes of operation. In most
cases, the same reaction kinetics apply to both solution- and melt-phase reaction processes.
Final Products
The continuous melt-phase PET processes generally produce polymer with an average intrinsic viscosity
of approximately 0.6 dl/g, which corresponds to a number-average degree of polymerization near 100
units. This product may be directly spun as clothing fiber, partially oriented yarn (POY), film, or it may be
cooled and chipped for on- or off-site use.
Recent increases in consumer recycling programs and consumer preference for unbreakable bottles has
created a very large market for polyester bottles. These bottles are molded from a higher molecular
weight polyester chip which is produced by a solid state process. Fundamentally, the step-growth model
can apply to solid-state polymerization. However, at this time, Aspen Polymers does not include a solid-
state polymerization (SSP) reactor model. Semi-rigorous SSP models can be developed using a series of
CSTR reactors. Solid phase polymer solutions can be treated as a liquid phase in Aspen Polymers. The
property system switches between liquid-phase property models and solid-phase property models when
the temperature drops below the melting point of the polymer component.
Batch Polyethylene-Terephthalate Processes

Polyethylene Terephthalate is also produced in batch and semi-batch processes, as shown in the
following figure. Usually, the process consists of two batch reactors in series. The role of the first reactor
is to reach high conversions of the terephthalate monomer while minimizing undesirable side reactions.
The role of the second reactor is to raise the molecular weight of the polymer to appropriate levels.
The first reactor is coupled to a column which separates the volatile reaction by-products from excess
ethylene glycol and evaporated oligomers. The heavy components are continuously returned to the
reactor during most of the batch cycle. Towards the end of the cycle, the evaporated ethylene glycol and
residual monomers are removed and accumulated for re-use in the next batch.
The batch esterification process commonly uses a semi-continuous feeding system for the solid TPA. In
most batch esterification processes, the reaction rate is limited by the rate of dissolution of TPA. This is
complicated by the relationship between the mass transfer rates and particle size.
To enhance TPA solubility, a portion of the polymer product is retained in the reactor at the end of the
cycle. The recycled product is used to start the next batch. This design allows the cycle to start at a
higher temperature, reducing the cycle time for each batch. The trade off between the batch cycle time
and the quantity of recycle polymer is one of the most interesting problems to examine using simulation
technology.
The batch transesterification process is typically operated in true-batch mode, without recycling polymer.
In this process, the monomers, ethylene glycol and DMT, are charged to the reactor at the beginning of
the cycle. The continuous removal of methanol from the batch reactor makes very high end- group
concentrations possible.
This version of Aspen Plus does not include an appropriate reactor model to simulate batch
polymerization reactors with overhead distillation columns. AspenTechs Polyester Technology Package
includes several modeling solutions for representing these types of batch processes in the Aspen Plus
and Aspen Custom Modeler environments.
Second Batch Stage
The liquid product from the batch esterification or transesterification is charged to a second batch stage.
In this stage, the reactor is evacuated as the temperature is increased. These operating profiles enhance
the removal of excess ethylene glycol from the reaction mixture, allowing these highly reversible reactions
to proceed.
As the polymer viscosity increases, the reactions become limited by the rate of mass transfer from the
liquid phase to the vapor phase due to decreased surface renewal rates and reduced agitator speeds.
Other Polyester Processes

Polybutylene-terephthalate (PBT) is an engineering plastic frequently used for machine parts, car body
panels, and other applications. Polybutylene terephthalate is analogous to PET, except butylene glycol is
used in place of ethylene glycol. Most PBT is manufactured from DMT through continuous
transesterification processes, although batch processes and direct esterification processes are also found
in industry.
In the PBT process, tetrahydrofurane, THF, is formed from butylene glycol end groups as an undesirable
reaction by-product. The transesterification process is favored over direct esterification because the acid
end groups in TPA catalyze the formation of THF.
Polypropylene-terephthalate (PPT) is used for carpet fiber and other applications. Like PET and PBT,
PPT can be manufactured from terephthalic acid or dimethyl terephthalate. In the PPT process, propylene
glycol is used as the diol monomer.
Polyethylene-naphthalate (PEN) manufacturing processes are under development by several polyester
producers. This new product has a higher melting point than PET, and is aimed at specific demands,
such as hot-fill bottles, which are not well satisfied by other polyesters. The dimethyl ester naphthalate
monomer is much more expensive than TPA or DMT, so PEN is frequently produced as a copolymer with
PET.
At this time, most PEN is produced in batch processes which are analogous to the batch PET process.
Copolymers of PEN and PET are being used for some bottling applications already. The similarities in the
chemical mechanism for PET and PEN make them relatively easy to copolymerize in various ratios,
resulting in several product grades with properties intermediate between pure PET and pure PEN.
Polyester Technology Package

Aspen Technology offers several solutions for polyester processes. The AspenTech Polyester
Technology Package provides steady-state simulation of melt-phase continuous processes and also
includes process models for batch polyester processes. The Polyester Technology Package is designed
for PET and PBT, but can be easily modified for analogous polyesters such as PEN, PTT, etc.
Aspen PolyQuestSM, jointly developed with Hosokawa Bepex corporation, is a simulation package
covering all varieties of solid-state PET processes. Aspen PolyQuest includes detailed and rigorous
models for reaction kinetics, diffusion, heat transfer, and crystallization, as well as a library of detailed unit
operation models for solid-state processing equipment. Aspen PolyQuest runs on the Aspen Custom
Modeler platform. The underlying equation-based models can be used for dynamic or steady-state
process simulation.
The models in these packages account for all the major side reactions in the process, such as thermal
scission, aldehyde formation, DEG formation, and cyclic trimer formation. The reaction kinetic models
consider the influence of several common catalysts and additives as well as acid catalysis and
uncatalyzed side reactions. The package includes reactor models which consider solid-liquid mass
transfer for the direct esterification process, and liquid-vapor mass transfer limited kinetics for the
polymerization reactors.
The Polyester Technology Package includes models of several common process configurations, including
both batch and continuous processes. The models predict various quality parameters such as the acid
end group concentration (acid value), intrinsic viscosity, vinyl end content, DEG content, conversion, etc.
Contact your Aspen Technology sales representative for more information about the Polyester
Technology Package, Aspen PolyQuest, and advanced consulting services.
Nylon-6
Nylon-6 is produced by ring-opening polymerization of -caprolactam. Water and caprolactam are fed to a
primary reactor where the ring-opening reaction takes place. The primary reactor may be a single (liquid)
phase tubular reactor, CSTR, or one of a variety of proprietary reactors.
The following figure illustrates a continuous melt-phase nylon-6 process:
VK Column
One of the most well known of these proprietary designs is the Vereinfacht Kontinuierliches (or VK)
column. The VK column is a reactor with a high aspect ratio which is filled to relatively high liquid levels.
The reacting mixture boils vigorously near the top of the VK column, resulting in considerable radial and
axial mixing. Below this well-mixed zone is a plug-flow zone in which the hydrostatic pressure is sufficient
to suppress boiling. Reactors of this type can be simulated using one or more two-phase CSTR reactors
(model RCSTR) in series with a single liquid-phase plug flow reactor (model RPlug).
The top of the VK column typically operates near atmospheric pressure. Heat exchangers inside the
upper section of the reactor bring the reactants to temperatures of 220-270C. Typical residence times
are in the order of three to five hours. A reflux condenser or distillation column over the reactor returns the
monomer and most of the water back to the VK column.
Although the initial stages of Nylon-6,6 polymerization are catalyzed by water, the water must be removed
in later stages to allow the condensation reactions to proceed to high conversion. Water removal is
accomplished by carrying out the reaction in a series of stages at successively lower pressures.
Secondary stages typically involve one or more CSTR reactors followed by vertical wiped-film
evaporators. Inert gas may be used to strip water from the polymer melt.
For some products, chain terminators are used to control the molecular weight of the product. Acetic acid
is commonly used, but any monofunctional acid or alcohol can be used to control molecular weight build-
up.
Horizontal finishing reactors may be used to increase the polymer molecular weight and reduce the
residual monomer and cyclic oligomer concentrations. In these devolatilization stages, the evaporation of
water, excess
caprolactam, aminocaproic acid, and cyclic oligomers is limited by the rate of mass transfer from the liquid
phase to the vapor phase.
Nylon-6,6
Nylon-6,6 is manufactured by two types of processes. In the most common process, dyadic nylon salt is
first produced by mixing adipic acid (ADA) in an aqueous solution of hexamethylene diamine (HMDA). A
newer process involves the direct melt polymerization of the two monomers.
Salt Preparation
In the traditional salting process, the formation of nylon salt ensures stoichiometric ratios of the two
monomers, allowing the production of high molecular weight polymers. In the salt solution process, solid
adipic acid is dissolved in an aqueous solution of HMDA. The resulting aqueous salt solution is
concentrated by further addition of the monomers and/or by partial evaporation.
An alternative salting process uses methanol as the primary solvent. Solutions of adipic acid and HMDA
in methanol are prepared separately in continuously stirred heated tanks. These solutions are mixed in a
reactor where the nylon salt is generated. Most of the nylon salt precipitates out of solution due to the low
solubility of the nylon salt in methanol. A small amount of the salt, however, remains dissolved in the
reactor, resulting in the generation of some short-chain oligomers. The salt slurry is centrifuged to remove
the solid salt. Methanol is used as a washing solution in the centrifuge to further purify the salt. The
methanol is purified in a distillation column and recycled. The solid nylon salt is dried and collected for
use on- or off-site.
Polymerization from Aqueous Salt Solutions

Most nylon-6,6 is produced in continuous processes made up of several stages. The primary stage
operates at high pressures and temperatures to control the loss of volatile monomers and to accelerate
the reactions. In the intermediate reactors, the operating pressure is reduced substantially and much of
the excess water is evaporated. The finishing stages of the process are made up of one or more wiped-
film evaporators which help to remove the remaining residuals.
A typical nylon-6,6 continuous process is shown here:
First Stage
In the first stage, aqueous salt solutions are fed to a reactor which operates at high temperatures (230-
290C) and pressures (> 250 psig). High temperatures are required to dissolve the salt and to accelerate
the reaction rates. The high pressure is required to avoid excess loss of HMDA, which is generated by
polymerization reactions. In the first reactor, the nylon salt dissolves and condensation reactions take
place between molecules of the dissolved salt and between the dissolved salt and polymer end groups.
Much of the water which enters with the salt and is generated by the condensation reactions is boiled off
in the first stage due to the high operating temperature.
In some processes, the salt solution is fed to a column over the first reactor. As the solution flows down
the column, excess water is driven off. Condensation reactions take place in the reactor at the bottom of
the column as well as in the trays of the column. The column also condenses evaporated HMDA,
returning it to the reactor vessel. Additives, such as titanium dioxide, are fed to the primary reactor vessel.
The reactor vessel is made up of two parts: a separation vessel and a heat exchanger tube-bank. The
separator vessel is located at the bottom of the column, where it receives the reflux from the column. The
liquid at the bottom of the separator is pumped through the tube-bank heat exchanger, which acts as the
reboiler for the column. The high circulation rates through the heat exchanger section of the reactor keep
the reactor contents well mixed.
Intermediate Stage
Liquid from the primary reactor must be throttled to lower pressures to remove water, which allows the
reversible condensation reaction to proceed to higher conversions. The depressurization and
devolatilization of the intermediate are carried out by several different techniques involving a series of
degassing vessels connected by throttle valves. In some processes, a loop- type reactor is used to
reduce the pressure.
Excess HMDA or adipic acid or monofunctional chain stoppers, such as acetic acid, may be added in the
intermediate stages of the process to control the molecular weight build-up. Catalysts and thermal
stabilizers are also added to the oligomer.
Final Stage
In the final stages of polymerization, wiped-wall evaporators are used to finish the reaction at high
temperatures (up to 300C) and medium vacuum pressures (760-200 torr). Typical finishing reactor
residence times range from 20-60 minutes. The removal of water and excess monomers from the liquid
phase may be limited by the mass transfer rate.
Melt-Phase Polymerization
Recent developments in nylon-6,6 polymerization have led to the development of continuous melt-phase
polymerization processes. Adipic acid and hexamethylene diamine solutions are fed to a tubular primary
reactor, which operates at very high pressures (approximately 1000 psig), temperatures around 275C,
and residence times of 15-30 minutes. Under these conditions, boiling does not occur in the reactor.
The pressure is throttled down to 250-350 psig through a series of valves or tubes of successively larger
diameter. The pressure profile must be adjusted to minimize cooling caused by the rapid evaporation of
steam, which can cause the polymer solution to freeze.
In the final stage, the polymer is brought close to chemical equilibrium (with dissolved water and excess
monomers) in a wiped film evaporator.
Polycarbonate
Polycarbonate is a relatively strong polymer with good optical and mechanical properties. It is used in
several applications including car body parts (frequently blended with PBT), specialty films, and laser disc
media.
Historically, most polycarbonate was produced by interfacial polymerization of bisphenol-A (BPA) with
phosgene. In the interfacial process, the reactions are relatively fast, but the reaction rate is limited by the
mass transfer rates of the reactants from the bulk liquid phases into the swollen polymer phase.
A limited amount of polycarbonate is produced from BPA and phosgene in a solution polymerization
process. The reaction is carried out by solution polymerization in pyridine. The pyridine solvent captures
chlorine from the phosgene groups, resulting in pyridine chloride as a reaction by-product.
Recently, the melt-phase polymerization of bisphenol-A with diphenyl carbonate (DPC) has become an
important industrial process. The melt polymerization process has a significant safety advantage over the
interfacial process because phosgene is highly volatile and extremely toxic. A typical melt-phase
polycarbonate process is shown here:
The monomers, BPA and DPC, are fed in a carefully controlled ratio to a series of CSTRs. Phenol, which
is generated as a reaction by-product, is vaporized in the reactors and must be condensed and recycled.
Distillation columns are used to recover residual monomers from phenol.
The CSTRs are followed by a series of wiped film evaporators and horizontal finishing reactors which
operate at successively lower pressures to enhance the removal of residual monomers and phenol.
These reactors are limited by the mass transfer rate of phenol from the melt.
Reaction Kinetic Scheme

This section gives a general overview of nucleophilic reactions and reaction nomenclature, as well as
specific information on polyester, nylon-6, nylon- 6,6, and melt polycarbonate reaction kinetics.
Nucleophilic Reactions
Step-growth polymerization involves reactions between monomers containing nucleophilic and
electrophilic functional groups. Nucleophilic groups are electron-strong groups, typically alcohols (~OH),
amines (~NH
2
), or water.
Electrophilic groups are electron-weak groups such as acids (~COOH), esters (~COO~), amides
(~CONH~), and isocyanates (~NCO). When two chemical species react, the species with the strongest
nucleophilic group is called the nucleophile; the other reactant bearing the strongest electrophilic group is
called the electrophile.
Nucleophiles and electrophiles participate in bimolecular reactions. Depending on the types of functional
groups in each reactant, the reaction mechanism may be nucleophilic substitution or nucleophilic addition.
Nucleophilic Substitution
In nucleophilic substitution reactions, a nucleophilic group from one reactant (the nucleophile) displace a
nucleophilic group in the other reactant (the electrophile), resulting in two new products. (Note:
Electrophilic groups are highlighted in each of the following figures.) Nucleophilic substitution reactions
tend to be highly reversible.
O
O CH
3
OH + CHO
HOH + CH
3
O C Nucleophilic
Electrophilic Species
Species
Nucleophilic
Species Forward Reaction
Reverse Reaction
Nucleophilic Addition
In nucleophilic addition reactions, the electrophile and nucleophile combine to form a new functional
group. These reactions are typically irreversible.
O CH
3
OH + NCO
CH
3
O NHC Nucleophilic
Species
Currently, the step-growth reaction generation algorithm is limited to condensation reactions.
Pseudocondensation reactions must be defined through the user reaction feature or through the
segment-based power-law reaction model.
In some reverse reactions and re-arrangement reactions, the electrophile may be a polymer or oligomer.
These reactions occur at the bonds which link two segments together. To fully describe these reactions,
the two segments in the electrophile must be identified. In this case, we refer to the electrophile as the
victim reactant and the nucleophile as the attacking reactant. The victim reactant includes a
nucleophilic segment and an electrophilic segment.
Attacking
Victim
Victim Nucleophilic
Nucleophilic
Species
Species O
O CH
3
OH + O(CH
2
)
2
O
C
CO
O O(CH
2
)
2
OH + CH
3
O
C C The following table lists
the role of electrophiles and nucleophiles in several step-growth polymerization processes, as well as the
typical reacting
functional groups, the characteristic repeat unit, and the by-product related to each polymerization
process:
Polymer Class Nucleophile Electrophile Repeat Unit Condensate
By-product
Polyester ~OH ~OH
~COOH
~COOH
~(C=O)O~ ~(C=O)O~ ~(C=O)O~
Polyamide ~COOH ~(C=O)NH~
Polyacetal (Polycarbonate)
H
2
O ~COOCH
3
CH
3
OH ~O(C=O)CH
3
CH
3
COOH
~NH
2
H
2
O
~OH
~O(C=O)Cl ~OH
~O(C=O)Oph
~NH
2
~NH
2
O CH CH
2
~O(C=O)O~ ~O(C=O)O~
HCl PhOH Polyurethanes
~OH
~(C=O)Cl ~N=C=O
~NH(C=O)O~ ~NH(C=O)O~
HCl none
Polyurea ~N=C=O ~NH(C=O)NH
~
none
Polyether ~OH ~OCH
2
C(OH)H~
none
Reaction Nomenclature
Polymerization reactions are classified by chemical mechanism, by the number of reacting components,
and by the influence a reaction has on the chain length distribution. This section describes the basic types
of reactions found in step-growth polymerization and serves as a glossary of reaction nomenclature.
Intermolecular reactions involve two or more molecules.
Intramolecular reactions involve two sites on the same molecule.
Condensation reactions are polymerization reactions which produce a small molecule as a by-product.
Typically, the condensate is a volatile compound such as water, methanol, acetic acid, or phenol. Step-
growth reactions involving chlorine end groups result in hydrochloric acid or chlorinated hydrocarbon
condensate products.
Reverse condensation reactions are where condensate molecules cleave an existing polymer chain,
producing two smaller chains. Reverse condensation reactions near the end of a polymer molecule can
generate free monomers.
Pseudocondensation reactions are nucleophilic addition reactions. These reactions involve
rearrangement of atoms in two different functional groups, resulting in a new functional group. No by-
products are produced by pseudocondensation reactions. Pseudocondensation reactions can involve two
monomers, a monomer and a polymer end group, or two polymer end groups.
Addition reactions are reactions in which small molecules, including free monomers, dyadic salts, and
cyclic monomers and dimers react with the end
of a growing polymer molecule. These reactions are responsible for the conversion of the monomers and
most of the conversion of functional end groups.
Combination reactions involve reactions between the end groups of two polymer molecules. In most
systems, combination reactions play an important role in molecular weight growth.
Rearrangement reactions occur between two polymer molecules, resulting in two new polymer molecules
with different molecular weights. These reactions may involve the end group of one molecule and an
internal site on another molecule, or they may involve internal sites on both molecules.
Ring opening reactions are intermolecular reactions between condensate or monomer molecules and
cyclic monomers or oligomers. Condensate molecules or monomers react with cyclic compounds,
opening the ring structure to produce linear oligomers or cyclic monomers.
Ring closing reactions are intramolecular reactions which occur between the two end groups of a linear
molecule. Ring-closing reactions which occur between two end groups of a branched or network molecule
are referred to here as intramolecular cyclization to differentiate them from reactions which form ring-
shaped molecules.
Ring addition reactions are intermolecular reactions between polymer end groups and cyclic monomers
or oligomers. The end group of the polymer links to the cyclic compound, opening the ring and
lengthening the chain of the linear molecule.
Cyclodepolymerization reactions are intramolecular reactions in which a polymer end group reacts with a
segment in the same molecule, forming a ring. The ring-shaped molecule is lost from the linear parent
molecule, reducing the molecular weight of the parent.
Terminal monomer loss involves the loss of a monomer unit at the end of a polymer chain due to thermal
degradation mechanisms.
Random scission involves the spontaneous cleavage of a polymer chain due to thermal degradation.
End group reformation reactions are those reactions which convert one type of end group into another
without influencing the chain length.
The following table summarizes the reactions for step-growth polymerization:
Reaction Class Reaction Mechanism Reaction Type Reaction Scheme Included
Inter- molecular
Nucleophilic M Substitution
Condensation - Monomer Addition
+MP2
+WPnMPn
W
Yes Yes
Condensation - Polymer Addition
+ +1
+
Pn+PmPn+
+
W
Yes
Reverse Condensation - Terminal Monomer Loss
W+P2
M+MWPnPn
M
Yes Yes
Reverse Condensation - Scission
+ -1
+
W+PnPn-
m+
P
m
Yes
Forward Polycondensation
Pn+PmPn+m
-1
+
M
Yes
Reverse Polycondensation
M+PnPn-m+
P
m
+1
Yes
Re-arrangement P n + P m P n + m -
q+
Pq
Yes
Ring Opening W + C n P n
No
Ring Addition P n + C m
P
n+
m
No
Nucleophilic Addition (Pseudo-condensation)
Monomer Addition M + M
P2PnMPn
No
+
+1
No
Polymer Addition P n + P m
P
n+
m
No
Intra- molecular
Pseudo-condensation Terminal or Thermal mechanisms
Monomer Loss P 2
M+
M
PnPn
M
No
-1
+
No
Scission P n P n -
m+
P
m
No
Nucleophilic Substitution
Ring-Closing P n C n
+W
No
Cyclodepolymerization P n P n -
m+
C
m
No
Nucleophilic Addition Ring-Closing P n C
n
No
Pn
= Linear polymer with n segments C
n
= Cyclic polymer with n segments (C
1
= cyclic monomer, such as caprolactam)
M = Monomer W = Condensate
Polyester Reaction Kinetics

In the direct esterification process, polyesters are produced by the reaction of diols, such as ethylene
glycol, with diacids, such as terephthalic acid. The esterification reactions generate one mole of water for
each mole of ester groups formed. The reactions are catalyzed by acid end groups in the polymer and
diacid monomer.
Side Reactions
Several of the key side reactions are also acid-catalyzed. In the PET process, these reactions include the
formation of diethylene glycol, or DEG, from ethylene glycol. The transesterification process does not
involve acids, and substantially less DEG is produced.
An analogous reaction generates tetrahydrofurane (THF) in the PBT process. Like DEG formation, THF
formation is accelerated by acid end groups. Since THF poses environmental concerns, the generation of
THF should be minimized. For this reason, PBT is usually produced by the transesterification route.
Metal acetate catalysts are used to accelerate the reaction rates in the later stages of the direct
esterification process and throughout the transesterification process. These catalysts accelerate the main
reactions and several side reactions including thermal scission and aldehyde formation.
In the transesterification process, acid end groups may be formed by thermal degradation reactions or by
exchange reactions with water, which may be formed as a reaction by-product. These acid end groups
participate in the reaction scheme, making transesterification kinetics a superset of esterification kinetics.
Polymerization Stage
The polymerization stage involves chain building reactions. There are two main growth mechanisms.
Condensation reactions occur between two polymer end groups, releasing water or methanol.
Polymerization reactions occur between diol end groups in different polymer molecules, generating a
molecule of free glycol.
The polymer end group distribution and molecular weight distribution are randomized by redistribution
reactions.
Polyester Production Final Stages

In the final stages of polyester production, high temperatures lead to thermal degradation reactions. In the
PET process, these reactions degrade glycol end groups, producing acid ends and free acetaldehyde.
Thermal scission reactions generate acid end groups and oxyvinyl end groups. Analogous reactions in
the PBT process yield butenol and 1,4-butadiene. Additional side reactions involving these vinyl groups
are the main source of color bodies in polyesters.
Cyclic compounds are formed by ring-closing and cyclodepolymerization reactions. Cyclic monomers, and
some cyclic dimers do not form in terephthalic polyesters because of steric limitations. Trace amounts of
larger cyclic oligomers, including trimers, tetramers, and pentamers, are commonly observed in
terephthalate polyesters. These cyclic compounds reduce the quality of the polyester. Cyclic oligomers
evaporate from the finishing reactors and condense in vapor vent lines, causing maintenance problems.
The reaction kinetics of terephthalate polyesters are summarized in the tables that follow.
The components involved in the reactions are:
Component ID
Databank ID
Component Structure Component Name
TPA C8H6O4-D3 Terephthalic acid
T-TPA C8H5O3-E Terephthalic acid end group
B-TPA C8H4O2-R Terephthalate repeat unit
DMT C10H10O4-
D2
O O HO
C C OH O O C
C OH
OOCCO
O Dimethyl terephthalate CH
3
O
C
C OCH
3
T-DMT C9H7O3-E O
O Dimethyl terephthalate end C
C OCH
3
group
MMT none O
O Monomethyl terephthalate HO
C
C OCH
3
H2O H2O H
2
O
Water
MEOH CH4O CH
3
OH
Methanol
Components In Polyethylene Terephthalate Processes
EG C2H6O2 HO(CH
2
)
2
OH
Ethylene glycol
T-EG C2H5O2-E ~O(CH
2
)
2
OH
Ethylene glycol end group
B-EG C2H4O2-R ~O(CH
2
)
2
O~
Ethylene glycol repeat unit
DEG C4H10O3 HO(CH
2
)
2
O(CH
2
)
2
OH
Diethylene glycol
T-DEG C4H9O3-E ~O(CH
2
)
2
O(CH
2
)
2
OH
Diethylene glycol end group
B-DEG C4H8O3-R ~O(CH
2
)
2
O(CH
2
)
2
O~
Diethylene glycol repeat unit T-VINYL C2H3O-E ~OCH=CH
2
Oxyvinyl end group
C3 none O T = C
O C TG T
Cyclic trimer
G G= O(CH
2
)
2
O
GT
Components In Polybutylene Terephthalate Processes
BD C4H10O2 HO(CH
2
)
4
OH
1,4 Butane diol
T-BD C4H9O2-E ~O(CH
2
)
4
OH
1,4 Butane diol end group
B-BD C4H8O2-R ~O(CH
2
)
4
O~
1,4 Butane diol repeat unit
T-BUTENOL C4H11O2-E ~O(CH
2
)
2
CH=CH
2
Butenol end group
THF C4H8O-4 o
Tetrahydrofurane
The following table summarizes the step-growth reactions associated with terephthalate polyesters. For
brevity, the table shows a subset of the reactions which actually occur - an analogous set of reactions
involving DEG are also generated by the step-growth model.
Reaction Type Stoichiometric Reactions - Direct Esterification Route
Condensation
O HO(CH
2
HO O OH 1 2
O HO(CH
2
)
x
OCO)x
OH +
C
C C OH + H
2
O
O O(CH
2
)
x
OH + HO C
O C OH 3 4
O O(CH
2
)
x
O
C
O C OH + H
2
O
O HO(CH
2
)
x
OH +
HO C
OC56
O HO(CH
2
)
x
OC
OC+H
2
O
O O(CH
2
)
x
OH +
HO C
OC78
O O(CH
2
)
x
OC
OC+H
2
O
Polymerization
C C Rearrangement
Reaction Type Additional Reactions - Transesterification Route
Condensation
Polymerization
End-group Exchange
x = 2 for polyethylene-terephthalate
x = 3 for polypropylene-terephthalate x = 4 for polybutylene-terephthalate
O O O(CH
2
)
x
OH + HO(CH
2
)
x
O
C
O OH 9
O(CH
2
O OH O O(CH
2
)
x
OH + HO(CH
2
C
C O C 10 11 12
)
x
O + HO(CH
2
)
x
OH
OO)x
O
O(CH
2
)
x
OC
C + HO(CH
2
)
x
OH
O O(CH
2
)
x
OH + O(CH
2
C
O C 13 14
OO)x
O
O(CH
2
)
x
OC
C + HO(CH
2
)
x
O
O
O OCH
3
15 16
O HO(CH
2
)
x
O C O HO(CH
2
)
x
OH +
CH
3
OC
C C OCH
3
+ CH
3
OH
O O(CH
2
)
x
OH + CH
3
OC
O C OCH
3
17 18
C C 19 20
21 22
O O O(CH
2
)
x
O
OCH
3
+ CH
3
OH
O
O O O HO(CH
2
)
x
OH +
CH
3
OC
C HO(CH
2
)
x
OC
C + CH
3
OH
O
O O O O(CH
2
)
x
OH +
CH
3
OC
C O(CH
2
)
x
OC
C + CH
3
OH
O O(CH
2
)
x
OH + HO(CH
2
)
x
O
C
23 24 O O C OCH
3
O(CH
2
)
x
OC
O C OCH
3
+ HO(CH
2
)
x
OH
OH
2
CH
3
O O 25 26
O HO C O O
+C
C C + CH
3
OH
The following table describes how to assign rate constants to each of the reactions listed in the previous
table:
Reaction No.
Attacking Nucleophilic Species
Victim Electrophilic Species
Victim Nucleophilic Species
1 EG TPA none 2 H2O T-TPA T-EG 3 T-EG TPA none 4 H2O T-TPA B-EG 5 EG T-TPA none 6 H2O B-TPA T-EG 7
T-EG T-TPA none 8 H2O B-TPA B-EG 9 T-EG T-TPA T-EG 10 EG T-TPA B-EG 11 T-EG B-TPA T-EG 12 EG B-TPA
B-EG 13 T-EG B-TPA B-EG 14 T-EG B-TPA B-EG 15 EG DMT none 16 MEOH T-DMT T-EG 17 T-EG DMT none 18
MEOH T-DMT B-EG 19 EG T-DMT none 20 MEOH B-TPA T-EG 21 T-EG T-DMT none 22 MEOH B-TPA B-EG 23 T-
EG T-DMT T-EG 24 EG T-DMT B-EG 25 H2O T-DMT none 26 MEOH T-TPA none
Many of the side reactions in the polyester process are not included in the reaction generation scheme,
and must be added to the model as user reactions. These reactions are:
Reaction Type Reaction Stoichiometry
DEG Formation
Thermal Scission
HO(CH
2
)
2
OH + HO(CH
2
)
2
OH U1
HO(CH
2
)
2
O(CH
2
)
2
OH
+H
2 O HO(CH
2
)
2
OH
+ HO(CH
2
)
2 O O(CH
2
U2
U3
HO(CH
2
)
2
O(CH
2
)
2
O+H
2O)2
OH + HO(CH
2
)
2
O O(CH
2
)
2
O(CH
2
)
2
O
+H
2OOC
O C O(CH
2
)
2
O U4
OC
O C OH +
H
2
C CHO
Reaction Type Reaction Stoichiometry
Acetaldehyde Formation
Cyclic Trimer Formation
The recommended power-law exponents for the reactants in the side reactions are:
Reaction No. Power-Law Exponents; Modeling Notes
U1 EG = 2 (Multiply group-based pre-exponential factor by 4.0) U2 EG = 1, T-EG = 1 (Multiply group-based pre-
exponential factor by
2.0) U3 T-EG = 2 (Multiply group-based pre-exponential factor by 1.0) U4 Reaction is first order with
respect to polyester repeat units, assume
concentration of repeat units is approximately equal to the concentration of B-TPA, set power-law exponents B-TPA =
1.0 B-EG = 1x10-8 U5 T-EG = 1 U6 T-EG = 1, T-VINYL = 1 U7 Reaction is first order with respect to linear molecule
with the
following segment sequence: T-TPA: B-EG : B-TPA : B-EG : B-TPA : T-EG option 1: assume this concentration =
TPA concentration and use power-law constant TPA = 1* option 2: use the following equation, based on the most-
probable distribution, to estimate the concentration of this linear oligomer. This equation can be implemented as a
user-rate constant correlation
[P
]
OC
O C O(CH
2
)
2
OH U5
OC
O O C OH + HCCH
3
O O(CH
2
)
2
OH + C
O C OCH CH
2
U6
OC
HCCH
3 O O C O(CH
2
)
2
O + TGHOT G T GH U7
U8
TG
+H
2
O
U9 U10
T
GT
G
TGTHG G T GH TG
+ HO(CH
2
)
2
OH
U11
U12
T
GT
G
TG TGTG G T GH O(CH
2
)
2
OH
+T
GT
G
2
=
NUCL T EG T DEG B EG ELEC T TPA B TPA [ T NUCL

- EG
]
22
0
2 [ B ELEC
- TPA
]
=2
2
-+-+-+
= - + - [ B NUCL - EG
]
[ ] [ ] [ ] *[ ] *[
[ ] *[ ]
T ELEC
- TPA
U8 H2O = 1, C3 = 1 (Multiply group-based pre-exponential factor by 6.0)

U9 Reaction is first order with respect to linear molecule with the
following segment sequence: T-EG : B-TPA : B-EG : B-TPA : B-EG : B-TPA : T-EG option 1: assume this
concentration = TPA concentration and use power-law constant TPA = 1* option 2: use the following equation, based
on the most-probable distribution, to estimate the concentration of this linear oligomer. This equation can be
implemented as a user-rate constant correlation
[P2
]
=
NUCL T EG T DEG B EG B DEG ELEC T TPA B TPA [ T NUCL

- EG
]
232
0
2 [ B ELEC
- TPA
]
=2
2
-+-+-+-
= - + - [ B NUCL - EG
]
[ ] [ ] *[ ] *[ ] [ ] *[ ]
U10 EG = 1, C3 = 1 (Multiply group-based pre-exponential factor by 12.0) U11 Reaction is first order with respect to
linear molecule with the
following segment sequence: ~B-EG : B-TPA : B-EG : B-TPA : B-EG : B-TPA : T-EG option 1: assume this
concentration = T-EG concentration and use power-law constant T-EG = 1* option 2: use the following equation,
based on the most-probable distribution, to estimate the concentration of this linear oligomer. This equation can be
implemented as a user-rate constant correlation
[P2
]
=
[ T NUCL - EG
]
[ B ELEC
- TPA
]
3
[ B NUCL - EG
]
3
0
NUCL = [ T - EG ] + [ T - DEG ] + 2 *[ B - EG ] + 2
*[ B -
DEG
] ELEC = [ T - TPA ] + 2
*[ B -
TPA ]
U12 T-EG = 1, C3 = 1 (Multiply group-based pre-exponential factor by
6.0)
* To avoid numerical problems, set power-law exponents to 101 - 8 for reactants
which do not appear in the rate expression
0
= Concentration zeroth moment, mol/L (approximately=0.5*([T-TPA]+[T-
EG]+[T-DEG]+[T-VINYL])
Nylon-6 Reaction Kinetics

Nylon-6 melt-phase polymerization reactions are initialized by the hydrolytic scission of caprolactam rings.
The reaction between water and caprolactam generates aminocaproic acid. The reaction kinetics in the
primary reactor are sensitive to the initial water concentration.
The carboxylic and amine end groups of the aminocaproic acid molecules participate in condensation
reactions, releasing water and forming polymer molecules. The resulting acid and amine end groups in
the polymer react with each other and with aminocaproic acid, releasing more water.
The amine end of aminocaproic acid and amine ends in polymer react with caprolactam through ring
addition. This reaction is the primary growth mechanism in the nylon-6 process.
Cyclic Oligomers
As the reactions proceed, intramolecular reactions involving linear polymer molecules generate cyclic
oligomers. Cyclic oligomers ranging from the dimer through rings ten units long are reported in the
literature. The concentration of each successive cyclic oligomer (dimer, trimer, etc.) falls off sharply, in
accordance with the most probable distribution.
Reactions involving cyclic compounds are not considered in the reaction generation algorithm in the step-
growth model. These reactions, including ring opening, ring closing, ring addition, and
cyclodepolymerization, must be specified as user reactions.
The following table summarizes key components in the nylon-6 melt polymerization process. The
component names in this table are used in the tables that follow.
Component ID Databank ID
Component Structure Component Name
CL C6H11NO -Caprolactam
ACA none Aminocaproic acid
T-NH2 C6H12NO-E-1 Amine end group
segment
T-COOH C6H12NO2-E-1 Acid end group
segment
R-NY6 C6H11NO-R-1 Nylon-6 repeat segment
CD none Cyclic dimer
H2O H2O Water
Major Reactions
The major reactions in the nylon-6 melt polymerization process are shown here:
Reaction Type User-Specified Reactions (Forward and Reverse
Reactions Defined Separately)
Ring Opening / Ring Closing
Ring Addition / Cyclodepolymerization
O
NH
(CH
2
OH
2
N
)
5
C OH
OH
2
N
(CH
2
)
5 C (CH 2
O NH
)
5
C OH
O NH
(CH
2
)
5 C NH (CH
2
)
5 C C (CH 2
NH O O
)
5
H
2
O
U1 H2O + CL ACA
U2 H2O + CD T-COOH : T-NH2 (=P
2
)
U3 ACA + CL T-COOH : T-NH2 (=P
2
)
U4 T-NH2 + CL R-NY6 : T-NH2
U5 ACA + CD T-COOH : R-NY6 : T-NH2 (=P
3
)
U6 T-NH2 + CD
R-NY6 : R-NY6 : T-NH2
Reaction Type Model-Generated Step-Growth Reactions (Define
Nylon-6 Repeat Unit as EN-GRP)
Condensation
Re-Arrangement
In the reaction stoichiometry equations above, the colon (:) indicates
connections between segments. Literature sources report rearrangement reactions are insignificant,
these reaction rates can be set to zero
The reactions U1-U6, which involve cyclic monomer and dimer, are not generated by the current version
of the Step-Growth model. These reactions must be defined as user reactions. However, the
stoichiometry of each of these reactions is shown.
Reactions 1-7 are considered in the reaction generation algorithm in the Step- Growth kinetics model.
The rate constants for these reactions can be assigned according to the identifiers summarized here:
Reaction No.
1. ACA + ACA T-COOH : T-NH2 + H2O
2. ACA + T-COOH T-COOH : R-NY6 + H2O
3. T-NH2 + ACA R-NY66 : T-NH2 + H2O 4. T-NH2 + T-COOH R-NY66 : R-NY6 + H2O
5. T-NH2 + T-NH2 : T-COOH T-NH2 : R-NY6 + ACA
6. T-NH2 + R-NY6 : T-COOH R-NY6 : R-NY6 + ACA
7. T-NH2 + R-NY6 : R-NY6 R-NY6 : R-NY6 + T-NH2 Attacking Nucleophilic Species
1 forward ACA T-ACA none 2 forward ACA T-COOH none 3 forward T-NH2 ACA none 4 forward T-NH2 T-COOH
none 5 forward T-NH2 T-NH2 T-COOH 6 forward T-NH2 T-NH2 R-NY6 7 forward T-NH2 R-NY6 R-NY6 1 reverse
H2O T-NH2 T-COOH 2 reverse H2O R-NY6 T-COOH 3 reverse H2O T-NH2 R-NY6 4 reverse H2O R-NY6 R-NY6 5
reverse ACA T-NH2 R-NY6 6 reverse ACA R-NY6 R-NY6 7 reverse T-NH2 R-NY6 R-NY6
The suggested power-law exponents are shown here:
U1 forward H2O = 1, CL = 1 U1 reverse ACA = 1 U2 forward H2O = 1, CD = 1 (Multiply group-based pre-exponential
factor by 2.0)
U2 reverse Reaction is first order with respect to linear dimer
P
2
with the following segment sequence: T-NH2 :T-COOH
option 1: assume
P
2
concentration = ACA concentration and use power-law constant ACA = 1* option 2: use the
following equation, based on the most-probable distribution, to estimate concentration of
P
2
The denominator in this equation can be implemented as a user rate constant, with
first-order power-law constants for T-NH2 and T-COOH. [ P
2]
=
[T[T-
NH
2
] - NH 2 ] + [ R -
NY
6]
[T[T-
COOH
] - COOH ] + [ R -
NY 6
]
0
U3 forward ACA = 1, CL = 1 U3 reverse See U2 reverse reaction U4 forward T-NH2 = 1, CL = 1 U4 reverse T-NH2 =
1 (this approximation assumes most T-NH2 end groups are attached to
repeat units)* U5 forward ACA = 1, CD = 1 U5 reverse Reaction is first order with respect to linear
trimer
P3
with the following segment sequence: T-NH2 : R-NY6 :
T-COOH
option 1: assume
P3
concentration = ACA concentration and use power-law constant ACA = 1* option 2: use the
following equation, based on the most-probable distribution, to estimate concentration of
P3
The denominator in this equation can be implemented as a user rate constant, with
first-order power-law constants for T-NH2, R-NY6, and T-COOH. [ P
2]
=
[T[T-
NH
2
] - NH 2 ] + [ R -
NY
6
]
[ T - COOH [ R -
] NY + [ 6 ] R -
NY
6]
[T[T-
COOH
] - COOH ] + [ R -
NY 6
]
0
U6 forward T-NH2 = 1, CD = 1 U6 reverse T-NH2 = 1 (this approximation assumes most T-NH2 end groups are
attached to
repeat units)*
*
To avoid numerical problems, set power-law exponents to
101
-
8
for reactants which do not appear in the
rate expression
0
= Concentration zeroth moment, mol/L (approximately = 0.5 * ([T-COOH] + [T-NH2])
The side reactions are thought to be catalyzed by acid end groups in aminocaproic acid and the polymer.
A first-order power-law coefficient can be used to account for the influence of the acid groups in these
components. Alternately, a user rate-constant subroutine can be developed to account for the influence of
the acid end groups.
Note that the forward and reverse terms of the reversible side reactions must be defined as two separate
user reactions in the model.
Nylon-6,6 Reaction Kinetics
The salt process involves a preliminary reaction to form the salt, which precipitates from solution. During
the salt formation, some of the salt remains in solution, leading to higher polymers. For a rigorous model,
it is a good idea to consider these oligomerization reactions, even in the salt precipitation reactor.
Accounting for these reactions is important when using the model to optimize the temperature, pressure,
and water content of the nylon salt crystallizer.
The model needs to consider three phase equilibrium (solid salt, liquid, and vapor). Three phase
equilibrium can be considered in Aspen Plus using the electrolyte chemistry feature. In version 10.0,
however, the CSTR model does not allow a component to appear simultaneously in chemistry reactions
and kinetic reactions. Another way to represent the solid-liquid equilibrium is to define an equilibrium
reaction between the components representing the dissolved and solid salt. Chemical equilibrium
equations can be defined using the Power-Law reaction kinetics model in Aspen Plus. Apply the mole-
gamma option to force the equilibrium equation to use the ratio of the molar activities as the basis of the
equilibrium constant. By using this assumption, the equilibrium constant is the same as the solubility
constant of the solid salt.
To model the reaction kinetics of the salt process, the dissolved salt should be considered as a
component in the reaction model. The models described in the open literature do this by considering the
salt as an AB type monomer. This treatment, however, fails to consider some of the reverse reactions
which can occur during polymerization. This approach assumes that reverse condensation reactions and
re-arrangement reactions always generate products with an equal number of adipic acid and HMDA units.
In reality, polymer chains with an unequal number of units can be formed because the reactions can
occur inside the repeat units which originally came from the reacting salts. Further, the reverse reactions
can generate free adipic acid or HMDA when the reaction occurs at the end of a polymer chain.
Reverse Rate Constant

The models in the literature use a reverse rate constant which is twice the reverse rate constant
experienced by an individual amine group. This factor of two accounts for the fact that each repeat unit
has two amine groups. In the approach described here, the reverse rate constants used in the model
should be the rate constant between two functional groups, for example between water and a single
amine group.
Considering salt as a component, there are several reversible reactions which must be considered in the
model. A number of condensation reactions occur including those between molecules of dissolved salt,
dissolved monomers, and polymer end groups. These reactions can be implemented in the step-growth
model through the user reaction feature. The step-growth model will generate the reactions which do not
involve the salt component.
The molecular weight distribution of nylon-6,6 is known to re-equilibrate when the polymer is exposed to
HMDA under pressure. Further, as vacuum is applied, free HMDA appears to be generated. These facts
indicate that rearrangement reactions are important in this process.
Modeling Approaches
There are two modeling approaches:
Simplified
Detailed
The component definitions for both modeling approaches are:
Component ID Databank ID Component Structure Component Name
Components Common to Simplified and Detailed Approach
ADA C6H10O4-D1 O
O
Adipic acid HO C
(CH
2
)
4
C OH
HMDA C6H16N2 H
2
N
(CH
2
)
6
NH
2
Hexamethylene diamine
DIS-SALT none O
O
Dissolved nylon-6,6 salt HO C
(CH
2
)
4
C
NH (CH
2
)
6
NH
2
SOL-SALT none O
O
Solid nylon-6,6 salt HO C
(CH
2
)
4
C O-
+H
3
N (CH
2
)
6
NH
2
MEOH CH4O CH
3
OH
Methanol
H2O H2O H
2
O
Water
Segments In Simplified Salt Process Model
T-COOH none O
O
Acid end group HO C
(CH
2
)
4
C
NH (CH
2
)
6
NH
segment
T-NH2 none O
O
Amine end group C
(CH
2
)
4
C
NH (CH
2
)
6
NH
2
segment
R-NY66 none O
O
Repeat unit segment C
(CH
2
)
4
C
NH (CH
2
)
6
NH
Segments In Detailed Salt Process Model and Melt-Process Model
T-ADA C6H9O3-E O
O
Adipic acid end group C
(CH
2
)
4
C OH
B-ADA C6H8O2-R
O O Adipic acid repeat unit C (CH
2
)
4
C
T-HMDA C6H15N2-E HN
(CH
2
)
6
NH
2
HMDA end group
B-HMDA C6H14N2-R HN
(CH
2
)
6
NH HMDA repeat unit
Note: The component names used in this table are used in the successive tables to document the
reactions.
In the simplified approach, the dissolved salt is treated as an AB monomer (a monomer with two
different types of functional groups). This is accomplished by defining the repeat unit as an EN-GRP
reactive group. The simplified approach is consistent with the modeling approach described in the open
literature.
Using this approach, the Step-Growth model will generate all of the main reactions. The solid-liquid phase
equilibrium can be represented as a chemical
equilibrium reaction using the Power-Law model or as two side reactions in the step-growth model. The
equilibrium constant of this reaction corresponds to the solubility constant of the salt.
The reactions for a simplified Nylon-6,6 salt process model are shown here:
Reaction Type
Phase Equilibrium Reactions (Use Power-Law Reaction Kinetics Model)
Solid/Liquid Equilibrium
Reaction Type
C1 DIS-SALT + H2O SOL-SALT
User-Specified Reactions (Forward and Reverse Reactions Defined Separately)
Salt formation
U1 HMDA + ADA DIS-SALT + H2O
Model-Generated Step-Growth Reactions (Define Reaction Type
Nylon-6,6 Repeat Unit as EN-GRP)
Condensation
3. T-NH2 + DIS-SALT R-NY66 : T-NH2 + H2O
Re-Arrangement
connections between segments
The detailed modeling approach treats the HMDA and ADA segments as discreet molecular units. Using
this assumption, the dissolved salt is a dimer made up of one hexamethylene diamine end group and one
adipic acid end group. This approach is more rigorous because it considers every possible reverse
reaction, including terminal monomer loss. To use this approach, define the HMDA repeat group as a
bifunctional nucleophile (NN-GRP), and the ADA repeat group as a bifunctional electrophile (EE-GRP).
The solid-liquid phase equilibrium (reaction C1) is represented as previously described. The reactions
involving the dissolved salt, U1-U6, must be defined as user reactions. Reactions 1-7, which do not
involve the salt, are generated by the model automatically.
The reactions for a detailed Nylon-6,6 salt process model are shown here:
Reaction Type
1. DIS-SALT + DIS-SALT T-COOH : T-NH2 + H2O 2. DIS-SALT + T-COOH T-COOH : R-NY66 + H2O 4. T-NH2 + T-
COOH R-NY66 : T-NY66 + H2O 5. T-NH2 + T-COOH : T-NH2 R-NY66 : T-NH2 + DIS-SALT
6. T-NH2 + T-COOH : R-NY66 R-NY66 : R-NY66 + DIS-SALT
7. T-NH2 + R-NY66 : R-NY66 R-NY66 : R-NY66 + T-NH2 Phase Equilibrium Reactions (Use Power-Law
Reaction Kinetics Model)
Solid/Liquid
C1 DIS-SALT + H2O SOL-SALT Equilibrium
User-Specified Reactions (Forward and Reverse Reaction Type
Reactions Defined Separately)
Salt formation
Condensation
Reaction Type
U1 HMDA + ADA DIS-SALT + H2O
U2 DIS-SALT + DIS-SALT T-HMDA : B-ADA : B-HMDA : T-ADA + H2O U3 DIS-SALT + ADA T-ADA : B-HMDA : T-
ADA + H2O U4 HMDA + DIS-SALT T-HMDA : B-ADA : T-HMDA + H2O
U5 DIS-SALT + T-ADA T-ADA : B:HMDA : B-ADA + H2O U6 T-HMDA + DIS-SALT B-HMDA : B-ADA : T-HMDA +
H2O
Model-Generated Step-Growth Reactions (Define B- HMDA as NN-GRP, B-ADA as EE-GRP)
Condensation
2. HMDA + T-ADA T-HMDA : B-ADA + H2O
3. T-HMDA + ADA B-HMDA : B-ADA + H2O
4. T-HMDA + T-ADA B-HMDA + B-ADA + H2O Re-Arrangement
In the reaction stoichiometry equations above, the colon (:) indicates connections
between segments
Rate Constant Identifiers

The rate constants can be assigned to model-generated reactions in the simplified model using the
identifiers summarized here:
Reaction No.
1. HMDA + ADA T-HMDA : T-ADA + H2O 5. T-HMDA + T-ADA : T-HMDA T-ADA : B-HMDA + HMDA
6. T-HMDA + B-ADA : T-HMDA B-ADA : B-HMDA + HMDA
7. T-HMDA + B-ADA : B-HMDA B-ADA : B-HMDA + T-HMDA Attacking Nucleophilic Species
1 forward DIS-SALT DIS-SALT none 2 forward DIS-SALT T-COOH none 3 forward T-NH2 DIS-SALT none 4 forward
T-NH2 T-COOH none 5 forward T-NH2 T-COOH T-NH2 6 forward T-NH2 T-COOH R-NY66 7 forward T-NH2 R-
NY66 R-NY66 1 reverse H2O T-COOH T-NH2 2 reverse H2O T-COOH R-NY66 3 reverse H2O R-NY66 T-NH2 4
reverse H2O R-NY66 R-NY66 5 reverse DIS-SALT T-NH2 R-NY66 6 reverse DIS-SALT R-NY66 R-NY66 7 reverse
T-NH2 R-NY66 R-NY66
A subset of these identifiers can be used to assign the same rate constant to several different reactions.
For example, reactions 3-7 can be lumped together by specifying T-NH2 as the attacking nucleophilic
species and by leaving the victim species identifiers blank (unspecified).
Rate constants can be assigned to reactions 1-7 in the detailed model using the identifiers summarized
here:
Reaction No. Attacking
Nucleophilic Species
1 forward HMDA ADA none 2 forward HMDA T-ADA none 3 forward T-HMDA ADA none 4 forward T-HMDA T-ADA
none 5 forward T-HMDA T-ADA T-HMDA 6 forward T-HMDA B-ADA T-HMDA 7 forward T-HMDA B-ADA B-HMDA 1
reverse H2O T-ADA T-HMDA 2 reverse H2O B-ADA T-HMDA 3 reverse H2O T-ADA B-HMDA 4 reverse H2O B-ADA
B-HMDA 5 reverse HMDA T-ADA B-HMDA 6 reverse HMDA B-ADA B-HMDA 7 reverse T-HMDA B-ADA B-HMDA
For example, reactions 3-7 can be lumped together by specifying T-HMDA as the attacking nucleophilic
Each reaction involving the dissolved salt must be defined as a user-reaction in the Step-Growth model.
The forward and reverse reactions are treated as two separate reactions. The stoichiometry of each
reaction was shown previously in the reactions table for the detailed modeling approach. The power-law
exponents are in the following table.
Several of the reverse reactions require a particular sequence of segments in order to occur. The
concentration of molecules with these particular sequences can be assumed (for example, assume the
linear trimer concentration is the same as the dissolved salt concentration) or they can be estimated from
statistical arguments. The following table shows both techniques. The statistical approach is more
rigorous, but it requires writing a user rate-constant or user kinetic subroutine to perform the calculations
as shown.
The power-law exponents for user-specified reactions in the detailed model are:
U1 forward HMDA = 1, ADA = 1 Multiply group-based pre-exponential factor by 4.0 U1 reverse H2O = 1, DIS-SALT =
1 U2 forward DIS-SALT = 2 U2 reverse Reaction is first order with respect to water and polymer molecule
P4
with the following segment
sequence: T-HMDA : B-ADA : B-HMDA : T-ADA
option 1: assume
P4
concentration = DIS-SALT concentration and use DIS-SALT = 1, H2O = 1* option 2: set
power-law exponent for H2O = 1 and use the following equation, based on the most-probable distribution, to estimate
concentration of
P4
(this equation can be implemented as a
user rate constant).
[P
]
=
[
T
-
ADA [ T
[2] - + ADA B ] - ADA ]
-
[2
B
- HMDA ] 4
[
T
HMDA [2] + B - HMDA ]
[
T
-
ADA [2 B
[2] - + ADA B - ] ADA ] T
HMDA B HMDA

0
U3 forward DIS-SALT = 1, ADA = 1, multiply group rate constant by 2.0 U3 reverse
Reaction is first order with respect to water and polymer molecule
[
-
[
T
-
HMDA [2] + ] - ]
P
3,
aa with the following segment
sequence: T-ADA : B-HMDA : T-ADA
option 1: assume
P
3,
aa concentration = ADA concentration and use power-law constants ADA = 1, H2O = 1*
option 2: set power-law exponent for H2O = 1 and use the following equation, based on the most-probable
distribution, to estimate concentration of
P
3,
aa (this equation can be implemented as
a user rate constant).
[P3
, aa ]
=
[T-[T-
ADA ADA ] + 2
[B]-
ADA
]
[ T - HMDA 2
[B-
] + HMDA 2 [ B -
] HMDA ]
0 U4 forward DIS-SALT = 1, HMDA = 1; multiply group rate constant by 2.0 U4 reverse
Reaction is first order with respect to water and polymer molecule
P
3,
BB with the following segment
sequence: T-HMDA : B-ADA : T-HMDA
option 1: assume
P
3,
BB concentration=HMDA concentration and use power-law constants HMDA=1, H2O=1*
option 2: set power-law exponent for H2O = 1 and use the following equation, based on the most-probable
distribution, to estimate concentration of
P
3,
BB (this equation can be implemented as
a user rate constant).
[P3
, aa ]
=
[ T - HMDA [ T -
HMDA
]]+2
[B-
HMDA
]
[ T - ADA 2
[B]-
+ ADA 2 [ B - ]
ADA ]
0 U5 forward DIS-SALT = 1, T-ADA = 1 U5 reverse H2O = 1, T-ADA = 1, set power law constants for B-ADA,
B-HMDA to 1E-10 to avoid
numerical problems U6 forward DIS-SALT = 1, T-HMDA = 1
U6 reverse H2O = 1, T-ADA = 1, set power law constants for B-ADA, B-HMDA to 1E-10 to avoid
numerical problems
*
To avoid numerical problems, set power-law exponents to
101
-
8
for reactants which do not appear in the
rate expression
0
= Concentration zeroth moment, mol/L (approximately = 0.5 * ([T-ADA] + [T-
HMDA])
Melt-Phase Polymerization
The best way to model the melt-phase polymerization of nylon-6,6 is to treat the HMDA and ADA
segments as discreet molecular as shown in the components table on page 116.
The following table shows the main reactions in the melt-phase polymerization of nylon-6,6:
Reaction Type
Model-Generated Step-Growth Reactions (Define B-HMDA as NN-GRP, B-ADA as EE-GRP)
Condensation
1. HMDA + ADA T-HMDA : T-ADA + H2O 2. HMDA + T-ADA T-HMDA : B-ADA + H2O
3. T-HMDA + ADA B-HMDA : B-ADA + H2O
4. T-HMDA + T-ADA B-HMDA + B-ADA + H2O Re-
5. T-HMDA + T-ADA : T-HMDA T-ADA : B-HMDA + HMDA Arrangement
6. T-HMDA + B-ADA : T-HMDA B-ADA : B-HMDA + HMDA
7. T-HMDA + B-ADA : B-HMDA B-ADA : B-HMDA + T-HMDA In the reaction stoichiometry equations above, the
colon (:) indicates
These reactions are generated by the Step-Growth model if the HMDA repeat group is defined as a
bifunctional nucleophile (NN-GRP), and the ADA repeat group as a bifunctional electrophile (EE-GRP).
Side reactions that are not shown may be included in the model as user reactions.
Rate constants can be assigned to reactions 1-7 using the identifiers for the detailed model summarized
on page 119.
For example, reactions 3-7 can be lumped together by specifying T-HMDA as the attacking nucleophilic
Melt Polycarbonate Reaction Kinetics

There is little information regarding melt-phase polymerization of polycarbonate available in the public
domain. From what is available, it is clear that the chemistry of the melt-polycarbonate process follows the
typical pattern for step-growth condensation involving two dissimilar monomers. The bisphenol-A
monomer behaves as a bifunctional nucleophile, and the diphenyl carbonate monomer behaves as a
bifunctional electrophile. The reactions generate phenol as a by-product. In later stages of the process,
rearrangement reactions regenerate small amounts of bisphenol-A monomer.
The following table summarizes the most convenient method for characterizing the components involved
in the melt polycarbonate process:
Component ID
Databank ID Component Structure Component Name
Components Common to Simplified and Detailed Approach
DPC none Diphenyl Carbonate
T-DPC C7H5O2-E Phenyl carbonate end
group
B-DPC CO-R Carbonate repeat unit
BPA C15H16O2 Bisphenol-A
T-BPA C15H15O2-E Bisphenol-A end group
B-BPA C15H14O2-R Bisphenol-A repeat unit
PHOH C6H6O Phenol
The following table shows the main reactions in this process. These reactions are generated by the model
if the carbonate group is defined as a bifunctional electrophile (EE-GRP) and the BPA group as a
bifunctional nucleophile (NN-GRP) .
Reaction Type
O OO
C
C
O
O
OC
HO OH
O OH
OO
OH
Model-Generated Step-Growth Reactions (Define B-BPA as NN-GRP, B-DPC as EE-GRP)
Condensation
1. BPA + DPC T-BPA : T-DPC + PHOH 2. BPA + T-DPC T-BPA : B-DPC + PHOH
3. T-BPA + DPC B-BPA : B-DPC + PHOH
4. T-BPA + T-DPC B-BPA + B-DPC + PHOH Re- 5. T-BPA + T-DPC : T-BPA T-DPC : B-BPA + BPA Arrangement 6.
T-BPA + B-DPC : T-BPA B-DPC : B-BPA + BPA
7. T-BPA + B-DPC : B-BPA B-DPC : B-BPA + T-BPA
The following table shows how to assign rate constants to each of the reactions shown in the previous
table:
1 forward BPA DPC none 2 forward BPA T-DPC none 3 forward T-BPA DPC none
4 forward T-BPA T-DPC none 5 forward T-BPA T-DPC T-BPA 6 forward T-BPA B-DPC T-BPA 7 forward T-BPA B-
DPC B-BPA 1 reverse PHOH T-DPC T-BPA 2 reverse PHOH B-DPC T-BPA 3 reverse PHOH T-DPC B-BPA 4
reverse PHOH B-DPC B-BPA 5 reverse BPA T-DPC B-BPA 6 reverse BPA B-DPC B-BPA 7 reverse T-BPA B-DPC
B-BPA
Rate constants can be assigned to several by leaving some of the reaction identifiers unspecified. For
example, the reverse reactions involving phenol can be lumped together by assigning phenol as the
attacking nucleophilic species and by leaving the names of the victim species unspecified.
The open literature does not describe the side reactions involved in this process, although side reactions
are certainly known to exist. These side reactions can be added to the model as user reactions.
Model Features and Assumptions

Model Predictions
The step-growth model calculates the component reaction rates and the rate of change of the zeroth and
first polymer moments ( 0 , i 1
) of the polymer chain length
distribution. The number average polymer properties (Pn, Mn) are calculated from the moments. These
component attributes can be used to calculate secondary properties, such as polymer viscosity, melting
point, end group concentrations, intrinsic viscosity, melt flow index, etc. Correlations relating secondary
properties to the polymer moments can be implemented using a User Prop-Set Property subroutine, as
described in the Aspen Plus User Guide.
The rate of change of polymer mass is calculated as follows:
R
Nseg
Rs,
i*
Mw i
p
=
1
Mw
p
This is the sum of the rates of change of segment masses.

Each segment type is assigned a value , which indicates the number of points of attachment
connecting the segment to other segments in the polymer chain:
Segment Type
End 1 Repeat 2 Branch-3 3 Branch-4 4
The rate of change of the zeroth moment (
0
) is calculated from the rate of change of the first
moment (
1
) and the segment type ():
0
t=
t 11 - 2
t The factor of 12 accounts for the fact that each connection links two segments (without this
correction the points of connection are counted twice). This method is best illustrated through these
examples:
Valid Reaction Type Stoichiometry
1
12
0
Yes Initiation
PMM + 2
M+M E + E +2 +1 +1
No Initiation
PM 1
M R +1 +1 0
Yes Propagation
(addition)
E+M R + E +1 +1 0
Yes Propagation
(insertion)
PMP
n
+
1n +
PMP
n*
+
1n
*
+
M R +1 +1 0
Yes Combination
PPP
n
+
m mn +
E+E R + R 0 +1 -1
Yes Combination
PPP
n
+
m mn +
E+E R -1 +0 -1
Yes Branching
PMP
n
+
1n +
R+M B3 + E +1 +1 0
Yes Branching
PPP
n
+
m mn +
R+E B3 + R 0 +1 -1
Yes Cross linking
PPP
n
+
m mn +
R+R B4 -1 +0 -1
M = Monomer; E = End group segment; B3 = Branch-3 segment; B4 = Branch-4
segment
This method lets you specify most classes of reactions. However, special care must be taken to ensure
that the reaction is defined in a manner that is consistent with the previous equation.
By default, the model solves the zeroth moment (ZMOM) and segment flow rates (SFLOW attributes) as
independent variables. This can cause a discrepancy between these variables, especially in flowsheets
with high polymer recycle flow rates. This discrepancy, in turn, can lead to convergence problems in
downstream reactors.
To avoid this problem, you can force the model to calculate the zeroth moment directly from the segment
flow rates by checking the explicitly solve zeroth moment option on the step-growth Options form. When
this option is selected, the model calculates the zeroth moment as:
=
- 2 This option cannot be invoked if two or more reaction models are referenced from a single
reactor block.
Phase Equilibria
The step-growth model can be used to simulate reactions in single-phase (vapor or liquid), two-phase
(VL), or three-phase (VLL) systems. Each step- growth reaction model is associated with a particular
reaction phase, specified on the Options sheet. The user can consider simultaneous reactions in multiple
phases by referring to two or more reaction models in a reactor.
Typical applications of this model include melt-phase polymerization and solution polymerization. Slurry,
suspension, and emulsion processes involving step-growth kinetics can also be simulated with this
model.
Interfacial polymerization involves a solvent phase, an organic monomer phase, and a polymer phase.
The reaction rate is usually limited by the rate of mass transfer of monomers from the organic phase to
the reacting polymer phase. The mass-transfer limits across the liquid-liquid interface are not taken into
account by the standard model. These systems can be simulated by developing a custom reactor model
in Aspen Custom Modeler or Aspen Plus, or by writing an appropriate concentration basis subroutine for
the step- growth model.
Solid-state polymerization involves crystalline and amorphous solid polymer phases and a vapor phase.
The reaction kinetics may be limited by the rate of mass transfer of volatile reaction by-products from the
amorphous solid phase to the polymer phase. None of the standard reactor models in Aspen Polymers
are designed for solid-state polymerization. Solid-state polymerization models can be developed in Aspen
Custom Modeler and interfaced to the step-growth polymerization model through the Aspen Custom
Modeler / Aspen Polymers Interface.
Mass transfer limitations in thin-film or horizontal finishing reactors can be considered by customizing the
Step-Growth model using the available concentration basis subroutine or by developing an appropriate
user reactor model in Aspen Plus or Aspen Custom Modeler.
Reaction Mechanism
The Step-Growth reaction model applies to condensation polymerization. In the future the model will be
extended to cover pseudocondensation and ring- addition polymerization. The model accounts for any
combination of monofunctional and bifunctional monomers. Cyclic monomers and multifunctional
monomers, however, are not included in the standard reaction scheme.
10
1
User-defined stoichiometric reactions can be added to the model to account for reactions which are not
included in the standard reaction scheme. These reactions use a power-law rate expression which can be
extended to more complex rate expressions through the application of a user-written Fortran subroutine.
Model Structure
This section outlines the structure of the Step-Growth kinetics model. It examines the theoretical
framework in detail. The assumptions and limits of the algorithms are documented.
Reacting Groups and Species

The first step in the development of any process simulation model is to determine the list of components.
In Aspen Polymers it is also important to decide how to characterize the polymer components. A polymer
can be broken down into segments any number of ways. For example, the nylon-6 repeat unit can be
treated as a segment, or it can be divided into two segments corresponding to the portions of the repeat
unit which came from the diacid and diamine monomers.
Segments
The preferred method of segmenting the polymer component is to define segments corresponding to the
monomers which are used to produce the polymer. This technique has two distinct advantages. First, the
property models in Aspen Polymers use the monomer as a reference point for molecular size. Second,
the reaction kinetics usually involve adding monomers to the end of growing polymer chains. Defining
segments corresponding to the monomers makes it easy to write reactions corresponding to monomers
and segments, for example monomer A segment A.
The Step-Growth model assumes that the polymer is segmented in this manner. For monadic polymers
such as nylon-6, this technique is straightforward. This method of segmenting the polymer is a bit unusual
for dyadic polymers, such as PET, because it treats them as alternating copolymers. Thus, a molecule of
PET with 100 PET units is defined as having a degree of polymerization of 200 in this model (100
terephthalate units and 100 glycol units).
Monofunctional monomers, such as benzoic acid, always correspond to an end-group segment in the
model. Bifunctional monomers can end up inside a linear polymer chain as a repeat unit, or may be
located at the end of the chain as an end group. Each symmetric bifunctional monomer (diacids, diols,
diamines, etc.) corresponds to one repeat segment and one end-group segment. Asymmetric bifunctional
monomers (monomers with two different types of end groups) correspond to one repeat unit and two end-
group segments. Multifunctional monomers can correspond to several segments, as shown:
Monomer Type
Monomer Formula
Corresponding Segment Formulas
End-Groups Repeat Unit Branch-3 Branch-4
Acid O
O
--- --- --- R C
OH R
C
Ester O
O
--- --- --- R C
OR' R
C
Amine R NH
2
R NH
--- --- ---
Alcohol R OH R O
--- --- ---
Diacid O
O
O
O
O
O
--- --- HO RC
C
OH RC
C
OH RC
C
Diester O
O
O
O
O
O
--- --- R'O RC
C
OR' RC
C
OR' RC
C
Carbonate O
O
O
--- --- RO C
OR C
OR C
Diamine H
2
N R NH
2
HN R NH
2
HN
R NH --- ---
Diol HO R OH O R OH OO
R --- ---
Amino acid O
--- --- RH
2
C OH Lactic acid --- ---
Branch agent ---
Branch agent
Reacting Functional Groups

The Step-Growth reaction model generates reactions based on the types of functional groups found in the
reactants. The model includes a list of pre- defined group types, as shown:
Description Type Examples
Nucleophilic repeat units have two electron-strong sites.
O RH
2
ONN
C
RHN
C
C
O
C
RHN OH O
O RHO OH RHO
C
C
O RO
R(OH)
3
O
C
RO
OH O
R(OH)
4
~O-R(OH)
2
~O-R(OH)O~
RO O
~O-R(OH)
3
~O-R(OH)
2
O~
O RO O
OH
O
O
HO(CH
2
RO O
NN-GRP
Electrophilic repeat units have two electron-weak sites.
)
X
OH HO OH
EE-GRP
HO C
Mixed repeat units have one electrophilic site and one nucleophilic site.
O
(CH
2
O
X
O
HO C
) C OH
Cl C Cl
EN-GRP
O
(CH
2
O)X
OH
HO COH
Description Type Examples
Nucleophilic leaving groups are electron-strong end groups.
N-GRP
Electrophilic leaving groups are electron-weak end groups.
O
(CH
2
O
O HO C
)X
COH
Cl C Cl
E-GRP
X
OH
Nucleophilic modifiers are groups with a single nucleophilic site.
HO(CH
2
) HO OH
NX-GRP
OH OH
Electrophilic modifiers are
EX-GRP groups with a single electrophilic site.
COH
Highlighted portion of component is the named reacting functional group.
Each functional group in the model is assigned a name and type. The names are used to distinguish
between different groups with the same chemical functionality.
The following table shows the types of functional groups found in common monomers and the
condensate products:
Monomer Type
O
O COH
C
Reacting Functional Groups Monomer Formula
Leaving Groups Segment Groups
Structure Type Structure Type Structure Type
Acid O
~OH N-GRP --- --- O
EX-GRP R OH R
C
Ester O
~OR N-GRP --- --- O
EX-GRP R C
OR' R
C
Amine R NH
2
~H E-GRP --- --- R NH
NX-GRP
Alcohol R OH ~H E-GRP --- --- R O
NX-GRP
Diacid O
O
~OH N-GRP --- --- O
O
EE-GRP HO RC
C
OH RC
C
Diester O
O
~OR N-GRP --- --- O
O
EE-GRP R'O RC
C
OR' RC
C
Carbonate O
~OR N-GRP --- --- O
EE-GRP RO C
OR C
Diamine H
2
N R NH
2
~H E-GRP --- --- HN
R NH NN-GRP
Diol HO R OH ~H E-GRP --- --- OO
R NN-GRP
Amino acid O
~H (amine) E-GRP ~OH (acid) N-GRP O
EN-GRP RH
2
NC
OH RHN
C
Lactic acid O
~H (alcohol) E-GRP ~OH (acid) N-GRP O
EN-GRP RHO C
OH RO
C
Reacting Functional Groups Monomer Type
Monomer Formula
Leaving Groups Segment Groups
Structure Type Structure Type Structure Type
Reacting Functional Groups In Common Types of Condensate Products
Water H
2
O
~H E-GRP ~OH N-GRP
Alcohol RO-H ~H E-GRP ~OR N-GRP
Reacting Species
Since polymer components do not have a fixed structure, polymerization reactions must be written in
terms of the polymer segments. The segments and standard components that make up the step-growth
reaction network are referred to as reacting species. Each of these reacting species is made up of one or
more reacting functional groups.
Once the reacting groups are defined, the structure of each reacting species is specified by defining the
number of each reacting group in each reacting species. It is not necessary to specify a zero when a
particular group is not in the species being defined.
Species Structure Validity

The model checks the species structures to verify they are valid and to see if there are any missing
species. Species structures are considered valid if they follow these rules:
Species may not be oligomer or polymer components.
Species may include one EE-GRP, NN-GRP, or EN-GRP, but no species may have more than one of
these three group types. Species may not contain more than one of any of these three groups.
Species which are end group segments must include one E-GRP or one N- GRP.
Species which are repeat segments may not include an E-GRP or N-GRP.
Species which are monomers must have a balanced number of electrophilic groups and nucleophilic
groups.
Structures are unique - no two species may have the same structure.
The model determines every valid combination of the specified functional groups. Any combination which
is not represented by a species structure is assumed to be a missing component. The model reports a
warning message describing the structure of the species which was not specified and drops all reactions
which would have involved this component. You can choose to ignore this warning if the missing
component is unimportant in the process being simulated.
Oligomer Fractionation
You can choose to include one or more oligomer components in the model. When this feature is used, the
model will fractionate the polymer distribution between the polymer component and the various oligomer
components. The fractionation algorithm assumes that the polymer follows the most probable distribution.
These assumptions are valid when the reactions are reversible and when the rate of rearrangement
reactions is faster than the rate of the condensation reactions.
The oligomer feature can be used to track the loss of volatile short-chain oligomers from the polymer
solution or melt. It can also be used to estimate oligomer concentrations to calculate reaction rates for
ring closing reactions or other reactions that require a particular sequence of segments. Tracking
oligomers, however, does require more simulation time and may make the model more difficult to
converge.
The Options form lets you adjust the tolerance for the oligomer fractionation calculations. When several
oligomers are tracked simultaneously it may be necessary to reduce the tolerance to improve reactor
convergence.
The logic of the step-growth oligomer fractionation algorithm is summarized here:
Assumptions
Polymer molecules consist of alternating nucleophilic and electrophilic segments Repeat segments in AB polymers,
which are made up of EN-GRP groups, act as both a nucleophile and an electrophile. The end groups act as either
electrophilic or nucleophilic segments, depending on which leaving group is attached to the end. The probability of a
particular segment being in a given point in the segment sequence is determined by the concentration of that
segment and the concentration of all other segments of that type (note: this assumption is equivalent to assuming the
most-probable distribution).
Equation
Definition of probability factors used to determine probability of a given sequence of segments:
Pa
=fai
N
afi
N
P
=
fjbEfj
bEP
a
bi
j
= Probability that nucleophilic segment a occupies the next nucleophilic position in the chain
Pb
= Probability that electrophilic segment b occupies the next electrophilic position in the chain
f
a
= Number of similar points of attachment in nucleophilic segment a (= 2 for repeat segments which are
composed of an NN-GRP)
f
b
= Number of similar points of attachment in electrophilic segment b (= 2 for repeat segments which are
composed of an EE-GRP)
N
a
= Concentration of nucleophilic segment a E
b
= Concentration of electrophilic segment b
i = Index corresponding to list of all nucleophilic segments
j = Index corresponding to list of all electrophilic segments
Example 1: calculation of expected concentration of oligomer with a sequence ab C ab =PP a b
0C
ab
= Expected oligomer concentration
0
= Concentration zeroth moment of polymer (concentration of all polymer molecules)
Example 2: calculation of expected concentration of oligomer with a sequence aBABa C aBABa =P a 2 P B 2
P
A
Reaction Stoichiometry Generation

The model predicts the stoichiometry of each step-growth reaction based on the structure of each of the
reactants. The step-growth reaction generation algorithm is summarized here:
Reaction Type Reaction Scheme Reaction Generation Algorithm
Condensation - Monomer Addition
M xa + M yb P 2,
xy +
W
ab
P n , xa M yb P n ,
xy W
ab Find every combination by which + +1
+
nucleophilic monomers,
M
segments
xa
, or end
M xa P n yb P n yx W
ab
P
xa
, can react with + , + ,1
+
electrophilic monomers,
M
yb
, or end
segments,
P
yb
, to give a condensate
molecule,
W
ab Condensation - Polymer Addition
P n , xa + P m , yb P n +
m,
xy +
W
ab Find every combination by which nucleophilic end segments,
P
xa
, can
react with end segments,
P
yb
, to give a
condensate molecule,
W
ab Reverse
Condensation - Terminal Monomer Loss
W ab + P 2 , xy M xa +
M
yb W ab + P n , xy P n -
1 , xa +
M
yb
Find every combination by which a condensate molecule,
W
ab
, can react with a polymer molecule at the boundary between a nucleophilic repeat segment, x, and an electrophilic
end group segment, y Reverse Condensation - Scission
W ab + P n , xy P n - m , xa +
P
m,
yb
Find every combination by which a condensate molecule,
W
ab
, can react with a polymer molecule at the boundary between a nucleophilic repeat
segment, x, and an electrophilic repeat segment, y
Reaction Type Reaction Scheme Reaction Generation Algorithm
Forward Polycondensation
P n , za + P m , yx P n + m -1 ,
yz +
M
xa Find every combination by which a
nucleophilic end group segment,
P
za
, can react with a polymer molecule at the boundary between a nucleophilic
repeat segment, x, and an electrophilic end segment, y Reverse Polycondensation
M za + P n , yx P n - m , yz +
P
m + ,1
xa
Find every combination by which a nucleophilic monomer,
M
xa
, can react with a polymer molecule at the boundary between a nucleophilic repeat segment, x, and an electrophilic
end segment, y Re-arrangement P n , za + P m , xy P n + m -
q , yz +
P
q,
xa Find every combination by which a
nucleophilic end group segment,
P
za
, can react with a polymer molecule at the boundary between a nucleophilic
repeat segment, x, and an electrophilic repeat segment, y
By default, the step-growth model generates all types of step-growth reactions described above. You may
turn off the reaction generation for a particular class of reactions by clearing the reaction from the
Reaction Options section of the Options form.
Model-Generated Reactions
There are two steps required to assign rate constants to model generated reactions. First, the rate
constant values are specified in the Step-Growth Rate Constant form (SG-RATE-CON sentence). Then
each set of rate constants is assigned a number for identification. Once the rate constants sets are
defined, they can be assigned to the generated reactions.
Rate Expression for Model Generated Reactions

The Step-Growth reactions model uses a modified power law rate expression, shown here:
Equation
T
ref
b
ii
-
Ea RT
T1-
T
1
ref
T
ref
rate =
[ Nucl ][ Elec ] f n f e P
C i k io
e
i
ref specified
T
T
U ( flag
)
unspecified rate [ Nucl ][ Elec ] f n f e P
C i k io
e-
RT Ea i
T b i U ( flag i
)i
Nomenclature
=
Symbol Description
[Nucl] Concentration of the attacking nucleophilic species, mol/L* [Elec] Concentration of the attacking electrophilic
species, mol/L*
f
n
Number of electrophilic leaving groups in the attacking nucleophilic species. This factor is 2 for diol and diamine
monomers. f
e
In reactions involving two victim species,
f
e
is the number of electrophilic groups in the electrophilic species.
This factor is 2 for repeat units which contain EE-GRP groups.
In reactions involving one victim species,
f
e
is the number of nucleophilic leaving groups in the electrophilic
species. This factor is 2 for diacid, diester, and carbonate monomers. P In reactions involving two victim species, P is
the probability of the victim
nucleophilic species being adjacent to the victim electrophilic species. This probability factor is calculated by the
model assuming the most probable distribution:
P
=
f vns i
N
vns f i
N
where:
f
vns
i
= Number of similar points of attachment in victim nucleophilic segment
(= 2 for NN-GRP repeat segments, 1 for all others) N
vns
= Concentration of victim nucleophilic segment
i = Index corresponding to list of all nucleophilic segments i Index corresponding to the rate constant set number. The
summation is performed over the specified list of rate constant set numbers.
Symbol Description
Ci
Catalyst concentration for rate constant set i. If the catalyst species is specified, this is the concentration of the
species. If the catalyst group is specified, this the group concentration. If both species and group are specified, this is
the concentration of the species times the number of the specified group in the specified species. If the catalyst is not
specified, this factor is set to one. k
o
Pre-exponential factor in user-specified inverse-time units*
Ea Activation energy in user-specified mole-enthalpy units (default =0) b Temperature exponent (default = 0) R
Universal gas constant in units consistent with the specified activation energy T Temperature, K T
ref
Optional reference temperature. Units may be specified, and they are converted to K inside the model. flag User flag
for rate constant set i. This flag points to an element of the user rate
constant array. U User rate constant vector calculated by the optional user rate constant
subroutine. The user flag indicates the element number in this array which is used in a given rate expression. When
the user flag is not specified, or when the user rate constant routine is not present, this parameter is set to 1.0. * The
concentration basis may be changed to other units using the Concentration
basis field on the Options sheet or using the optional concentration basis subroutine.
The reactions follow second order kinetics: one order with respect to the nucleophilic reactant and one
order with respect to the electrophilic reactant. Catalysts may make the reaction third order (one order
with respect to catalyst).
The rate constants for the model-generated reactions are assumed to be on a functional group basis. The
model applies correction factors to account for the number of like functional groups in each of the
reactants. For example, in a reaction between a diol monomer and a diacid monomer, the specified rate
constant is multiplied by four to account for the two acid groups in the diacid and the two alcohol groups
in the diol.
Some reactions occur inside polymer chains at the intersection of two segments. The model applies a
probability factor to estimate the concentration of the given segment pair. This probability is based on the
most probable distribution. It assumes that the segments in the polymer alternate between nucleophilic
segments and electrophilic segments. Repeat segments composed of an EN-GRP functional group
behave as both nucleophiles and electrophiles, so these segments can alternate with themselves.
The standard rate expression is modified using the optional user rate constant feature. The rate constant
form includes a parameter called the user flag which identifies an element in an array of user rate
constants. This array is calculated by a user-written Fortran subroutine. The standard rate expression is
multiplied by the user rate constants.
Assignment of Rate Constants to Model- Generated Reactions

Six qualifiers are used to assign each set of rate constants to internally- generated step-growth reactions,
the:
Attacking nucleophilic reactant name (A-NUCL-SPEC)
Attacking electrophilic leaving group name (A-ELEC-GRP)
Victim electrophilic reactant name (V-ELEC-SPEC)
Victim nucleophilic group name (V-NUCL-GRP)
Victim electrophilic species name (V-ELEC-SPEC)
Victim electrophilic group name (V-ELEC-GRP)
The following table contains an example illustrating how these identifiers are used to distinguish between
reactions. Note that the victim electrophilic species is only used for reactions which occur at the
intersection of two segments in a polymer molecule.
O O HO(CH
2
)
2
OH +
HOC
O COH 1 2
O HO(CH
2
)
2
OC
COH + H
2
O
O O O(CH
2
)
2
OH + HOC
HO(CH
2
O COH 3 4
O O(CH
2
)
2
O
C
COH + H
2
O
O HO(CH
2
HOC
OC56
O HO(CH
2O)2
OH +
)
2
OC
C+H
2
O
O O O(CH
2
)
2
OH +
HOC
C78
O O(CH
2
)
2
OC
OC+H
2
O
O O HO(CH
2
)
2
OH +
HOC
10 O COCH
3
9
O HO(CH
2
)
2
OC
COCH
3
+H
2
O
HO(CH
2
O
O COCH
3
11 12
O HO(CH
2
)
2
OCO)2
OH +
HOC
COH + CH
3
OH
Reaction Identifiers
Attacking Species Victim Species
A-Nucl- Reaction
Spec A-Elec-Grp V-Elec-Spec V-Elec-Grp V-Nucl-Spec V-Nucl-Grp
1 ~H in
alcohol
O
O none ~OH in acid
C C 2 ~H
3 ~H in
alcohol
OOH
2
)
2
OH
HOC COH O
OOC
COH O C
O C ~O(CH
2
)
2
OH ~O(CH
2
)
2
O~
~O(CH
2
O
OC
C none ~OH in acid
4 ~H
5 ~H in
alcohol
OOH
2
)
2
OH
HOC COH O
OOC
COH O C
O C ~O(CH
2
)
2
O~ ~O(CH
2
)
2
O~
HO(CH
2
none ~OH in acid
6 ~H
7 ~H in
alcohol
O
OO
OCCH
2
)
2
OH
C COH O
OOC
COC
O C ~O(CH
2
)
2
OH ~O(CH
2
)
2
O~
~O(CH
2
none ~OH in acid
8 ~H
9 ~H in
alcohol
O
OO
OCCH
2
)
2
OH
C COH O
OOC
COC
O C ~O(CH
2
)
2
O~ ~O(CH
2
)
2
O~
HO(CH
2
none ~OH in acid
10 ~H
11 ~H in
alcohol
O
OO
OCCH
2
)
2
OH
HOC
COCH
3
O
O
O O COCH
3
C
O C ~O(CH
2
)
2
OH ~O(CH
2
)
2
O~
HO(CH
2
C
)
2
OH
O
O O HOC
COCH
3
C
O C none
~OCH
3
12 CH
3
OH
~H
O
OOC
COCH
3
C
O C ~O(CH
2
)
2
OH ~O(CH
2
)
2
O~
It is not necessary to specify all of the reaction identifiers. For example, the only time it is necessary to
specify the attacking nucleophilic species and the attacking electrophilic group is when this species
contains more than one type of group and the two groups are not equally reactive.
Sets of reactions may be grouped together by making more general specifications. For example, if the
attacking electrophilic group and victim nucleophilic group are the only two identifiers specified, then the
rate constants are assigned to all reactions involving the named groups.
When more than one reaction set is specified, the sets are processed in reaction set number order, for
example, reaction set one is processed before reaction set two, three, etc. When a match is found for a
given reaction, the rate constant assignment algorithm moves to the next reaction, ignoring the remaining
reaction sets. The algorithm is designed to find the special cases first, and then move on to the general
cases.
Several examples illustrating the concept of rate constant assignment follow. These examples are based
on the set of reactions provided previously.
Rxn- Sets
Reaction Identifiers
RC- Sets
A-Nucl- Spec
A-Elec- Grp
V-Elec- Spec
V-Elec- Grp
V-Nucl- Spec
V-Nucl- Grp
Case 1 Assign rate constant sets 1 and 2 to all of the model-generated reactions 1 1, 2 unspecified unspecified
unspecified unspecified unspecified unspecified Case 2 Assign rate constant sets 1 and 2 to reactions between
alcohol groups in ethylene glycol
and any acid groups Assign rate constant sets 3 and 4 to reactions between alcohol groups in the polymer and any
acid groups Assign rate constant set 5 to reverse reactions involving methanol Assign rate constant set 6 to reverse
reactions involving water 1 1, 2 HO(CH
2
)
2
OH
unspecified unspecified unspecified unspecified ~OH in
acid 2 3, 4
~O(CH
2
)
2
OH
unspecified unspecified unspecified unspecified ~OH in
acid 3 5 H
2
O unspecified unspecified unspecified unspecified unspecified 4 6 CH
3
OH unspecified unspecified unspecified unspecified unspecified Case 3 Assign rate constant
sets 1 and 2 to reactions between alcohol groups in ethylene glycol
and terephthalic acid Assign rate constant sets 3 and 4 to all other reactions involving acid groups Assign rate
constant set 5 to reactions between water and glycol end groups Assign rate constant set 6 to all other reverse
reactions involving water Assign rate constant set 7 to reactions between ethylene glycol and the methylester end
groups in the polymer Assign rate constant 8 to all other reactions 1 1, 2 HO(CH
2
unspecified unspecified unspecified unspecified
2 3, 4 unspecified unspecified unspecified unspecified unspecified ~OH in
acid 3 5 H
2
)
2
OH
O O HOC COH O unspecified unspecified unspecified ~O(CH 2
unspecified
46H
2
)
2
OH
O unspecified unspecified unspecified unspecified unspecified 5 7 HO(CH
2
)
2
OH
unspecified O C
O COCH
3
unspecified unspecified
~OCH
3
6 8 unspecified unspecified unspecified unspecified unspecified unspecified
User Reactions
The model cannot predict all types of reactions based on the specified structures. Reactions which are
not predicted by the model can be included as user-specified reactions. These can include thermal
scission reactions, monomer or segment reformation, end-group modification, etc.
The user-specified reactions apply a modified power-law rate expression, as shown here:
Equation
T
ref
k
inet
,
Ea
TTR
-
bioi-i
11 =
[
Catalyst ] ek
ref
T
T
ref
flagU ( i
)
T
ref
specified
unspecified
k
inet
,
=[
Catalyst i ] ek o i -
Ea
i
Ti
flagU ( i
)
Assign User Rate Constants is used:
RT b rate m =
(a
)i
Assign User Rate Constants is not used:
activity rate
=m(j
i)(mkC j
C mj j mj )
inet
,
k inet ,
= Nomenclature
Symbol Description
m User reaction number i Rate constant set number j Component number Product operator C
j
a m j Concentration* of component j, mol/L
i
Catalyst order term for catalyst i (default = 1)
mj
Power-law exponent for component j in reaction m
k
o
Pre-exponential factor in user-specified inverse-time and concentration units*
k i,net
Net rate constant for set i
ref
Optional reference temperature. Units may be specified, they are converted to K in the model. flag User flag for rate
constant set i. This flag points to an element of the user rate constant
array. U User rate constant vector calculated by the optional user rate constant subroutine. The
user flag indicates the element number in this array which is used in a given rate expression. When the user flag is
not specified, or when the user rate constant routine is not present, this parameter is set to 1.0.
* The concentration basis may be changed to other units using the Concentration
basis field on the Options sheet or using the optional concentration basis subroutine.
You can modify the standard rate expression using the optional user rate constant feature. The rate
constant form includes a parameter called the user flag which identifies an element in an array of user
rate constants. This array is calculated by a user-written Fortran subroutine. The standard rate expression
is multiplied by the user rate constants as shown.
Assignment of Rate Constants to User Specified Reactions

There are two options for assigning rate constants to user-specified reactions. By default, the model
assumes there is exactly one set of rate constants for each reaction (for example, rate constant set i is
used for reaction i).
Alternately, you may use the Assign User Rate Constant sheet to assign one or more sets of rate
constants to each reaction. This feature is convenient in two situations:
Models with a large number of user side reactions when the rate constants of the various reactions are
equal or are related to each other algebraically.
Reactions catalyzed by several catalysts simultaneously.
Conventional and Power-Law Components

Conventional components and segments can appear as reactants or products in the reaction
stoichiometry. Each reaction must be mass balanced (the mass of the products must be equal to the
mass of the reactants).
The power-law components can include conventional components, segments, or oligomers. Power-law
coefficients can be specified for components which do not appear in the reaction stoichiometry, such as
catalysts or inhibitors.
The model allows the reactants to have power-law constants of zero, but this is not recommended
because it can lead to numerical problems in the reactor models. For example, if a reaction AB is
zeroth order with respect to component A, the reaction could have a positive rate even when component
A is not present. This causes non-negativity violation integrator errors in RPlug and RBatch and
causes convergence errors in RCSTR. To avoid these problems, specify a very small power-law
coefficient, such as 1 10-8 .
A user-specified reaction can be accelerated by several different catalysts. In this situation, use the
Assign User Rate Constants form to link multiple sets of rate constants to each reaction. Each set of rate
constants may be associated with a particular catalyst.
When the side reaction kinetics are complicated, it can be easier to write the kinetics in the context of the
available user kinetic subroutine. This subroutine is called from the Step-Growth reaction model. The
argument list for this user-written Fortran subroutine includes the step-growth rate constants, user
rate constants, species concentrations, group concentrations, species structures (number of each group
in each species), and others.
User Subroutines
The Step-Growth model can be customized by applying user-written subroutines. There are three types of
subroutines available. The concentration basis for the model can be changed through a user basis
subroutine. This subroutine can also be used to calculate the volume (RCSTR and RBatch) or area
(RPlug) of the reacting phase. A user rate-constant subroutine can be used to extend the standard rate
expression for model-generated or user- specified reactions. A user kinetics routine can be used to add
reactions to the model which are too difficult to represent using the power-law approach, or to calculate
user attributes for polymer characteristics which are not tracked by Aspen Polymers. These routines can
be used together in any combination.
User Basis Subroutine

The user basis subroutine can be used to calculate the component concentrations and the reacting-phase
volume (area) basis used in the component and attribute conservation equations. Use this subroutine
when rate constants are available in unusual concentration units not found in Aspen Polymers, or when
the reacting phase volume or area calculated by the reactor model is not consistent with the real reactor
(for example, in plug flow reactors with fixed liquid level).
This subroutine can also be used in conjunction with Fortran blocks and user component attributes to
calculate mass-transfer rates and to account for the influence of mass-transfer limitations on the
component concentrations in the reacting phase.
The argument list for the user basis routine is provided here. This argument list is prepared in a Fortran
template called USRMTS.F, which is delivered with Aspen Polymers.
User Subroutine Arguments
SUBROUTINE USRMTS
1 SOUT, NSUBS, IDXSUB, ITYPE, XMW, 2 IDSCC, NPO, NBOPST, NIDS, IDS, 3 NINTB,
INTB, NREALB, REALB, NINTM, 4 INTM, NREALM, REALM, NIWORK, IWORK, 5 NWORK,
WORK, NCPM, IDXM, X, 6 X1, X2, Y, DUM1, FLOWL, 7 FLOWL1, FLOWL2, FLOWV,
FLOWS, VLQ, 8 VL1, VL2, VV, VSALT, VLIQRX, 9 VL1RX, VL2RX, VVAPRX, VSLTRX,
RFLRTN, * IFLRTN, CRATES, NTCAT, RATCAT, CSS, 1 VBASIS, IPOLY, NSEG, IDXSEG,
AXPOS, 2 TIME )
Argument Descriptions
Variable Usage Type Dimension Description
SOUT Input REAL*8 (1) Stream vector NSUBS Input INTEGER Number of substreams in stream vector IDXSUB
Input INTEGER NSUBS Location of substreams in stream vector ITYPE Input INTEGER NSUBS Substream type
vector
1=MIXED 2=CISOLID 3=NC XMW Input REAL*8 NCC Conventional component molecular
weights IDSCC Input HOLLERITH 2,NCC
Conventional component ID array NPO Input INTEGER Number of property methods NBOPST Input INTEGER 6,
NPO Property method array NIDS Input INTEGER Number of reaction model IDs NINTB Input INTEGER User-
specified length of INTB array INTB Retention INTEGER NINTB Reactor block integer parameters (See
Integer and Real Parameters, page 154) NREALB
Input INTEGER User-specified length of REALB array
REALB Retention REAL*8 NREALB Reactor block real parameters (See
Integer and Real Parameters, page 154) NINTM
Input INTEGER User-specified length of INTM array INTM Retention INTEGER NINTM User subroutine integer
parameters (See
Integer and Real Parameters, page 154) NREALM
Input INTEGER User-specified length of REALM array REALM Retention REAL*8 NREALM User subroutine real
parameters (See
Integer and Real Parameters, page 154) NIWORK
Input INTEGER Length of user subroutine integer work
vector IWORK Work INTEGER NIWORK User subroutine integer work vector (See
Local Work Arrays, page 155) NWORK Input
INTEGER Length of user subroutine real work
vector WORK Work REAL*8 NWORK User subroutine integer work vector (See
Local Work Arrays, page 155) NCPM Input
INTEGER Number of components present in the
mixed substream (See Packed Vectors, page 155) IDXM Input REAL*8 NCPM Component sequence numbers (See
Packed Vectors, page 155) X Input REAL*8 NCPM
Overall liquid mole fractions X1 Input REAL*8 NCPM First liquid mole fractions X2 Input REAL*8 NCPM Second
liquid mole fractions Y Input REAL*8 NCPM Vapor phase mole fractions Dum1 Dummy REAL*8 (1) Argument
reserved for future application
FLOWL Input REAL*8 Total liquid flow rate, kmol/sec FLOWL1 Input REAL*8 First liquid flow rate, kmol/sec FLOWL2
Input REAL*8 Second liquid flow rate, kmol/sec FLOWV Input REAL*8 Vapor flow rate, kmol/sec FLOWS Input
REAL*8 Salt flow rate, kmol/sec VL Input REAL*8 Total liquid molar volume, m3/ kmol VL1 Input REAL*8 First liquid
molar volume, m3/ kmol VL2 Input REAL*8 Second liquid molar volume, m3/ kmol VV Input REAL*8 Vapor molar
volume, m3/ kmol VSALT Input REAL*8 Salt molar volume, m3/ kmol VLIQRX Input REAL*8 Volume* of liquid in
reactor, m3 VL1RX Input REAL*8 Volume* of first liquid in reactor, m3 VL2RX Input REAL*8 Volume* of second liquid
in reactor, m3 VVAPRX Input REAL*8 Volume* of vapor in reactor, m3 VSLTRX Input REAL*8 Volume* of salt in
reactor, m3 RFLRTN Retention REAL*8 (3, 1) Real retention for FLASH IFLRTN Retention INTEGER (3, 1) Integer
retention for FLASH CRATES Output REAL*8 NCC Component rates of change, kmol/m3-sec NTCAT Input
INTEGER Number of component attributes RATCAT Output REAL*8 NTCAT Component attribute rates of change,
cat/m3-sec CSS Output REAL*8 NCC
Concentration vector for the active phase VBASIS Output REAL*8 Holdup basis used to calculate reaction
rates* IPOLY Input INTEGER Reacting polymer
component index NSEG Input INTEGER Number of segment components IDXSEG Input INTEGER NSEG Segment
component index vector AXPOS Input REAL*8 RPlug only: axial position, m TIME Input REAL*8 RBatch only: time,
sec
* When using molar concentrations, this parameter is volume of the reacting phase
in 3m in RCSTR and RBatch or the cross-sectional area of the reacting phase in m3 in RPlug.
Example 1 illustrates how to use the user basis routine to convert the concentration basis from the
standard molar concentration basis (mol/L) to a mass concentration basis (mol/kg). (Note: the current
version of Aspen Polymers supports several concentration basis through the CONC-BASIS keyword
located on the Options form, we retain this example as a demonstration). Using these units, the reaction
rates are calculated in units of mol/kg-sec. These rates are multiplied by the holdup basis (VBASIS) for
the reactor in the Step-Growth model. For this reason, the holdup basis must be consistent with the
concentration basis, e.g., it must be in kg. The holdup basis pertains to the reacting phase, it does not
include the phases which do not react.
Example 1: A User Basis Routine For the Mass-Concentration Basis
Ci
=
X
i M Liquid
C
i
= Mass-concentration of component i
X
i
= Mole fraction of component i

M
Liquid
= Average liquid phase

molecular weight of components in the
CALL PPMON_VOLL( TEMP, PRES, X, NCPMX, IDXM, 1 NBOPST, GLOBAL_LDIAG, 1, VLQ,
DVS, KER) C-unpack the mole fraction vector into the molar concentrations...
CALL SHS_UNPACK ( X , NCPMX, IDXM, CSS ) C --------------------------
------------------------------------- C C concentration (mole/kg)=(mole I /
mole liquid )*( mole liquid/kg) C C -----------------------------------------
----------------------
DO 10 I = 1, NCOMP_NCC
CSS(I) = CSS(I) * 1.D3 / STWORK_XMWL 10 CONTINUE C -----------------
---------------------------------------------- C C reacting phase basis must
be consistent with concentration basis (kg) C liquid mass inventory = liquid
volume * density C C --------------------------------------------------------
-------
VBASIS = VLIQRX * STWORK_XMWL * 1.D-3 / VLQ RETURN
Note: This excerpt does not include the argument list and declarations section of the user basis routine.
The plug flow reactor model in Aspen Plus assumes that the vapor and liquid move at the same velocity
through the reactor (e.g., no-slip conditions). This assumption is not consistent with the physical reality of
polymer finishing reactors or wiped-film evaporators. The subroutine in Example 2 gets around the no-slip
assumption in RPlug, allowing you to specify the volume occupied by the liquid phase. In this example,
the user specifies the first integer argument in the RPlug block as 1 and specifies the first real argument
as the volume fraction of the reactor occupied by the liquid phase.
Example 2: A User Basis Routine to Specify Liquid Volume in RPlug
UFRAC = 1.D0 IF ( REALB(1) .NE. RGLOB_RMISS ) UFRAC = REALB(1) IF (
INTB(1).EQ.1 ) THEN
C - unpack the mole fraction vector into the
molar concentrations... CALL SHS_UNPACK ( X , NCPMX, IDXM, CSS ) C -
concentration = mole fraction divided by molar
volume of phase DO 20 I = 1, NCOMP_NCC
CSS(I) = CSS(I) / VLQ 20 CONTINUE C - multiply total reactor volume by
user-specified
volume fraction - VBASIS = ( VLIQRX + VVAPRX ) * UFRAC C - this line makes
RPlug calculate liquid residence
time (not L+V) SOUT(NCOMP_NCC+8)=(SOUT(NCOMP_NCC+9)/ SOUT(NCOMP_NCC+6)) / VLQ
RETURN END IF
User Rate-Constant Subroutine

The user rate constant subroutine can be used to modify rate constant parameters for model-generated
and user-specified reactions. Use this routine to modify the standard power-law rate expression for non-
ideal reaction kinetics.
The user rate constant feature can be used to modify the standard power-law rate expression. This
subroutine returns a list of real values which are stored in an array RCUSER. The length of this array is
defined by the keyword NURC (number of user rate constants) in the user rate constant subroutine form
(USER-VECS secondary keyword). Each of the elements in the user rate constant array can store a
different user rate constant. The USER-FLAG keyword in the SG-RATE-CON and RATE-CON forms is
used to specify which user rate constant is used with a particular set of rate constants.
Elements 1-NURC of RCUSER are calculated by a user rate-constant subroutine. The standard rate
expression is multiplied by the USER-FLAGth element of the user rate constant vector RCUSER. By
default, the USER-FLAG keyword is set to zero. The zeroth element of the RCUSER array is set to a
value of 1.0, so the rate expression remains unmodified unless the USER- FLAG keyword is specified.
The argument list for the subroutine is provided here. This argument list is prepared in a Fortran template
called USRRCS.F, which is delivered with Aspen Polymers.
SUBROUTINE USRRCS
INTB, NREALB, REALB, NINTR, 4 INTR, NREALR, REALR, NIWORK, IWORK, 5 NWORK,
WORK, NCPM, IDXM, X, 6 X1, X2, Y, DUM1, VL, 7 VL1, VL2, VV, VSALT, IPOLY, 8
NSEG, IDXSEG, NOLIG, IDXOLI, NSGOLG, 9 NGROUP, IDGRP, NSPEC, IDXSPC, NFGSPC,
* CSS, CGROUP, TEMP, PRES, NURC, 1 RCUSER, CATWT )
vector
weights IDSCC Input HOLLERITH 2, NCC
NPO Property method array (used by FLASH) NIDS Input INTEGER Number of reaction model IDs IDS Input
HOLLERITH 2,NIDS Reaction model ID list:
i,1 reactor block ID i,2 reactor block type i,3 reaction block ID i,4 reaction block type i,5 user subroutine ID NINTB
Input INTEGER User-specified length of INTB array INTB Retention INTEGER NINTB Reactor block integer
parameters (See
Input INTEGER User-specified length of REALB array REALB Retention REAL*8 NREALB Reactor block real
parameters (See
Integer and Real Parameters, page 154) NINTR
Input INTEGER User-specified length of INTM array INTR Retention INTEGER NINTR User subroutine integer
parameters (See
Integer and Real Parameters, page 154) NREALR
Input INTEGER User-specified length of REALM array REALR Retention REAL*8 NREALR User subroutine real
parameters (See
Integer and Real Parameters, page 154)
NIWORK Input INTEGER Length of user subroutine integer work
vector IWORK Work INTEGER NIWORK User subroutine integer work vector
(See Local Work Arrays, page 155) NWORK Input
vector WORK Work REAL*8 NWORK User subroutine integer work vector
(See Local Work Arrays, page 155) NCPM Input
Packed Vectors, page 155) X Input REAL*8 NCPM Overall liquid mole fractions X1 Input REAL*8 NCPM First liquid
mole fractions X2 Input REAL*8 NCPM Second liquid mole fractions Y Input REAL*8 NCPM Vapor phase mole
fractions Dum1 Dummy REAL*8 (1) Argument reserved for future application VL Input REAL*8 Total liquid molar
volume, m3/kmol VL1 Input REAL*8 First liquid molar volume, m3/kmol VL2 Input REAL*8 Second liquid molar
volume, m3/kmol VV Input REAL*8 Vapor molar volume, m3/kmol VSALT Input REAL*8 Salt molar volume, m3/kmol
IPOLY Input INTEGER Reacting polymer component index NSEG Input INTEGER Number of segment components
IDXSEG Input INTEGER NSEG Segment component index vector NOLIG Input INTEGER Number of oligomer
components IDXOLI Input INTEGER NOLIG Oligomer component index vector NSGOLG Input INTEGER NSEG,
NOLIG
Segment frequency vector: contains number of each segment in each oligomer NGROUP Input INTEGER Number of
functional groups IDGRP Input HOLLERITH NGROUP Functional group ID vector NSPEC Input INTEGER Number
of reacting species IDXSPC Input INTEGER NSPEC Reacting species component index
vector NFGSPC Input INTEGER NSPEC,
NGROUP
Group frequency vector: contains number of each functional group in each species CSS Input REAL*8 NCC
Concentration vector for reacting species CGROUP Input REAL*8 NGROUP Concentration vector for reacting groups
TEMP Input REAL*8 Temperature, K PRES Input REAL*8 Pressure, Pa NURC Input INTEGER Number of user rate
constants (See User
Rate-Constant Subroutine, page 144)
RCUSER Output REAL*8 NURC User rate constant vector (See User
Rate-Constant Subroutine, page 144) CATWT Input
REAL*8 Catalyst weight, kg (in RPLUG,
weight/length)
Example 3 illustrates how to use this subroutine to implement complex rate expressions in the Step-
Growth model.
Example 3: Implementing a Non-Ideal Rate Expression
Suppose a side reaction QZ is first order with respect to component Q and first order with respect to a
catalyst C. The effectiveness of the catalyst is reduced by inhibitor I according to the following equation: [
C
eff
]
=
1+([aC
+ actual bT ] )
[I]
Where: [ C
eff
] = Effective catalyst concentration, mol/L

[C
actual
] = Actual catalyst concentration, mol/L

[ ]I = Inhibitor concentration, mol/L
T = Temperature, K
a,b = Equation parameters
The net rate expression can thus be written as:
rate =
[Q
]
1
+([aC
+ actual
bT ] )
[I
]
ko
e-
RE
*
T1-
T
1 ref
Where:
k
o
= Pre-exponential factor, (L/mol)/sec

E* = Activation energy
R = Gas law constant T
ref
= Reference temperature for k

o
[Q] = Concentration of component Q, mol/L

The standard rate expression for side reactions is:
rate k o
e-
RE
*
T1-
T
1
Ci
*U(j
)i
Where:
= Product operator C i
=
ref
= Concentration of component i

i
= Power-law exponent for component i

U = User rate constant
j = User rate-constant flag
Suppose the rate constant for the uninhibited reaction is 3 10 -
3 (L/mol)/min at 150C, with an
activation energy of 20 kcal/mol, and the inhibition rate constants are A=0.20 L/mol, B=0.001 L/mol-K.
The stoichiometric coefficients and power-law exponents are specified directly in the Stoic and PowLaw-
Exp keywords. The Arrehnius rate parameters and reference temperature are also specified directly in the
model.
The parameters for the user rate constant equation can be specified using the optional REALRC list.
Including the parameters in the REALRC list allows the model user to adjust these parameters using the
standard variable accessing tools, such as Sensitivity, Design-Specification, and Data-Regression.
The resulting model input is summarized below:
USER-VECS NREALRC=2 NUSERRC=1 REALRC VALUE-LIST=0.2D0 0.001D0 STOIC 1 Q -1.0
/ Z 1.0 POWLAW-EXP 1 Q 1.0 / C 1.0 RATE-CON 1 3D-3<1/MIN> 20.000<kcal/mol>
TREF=150.0<C> URATECON=1
The power-law term from this equation is:
rate =
ko
e-
RE
*
T1-
T
1 ref
[ C ][ Q
]
Where:
[C] = Catalyst concentration, mol/L k
o
= Pre-exponential factor
Thus, the required user rate constant is:
U(j
=1
)
=
1(1
+(a+
bT )[ I
]
Where:
[I] = Inhibitor concentration, mol/L
T = Temperature, K
a, b = Equation parameters
An excerpt from the user rate constant subroutine for this equation is shown below:
C - Component Name - INTEGER ID_IN(2) DATA ID_IN /'INHI','BITO'/
C ====================================================================== C
EXECUTABLE CODE C
====================================================================== C -
find location of inhibitor in the list of components -
IF ( IDSCC(1,I).EQ.ID_IN(1).AND.IDSCC(2,I).EQ.ID_IN(2) ) I_IN=I 10
CONTINUE C - get the concentration of the inhibitor -
C_IN = 0.0D0 IF ( I_IN .GT.0 ) C_IN = CSS( I_IN ) C -------------------------
--------------------------------------------- C Parameters: each REALR
element defaults to zero if not specified C ---------------------------------
-------------------------------------
A = 0.0D0 IF ( NREALR .GT. 0 ) A = REALR( 1 ) B = 0.0D0 IF ( NREALR .GT. 1 )
B = REALR( 2 ) C ------------------------------------------------------------
---------- C User rate constant #1 U(1) = 1 / ( 1 + (A+BT)[I] ) C -----------
-----------------------------------------------------------
IF ( NURC.LT.1 ) GO TO 999
RCUSER(1) = 1.0D0 / ( 1.0D0 + ( A + B*TEMP ) * C_IN ) END IF 999 RETURN
User Kinetics Subroutine

The user kinetics subroutine is used to supplement the built-in kinetic calculations. Use this subroutine
when the side reaction kinetics are too complicated to represent through the user rate constant routine, or
when previously written Fortran routines are to be interfaced to the Step-Growth model.
The argument list for this subroutine is provided here. The argument list and declarations are set up in a
Fortran template called USRKIS.F, which is delivered with Aspen Polymers.
SUBROUTINE USRKIS(
INTB, NREALB, REALB, 4 NINTK, INTK, NREALK, REALK, NIWRK, 5 IWRK, NWRK, WRK,
NCPMX, IDXM, 6 X, X1, X2, Y, DUMXS, 7 FLOWL, FLOWL1, FLOWL2, FLOWV, DUMFS, 8
VLQ, VLQ1, VLQ2, VVP, VOLSLT, 9 VLIQRX, VL1RX, VL2RX, VVAPRX, VSLTRX, *
IPOLY, NSEG, IDXSEG, NOLIG, IDXOLI, 1 NSGOLG, NGROUP, IDGRP, NSPEC, IDXSPC, 2
NFGSPC, CSS, CGROUP, TEMP, PRES, 3 RFLRTN, IFLRTN, CRATES, NTCAT, RATCAT, 4
NRC, PREEXP, ACTNRG, TEXP, TREF, 5 IUFLAG, NURC, RCUSER )
vector
NPO Property method array (used by FLASH) NIDS Input INTEGER Number of reaction model IDs IDS Input
HOLLERITH 2,NIDS Reaction model ID list:
i,1 reactor block ID i,2 reactor block type i,3 reaction block ID i,4 reaction block type i,5 user subroutine ID NINTB
Input INTEGER User-specified length of INTB array INTB Retention INTEGER NINTB Reactor block integer
parameters (See
Input INTEGER User-specified length of REALB array REALB Retention REAL*8 NREALB Reactor block real
parameters (See
Integer and Real Parameters, page 154) NINTK
Input INTEGER User-specified length of INTM array INTK Retention INTEGER NINTK User subroutine integer
parameters (See
Integer and Real Parameters, page 154) NREALK
Input INTEGER User-specified length of REALM array REALK Retention REAL*8 NREALK User subroutine real
parameters (See
Integer and Real Parameters, page 154) NIWORK
Input INTEGER Length of user subroutine integer work
Packed Vectors, page 155) X Input REAL*8
NCPM Overall liquid mole fractions
X1 Input REAL*8 NCPM First liquid mole fractions X2 Input REAL*8 NCPM Second liquid mole fractions Y Input
REAL*8 NCPM Vapor phase mole fractions Dum1 Dummy REAL*8 (1) Argument reserved for future application
FLOWL Input REAL*8 Total liquid flow rate, kmol / sec FLOWL1 Input REAL*8 First liquid flow rate, kmol / sec
FLOWL2 Input REAL*8 Second liquid flow rate, kmol / sec FLOWV Input REAL*8 Vapor flow rate, kmol / sec FLOWS
Input REAL*8 Salt flow rate, kmol / sec VL Input REAL*8 Total liquid molar volume, m3/kmol VL1 Input REAL*8 First
liquid molar volume, m3/kmol VL2 Input REAL*8 Second liquid molar volume, m3/kmol VV Input REAL*8 Vapor molar
volume, m3/kmol VSALT Input REAL*8 Salt molar volume, m3/kmol VLIQRX Input REAL*8 Volume* of liquid in
reactor, m3 VL1RX Input REAL*8 Volume* of first liquid in reactor, m3 VL2RX Input REAL*8 Volume* of second liquid
in reactor, m3 VVAPRX Input REAL*8 Volume* of vapor in reactor, m3 VSLTRX Input REAL*8 Volume* of salt in
reactor, m3 IPOLY Input INTEGER Reacting polymer component index NSEG Input INTEGER Number of segment
components IDXSEG Input INTEGER NSEG Segment component index vector NOLIG Input INTEGER Number of
oligomer components IDXOLI Input INTEGER NOLIG Oligomer component index vector NSGOLG Input INTEGER
NSEG, NOLIG
Segment frequency vector: contains number of each segment in each oligomer NGROUP Input INTEGER Number of
functional groups IDGRP Input HOLLERITH 2,NGROUP Functional group ID vector NSPEC Input INTEGER Number
of reacting species IDXSPC Input INTEGER NSPEC Reacting species component index
vector NFGSPC Input INTEGER NSPEC,
NGROUP
Group frequency vector: contains number of each functional group in each species CSS Input REAL*8 NCC
Concentration vector for reacting species CGROUP Input REAL*8 NGROUP Concentration vector for reacting groups
TEMP Input REAL*8 Temperature, K PRES Input REAL* Pressure, Pa RFLRTN Retention REAL*8 3,(1) Real
retention for FLASH IFLRTN Retention INTEGER 3,(1) Integer retention for FLASH CRATES Output REAL*8 NCC
Component rates of change, kmol / m
3
- sec NTCAT Input INTEGER Total number of component attributes
RATCAT Output REAL*8 NTCAT Component attribute rates of change,
cat / m
3
- sec NSGRC Input INTEGER Number
of sets of step-growth rate
constants PREEXP Input REAL*8 NSGRC Pre-exponential factors, 1/sec (See
Step-Growth Rate Constants, page 153) ACTNRG
Input REAL*8 NSGRC Activation energies, J/kmol-K TEXP Input REAL*8 NSGRC Temperature exponents, unitless
TREF Input REAL*8 NSGRC Reference temperatures, K IUFLAG Input Integer*8 NSGRC User rate constant flags
(See User Rate-
Constant Subroutine, page 144)
NURC Input INTEGER Number of user rate constants RCUSER Output REAL*8 NURC User rate constant vector
(See User
Rate-Constant Subroutine, page 144)
* Area in RPlug
The user kinetic subroutine returns the rate of change of the reacting species and the Class 2 component
attributes (zeroth moment and segment flow rates). The subroutine may be applied to calculate user
component attributes (CAUSRA etc.) to track color or other polymer properties which are related to the
thermal history of the polymer.
Example 4 illustrates how the concentration of a color body can be tracked through user kinetics routine.
The example assumes that the polymer color is proportional to the amount of unknown color bodies
which are generated by side reactions. These unknown side reactions are sensitive to the thermal history
of the polymer, according to an Arrehnius rate expression. The activation energy and pre-exponential
factors of this expression are stored as the first and second REAL parameters for the user kinetics model.
Example 4: Tracking Polymer Color Using User Attributes in a Step- Growth User Kinetics Model
INTEGER IDUSRA(2) DATA IDUSRA /'CAUS','RA '/ C.....GAS CONSTANT IN KCAL/MOL-
K...
RGASKC = 1.987D-3 C.....locate CAUSRA attribute: LUSRA points to
location in SOUT...
LUSRA = SHS_LCATT( 1, IPOLY, IDUSRA ) C.....LURAT points to this attribute in
the RATCAT vector...
LURAT = LUSRA - NCOMP_NVCP C ------------------------------------------
---------------------------- C Get the rate constants from the list of REAL
parameters in the C user-kinetics section of the Step-Growth Subroutine form
C REAL(1) A_CF Color Formation pre-exponential, 1/min C REAL(2) E_CF Color
Formation activation energy, kcal/mol-K
C ----------------------------------------------------------------------
A_CF = 0.D0 E_CF = 0.D0 IF ( NREALK .GT. 1 ) THEN
IF ( REALK( 1 ) .GE. RGLOB_RMISS ) REALK( 1 ) = 0.D0 IF ( REALK( 2 ) .GE.
RGLOB_RMISS ) REALK( 2 ) = 0.D0 A_CF = REALK( 1 ) / 60.D0 E_CF = REALK( 2 )
END IF C Calculate color formation rate in color-units/cubic-meter/second
RATCAT( LURAT ) = A_CF * DEXP( -E_CF / ( RGASKC*TEMP ) ) RETURN
Step-Growth Rate Constants

The step-growth reaction rate constants can be applied in the user kinetics subroutine. The rate constants
are passed to this model as a set of arrays which are stored in rate constant set number order (the
element number of the array corresponds to the reaction set number). These parameters are stored in SI
units. The concentration basis for the pre-exponential factors are in molar concentration (mol/L) units.
When a user concentration basis subroutine is used, the pre-exponential factors are assumed to be in
units which are consistent with the user-calculated concentrations.
The user rate constants are also passed to the user kinetic subroutine. These parameters can be used
as is, or they can be used with the step-growth rate constants to build rate expressions consistent with
those used by the standard model. The array UFLAG is used to designate which user rate constant (if
any) is assigned to a given set of step-growth rate constants. For example, if IUFLAG(2) = 1, then user
rate constant 1 is assigned to step- growth rate constant set 2, and the pre-exponential factor can be
adjusted accordingly. Example 5 illustrates how to apply user rate constants and step- growth rate
constants in a user kinetics model.
Example 5: How to Apply User Rate Constants and Step-Growth Rate Constant in a Step-Growth
User Kinetics Model
C set work space to calculate net rate constants
LPREEX = 0 LNETRC = LPREEX + NSGRC C ----------------------------------------
------------------------------ C Multiply step-growth pre-exponential factors
by user rate constants C and store the results in the work array. C ---------
-------------------------------------------------------------
DO 10 IR = 1, NSGRC
IRCU = IUFLAG( IR ) IF ( IRCU .EQ. 0 ) THEN
WORK( LPREEX + IR ) = PREEXP( IR ) ELSE
WORK( LPREEX + IR ) = PREEXP( IR ) * RCUSER( IRCU ) END IF 10 CONTINUE C --
--------------------------------------------------------------------
C Calculate the net rate constants C ----------------------------------------
------------------------------
DO 20 IR = 1, NSGRC
IF ( TREF(IR) .EQ. 0 ) THEN
TTERM1 = 1/TEMP TTERM2 = TEMP**TEXP(IR) ELSE
TTERM1 = 1/TEMP - 1/TREF(IR) TTERM2 = ( TEMP / TREF )**TEXP(IR) END IF ETERM
= DEXP( -ACTNRG(IR) * TTERM1 / PPGLOB_RGAS ) WORK( LNETRC+ IR ) = WORK(
LPREEX+ IR ) * ETERM * TTERM2 20 CONTINUE
Note: The work array is used to store intermediate results in the calculations. The size of the work array
must be specified in the subroutine form and must be large enough to avoid overwriting the end of the
array.
INCL-COMPS List
The reactor models in Aspen Polymers use mass-balance equations for each reacting component. In
order to make the reactor models fast, components which do not appear in the reactions are excluded
from these calculations.
The list of reacting components is automatically generated by the Step- Growth model. This list includes
the polymer component, listed oligomers, components which appear in the list of reacting species,
components which appear as products or reactants in the user-specified reactions, and components in
the INCL-COMPS component list.
When user concentration basis or user kinetics subroutines are applied in a model, these subroutines can
include reactions involving components which do not otherwise appear in the list of reacting components.
These components should be added to the INCL-COMPS list to ensure they appear in the mass-balance
equations.
Integer and Real Parameters

Each user model has two sets of integer and real parameters. The first set comes from the subroutine
form of the reactor block. The second set comes from the subroutine form of the step-growth reactions
model. Each of these parameters are retained from one call to the next, thus these parameters can be
used as model inputs, outputs, or retention.
The reactor block integer and real parameters can be used to specify data which are specific to a
particular unit operation, such as reactor geometry, mass transfer coefficients, etc. The integer and real
parameters in the subroutine forms can be used to specify global parameters, such as rate constants or
physical property parameters.
Local Work Arrays
You can use local work arrays by specifying the model workspace array length on the STEP-GROWTH
Subroutine form. These work areas are not saved from one call to the next. All three user subroutines
share a common work area, so you must zero out the work space at the start of each subroutine.
Packed Vectors
Aspen Plus frequently uses a technique called packing to minimize simulation time. The user models
previously described use packed vectors to track the mole fractions of each phase (vectors X, X1, X2,
and Y). These vectors contain NCPM elements (Number of Components Present in the Mixed
substream). The component index associated with each element is listed in the vector IDXM. All other
vectors used by the model, including the rates vectors and the component concentration vectors, are
unpacked.
Example 6: Calculating Unpacked Component Concentrations
Calculate unpacked component concentrations of the first liquid phase given the packed mole fractions of
the first liquid phase and the molar volume of the first liquid phase.
IF ( VL1 .GT. 0.D0 .AND. FLOWL1.GT.0.D0 ) THEN
DO 10 I = 1, NCPM
CSS(I) = X1( IDXM( I ) ) / VL1 10 CONTINUE
END IF
Note: NCPM steps were required to load the concentration vector. Since NCPM is always less than or
equal to NCC (total number of conventional components), there is a reduction in the required number of
steps to perform the operation.
Specifying Step-Growth Polymerization

Kinetics
Accessing the Step-Growth Model
To access the Step-Growth polymerization kinetic model: 1 From the Data Browser, click Reactions. 2
From the Reactions folder, click Reactions. 3 The Reactions object manager appears. 4 If the kinetic
model already exists, double-click the desired Reaction ID in
the object manager or click Edit to get to the input forms. 5 To add a new model, from the Reactions
object manager, click New. If
necessary, change the default ID for the reaction.
6 Select Step-Growth as the reaction type and click OK.
Specifying the Step-Growth Model

The Step-Growth model input forms are divided into two folders: Specifications and User Subroutines.
Use the Specifications forms to define reacting species and functional groups, enter reaction rate
constant parameters, and include user side reactions.
Use this sheet
To
Species Define reacting species and functional groups
Specify the name of the polymer being produced Specify the names for linear oligomers (optional) Reactions
Generate and display model-generated reactions Rate Constants Specify reaction rate constants for model-
generated reactions User Reactions Specify reaction stoichiometry and enter rate constants for user-
specified reactions User Rate Constants
Specify catalysts and reaction rate constants for user-specified reactions Assign User Rate Constants
Assign one or more sets of rate constants to each user-specified reaction Options Specify the reacting phase and
concentration basis.
Change reaction convergence parameters. Select report options.
Use the User Subroutines forms to specify the names and parameters for optional user subroutines.
Use this sheet To
Kinetics Specify the name of the user kinetics routine and give the
integer and real arguments for the user arrays for this routine Rate Constants Specify the
name of the user kinetics routine, the number of
user rate constants calculated by the routine, and to give the integer and real arguments for the user arrays for this
routine Basis Specify the name of the user concentration and reacting phase
volume basis routine and give the integer and real arguments for the user arrays for this routine
Specifying Reacting Components

You must specify the reacting species and functional groups on the Step- Growth Specifications Species
sheet.
First specify the polymers and oligomers produced: 1 In the Polymer field, specify the polymer produced.
2 In the Oligomers field, list oligomers that you want the model to track.
3 In the species definition table, specify the functional groups contained in
each reacting species and define each group type.
The structure of reacting species in terms of the reactive functional groups they contain must be defined.
To do this: 1 In the Group field specify an ID name for each functional group type
present in the reacting species. 2 For each group, select a type from the group type field. 3 List the
species in the Species field.
These species can be monomers, condensates, or segments. The resulting form is a spreadsheet, with
each column representing a functional group and each row representing a reacting species. The cells in
the spreadsheet correspond to the number of each functional group in each species. 4 In the number field
for each species, specify the number of each defined
functional group contained in that species. Unspecified fields are interpreted as zeros.
Listing Built-In Reactions

The step-growth model generates reactions based on the functional group definition of reacting species.
You can view the system-generated reactions, by clicking the Generate Reactions button on the
Specifications Reactions sheet.
In the Reaction summary listing for each reaction, the first column indicates the reaction type. The second
column lists the reactants, and the last column lists the products. The Data Browser window can be
resized to better view the reaction listing.
Specifying Built-In Reaction Rate Constants

You can define the catalysts and rate constants for system-generated reactions. The model applies a
modified power-law rate expression, which can be customized through a user-written rate constant
subroutine. By default, the model assumes concentrations are in mol/liter. Another concentration basis
can be applied through a user-written basis subroutine.
To specify rate constants: 1 Go to the Rate constants sheet. 2 In the reaction No. field, assign a unique
integer identifier for a set of rate
constant parameters. 3 In the Catalyst Species field, specify the name of a catalyst species
associated with the rate constant set. You can leave this field unspecified if the reaction is uncatalyzed, or
if the catalyst is defined as a functional group. 4 In the Catalyst Group field, specify the name of a catalyst
functional
group associated with the rate constant set. You can leave this field unspecified if the reaction is
uncatalyzed, or if the catalyst is defined as a species.
5 Enter the rate constant parameters: ko for Pre-exponential factor, Ea for
Activation energy, b for Temperature exponent, Tref for Reference temperature. 6 Request any user rate
constant expression in the User flag field. 7 Repeat these steps as needed to specify the list of rate
constant
parameters.
Assigning Rate Constants to Reactions

You can assign rate constants to individual reactions using the reaction stoichiometry, or you can assign
rate constants to sets or reactions using the appropriate reaction identifiers.
To assign the rate constants set: 1 Click the Assign Rate Constants button on the Specifications Rate
constants sheet. 2 Click the Global tab to assign rate constants to a set of reactions or use the
Individual sheet to assign rate constants to individual reactions. 3 Go to the Rate Constant Sets field,
select from the list of pre-defined rate
constant sets for each reaction.
Including User Reactions

You can add user reactions to the built-in set. For this you must specify a reaction stoichiometry and the
associated rate constants. The model applies a modified rate expression, which can be customized
through a user-written rate constant subroutine.
To add user reactions use the following options found on the Specifications User Reactions sheet:
Click To
New Add new reactions to the scheme Edit Specify reaction stoichiometry and power-law
exponents Rate Constants Specify reaction rate constant parameters for the
reactions
Click to select a reaction. Click a reaction then Control-Click to include additional reactions for multiple
selections. Double-click to edit a reaction.
In addition, you can use the following buttons:
Click To
Hide/Reveal
Exclude/Include calculations
a reaction from the
Delete
Permanently remove a reaction from the model
Adding or Editing User Reactions
In the User Reactions sheet, to add a new reaction to the scheme or edit an existing reaction, open the
Edit subform. When you open the Edit subform, a unique number is assigned in the Reaction no. field, to
the reaction being added.
To add or edit your reaction: 1 On the Edit subform, specify the Component ID and stoichiometric
Coefficient for the reactants. Reactants must have a negative coefficient. 2 Specify the Component ID
and stoichiometric Coefficient for the
products. Products must have a positive coefficient.
3 Click to check the Completion Status
- or - Click Close to return to the reaction summary.
Specifying Rate Constants for User Reactions

All the rate constants for user-specified reactions are summarized in a grid on the User Rate Constants
tab:
1 In the
k
o field, enter the pre-exponential factor.
2 In the field, enter the activation energy. 3 In the b field, enter the temperature exponent.
4 In the
T
ref field, enter the reference temperature.
Note: Use the Catalyst Species field to associate a rate constant with a particular catalyst. If you leave
this field blank the model drops the catalyst term from the rate expression. Use the Catalyst Order field to
specify the reaction order with respect to the catalyst (the model assumes first order by default).
Assigning Rate Constants to User Reactions

By default, the model assumes one set of rate parameters for each reaction. (For example, rate constants
in row 1 apply to user reaction 1). Alternately, you may assign one or more rate constants to each
reaction using the Assign User Rate Constants form.
When several rate constants are assigned to a reaction the model calculates a net rate constant by
summing all of the listed rate constants and multiplying the sum by a specified activity.
To assign rate constants to user reactions: 1 On the Assign User Rate Constants form, use the Activity
field to
specify the activity factor.
E
a
2 In the Rate Constant Sets field, select from the list of pre-defined rate
constant sets for each reaction.
Selecting Report Options

You can select which format to use for the step-growth reactions in the report file. On the Options sheet,
go to the Report frame to request a reaction report. Then, select a Summary or Detailed format.
Selecting the Reacting Phase

The Options form lets you specify the phase in which the reactions occur.
Select the appropriate phase from the list in the Reacting Phase field. All of the reactions in a particular
step-growth object are assumed to take place in the same phase.
Note: You must specify the Valid Phases keyword for each reactor model referencing the kinetics to
ensure the specified reacting phase exists.
If the Reacting Phase option is set to Liquid-1 or Liquid-2 the model assumes two liquid phases exist.
When the named phase is not present, the model prints a warning message and sets the reaction rates to
zero. There are two options for handling phase collapse:
Select the Use bulk liquid phase option to force the model to apply the specified reaction kinetics to the
bulk phase when the named phase disappears.
Select the Suppress warnings option to deactivate the warning messages associated with phase
collapse.
These options are especially convenient when modeling simultaneous reactions in two liquid phases
using two step-growth models. In this situation, you would typically select the Use bulk liquid option for
one phase and not the other (to avoid double-counting reactions when one phase collapses).
Specifying Units of Measurement for Pre- Exponential

Factors
Reaction rates are defined on a molar basis (moles per volume per time) . The time units for the pre-
exponential factors are specified directly on the Rate Constant forms.
By default, the concentration units are presumed to be in SI units (kmole/m3 or mole/L).
You change the concentration basis to other units using the Concentration Basis field of the Options
sheet. Alternately, you may apply a user basis subroutine.
Including a User Kinetic Subroutine
Use the User Subroutines Kinetics form to specify parameters for user kinetics calculations: 1 In
subroutine Name, enter the name of the Fortran subroutine. 2 Specify the size of vectors for Integer, Real
in Number of parameters,
and Length of work arrays. 3 Enter integer and real parameter values in Values for parameters
columns. 4 Click Include Comps to specify components to be included in material
balance convergence.
Including a User Rate Constant Subroutine

Use the User Subroutines Rate Constants form to specify parameters for user rate constants calculations:
1 In subroutine Name, enter the name of the Fortran subroutine. 2 Specify the size of vectors for Integer,
Real and No. const. in Number
of parameters. 3 Specify the size of vectors of Integer and Real in Length of work
arrays. 4 Enter integer and real parameter values in Values for parameters
columns.
Including a User Basis Subroutine

Use the User Subroutines Basis form to specify parameters for basis calculations: 1 In subroutine Name,
enter the name of the Fortran subroutine. 2 Specify the size of vectors for Integer and Real in the Number
of
parameters and Length of work arrays. 3 Enter integer and real parameter values in Values for
parameters
columns.
References
Billmeyer, F. W. (1971). Textbook of Polymer Science. New York: Wiley.
Gupta, S. K, & Kumar, A. (1987). Reaction Engineering of Step-Growth Polymerization. New York:
Plenum.
Jacobsen, L. L., & Ray, W. H. (1992). Unified Modeling for Polycondensation Kinetics. J. Macromol. Sci.-
Rev. Macromol. Chem. Phys.
Kaufman, H. S., & Falcetta, J. J. (Eds). (1977). Introduction to Polymer Science and Technology: An SPE
Textbook. New York: Wiley.
McKetta, J. J. (Ed.). (1992). Encyclopedia of Chemical Processing and Design, 39 & 40. New York:
Marcel Dekker.
Rodriguez, F. (1989). Principles of Polymer Systems. New York: Hemisphere.
9 Free-Radical Bulk Polymerization
Model
This section covers the free-radical bulk/solution polymerization model available in Aspen Polymers
(formerly known as Aspen Polymers Plus).
Free-Radical Bulk/Solution Processes, 164
Polymer Properties Calculated, 190
Specifying Free-Radical Polymerization Kinetics, 193
Several example applications of the free-radical bulk/solution polymerization model are given in the
Aspen Polymers Examples & Applications Case Book.
The Examples & Applications Case Book provide process details and the kinetics of polymerization for
specific monomer-polymer systems.
The free-radical bulk/solution polymerization model is applicable to bulk and solution polymerization
processes. Some examples of applicable polymers are:
General purpose polystyrene - Made by polymerization of styrene monomer with or without solvent fed
continuously to reactor.
High impact polystyrene - Made by polymerization of an unsaturated rubber dissolved in styrene in a
solution process. Also produced in mass- suspension processes.
Poly(vinyl chloride) - Produced in bulk polymerization using monomer- soluble free radical initiators.
Most of the homopolymers and copolymers of vinyl chloride, however, are produced by suspension
polymerization.
Poly(vinyl acetate) - Produced industrially by the polymerization of vinyl acetate in bulk or solution
processes. Also produced in suspension and emulsion processes. Both batch and continuous processes
are used.
9 Free-Radical Bulk Polymerization Model 163
Poly(vinyl alcohol) - Poly(vinyl acetate) is converted into the corresponding poly(vinyl alcohol) by direct
hydrolysis or catalyzed alcoholysis. The reaction can be catalyzed by strong acids or strong bases.
Poly(methyl methacrylate) - The vast majority of commercially prepared acrylic polymers and
methacrylic polymers are copolymers. Commercially they are prepared by solution polymerization. They
are also produced by emulsion polymerization and suspension polymerization.
Low density polyethylene - Made by high pressure, free radical processes in either a tubular reactor or a
stirred autoclave. Typical commercial processes include staged compression, initiator injection, partial
conversion of ethylene to polymer, separation of ethylene from polymer, extrusion of molten polymer, and
cooling of ethylene.
The Free-Radical model may also be used to simulate suspension polymerization processes in which
the polymer is completely soluble in the organic (monomer) phase. Two reaction models can be applied
together to represent reactions in each liquid phase. An example of this process is:
Poly(styrene) - Poly(styrene) may be produced in a continuous suspension process in a series of CSTR
type reactors.
Free-Radical Bulk/Solution Processes

Free-radical polymerization accounts for a large proportion (more than 40% by weight) of the commodity
grade polymers. It is employed in the synthesis of monosubstituted countless homo- ethylenes
and copolymers ( RHC =
CH using 2
)
monomers that are either or 1,1-disubstituted ethylenes ( R 1 R 2 C = CH
2
)
.
Free-radical polymerization usually takes place with the monomer in the liquid phase. Several types of
processes are used. A solvent or suspending medium may be used, and the polymer formed may be
soluble, insoluble, or swelled by the monomer and solvent. Commercially important processes for free-
radical polymerization include bulk, solution, suspension, and emulsion polymerization.
Bulk and Solution Polymerization

Bulk and solution polymerization processes are characterized by the fact that the reactions proceed in a
single phase. Typically the monomers are fed to a reactor with or without a solvent. A small amount of
initiator is also fed. At the reaction temperature, the initiator decomposes to form radicals that initiate the
polymerization reactions. The polymer formed is usually soluble in the monomer/solvent mixture.
However, in some systems, such as PVC, the polymer is insoluble and forms a separate phase.
The most commonly used reactor types include batch, semi-batch, continuous stirred-tank and tubular
reactors. Flowsheets consisting of several reactors in series are common. The main technical challenges
with bulk/solution polymerization processes are heat removal, handling of the highly viscous
164 9 Free-Radical Bulk Polymerization Model
liquid, and recovery of residual monomer/solvent. Several modes of heat removal can be employed,
including jacket cooling, internal cooling coils/baffles, external heat exchangers and reflux condensors.

Most free-radical polymerizations have at least four basic reaction steps:
Initiation
Propagation
Chain transfer to a small molecule (i.e. monomer, solvent or transfer agent)
Termination
These reactions occur simultaneously during the polymerization. For branched polymers additional
reactions for long and short chain branching can also be present. A comprehensive kinetic scheme for the
free-radical homo- and copolymerization of up to N
m
monomers has been built into Aspen Polymers. The scheme includes
most of the reactions commonly used for modeling free- radical polymerization. The model also includes
several optional reactions:
Terminal double bond polymerization
Pendent double bond polymerization (for diene monomers)
Head-to-head propagation (for asymmetric monomers)
Cis- and trans- propagation (for diene monomers)
Primary and secondary decomposition of bifunctional initiators
Reactions such as depropagation and random chain scission are not included in the current model.
These reactions may be added to the built-in scheme in the future.
The main reactions in the current built-in free-radical kinetic scheme is shown here :
Built-in Free-Radical Polymerization Kinetic Scheme
The nomenclature used in the free-radical kinetic scheme is shown here:

Symbol Description
Symbols Used in the Population Balance Equations
A
k
Chain transfer agent of type k
BB 21
, Reaction by-products (optional for some reactions)
C
k
Coinitiator or catalyst of type k
D
n
Dead polymer chain of length n ( = n 1 , n 2
, ... n
m)Dn
jk
Polymer chain of length n containing an undecomposed bifunctional initiator fragment of type k attached to
penultimate segment of type j
Dn
=i
Polymer chain of length n containing a terminal double bond of type i
Dn
)(vinyli
Polymer chain of length n reacting at an internal double bond of type i (e.g., a diene segment of type i in the vinyl
configuration) f TDB ij
Fraction of reactions between species i and j resulting in the formation of a terminal double bond of type i I
k
Standard initiator of type k
Ik
B
Bifunctional initiator of type k
M
j
Monomer of type j
P
n
i Live polymer chain of length n having an active segment of type i
Pn
)(cisi
Live polymer chain of length n having an active diene segment of type i in the cis configuration.
Pn
(transi
) Live polymer chain of length n having an active diene segment of type i
in the trans configuration. R Primary radicals S
k
Solvent of type k (for solution polymerization)
X
k
Inhibitor of type k
21
, Stoichiometric coefficients for reaction by-products B
1
,B
2
k
Initiator efficiency factor for initiator k
A
k
Chain transfer agent of type k
BB 21
, Reaction by-products (optional for some reactions)
C
k
Coinitiator or catalyst of type k
D
n
Dead polymer chain of length n ( = n 1 , n 2
, ... n
m ) Symbol Description
Symbols Used in Reaction Rate and Moment Balance Equations
a , b , c Coefficients for the induced (thermal, radiation) initiation rate
C Concentration of a reacting non-polymeric species. The following
subscripts are used to identify the component:
Symbol Description
Ak Chain transfer agent k Ck Catalyst or coinitiator k Ik Initiator or bifunctional initiator k Mi Monomer i Sk Solvent k
Xk Inhibitor k k Net rate constant (see Equation 3.1 on page 170 ). The following
subscripts are used to identify the reaction types: bs Beta scission bid Bifunctional initiator primary decomposition cis
Cis-propagation ic Catalyzed initiation id Standard initiator decomposition hth Head-to-head propagation p
Propagation (polymerization) pdb Pendent double bond polymerization pi Primary chain initiation scb Short chain
branching si Special initiation (induced initiation) sid Secondary decomposition of bifunctional initiator tc Termination
by combination td Termination by disproportionation tdbp Terminal double bond polymerization tra Chain transfer to
agent trans Trans-propagation trm Chain transfer to monomer trp Chain transfer to polymer (long chain branching) trs
Chain transfer to solvent x Inhibition N Number of (A=agents, BI=bifunctional initiators, C=catalysts,
CI=coinitiators, I=standard initiators, M=monomers, S=solvents, X=inhibitors) N r k
Number of radicals (1 or 2) formed from the decomposition of initiator of type k 21
, Stoichiometric coefficients for reaction by-products B
1
,B
2
k
Initiator efficiency factor for initiator k
f TDB ij
Fraction of reactions between species i and j resulting in the formation of a terminal double bond of type i 0 i
Zeroth moment of live polymer with respect to active segment of type i
1j
First moment of live polymer with respect to segment j
0
Zeroth moment of bulk polymer (live + dead)
Symbol Description
1j
First moment of bulk polymer (live + dead) with respect to segment j
2
Second moment of bulk polymer (live + dead)
a
=j
Moment a (a=0, 1, 2, etc) of polymer molecules with terminal double bond of type j ji,
Flow rate of dyads consisting of i and j segments (these values are stored in the DYADFLOW attribute) i Molar
fraction of diene segment i in the vinyl configuration (zero for non-
diene segments) (related to VINYLFRA attribute) k
Concentration of undecomposed initiator fragment k in the bulk polymer (live + dead) (related to FRAGFLOW
attribute)
In the discussion that follows, a polymer chain is considered to be made up of monomer units or
segments derived from the propagating monomers. Typically there will be one segment type associated
with each monomer. However, it is possible to define several segment types associated with a single
monomer. This may be necessary, for example, for modeling the tacticity asymmetric of a monomer
polymer, or ( RHC head-to-head = CH 2 )
.
versus head-to-tail incorporation of an
Polymer Chain Terms

The term live polymer chain ( P
ni
) refers to growing polymer chains containing n segments, with a

radical attached to a segment of type i, i.e., segment formed from monomer i. The term dead polymer
chain ( D
n
) refers to terminated polymer chains

that do not have an attached radical. The term bulk polymer chain is used to refer to the sum of the live
and dead polymer chains. The subscript n refers to the chain length in terms of the number of segments
or monomer units incorporated in the polymer chain. Live chains are reactive and can participate in the
polymerization reactions while dead chains are usually considered inert, except when long chain
branching reactions are important.
The radical attached to one end of a live polymer chain is considered to be mobile and moves away from
the initiator fragment with every addition of a monomer molecule. It is believed that after a few monomer
additions the chemistry of the initiator fragment and developing chain microstructure will not have a strong
influence on the mode of monomer addition.
The free-radical kinetic model assumes that the reactivity of a live polymer chain depends only on the
active segment containing the radical, and is independent of the polymer chain length and other structural
properties. This assumption was used in writing the rate expressions for the reactions shown in the Built-
in Free-Radical Polymerization Kinetic Scheme figure on page 166. For example, in the propagation
reaction, the rate of propagation ( R
ij p
) is
independent of the polymer chain length. It depends only on the concentration of monomer j and the
concentration of live polymer chains with active segments of type i. Models using this assumption are
referred to as terminal models in the polymerization literature.
For copolymerization, the built-in kinetics routine allows the user to specify the number of monomers
used. Similarly, the user has the flexibility to specify the number of each type of reactive species used in
the polymerization, e.g. initiators, chain transfer agents, solvents and inhibitors. The user can easily setup
the built-in kinetics to model a specific free-radical polymerization by selecting a subset of the reactions
shown in the Built-in Free-Radical Polymerization Kinetic Scheme figure on page 166. It is necessary that
the subset include a chain initiation and a propagation reaction. Frequently, at least one termination,
chain transfer, or inhibition reaction to produce dead polymer is also selected.
The rate constants for each reaction in the built-in kinetics is calculated at the reaction temperature and
pressure using the modified Arrhenius equation shown below with user specified parameters: pre-
exponential (or frequency) factor, activation energy, activation volume, and reference temperature:
Rate Constant
kk =
exp
-
R Ea
-
VP
11
-
ref
(3.1)
Where:
k
o
o
TTR

= Pre-exponential factor in l/sec for first order reactions,

and m 3 / kmol - s for second order reactions
Ea = Activation energy in mole-enthalpy units
V = Activation volume in volume/mole units
P = Reaction pressure
R = Universal gas constant
T ref
= Reference temperature
fg
= Gel effect factor from optional built-in or user-defined gel

effect correlation
The second term in the exponential function contains an activation volume that is important for high
pressure polymerization systems. For low to moderate pressures, the activation volume is typically set to
default value of zero. This term is used to account for the pressure dependence of the reaction rate
constant.
The free-radical model allows the rate expression to be modified by a gel effect term, f
g
. The gel effect term can be calculated using one of several built-in correlations or it can
be calculated by an optional user-defined gel effect subroutine.
The model allows any number of bifunctional initiators, however the maximum number of unique
bifunctional initiators (used throughout the flowsheet) must be specified on the Polymers, Options
subform. This parameter is used to dimension the FRAGFLOW polymer component attribute, which is
used to track the flow rate of undecomposed initiator fragments. The FRAGFLOW attribute must be
included in the attribute list in the Polymers,
Polymers subform. Bifunctional and standard initiators can be used in the same model.
Initiation
The initiation step involves the generation of reactive free-radicals followed by the addition of a monomer
molecule (chain initiation) to form chain radicals of unit length ( Pi 1
) . The non-chain or primary radicals ( R
) may be generated by the thermal
decomposition of a chemical initiator, a catalyzed initiation reaction involving electron transfer from ions,
or by thermal/radiation induced mechanisms. Three types of standard initiation reactions are included in
the built-in kinetics:
Initiator decomposition reaction
Induced initiation reaction
Catalyzed initiation reaction
The initiator decomposition reaction accounts for primary radical generation from the thermal
decomposition of chemical initiators.
The induced initiation reaction can be configured to account for the generation of radicals by thermal and
radiation induced mechanisms from the monomers themselves, with or without the use of a coinitiator or
promoter.
The catalyzed initiation reaction can be used to account for redox initiation, which has found wide
application in aqueous emulsion polymerization systems.
The most commonly used radical generation method is the thermal decomposition of chemical initiators
(usually peroxide or azo compounds) which decompose to form radicals when heated to an appropriate
temperature. Only small amounts of the chemical initiator (less than 1 wt. % based on monomer) are
needed. However, due to their high activation energies chemical initiators have a relatively narrow useful
temperature range (approx. 30C) over which the decomposition rates are neither too fast nor too slow.
Some processes, notably bulk polystyrene polymerization, use initiators with two active sites. These
bifunctional initiators decompose in two stages, providing greater control over the molecular weight
distribution of the product.
The free-radical model includes two reactions associated with bifunctional initiators:
Bifunctional initiator decomposition (primary decomposition)
Secondary initiator decomposition (primary decomposition)
The primary decomposition reaction generates a pair of radicals, an undecomposed initiator fragment,
and optional by-products. The undecomposed fragment is tracked using the FRAGFLOW polymer
component attribute.
The initiator fragment decomposes in the secondary decomposition reaction, generating a free radical
and a polymeric radical.
Initiator Decomposition Reaction
The initiator decomposition reaction is modeled as a first order thermal decomposition reaction:
Ik
rkk RN
+ 1,1
k B + 2,2 k B CkR id k
= k id
Ik
This rate expression )( R id

k
describes the rate for the thermal decomposition of

standard initiator k. The symbols
B1
and
B2
represent optional user-specified reaction by-

products. This feature lets you track the formation of low- molecular weight decomposition by-products,
such as carbon dioxide, which may be generated as the initiators decompose. The byproduct formation
rates are determined by:
R
kB 1
,
=
,1 idk Ck k
Ik
R kB 2 , = ,2 idk Ck k
Ik
For mass balance purposes, the polymer mass generation rate is incremented by the initiator mass
consumption rate, less the mass formation rate of by- products.
The rate expression for the formation of primary radicals from the thermal decomposition of standard
initiators is given by:
R
id rad
=
N
I
CkN r
k
idk k
k
=
1
There are a number of user specifiable parameters associated with this reaction. The user can specify
more than one initiator to model systems where multiple initiators with different half-lives are used to
control the initiation rate over the course of the polymerization. Depending on the initiator, either one or
two primary radicals may be formed, hence the parameter N
rk
Ik
should be set to 1 or 2. Bifunctional initiators, which can produce up to four radicals, are
handled explicitly using another set of reactions described below. A fraction of the radicals generated by
decomposition undergo radical recombination in the radical-cage, leading to stable byproducts. The
initiator efficiency factor,
, is used to specify the fraction of radicals

which are not destroyed by the cage effect. The efficiency factor can be adjusted using an efficiency gel
effect correlation as described later in the text.
The rate constant
k id k
is calculated using a modified Arrhenius equation (Equation 3.1 on page 170)

with three parameters: pre-exponential factor, activation energy and activation volume. As noted
previously, the activation volume accounts for the pressure dependence of the rate constant. This
parameter is typically non-zero only at high pressures. Appendix B lists initiator decomposition rate
constant parameters (pre-exponential factor and activation energies) for many commonly used initiators.
These rate parameters are included in the INITIATOR databank and are automatically loaded into the
model each time the reaction network is generated.
The standard rate expression can be modified using an optional built-in or user-defined gel effect
correlation as described later in the text.
Induced Initiation Reaction
Free-radicals can also be generated from some monomers by thermal, radiative (UV, electron beam or
gamma rays) or induced mechanisms. For example, styrene at temperatures above 120C has a
significant thermal initiation rate. The thermal initiation mechanism for styrene is believed to be 3rd-order
in monomer (Hui & Hamielec, 1972). This reaction results in the formation of significant amounts of cyclic
dimers and trimers which have to be removed during devolatilization. Hence, thermal initiation is not
favored commercially.
Radiation initiation has been used mainly for polymer modification to induce branching, crosslinking or
grafting reactions. The induced initiation reaction, shown below, can be configured to model both these
initiation mechanisms:
M
j
+Ck
P1j
+ 11
kj B + 22 kj B R kj = k kj )(hCC bj
M cj For thermal initiation, the rate should be
aj si si Ck j
CkR si
j
= j si
bj Mj
(set a j , c
j
to zero).
For radiation initiation, the rate should be
hCkR si
j
= j si
Mj bj
)( cj (set
aj
to zero)
The induced initiation reaction can also account for the effects of using an initiator or promoter )(
Ck
to increase the rate of radical generation.

The parameters

1
and
are optional stoichiometric coefficients related to

by-products
B1
and
B2
. The byproduct formation rates are determined by:

R B kj
1
=
1 kj hCCk si
j
aj Ck
Mj bj
)(
cj R B kj
2 = 2 kj hCCk si
j
aj Ck
Mj bj )( cj The molar consumption rate of the monomer is equal to

R si kj
. If a promoter is
specified in the reaction, its molar consumption rate is also set to
R kj si
. The mass generation

rate of the polymer is set equal to the mass consumption rate of the monomer (
Mj
) and promoter (
Ck
).
The special initiation reactions generate live polymer directly, thus this reaction does not contribute to
radical generation.
Catalyzed Initiation Reaction
The catalyzed initiation reaction is similar to the initiator decomposition reaction except that a catalyst
concentration term is included in the reaction rate expression:
CI k
+j
rkkj CRN
+ j + 1,1
kj B + 2,2 kj B CCkR ci kj
= kj ci
Ik
Cj This rate expression )( R ci

kj
describes the rate of consumption of initiator k. The catalyst rate is set to zero,
assuming that the catalyst is not consumed by this reaction. The corresponding rate expression for the
formation of primary radicals is given by:
R
ic rad
N
IN
CI
rkj
CCkN kj kj ic k
=1j
=
1
Ik
Cj
The parameters
1
and
are optional stoichiometric coefficients related to

by-products
B1
and
B2
. The byproduct formation rates are determined by:

R
B kj
1
= 1 kj CCk ic
kj
Ik
Cj R B kj
2 = 2 kj CCk ic
kj
Ik
Cj For mass balance purposes, the polymer mass

generation rate is incremented by the initiator mass consumption rate, less the mass formation rate of by-
products.
Primary Chain Initiation

To complete the initiation process, the reactive primary radicals ( R
) react with monomer by the
primary chain initiation reaction to form polymer chain radicals of unit length. The chain initiation reaction
is shown below:
R+Mj
P1
j
R pi j
=
k pi j
C Mj
R
The chain radicals grow by successive addition of monomer molecules to form long chain polymer
molecules. It is common practice to set the chain initiation rate constants equal to the propagation rate
constant each monomer.
The primary chain initiation reaction consumes primary radicals:
R
rad pi
=
-N
M
RCk i
pi
Mi
q
i
=
1
Bifunctional Initiator Primary Decomposition Reaction

The bifunctional initiator decomposition reaction is modeled as a first order thermal decomposition
reaction:
Ik
B
RR
+ kk + 1,1
k B + 2,2 k B CkR bid k
=k
bid
Ik
This rate expression )( R bid

k
describes the rate for the primary decomposition of bifunctional initiator k.

Each primary decomposition reaction generates an undecomposed fragment. The generation rate of
undecomposed fragments is equal to the initiator decomposition rate:
R kF
)(
=
Ck bid k
Ik
The symbols
B1
and
B2
represent optional user-specified reaction by- products. This feature allows

you to track the formation of low-molecular weight decomposition by-products, such as carbon dioxide,
which may be generated as the initiators decompose. The byproduct formation rates are determined by:
R
kB 1
,
=
,1 bidk Ck k
Ik
R kB 2 , = ,2 bidk Ck k
Ik
For mass balance purposes, the polymer mass generation rate is incremented by the bi-initiator mass
consumption rate, less the mass formation rate of by- products.
The rate expression for the formation of primary radicals from the primary thermal decomposition of
bifunctional initiators is given by:
NR
bid rad
=
BI
CkN r
k
bidk
k
Ik k
=
1
The user can specify more than one bifunctional initiator to model systems where multiple initiators with
different half-lives are used to control the initiation rate over the course of the polymerization.
The model assumes that the each site in the bifunctional initiator generates two radicals. A fraction of the
radicals generated by decomposition undergo radical recombination in the radical-cage, leading to stable
byproducts. The initiator efficiency factor,
k
, is used to specify the fraction of radicals which are not destroyed by the
cage effect. This factor can be adjusted using a built-in or user-defined efficiency gel effect correlation.
The rate constant
k bid k

parameter is typically non-zero only at high pressures.
The rate expression can be modified using an optional built-in or user-defined gel effect correlation as
described later in the text.
To complete the initiation process, the reactive primary radicals ),( RR
k react with monomer

by the chain initiation reaction to form polymer chain radicals of unit length. Note that the undecomposed
initiator fragment k is conserved in the polymer chain )( kjP 1
,
. This fragment is eventually destroyed by the secondary

decomposition reaction described in the next sub-section. The chain initiation reactions are shown below:
R+Mj
P1
j
R pi j
=
k pi j
C Mj
R
PMR k
+ j kj
,1
RCkR pi
j
=j
pi
kMj
The chain radicals grow by successive addition of monomer molecules to form long chain polymer
molecules.
Bifunctional Initiator Secondary Decomposition Reaction

The secondary bifunctional initiator decomposition reaction is modeled as a first order thermal
decomposition reaction:
Dn
kj ,
k
PR
+ nk j
+ 1,1
k
B + 2,2 k B R kF )( = k sid k
k
This rate expression )(

R )(kF
describes the rate for the decomposition of

bifunctional initiator fragment k. In this equation
(
k
)
is the concentration of undecomposed
fragments of type k, which is calculated from the FRAGFLOW polymer attribute.
The model assumes that the secondary decomposition reaction generates a primary radical and a live
end group (polymer radical). A fraction of the radical pairs generated by decomposition recombine in the
radical-cage,
leading to stable byproducts. The
initiator efficiency factor,
k
, is used to specify the fraction of

radicals which are not destroyed by the cage effect. This factor can be adjusted using a built-in or user-
defined efficiency gel effect correlation.
The generation rate of primary radicals from this reaction can be written as:
R
sid rad
=
N
BI
sidk k k
kk
=
1
Each fragment decomposition event generates a new live end. The model assumes that the fragments
are randomly distributed across the bulk polymer molecules and that the penultimate segment attached to
the fragment becomes a live end. The generation rate of live ends of type i from the decomposition of
initiator fragment k can be written as:
jd 0
)( dt
=
sidk
k
k
1jk1
0
The byproduct formation rates are determined by:

R kB
1
,
=
,1 sidk k k
k
R kB 2 , = ,2 sidk k k
k
The mass generation rate of polymer is adjusted to account for mass lost in the form of reaction by-
products.
The user can specify more than one bifunctional initiator to model systems where multiple initiators with
different half-lives are used to control the initiation rate over the course of the polymerization.
The rate constant
k sid k

parameter is typically non-zero only at high pressures.
The rate expression can be modified using an optional built-in or user-defined gel effect correlation as
described later in the text.
Propagation
The chain radicals grow or propagate by the addition of monomer molecules to form long polymer chains
(Pni
) . The propagation reaction is represented by:
Pni
+ M j P n j +1
R p ij
=
k p ij
C Mj P n i where monomer j is being added to a polymer chain of length n, with an active segment of type
i. The resulting polymer chain will be of length n+1 and the active segment will be of type j. The active
segment type usually represents the last monomer incorporated into the polymer chain.
For copolymerization, there will be N m * N
m
propagation reactions having different reactivities. For

example, with two monomers, the monomer being added could be monomer 1 or monomer 2 while the
active segment type
could be segments from monomer 1 or monomer 2. Hence there will be four rate constants ( k 11 , k 12 ,
k 21 , k
22
) where the first subscript refers to the active segment type while the
second subscript refers to the propagating monomer type. For the terminal model the rate of propagation
is dependent only on the active segment and propagating monomer concentrations.
This copolymerization scheme can be adapted for modeling the stereoregularity (isotactic, syndyotactic or
atactic) of monomer addition in homopolymerization.
Head-to-Head Propagation
When reactions occur between substituted vinyl monomers or 1,3 dienes, the repeat units usually join the
chain in a head-to-tail configuration, as shown below (here HTT = head-to-tail). A portion of the
monomers may join the chain in the head-to-head configuration, as shown in the second reaction below.
Head-to-head unions can also result from termination by combination as described later.
R
head-to-tail dyad H C CH
2
*
+
head-to-head dyad
The head-to-head dyads disturb the normal regularity of the chain. As a result, the head-to-head fraction
of the polymer can have a strong influence on the crystallinity of the polymer, and thus influence the
mechanical properties of the final product.
The model can track head-to-head additions using the optional HTH Propagation reaction. The polymer
attributes HTHFLOW and HTHFRAC (head-to-head flow and fraction) must be included in the list of
attributes on the Polymers, Polymers subform.
The model does not explicitly track normal head-to-tail additions. Instead, the standard propagation
reaction is used to track the total (head-to-head and head-to-tail) propagation rate. The head-to-head
propagation reaction explicitly tracks the head-to-head propagations. This design allows the user to fit the
overall propagation rate first, and then refine the model by adding head-to-head additions.
The HTHFLOW attribute is a scalar value. The overall rate of change of the head-to-head flow
hth
HTT Propagation
HC
HC
2
H C CH
2
R
R
*
R
R
HTH Propagation C H
2
CH* + R C H
2
HC
R
H C R CH
2
*
R is calculated by summing the head-to-head additions across all pairs of
monomers. Termination by combination also generates head-to-head pairs as discussed later. The net
rate expression for head-to- head dyads can be written as:
R
hth
=
Nmon Nmon
[ ( kCkC Mi
j
ij hth
+ Mj
i
ji hth
) + tcji k ij
]
i
=1j
=
1
0
0
Chain Transfer to Small Molecules
Chain transfer to small molecules such as monomer, solvent or chain transfer agent usually involves the
abstraction of hydrogen from the small molecule by the chain radical and leads to the termination of the
live chain. At the same time, a new primary transfer radical is formed which can start chain
polymerization. The effect of chain transfer on the polymerization kinetics depends on the reactivity of the
transfer radical. When the transfer radical is very reactive, as is the case when the chain initiation rate
constant is greater than the propagation rate constant, chain transfer will not lower the polymerization rate
or conversion, but will reduce the molecular weight of the polymer. However, if the transfer radical is less
reactive than the monomer- based propagating radical, as in the case of low chain initiation rate constant,
both the conversion and molecular weight of the polymer will be lowered.
Chain Transfer to Solvent or Agent

Chain transfer to solvent and chain transfer to a transfer agent have the following rate expressions:
Pni
+AkDn+R
R tra
ij
= k tra
ij
CAk
P
ni
Pni
+SkDn+R
R trs
ij
= k trs
ij
CSk
Pni
For transfer to agent or solvent the transfer radicals are assumed to have the same reactivity as the
primary radicals formed by initiation. The case where the transfer radical has a different reactivity than the
primary radical may be added in a future version.
Chain Transfer to Monomer Generation of Terminal Double Bonds

In the chain transfer to monomer reaction, the live polymer end )(
P
n abstracts a hydrogen from
a monomer molecule, resulting in a dead polymer chain )(
Dn
. The monomer, which loses a hydrogen, becomes a live polymer end group with an
unreacted double bond )(
P 1=
. Subsequent propagation reactions segment at

generate the opposite long-chain end of polymer the chain
radicals ( P =n )
. with These a terminal initial reaction double-bond steps are shown below:
P
n
Chain Transfer
Terminal double bond segment
P
1=
to Monomer
+MD
n
+P
1=
Propagation
+ n-1 M
P
n=
Terminal double bond segment

The terminal double bond segments can react with live end groups through terminal double bond
polymerization reactions as described later in this section. These reactions lead to the formation of a
molecule with a long chain branch.
The model optionally tracks terminal double bonds using the polymer component attribute TDBFLOW,
which contains one element for each type of segment.
The chain transfer to monomer reaction does not always generate a terminal double bond. The terminal
segment may undergo a re-arrangement reaction, which ( f TDB ij
)
destroys can be used the double to specify bond the site. fraction The model of chain parameter transfer
to TDB monomer
fraction
reactions that generate a terminal double bond.
The reaction PfDMP n
i
+j
rate n + of ij
TDB the 1
chain ( transfer )
to monomer reaction is defined as:
ij
i nMj j = + 1
- Pf TDB ij
j 1 PCkR trm
ij
= trm
Where
( R trm
ij
)
is the rate of consumption of monomer j and live polymer end groups of type i and the
generation rate rate of terminal double bonds of type j
( R of trm =j
live )
is defined ends of by:
type j. The generation
PCkfR trm
j
=
= ij
TDB
ij trm
i nMj
Chain transfer to polymer, which is also included in the kinetic scheme, is discussed in the section that
follows on Termination.
Termination
Bimolecular termination of radicals may involve primary radicals ( R
) and
chain radicals ( P n
j
) . However, the concentration of primary radicals is usually much lower than the
concentration of chain radicals. Hence, only bimolecular termination involving chain radicals is included in
the built-in kinetic scheme. In termination, the chain radicals are destroyed and live chains are converted
to dead polymer chains.
Intermolecular termination occurs by one of two mechanisms, combination (coupling) or
disproportionation. Many monomers (e.g. MMA) show both types of termination while other monomers
(e.g. styrene) terminate predominantly by combination. The mode of termination has a strong influence on
the average polymer chain length and chain length distribution, especially when chain transfer is not
significant. When the combination reaction is dominant, the polydispersity (in a single CSTR) will
approach 1.5. The polydispersity approaches 2.0 when disproportionation is dominant.
Termination by Combination
In termination by combination, two live polymer end groups react with each other, forming a single dead
chain with a head-to-head segment pair. Each of these reactions, on average, doubles the molecular
weight of the polymer.
The figure below shows an example for poly(styrene).
P
nCH
2
P
m
D
n+m
CH + HC C H
2
The reaction rate depends on the concentration of the live end groups:
Pn
P D R kPP
CH
2
HCHC
CH
2
i
+jm
n+
m ij tc
=
ij
j i tc n
n
The formation of head-to-head segment dyads can be tracked by including the optional HTHFLOW and
HTHFRAC (head-to-head flow and head-to-head fraction) attributes in the attribute list on the Polymers,
Polymers subform. Head-to-head sequences can contribute to thermal instability and may cause
degradation during storage or subsequent processing.
Termination by Disproportionation
In disproportionation reactions, the radical at the end of one chain attacks a hydrogen atom at the
second-to-last carbon atom in the second chain, forming two dead polymer molecules with no net change
in molecular weight. Disproportionation results in one of the dead chains having a saturated end- group
while the other will have an end-group with a terminal double bond. For example:
P
n
P
mD
n=
D
m
H
CH
3
CH
3
CH
3
CH
3
CH C
+C
CH
2
CH
C
+ HC
CH
2
CO
C
O
CO
C
O
OCH
3
OCH
3
OCH
3
OCH
3
The reaction rate depends on the concentration of the live end groups:
DfPP n
i
+jm
ij
TDB
()
j
ini=n
+1
- DDf TDB
ij
n
+ m PPkR td ij
= ij td
n
The formation of terminal double bonds can be tracked by including the TDBFLOW and TDBFRAC
(terminal double bond flow and fraction) in the list of attributes on the Polymers, Polymers subform.
Terminal double bonds can contribute to thermal instability and may cause degradation, branching and
gelation during storage or subsequent processing.
The chain transfer to monomer reaction does not always generate a terminal double bond. The terminal
segment may undergo a re-arrangement reaction, which ( f TDB ij
)
destroys can be used the double to specify bond the site. fraction The model of chain parameter transfer
to TDB monomer
fraction
reactions terminal that generate a terminal double bonds of type i by double disproportionation
bond. The generation ( R td
=i
)
is defined rate of
by:
PPkfR td
i
=
= ij
TDB
ij
i
j td
n
n
Inhibition
Inhibition is included as an additional termination mechanism. This involves reaction between a chain
radical and a small molecule (inhibitor or impurities) to form a dead chain:
DXP n
i
+
k
n PCkR x ik
= ik
x
i nXk
The model assumes that the inhibitor is consumed by the reaction; the polymer mass generation rate is
adjusted accordingly.
Gel effect in Termination

Bimolecular termination reactions between chain radicals become diffusion controlled at high polymer
concentration or high conversion. This leads to an increase in the polymerization rate and molecular
weight. This condition is known as the gel effect or Trommsdorff effect. At high conversions the increased
viscosity of the reaction medium imposes a diffusional limitation on the polymer chains, leading to lower
effective termination rates. Eventually at high enough conversions, even the propagation, initiation, and
chain transfer rates may be affected by the diffusional limitation.
The diffusional limitation is modeled by multiplying the low conversion reaction rate coefficients by a gel-
effect factor that will lower their effective value with increasing conversion. The free-radical model
includes an option to modify the reaction rate expressions using a built-in or user-defined gel-effect
correlation, as described later in this chapter.
Long Chain Branching

Chain Transfer to Polymer
The polymer radical in one chain can transfer to a repeat unit in a second chain. This chain transfer to
polymer reaction always generates a long chain branch, since subsequent propagation from the live site
causes the backbone molecule to grow a new branch.
The chain transfer to polymer reaction can be written as:
Pni
+DmDn+Pmj
R trp ij
=
k trp ij
mDP j i m n
Where m
j
represents the number of repeat groups of type j in the molecule to which the radical is
transferred.
Each transfer reaction generates one long chain branch. The optional polymer component attributes LCB
and FLCB are used to track the molar flow rate of long chain branches and the long chain branching
frequency (branch point per thousand repeat units).
Terminal Double Bond Polymerization

Polymer chains with terminal double bonds are formed by several reactions, including chain transfer to
monomer, termination by disproportionation, beta- scission and beta-hydride elimination.
These terminal double bond groups can participate in propagation reactions in much the same manner as
a monomer molecule. The resulting terminal double bond propagation reactions generate a long chain
branch since the propagation reaction goes through the terminal double bond, leaving the polymer
molecule attached to the TDB group attached to the backbone of the growing live polymer molecule.
D
n=
Terminal Double Bond
Polymerization
P
m
+
P
n+m
Propagation + Termination
Each terminal double bond propagation reaction generates one long chain branch. This reaction can also
transfer the live end from one type of segment to another (e.g., from segment i to segment j).
The optional polymer component attributes LCB and FLCB are used to track the molar flow rate of long
chain branches and the long chain branching frequency (branch point per thousand repeat units).
The rate of terminal double bond polymerization,
Molecule with long-chain branch
R tdbp ij
between live end i and

terminal double bond segment j can be written as:
DP
ni
+j
=m
P mn
j+
DPkR tdbp
ij
= ij
tdbp
i
j
=n
m
The concentration of terminal double bond segments is calculated from the optional polymer component
attribute TDBFLOW.
Short Chain Branching

The radical in a live end group can undergo a backbiting reaction in which the radical in live end
segment i is transferred to a hydrogen atom in segment j in the same chain, forming a short chain branch.
Short chain branches, typically five or six carbon atoms in length, are quite morphologically different than
long chain branches, which are formed by a number of reactions.
The backbiting reaction leads to short chain branches if the backbone radicals are stable and can
continue propagation. The total rate of short chain branching,
R SCB
, depends on the live end group concentrations,

i
, and the
rate constants for the short chain branching reaction,
k scb i
:
PP n
i
jn
R SCB
=i
k scb i
Short chain branching is tracked by the optional polymer component attribute SCB. The short chain
branching frequency (short chain branches per thousand repeat units) is reported in the optional polymer
attribute FSCB.
For some polymers (e.g. polypropylene) the backbone radical can be highly unstable and will result in the
scission of the chain into a dead polymer chain with a terminal double bond and a short live chain one to
six carbon atoms long. Use the beta scission reaction (see below) to track these types of reactions.
Beta-Scission
A simplified beta-scission reaction is included in the built-in kinetics. It is limited to reactions where a live
chain undergoes scission to form a dead chain of the same length and a primary radical:
DfP n
i
i
TDB
i=n
+ 1(
- RDf TDB
i
)n
+ PkR bs i
=i
bs
in
This reaction can be used to simulate backbiting reactions which form short- chain polymer radicals (see
Short Chain Branching).
The beta scission reaction usually generates a terminal double bond corresponding to the live end i. In
some special cases, the double bond may not form or may be unstable. The terminal double bond
fraction parameter,
f TDB i
, can be used to specify the fraction of beta-scission reactions which generate a terminal double
bond (by default, this parameter is unity). Thus, the rate of generation of terminal double bonds from the
beta-scission reaction,
R td =i
, can be defined as:

PPkfR td
i
=
= ij
TDB
ij
i
j td
n
n
Reactions Involving Diene Monomers

Cis and Trans Propagation
Propagation reactions involving 1,3-diene monomers, such as butadiene or isoprene, can generate three
types of repeat segments as shown below.
*+
Normal Propagation
Cis Propagation
Trans Propagation
CH
2
*+
*+
CH*
Vinyl Configuration
CH
2
CH
2
*
CC
Cis Configuration
H
H
CH
2
H
CC
Trans Configuration
H
CH
2
*
Although these segments may exhibit different physical properties, it is convenient to lump them together
as a single repeat segment, and track the various segment configurations using the optional polymer
component attributes CIS-FLOW and TRANSFLO. Likewise, the three types of propagation reactions are
lumped together under the standard propagation
reaction. Optional Cis-Propagation and Trans-Propagation reactions are used to specify the rate
parameters for reactions that generate segments with the cis- or trans- configurations.
This design is intended to keep the model development process as simple as possible. The user can add
cis/trans/vinyl accounting a working model without changing any of the existing rate parameters.
The new CIS-FLOW and TRANSFLO attributes are dimensioned NSEG and correspond to the bulk
polymer. The flow rate of each diene segment in the vinyl configuration can be calculated by taking a
mole balance across the various configurations taken by diene segments. The optional polymer attributes
CIS-FRAC, TRANSFRA, and VINYLFRA report the molar fraction of each type of diene segment in each
of the three configurations (an additional cross link configuration is also tracked as discussed later).
The rate of formation of segments of type j with cis configuration,
R cis
j
, is calculated by
summing over all types of live end groups i:
PMP
ni
+
j
cisj
)( n +
1
R cis
j
=i
Ck cis ij
Mj
0i
Likewise, the rate of formation of segments of type j with trans configuration, R trans j
, is calculated by summing over all types of live end groups i:
PMP
ni
+
j
transj
(n+
1
) R trans
j
=i
Ck trans
ij
Mj
0i
In the equations above,

k cis ij
and
k trans ij
are, respectively, the net rate constants for cis and trans
propagation of monomer j onto a chain with a live end i. The standard reaction scheme does not include
any reactions which consume the cis and trans end groups. Further, the model does not constrain the cis
and trans reaction rates in any manner; the model user must ensure that the cis and trans propagation
rates are lower than the net propagation rate.
Pendent Double Bond Polymerization

Diene segments in the vinyl configuration contain a pendent double bond that hangs off the main
polymer chain. Live chains can react with these double bonds in a pendent double bond polymerization
reaction, analogous to normal propagation. These reactions generate a short cross-link between two long
linear chains, as shown below.
*+
Reaction Pathway
*
Propagation
CH
2
CH*
Pendent double bond PDB Polymerization

Cross-linked molecule
*
ij The pendent double bond polymerization rate (
R PDB
) depends on the
concentration of live ends of type i (
0i
) and the concentration of pendent

(vinyl) double bonds of type j in the bulk polymer phase (
vinylj
):
)( 10
)( 1
DP n
i
+
vinylj )( m
P mn
j+
R PDB ij
= k ij
pdb vinylji The model assumes the reaction generates a new

live segment of type j. The reaction model does not distinguish between subsequent propagation from
this new live site from normal propagation reactions involving live end groups.
Each pendent double bond polymerization reaction involving diene segment j generates a new cross-link
of type j. The flow rate of cross-links is tracked by the optional polymer component attribute XLFLOW.
The cross-linking density is (moles of links per mass of polymer) is tracked by polymer attribute
XDENSITY.
The concentration of vinyl groups (pendent double bonds) is determined by a mole balance. The flow of
pendent double bonds of type i ( )(iPDB ) is calculated by subtracting the concentration of other possible
configurations (cis, trans, or cross-link):
iPDB )( = SFLOW _()( i - CIS FLOW )( i + TRANSFLO )( i + XFLOW ))( i This flow rate is used to
determine the concentration of pendent groups.
When the degree of cross-linking is extensive, the polymer can form a gel phase. The current version of
the Free-Radical kinetics model does not account for gelation. This limits the model to situations with a
low degree of cross-linking.

Following are the model features and assumptions used in the free-radical polymerization model available
in Aspen Polymers.
Calculation Method
In the Aspen Polymers free-radical bulk/solution polymerization model, the polymer chain length
distribution averages and molecular structure properties are calculated using the population balance and
method of moments approach, based on the built-in kinetics shown in the Built-in Free-Radical
Polymerization Kinetic Scheme figure on page 166.
Population balance equations are used to account for the concentration of live polymer chains and
combined polymer chains of length n. The f-th live and combined polymer chain length distribution
moments are defined as follows:

jf
nf
Pnj
n
=
0
nf
Nm
Pn
j
n
=
0
j=1+
D
n
For homopolymerization the index f is a scalar variable and the active segment superscript j may be
dropped for the live polymer moment definition as there is only one segment type. Hence, for
homopolymerization there will be one zeroth moment, one first moment, one second moment and so on
for the live and combined polymer. However, for copolymerization, the index f will be a vector whose
elements denote the monomer with respect to which the moment is defined. For copolymerization with
respect to every active segment, there will be one zeroth moment, N
m
first moments,
N
m
+
Nm(N2
m
-
)1
second moments and so on.
For example, for copolymerization with three monomers, the vector index f can have the following values
for the first moment:
f=
001
,
0
01
0
01
representing the first moment with respect to segment one, two and three respectively. The application of
the moment definitions to the live and bulk polymer population balance equations yields the live and bulk
polymer chain length distribution moment equations. The general moment equations are listed in the
following figures. The various zeroth, first, second, etc. moment equations can be generated from these
by substituting the appropriate values for the index f.
The live polymer chain length distribution moment equation is shown here:
d
i f dt
=[
( RCkjn
-)]
f
Ck hCCk 1 1
=
j pi
Mj
+N
M
ij trm Mj
0i
+ N CI
jk
a
jk si
Ck
jk c jk
i
=
k
=b
Mj
)(
+
N
BI
sidk
k
k
fk
ki 1 1
0
1
0
+ N
M Ck f
()
-
-fj
i = 1 ij p
Mj
f
a
=
0
af - j i a
NM
Ck
p
ji
i=1j
jf
=
= Mi +
N
M
k
trp ij
jf +
0i
-N
M k trp
iji 1
fj
i
1
i
1
+
N
M
k
scb ij
if
-N
M k scb
ji
jfi
=
1
i
=1
N-
M
( kk
td ij
+ ij tc
)
0ifj
i
=
1
+
NM
k
tdb ij
f
=f
j
=i
af
-
N
M iji
= tdb i
a
i
1
jf=1=
0
-
k
0+
NM
k
ij pdb
f
f

jii=1a
=
0
=
a
afa
-
-
N
Mk
pdb
iji
1
fj
i
1
where j
contains some terms for reactions leading to the formation of dead polymer
j=
k
bs j
+N
M
Ck trm ji
Mi
+N
M k trp
iji 1
+N
A Ck tra
jk
Ak
+N
S Ck trs
jk
Sk
+N
i
=
1
i
=1
k
=1k
=k
= X 1 Ck x
jk 1 Xk
The moments with respect to terminal double bonds are approximated:

1i
=
i0=1
0
i2=i0=
2
0
etc ...
In the final term of the equation, the symbol
i
represents the molar fraction of diene segment i in

the vinyl configuration (attribute VINYLFRA). This term is zero for all segments that are not dienes.
The term
0k
represents the concentration of polymer molecules containing an undecomposed initiator

fragment associated with bifunctional initiator k.
The bulk polymer chain length distribution moment equation is shown here:
d
f dt
=
N
M [ ( j = 1 RCkjn - ) ] f
j pi
Mj
+N
i
=
1
+()
( )( ) = =
=M
Ck trm ij
Mj
0i
hCCk si
j
aj
bj C
Mj
cj
+
N
M
Ck ij p j
1 Mj
a
f
0
fa
j
af -
ai
-
N
M Ck p
ji
i
1 fMi j
-
N
M i = 1 = =
N
M
k
tc ij
0i
fj
j
=
1
+12
NMi1f

fa
0
k
tc ij
ai
af j
-
+
N M N
M
k
tdb ji
f
i
=j
=a
=
af
af j
-
i
a
=
-
N M N
i
=1j
N i
=1=
1Mk
tdb ij
ji f
0
=
-MN
M k tdb
iij 0
jf
=
110
=
1
j
+
N M N
M
k
pdb
ji
f
i
=j
=a
=
af
af j
-
a
+i
-
N M N M i = 1 j
=1
= = ij pdb
i f j N
MN
M ij
pdb
if
ji
1j
1
For copolymers, segment-segment dyad rate equation is:

( Mi
)
jitc ji k
1
- k 10
+110
1
d
ji , dt
=
kCkCk
iij p
0
Mj
+ p jji
0 + 00,
Quasi-Steady-State Approximation (QSSA)
Users may invoke the Quasi-Steady-State Approximation (QSSA) for the live moment equations. Invoking
QSSA converts the live moment differential equations (ODE) to algebraic equations, which are solved
internally in the kinetics routine. Assuming QSSA is equivalent to assuming that the live moments attain
their steady-state values instantaneously. This approximation makes the system of ODEs much easier to
integrate by reducing stiffness.
Comparison of the results with and without QSSA for most free-radical polymerization systems, where the
chain lifetimes are short compared to the residence time, show negligible differences. Therefore it is
usually reasonable to use the QSSA. However, users should check the validity of this approximation by
running cases with the QSSA switch set to YES and NO for their particular system. By default the QSSA
is turned off (QSSA switch is set to NO). Users have the option of invoking the QSSA for all the live
polymer moment equations, or selectively for only the zeroth, first, or second moment of live polymer.
Phase Equilibrium
The polymerization model currently considers a single-phase system (vapor or liquid), two-phase system
(vapor and liquid), or three-phase (VLL) system when calculating concentrations for the reaction kinetics.
For single-phase systems, the reacting phase may be either vapor or liquid. In multi-phase systems,
reactions can occur in one or more phases simultaneously. Each reaction object is associated with a
single reacting phase, identified on the options form.
By default the reacting phase is assumed to be the liquid phase (for VLL systems, the reacting phase
must be specified). Several reaction models can be referenced from a single reactor block to account for
reactions in each phase.
Gel Effect
Bimolecular termination reactions between chain radicals become diffusion controlled at high polymer
concentrations or high conversion leading to an initial increase in the polymerization rate and molecular
weight. This condition is known as the gel effect or Trommsdorff effect. At high polymer concentrations,
the increased viscosity of the reaction medium imposes a diffusional limitation on the polymer chains,
which leads to lower effective termination rates. Typically the termination rate coefficients are affected first
by the gel effect because they involve diffusion of two bulky polymer radicals. Eventually at high enough
conversions, even the propagation, initiation, chain transfer reactions, and the initiator efficiency are
lowered by the gel effect. Hence, in general it may be necessary to allow gel/glass effects for all the
polymerization reactions in the built-in kinetic scheme.
Diffusional Limitation
The diffusional limitation is usually modeled by multiplying the low conversion reaction rate coefficients, k
o
, by a gel effect factor, GF, that decreases with increasing conversion.

Hence the effective rate coefficient for a reaction is given by:
k eff =
ko
GF
Several empirical and semi-empirical correlations relating the gel effect factor to conversion and operating
conditions are available in the literature. Currently two of these have been implemented as built-in
correlations. Users will be able to use these gel effect correlations simply by specifying the correlation
number and the parameters. The built-in correlations are:
Correlation Number 1:
GF
=
a
11
+
a2
X
pa
3
Where:
X
p
= Weight fraction of polymer

This correlation has three user specified parameters, a 1
,a
2
,
and a
3
.
Correlation Number 2:
GF
=

[()]
10 exp
With:
A=a1+
a2TB=a3+
a4TC=a5+
a6TD=a7+
a 8 T Where:
X
p
1
Aa9
X
p
- BX p + CX 2 p +
DX
3p
= Weight fraction of polymer

T = Temperature in Kelvin
This correlation has ten user specified parameters, a
1
to a
10
.
Users may also include their own gel effect correlation by specifying a correlation number greater than
the number of built-in gel effect correlations (currently two) . In this case, users must provide the
correlation for the gel effect factor in the form of a Fortran subroutine. The user gel effect subroutine
argument list is documented here:
User Gel Effect Subroutine Arguments
Subroutine USRGEL ( ICORR, MAXGP , GPAR ,WFTFRP , GF, + SOUT ,NSUBS
,IDXSUB,ITYPE , + NINTK ,INTK ,NREALK,REALK , + NPO ,NBOPST,IDS ,NCK , + NITG
,ITG ,NREA ,REA )
Variable I/O Type-Spec Dimension Description
ICORR I I Gel effect correlation number MAXGP I I Maximum number of gel effect
parameters GPAR I R MAXGP Gel effect parameters
WTFRP I R Weight fraction of polymer GF O R Gel effect factor SOUT I R Outlet stream NSUBS I I Number of
substreams IDXSUB I I NSUBS Location of substreams in stream
vector ITYPE I I NSUBS Substream type vector
1 = MIXED 2 = CISOLID 3 = NC NINTK I I Number of integers for model INTK I/O I NINT Integer array for model
NREALK I I Number of reals for model REALK I/O R NREAL Real array for model NPO I I Number of property
methods NBOPST I I 6, NPO Property method array IDS I I 2, 13 Block IDs
i, 1 Block ID i, 2 to i, 4 used by system i, 5 kinetic subroutine name NCK I I Total number of components NITG I I
Length of integer array for kinetics ITG I I NITG Integer array for kinetics NREA I I Length of real array for kinetics
REA I R NREA Real array for kinetics
Polymer Properties Calculated

The following variables can be calculated by the built-in kinetics routine based on the polymer attributes
and the subset of the built-in kinetics used for a specific simulation:
Zeroth, first and second moments for the combined polymer
Zeroth and first moments for the live polymer
Number, weight and z-average degree of polymerization and polydispersity index for the combined
polymer (DPN, DPW, DPZ, PDI)
Number, weight and z-average molecular weight for the combined polymer (MWN, MWW, MWZ)
Average molecular weight of segments in combined polymer (MWSEG)
Copolymer segment composition for combined polymer (SFLOW, SFRAC)
Mole fraction of combined polymer chains that are live (LDFRAC)
Number average degree of polymerization for live polymer (LDPN)
Live polymer active segment composition (LEFLOW, LEFRAC)
Copolymer segment composition for live polymer (LSFLOW, LSFRAC)
Copolymer dyad flow rates (DYADFLOW), fractions (DYADFRAC), and the number-average block
length with respect to each type of monomer (BLOCKN).
Total number of short and long chain branches (SCB, LCB)
Short and long chain branching frequencies (FSCB, FLCB)
Flow rate and fraction of head-to-head dyads (HTHFLOW, HTHFRAC)
Flow rate of cis-, trans-, and cross-link segments configurations corresponding to each type of diene
monomer (CIS-FLOW, TRANSFLO, XLFLOW)
Fraction of diene segments in the cis-, trans-, and vinyl configuration (CIS-FRAC, TRANSFRA,
VINYLFRA)
These parameters are stored as component attributes defined in Chapter 2.
These variables, except for the branching frequencies, are related to the moments by the relationship
shown here:
DPN
N
m
N
m
==
m
i
(i
)
(j
)
SFRAC I
i
i
1
()
11
LDPN
=i
=
1N0
0=
1
()
=
(i
)N
m
(i
)
i
LSFRAC ( I
)
=
(i
)N
m
1
(i
)
=
1
i
=
1
PDI
ii
N
m
=
j
1
(j
)
LEFRAC I
0=
N
=
m
1
20
1( )
LPFRAC
=
0
()
=
N
j
j
j
(m0
)
()
=
1
The branching frequencies are calculated from the rate of chain transfer to polymer and the rate of
backbiting reactions. The branching frequencies are reported in terms of number of branches per
thousand segments in the polymer.
Structural Properties
Frequently some of the polymer properties are reported in terms of other properties that are related to
these structural properties. These include properties such as melt flow rate or melt index, viscosity
numbers, or K- values, etc. User-property subroutines can be set up for calculating some of these
polymer properties from the polymer moments and structural properties.
User Profile Properties

In addition to the polymer properties reported through the component attributes, additional results are
reported through User Profile variables. The following user profile variables are currently available in the
built-in free- radical kinetics routine:
Profile Number
Profile Type Units
1 Conversion of monomer to polymer Fraction 2 Rate of polymerization (propagation) KMOL/S/CUM 3 Heat of
polymerization KCAL/S/CUM 4 Reacting phase volume
(or volume flow)
CUM or CUM/S
5 Reacting phase total moles
(or mole flow)
KMOL or KMOL/S 6 Reacting phase average molecular
weight
KG/KMOL
7 Rate of chain termination by
combination
KMOL/S/CUM
8 Rate of chain termination by
disproportionation
KMOL/S/CUM
9 Rate of chain termination by inhibition KMOL/S/CUM 10 Rate of initiation of radicals KMOL/S/CUM 11 Rate of
induced initiation KMOL/S/CUM 12 Rate of chain transfer to monomers KMOL/S/CUM 13 Rate of chain transfer to
polymer KMOL/S/CUM 14 Rate of chain transfer to agents KMOL/S/CUM 15 Rate of chain transfer to solvents
KMOL/S/CUM 16 Rate of beta scission KMOL/S/CUM 17 Rate of short chain branching KMOL/S/CUM 18
Concentration of initiators KMOL/CUM 19 Concentration of catalysts KMOL/CUM 20 Concentration of coinitiators
KMOL/CUM 21 Concentration of monomers KMOL/CUM 22 Concentration of transfer agents KMOL/CUM
Profile Number
Profile Type Units
23 Concentration of solvents KMOL/CUM 24 Concentration of inhibitors KMOL/CUM 25 Concentration of polymer
KMOL/CUM
For more information, see Adding Gel-Effect on page 196.
Rates and Concentrations

The rates and concentrations reported via the user profiles can be used to calculate additional
information, such as the kinetic chain length and fraction of dead chains with terminal double bond
segments. These user profile variables can only be accessed if you are calling the free-radical kinetics
from a batch reactor (RBatch) or a plug flow reactor (RPlug).
Specifying Free-Radical Polymerization

Kinetics
Accessing the Free-Radical Model
To access the Free-Radical polymerization kinetic model: 1 From the Data Browser, click Reactions. 2
From the Reactions folder, click Reactions. The Reactions object manager appears. 3 If the kinetic model
already exists, double-click the desired Reaction ID in
necessary, change the default ID for the reaction. 5 Select Free-Rad as the reaction type and click OK.
Specifying the Free-Radical Model

The Free-Radical model input forms are listed below:
Use this sheet To
Species Define reacting species Reactions Specify reactions and rate constant parameters Rate Constants
Summarize rate constant parameters Options Specify reacting phase and select additional
options Gel Effect Supply gel-effect correlation parameters
Specifying Reacting Species
You must specify the reacting species in the Species sheet: 1 In the Polymer field, specify the polymer
produced. 2 In the Monomers field, list the reacting monomers. For each monomer, in
the goes to field, specify the polymer segment that the monomer converts to. 3 Continue listing other
types of reacting species, e.g. solvents, transfer
agents, etc. 4 Select the Generate Reactions option if you want the reactions to be
generated automatically. After going through the reaction generation once, it is recommended that you
turn off this feature. Otherwise, the reaction generation is performed repeatedly.
Listing Reactions
The Free-Radical model generates reactions based on the list of reacting species. You can view the
system-generated reactions, then assign rate constant parameters to these reactions.
You can view a list of the system-generated reactions on the Reactions sheet. In the Reaction summary
listing for each reaction, the first column indicates the reaction type. The second column lists the
reactants, and the last column lists the products. The Data Browser window can be resized to better view
the reaction listing. Use the following options:
Click To
New Add new reactions to the scheme Edit Edit the current reaction indicated by the row
selector Rate Constants Specify reaction rate constant parameters for the
reactions
Click To
Hide/Reveal
a reaction from the
Delete
Adding Reactions
To add a new reaction to the scheme click New to open the Add Reaction subform:
1 In Reaction type, select a type for the new reaction. The Reaction
scheme for that type is displayed. 2 In the reactant fields (for example, Initiator, Catalyst) enter the
reactants of the categories allowed for that reaction type. 3 Where applicable, specify reaction by-
products and stoichiometric
coefficients. 4 Click Cancel to discard the new reaction
- or - Click New to add a new reaction - or -
Click to check the Completion status - or - Click Done to return to the reaction summary.
Editing Reactions
To edit a reaction, click Edit to open the Edit Reaction subform: 1 Modify the Reaction type as needed.
The Reaction scheme for that type is displayed. 2 Modify reactants as needed.
3 Click to check the Completion status
- or - Click Done to return to the reaction summary.

To assign rate constants to user reactions, click Rate Constants to open the Rate Constant Parameters
subform. Alternately, move to the Rate Constants summary form for a grid-style form displaying rate
constants for all reactions. For each reaction, enter: 1 In the ko field, enter the pre-exponential factor. 2 In
the Ea field, enter the activation energy. 3 In the V field, enter activation volume. 4 In the Tref field, enter
reference temperature. 5 In the Efficiency field, enter initiator efficiency for initiation reactions. 6 In the No.
radicals field, enter the number of primary radicals formed in
initiation reactions. 7 In the TDB frac field, enter the fraction of reactions that generate a
terminal double bond. 8 In the Gel Effect field, specify the number of the gel-effect sentence
number associated with the specified reaction rate. 9 In the Efficiency Gel Effect field, specify the
number of the gel-effect
sentence associated with initiator efficiency.
10 Click the stoichiometry list and select a new reaction. Enter rate constants
for the new reaction. You can use the Prev and Next buttons to select the previous or next reaction in the
list (or move to another row when using the Rate Constants summary form).
Adding Gel-Effect
Use the Gel-Effect sheet to add gel effect to reactions: 1 To activate the form, click Use Gel Effect. 2 In
Sentence ID, enter a unique integer identifier. 3 In the Corr. No. field, specify a gel effect correlation
number (use a
number greater than 100 for user-defined gel effect correlations). 4 In Parameters, list the parameters
for the gel effect correlation.
When the specified correlation number is larger than the number of built- in correlations, you must also
enter the gel-effect subroutine name in the Subroutine box. 5 To repeat steps 1-4 for additional gel-effect
correlations, in the Sentence
ID field, click New.
Selecting Calculation Options

You can select additional simulation options for the model such as QSSA, special initiation options, and
gel-effect on the Options sheet.
Option Field Description
QSSA Apply the quasi-steady-state approximation.
This activates additional options in the Apply QSSA to frame on the right side of the form. Inside this frame, select the
moments for which you would like to apply the QSSA approximation. Special Initiation
Activate the Special Initiation Parameters frame at the bottom of the form. In this frame, list the monomers affected,
and enter the special initiation coefficients and radiation intensity. Reacting Phase Specify the phase in which
reactions occur.
All of the reactions in the free-radical reaction object are assumed to take place in the same phase. You can use two
(or more) free-radical models in the same reactor to account for simultaneous reactions in multiple phases (see the
SuspensionEPS example).
If the Reacting Phase option is set to Liquid phase 1 or Liquid phase 2 the model assumes two liquid
phases exist. When the named phase is not present, the model prints a warning message and sets the
reaction rates to zero. There are two options for handling phase collapse:
collapse.
ensure the reactor models are consistent with the reaction models.
Specifying User Profiles

User profiles may be tabulated in RBatch and RPlug reactors. To specify user profiles, go the reactors
User Subroutine form User Variables sheet: 1 In the Number of user variables field, enter the number of
user variable
profiles to be tabulated. For a list of user profiles available in the free-radical model, see Polymer
Properties Calculated on page 192. 2 In the Variable No. field, list the profile numbers in order.
You must enter the profiles sequentially, without omissions. 3 For each profile, enter a profile Label
and a Units Label.
Although these labels are displayed, the reactor model does not perform unit conversions on the user
profiles. The user profile variables are totals. For example, the reported propagation rate is summed over
all propagation reactions. 4 To view user profile results, go to the User Variables sheet of the
reactors Profiles form.
References
Arriola, D. J. (1989). Modeling of Addition Polymerization Systems, Ph.D. Thesis. University of Wisconsin-
Madison, WI.
Wiley.
Billmeyer, F. W. (1971). Textbook of Polymer Science. New York: Wiley- Interscience.
Choi, K.Y. & Kim, K.J. (1987). Steady State Behavior of a Continuous Stirred Tank Reactor for Styrene
Polymerization with Bifunctional Initiators. Chemical Engineering Science.
Choi, K.Y., Liang, W.R., and G.D. Lei (1988). Kinetics of Bulk Styrene Polymerization Catalyzed by
Symmetrical Bifunctional Initiators. Journal of Applied Polymer Science Vol. 35, 1547-1562.
Choi, K.Y., & Lei, G.D. (1987). Modeling of Free-Radical Polymerization of Bifunctional Initiators. AICHE
Journal Vol. 33 No. 12, 2067-2076.
Friis, N., & Hamielec, A. E. (1976). Gel-Effect in Emulsion Polymerization of Vinyl Monomers. ACS Symp.
Ser., 24.
Ham, G. E. (Ed.). (1967). Vinyl Polymerization Volume 1. New York: Marcel Dekker.
Hui, A. E., & Hamielec, A. E. (1972). Thermal Polymerization of Styrene at High Conversion and
Temperatures. An Experimental Study. J. of Applied Polym. Sci., 16, pp. 749-769.
Kim, K.J., and Choi, K.Y. (1989). Modeling of Free Radical Polymerization of Styrene by Unsymmetrical
Bifunctional Initiators. Chemical Engineering Science, Vol. 44 No. 2, pp. 297-312.
Lenz, R. W. (1968). Organic Chemistry of Synthetic High Polymers. New York: Wiley-Interscience.
Marten, F. L., & Hamielec, A. E. (1979). High Conversion Diffusion Controlled Polymerization. ACS Symp.
Ser., 104.
Ray, W. H., & Laurence, R. L. (1977). Polymerization Reaction Engineering. In Chemical Reactor Theory.
New Jersey: Prentice-Hall.
Villalobos, M.A., Hamielec, A.E., and P.E. Wood (1991). Kinetic Model for Short-Cycle Bulk Styrene
Polymerization through Bifunctional Initiators. Journal of Applied Polymer Sciene V 42, 629-641.
10 Emulsion Polymerization Model
This section covers the emulsion polymerization model available in Aspen Polymers (formerly known as
Aspen Polymers Plus).
Emulsion Polymerization Processes, 200
Polymer Particle Properties Calculated, 218
Specifying Emulsion Polymerization Kinetics, 219
The Aspen Polymers Examples & Applications Case Book illustrates how to use the emulsion model to
simulate styrene butadiene copolymerization.
The emulsion polymerization model is applicable to emulsion polymerization processes where nucleation
occurs by both the micellar and homogeneous mechanisms or to seeded polymerization. Some of the
applicable polymers are described below:
Styrene - A component of synthetic rubber and paper coating
Butadiene - Synthetic rubber, impact modifier in ABS and HIPS
Tetrafluroethylene - Polytetrafluroethylene (PTFE), fluoropolymers Viton
Vinylacetate - Polyvinylacetate (PVA) adhesives, paint formulation
Methylmethacrylate - Surface coating applications.
Acrylic Acid - Minor component in paints
2-chloro-1,3-butadiene (chloroprene) - Neoprene rubber
Butyl Acrylate - Surface coatings
Butyl Methacrylate - Comonomer in surface coatings
Vinyl Chloride - PVC used in floor covering and coatings
10 Emulsion Polymerization Model 199
A wide variety of processes are used in emulsion polymerization. The processes that can be modeled
using the Aspen Polymers emulsion polymerization model are those that follow micellar, homogeneous,
or seeded polymerization.
An example of a process that follows micellar nucleation and subsequent growth is the production of SBR
latex in semi-batch reactors for paper coating applications. The following lists polymeric products made by
emulsion polymerization:
Emulsion paints, made from a number of monomers (styrene, butadiene, acrylates, etc.) and a variety of
other ingredients
Adhesives, from slightly plasticized poly(vinyl acetate) and poly(ethylene- co-vinyl acetate) - a pressure
sensitive adhesive
SBR, for carpet backing and for coating paper and card board along with china clay, thus facilitating
printing on surfaces
Non-woven fabrics, which have their fabrics pre-coated with polymer and then heat pressed (these are
termed thermoformable felts)
ABS (Acrylonitrile-Butadiene-Styrene), used in high impact strength material made by swelling of a
polybutadiene latex with a mixture of styrene and acrylonitrile and polymerizing further. HIPS (High-
Impact PolyStyrene) made from bulk polymerized polystyrene in the presence of polybutadiene
Emulsion Polymerization Processes

Emulsion polymerization is an industrially important process for the production of polymers used as
synthetic rubber, adhesives, paints, inks, coatings, etc. The polymerization is usually carried out using
water as the dispersion medium. This makes emulsion polymerization less detrimental to the environment
than other processes in which volatile organic liquids are used as a medium.
In addition, emulsion polymerization offers distinct processing advantages for the production of polymers.
Unlike in bulk or solution polymerization, the viscosity of the reaction mixture does not increase as
dramatically as polymerization progresses. For this reason, the emulsion polymerization process offers
excellent heat transfer and good temperature throughout the course of polymer synthesis. This process is
always chosen when the polymer product is used in latex form.

In emulsion polymerization, free-radical propagation reactions take place in particles isolated from each
other by the intervening dispersion medium. This reduces termination rates, giving high polymerization
rates, and simultaneously makes it possible to produce high molecular weight polymers.
200 10 Emulsion Polymerization Model
One can increase the rate of polymerization without reducing the molecular weight of the polymer.
Emulsion polymerization has more recently become important for the production of a wide variety of
specialty polymers.
Particle Formation
To appreciate the complexities of emulsion polymerization, a basic understanding of the fundamentals of
particle formation and of the kinetics of the subsequent particle growth stage is required. A number of
mechanisms have been proposed for particle formation. It is generally accepted that any one of the
mechanisms could be responsible for particle formation depending on the nature of the monomer and the
amount of emulsifier used in the recipe.
The two common mechanisms for particle formation are:
Micellar nucleation
Homogeneous nucleation
With micellar nucleation, micelles, which are aggregates of emulsifier molecules, act as the site of
nucleation.
With homogeneous nucleation, the radicals produced in the aqueous phase polymerize with dissolved
monomer and precipitate out to form precursor particles. The precipitated precursor particles coagulate
with each other until a stable particle is formed.
Micellar Nucleation
Micellar nucleation is considered to be the primary mechanism for particle formation (Harkins, 1945;
Smith & Ewart, 1948) in those emulsion polymerization systems for which the monomer is very sparingly
soluble in water, and where the concentration of emulsifier is above the critical micelle concentration
(CMC). As the name implies, the micelles, which are formed when the emulsifier concentration is above
the CMC, act as the site for particle nucleation.
The reaction mixture consists of water, monomer, emulsifier and a water- soluble initiator. The monomer
is dispersed in the form of droplets in the water by agitation. The droplets formed are stabilized by the
emulsifier molecules which are adsorbed on the droplet surface. In addition to the droplets, monomer is
also found dissolved in the aqueous medium and solubilized inside the micelles.
Similarly, the emulsifier is found in three locations: in the micelles, dissolved in the aqueous medium, and
adsorbed on the monomer droplets. Since a water soluble initiator is used, the initiator molecules will be
mainly found dissolved in the water medium.
When a typical emulsion polymerization recipe is heated, the initiator dissociates in the aqueous medium
and produces initiator radicals. Upon propagating with monomer in the water phase the initiator radicals
form oligomeric radicals and enter the micelles, which are aggregates of emulsifier molecules inside
which a small amount of monomer is entrapped. The capturing of a radical by micelle and reaction with
the entrapped monomer signifies the formation of a particle from a micelle. As the propagation takes
place in the newly created particle, a thermodynamic potential difference is created for the diffusion of the
monomer from the monomer droplets into the growing particles.
As the particles grow, some of the micelles disintegrate and cover the growing particles to stabilize them.
Therefore, the micelles are not only consumed in the formation of polymer particles, but also in the
stabilization of growing polymeric particles. In fact, approximately one percent of the micelles are used in
the formation of particles. When no micelles remain in the reaction mixture, micellar nucleation ceases.
Stage I
The time required for particle nucleation to be complete is also called the nucleation time or the
nucleation period, and usually lasts 10-15 minutes in conventional polymerization systems. This is
commonly referred to as the seed stage, or Stage I, in the emulsion polymerization industry. After the
nucleation or seed stage, the number of particles in the reaction mixture remains constant if particles do
not agglomerate.
Stage II
The stage following the seed stage is called the growth stage or Stage II of the emulsion polymerization.
In Stage II, the polymer particles grow through a steady diffusion of monomer from the monomer droplets
to the particles. Since the number of particles remains constant and the particles are saturated with
monomer, this stage is marked by a constant rate of polymerization and could easily be observed on a
conversion vs. time plot. Stage II is considered complete when the monomer droplets are totally depleted.
Stage III
In Stage III, the monomer finishing stage, the reaction mixture consists of the monomer swollen polymer
particles and the aqueous medium. Further polymerization of the monomer in the particles takes place.
This results in a decrease of the particle size due to higher density of the polymer compared to the
monomer. During Stage III, the concentration of monomer dissolved in the aqueous phase falls rapidly, as
does the concentration in the polymer particles. The final product obtained at the end of Stage III is called
latex.
The following figure illustrates the stages in a micellar nucleation emulsion polymerization reaction:
Particle Number and Nucleation Time
The number of particles, usually in the range of 1016
to 1018
per liter of latex, is an important
parameter in emulsion polymerization. Smith and Ewart have derived mathematical expressions for the
number of particles under the following assumptions (Smith & Ewart, 1948):
Particles as well as micelles are equally effective in capturing radicals from the aqueous phase
Temperature of the reaction is constant
Volumetric growth rate of polymer particles is constant
With these assumptions, the particle number and nucleation time are given by the following equations:
4.0 N
p
=
37.0
NR
aI q
s
( EA s
) 6.0
(3.2)
t
v
nuc
=
0.
65
vq
061
.0.
4
ARIs
E
Na
(3.3)
RIN
a
is the rate of generation of radicals in the water phase, and

qv
s
is the volumetric growth

rate of swollen polymer particles. They are determined from the following equations:
R I = 2 fk d
I
(3.4)
qv
s
=
kpMp
nN
a
MW d
pm
1
p
(3.5)
Where:
f = Initiator efficiency
k
d
= Rate constant for initiator dissociation

I = Initiator concentration
N
a
= Avogadro's number
k
p
= Propagation constant
M
p
= Monomer concentration inside the particles

n = Average number of radicals per particle MW
m
= Molecular weight of the monomer
d
p
= Density of polymer
= Volume fraction of polymer in the particle phase
Homogeneous Nucleation
Homogeneous nucleation is the mechanism for particle formation when monomers are more water
soluble and level of emulsifier is not high enough for the formation of micelles in the recipe.
The following figure shows a detailed picture of kinetic events that take place during particle formation by
homogeneous nucleation:
When the reaction mixture is heated the initiator molecules dissolved in the water medium dissociate and
produce the initiator radicals. These initiator radicals react with the dissolved monomer and quickly
propagate into an oligomeric radical in the water phase.
As the size of the oligomeric radical increases it becomes insoluble in water and precipitates out of the
water phase. This event signifies the formation of a primary polymer particle from the growing oligomeric
radical in the water phase. However, these primary particles are not stable, and, hence, coagulate with
each other until enough surface charge is developed to stabilize the particles. These surface charges are
provided by the ionic end of the initiator molecules. In addition, the coagulated particles are also stabilized
by ionic and non-ionic emulsifier added to the emulsion recipe.
Once a stabilized particle is formed, it grows by getting a steady supply of monomer from monomer
droplets by diffusion. As the particles grow and
become large, the oligomeric radicals that are formed in the water phase are directly absorbed by the
particles. After sufficient number of particles are formed that are able to absorb all of the radicals in the
water phase, no new particles are formed in the water phase and the number of particles becomes
constant. Also in homogeneous nucleation the particle number reaches a constant value, as in micellar
nucleation. The subsequent growth stage is similar to the growth stage in the micellar nucleation.
Particle Formation Rate

The rate of particle formation by homogeneous nucleation can be derived by considering the water phase
kinetics and rate of precipitation of the polymers at an assumed critical chain length (jcr). Assuming the
aggregation number ( N
agg
) for the formation of stable particles from the precipitated precursor

particles, the rate of particle formation by homogeneous nucleation is given by:
R
homo
= dN dt
=
Na(i+
k de nN N agg
/
N
a
k pw M w k pw + k tw R w
+Mkw
ap A p +
k am A
m
jcr
+
1
In the above equation R

w
refers to the concentration of live radicals in the water phase and is given
by:
R
w
=
k(i+
k de nN / N
a
jcr
+
pw M w + k tw R w
+ k ap A p +
k am A m
1

-
-
1
Where:
=
k pw M
w k pw M w + k tw R w
+ k ap A p + k am A
m
Refer to the table of page 208 for the explanation of the symbols in the above equations.
Particle Growth
Stage II, the growth stage, starts after the completion of the seed stage in the in situ seed process . In the
in situ seed process, the micelles are used for the generation of the seeds. In the case of an external
seed process, a well characterized seed is used as the starting material for emulsion production. If quality
control tests indicate that the particle number and particle size distribution of the seed particles will not
result in the desired end-product specifications, the batch is normally terminated. Therefore, in the growth
stage it can be assumed that the desired number of particles, with the desired particle size distribution
has already been formed.
It is generally agreed that the growth process is a well understood process and amenable to control. The
growth reaction is responsible for developing molecular properties (molecular weights, composition, etc.)
and morphology (core-shell, particle size distribution). Since the growth reaction lasts about
10-12 hours, there is great potential for optimizing the reaction time by increasing temperature or by
keeping the particles saturated with monomer.
Once inside a particle, radicals induce the usual free-radical polymerization steps such as propagation,
termination, chain transfer, etc. A growing radical can escape from a particle and return to the aqueous
medium to participate in an aqueous phase termination reaction or enter into another particle. During
Stage II, monomer continuously diffuses from the monomer droplets into the particle phase, providing a
steady monomer supply for the growing polymer particle.
As the particles grow, the emulsifier molecules are continuously adsorbed onto or desorbed from the
particles to maintain thermodynamic equilibrium. This dynamic exchange between various phases when
added to the regular polymerization kinetics makes emulsion polymerization a more complex process
than bulk or solution polymerization processes. The following figure illustrates the transport processes
and reactions in a latex particle:
Radical Balance
The radical balance in the aqueous phase is controlled by the kinetic events that are responsible for the
radical generation and the radical consumption in
that phase. Radicals are generated in the dispersant phase by two kinetic events:
Initiator decomposition in the aqueous phase
Desorption of radicals from the particle phase into the aqueous phase
Radicals are depleted from the aqueous phase by two kinetic events:
Termination of a live radical with another live radical in the aqueous phase
Diffusion of a radical from the aqueous phase into a particle or a micelle
Aqueous Phase Rate

The rate of production of radicals in the aqueous phase is considered equal to the rate of depletion of the
radicals from the aqueous phase. This is an application of the stationary state hypothesis or quasi-steady-
state approximation (QSSA):
k de N p n + R I N a = k a R w N a + 2 k tw R w 2
N
a
(3.6)
The previous equation can also be written as:
= + mn - Y 2
(3.7)
With:
=
vN2
=
2 v = wa
(3.8)
tpp
= as NRk awa kN
tpp
kN
Rk
v2
(3.9)
m
RIsN
aNpk
tp
kv
Nk
(3.10)
Y
=
de s a
tp
=
2
N p k tp k
tw k a 2 v
sN
a 2 (3.11)
The emulsion polymerization model nomenclature is shown here:
Symbol Description
a
m
Area of a single micelle (m3)
a
p
Area of a single particle (m3)
A
m
Area of micelles (m2/m3 of aqueous phase)
A
p
Area of particles (m2/m3 of aqueous phase)
As Area coverage by emulsifier (m2/kmol) d
p
Density of polymer (kg/m3)
E Emulsifier concentration (kmol/m3) F ( )v , t Volume density function for particle size distribution (m-3)
Symbol Description
f Initiator efficiency
[ ]I Initiator concentration in the aqueous phase (kmol/m3)
k
a
Absorption constant for particles (s-1)
jcr Critical chain length
p
Volume fraction of polymer in polymer particle
k
d
Initiator dissociation constant (s-1)
k
de
Rate constant for the desorption of radicals from the particles (m3/s) k
am
Rate constant for the absorption of radicals by micelles (m/s) k
ap
Rate constant for the absorption of radical by the particles (m/s) k
p
Rate constant for propagation in particle phase (m3/kmol-s)
k
pw
Rate constant for propagation in the aqueous phase (m3/kmol-s) k
act ij Rate constant for activated initiation (m3/kmol-s)
k
ox ij Rate constant for oxidation (m3/kmol-s)
k
re ij Rate constant for reduction (m3/kmol-s)
k
tw
Rate constant for the termination in the aqueous phase (m3/kmol-s) K
i
pm Partition coefficient for the i-th component between polymer
particles and monomer droplets M
p
Concentration of monomer in the polymer phase (kmol/m3)
Mw
m
Molecular weight of monomer (kg/kmol)
M
w
Monomer concentration in aqueous phase (kmol/m3)
n Average number of radicals per particle N
p
Number of particles per unit volume of aqueous phase (no./m3) N
a
Avogadro number
N
agg
Aggregation number
N
n
Number of particles containing n radicals per unit volume (no./m3-s) R
homo
Rate of particle generation by homogeneous nucleation (no./m3-s)
R
w
Radical concentration in the aqueous phase (kmol/m3)
R
I
Rate of initiator dissociation (kmol/m3-s)
t
nuc
Nucleation time(s) v
Volume of a single unswollen particle (m3)
Symbol Description
v
m
Volume of a single micelle (m3)
v
h
Volume of a single particle formed by homogeneous nucleation (m3) qv Volumetric growth rate of a single particle
(m3/s) v
s
Volume of a swollen particle (m3)
qv
s
Volumetric growth rate of a swollen particle (m3/s)
Rate of radical absorption by N

p
particles (Kmol/s)
i
Total rate of radical generation (Kmol/s- m3)
0
Zeroth moment of the particle size distribution (no./m3 of aqueous phase)
1
First moment of the particle size distribution (m3/m3 of aqueous phase)
2
Second moment of the particle size distribution (m6/m3 of aqueous phase)
3
Third moment of the particle size distribution (m9/m3 of aqueous phase)
Particles containing n radicals are produced by three kinetic events:
Absorption of a radical from the aqueous phase by a particle containing (n-1) radical. The total rate of
this event is given as:
Nn
-1
N
p
Radical desorption from a particle containing (n+1) radicals. The total rate of this event is given as: kN
de1n+ 1)(n+ Termination in a particle containing (n+2) radicals. The total rate of this
reaction is given as:
nnkN
n
+
2
tp )]1)(2[(
++v
Particle Phase
Particles containing n free-radicals are depleted in the particle phase in three analogous ways. By
equating the rate of formation to the rate of depletion of particles containing n free-radicals the recurrence
formula is obtained:
Nn-1
(
nkNNN a /
p ) + n + 1 de ( + 1 ) + kN n + 2 tp
)1)(2(
n
+
n+N
a
=
knkNNN
n
()
a/
p + de + nn
)1( - tp N
a
v
(3.12)
This recurrence formula was first developed by Smith and Ewart, in a slightly modified form (Smith &
Ewart, 1948). Equation 3.12 can be solved for the
average number of radicals per particle, n . The general solution as given by O'Toole is as follows
(O'Toole, 1965):
n
=
aI m
(a
)4
Im
-
1
(a
) (3.13)
In Equation 3.13, I m
(a
) and I m-1
(a
) are modified Bessel functions of the first kind with parameters m
and a. Equation 3.10 gives the definition of m. a is calculated as a function of , defined in Equation 3.8,
according to:
a = 8 (3.14)
The simultaneous solution for n (Equation 3.13) and the stationary steady state equation for the radical
balance in the aqueous phase (Equation 3.6) completely define the kinetics of the emulsion
polymerization.
Kinetics of Emulsion Polymerization

A general emulsion polymerization kinetics scheme involves simultaneous free-radical polymerization
taking place in the dispersant phase, particle phase and the monomer droplet phase. However, in general
the monomer droplet phase is regarded as an inert phase supplying monomer to the particle phase
during reaction. In conventional emulsion polymerization, initiator decomposition takes place in the
dispersant phase and the initiator radicals enter the polymer particle phase.
The polymer particle phase is considered to be the site for all the polymerization reactions. There is a
dynamic exchange of radicals between the particle phase and the dispersion phase. The average number
of radicals per particle is dependent on the steady state that is reached as a result of this exchange. The
free-radical kinetics scheme used in the model is that used in the free-radical polymerization model.
Emulsion polymerization can handle activated initiation, redox initiation, absorption and desorption, and
much of the kinetics described in the free free-radical Reaction Kinetic Scheme section on page 165, but
not short chain branching or beta scission.
Activated Initiation
The mechanism for activated initiation is given as:
Ik+Aj
- - kj
nR+x
*
Where:
I
k
k
act
kj
= Initiator molecule
A
j
= Activator molecules which promote the dissociation of

the initiator molecules
R = Primary radical produced in the initiation reaction
x * = Waste products that do not participate in the
polymerization reactions
In emulsion polymerization water soluble persulfate initiators are normally employed as initiators. In
addition, water soluble sodium bisulfite is used as an activator in many emulsion polymerization reactions
for accomplishing activated initiation of persulfates.
For the above given mechanism, R
act kj
, the radical generation rate for activated initiation, is given by

the following equation:
R
act kj
= dR
dt
=
n kj f kj k act kj
CIkC
A
j
Where:
k
act kj = Rate constant for activated initiation
C
I
k
= Concentration of initiator in the aqueous phase

C
A
j
= Concentration of activator in the aqueous phase

n
kj
= Number of radicals produced per initiator molecules

f
kj
= Efficiency factor
Redox Initiation
The mechanism for redox initiation is given as:
FeI
k
+ ++
- - k ox k
FeRn k
+ +++ + *Y (oxidationslow)
Fe
+++
+ Re - - k re
Fe ++ + *x (reductionfast)
Similar to activated initiation, redox initiation is used in emulsion polymerization reactions to promote
decomposition of initiators at a much lower temperature. For example, redox initiation is employed in cold
rubber production. It is also used in emulsion polymerization reactions where high radical flux is needed.
Ik
(the initiator, oxidant, or sometimes catalyst) decomposes in the presence

of the reduced (ferrous) ions, Fe++, to form one free radical, R
, and the oxidized (ferric) ion,

Fe+++. The reductant, Re, reacts with the ferric Fe+++ ion reducing it to ferrous Fe++. x* and Y* are
inactive byproducts of the reactions.
The activator system (or redox couple), a Ferrous salt (e.g. ferrous sulfate heptahydrate) plus a reductant
(e.g. SFS, Sodium Formaldehyde Sulphoxylate), activates the initiator and regenerates the ferrous ion as
previously shown.
Multiple initiators are common: for example, KPS (Potassium persulfate) and tBHP (tert -butyl
hydroperoxide). KPS is used initially. At high conversion, the monomer concentration in the polymer
phase is low and the
OS 42 -
radicals cannot diffuse into

the polymer phase because they are hydrophyllic. tBHP,
on the other hand, partitions into both the aqueous and the polymer phases and is, therefore, used for
finishing in redox systems.
In the case of two initiators, two oxidation reactions and one reduction reaction should be specified.
As the ferrous and ferric ions get regenerated in the redox reaction, it is assumed that the total iron
concentration remains constant in the reaction. As the rate of reduction is much faster than the rate of
oxidation, a stationary state hypothesis is assumed for the ferrous and ferric ions.
Assuming stationary state hypothesis for the ferric and ferrous ion concentration in the redox initiation
mechanism, one can derive an equation for the rate of generation of the radicals by the redox initiation as
follows:
dR
CCk
red
Fe Re
Ckfn oxkk k
I dt
k
CkCk
k
red
Re
Where: C
Fe t
t
k ox
kkI
+
= Total concentration of the iron in the aqueous phase
k ox k
= Rate constant for oxidation step of initiator k

k red
= Rate constant for reduction step
C
I
k
= Concentration of initiator k in the aqueous phase

C Re
= Concentration of reductant in the aqueous phase

nk
= Number of radicals produced per initiator molecule, k

(default=1)
fk
= Efficiency factor for initiator k (default=1)

In thermal decomposition, typically each initiator molecule produces two radicals. The cage effect is when
the radicals annihilate each other before they are able to diffuse out of the cage into the aqueous phase.
This effect is captured by the radical efficiency term for thermal decomposition.
In redox initiation, only one radical is generated from the initiator. Consequently, there is no cage effect
because there is only one radical in the cage. Therefore, in redox initiation, there is typically no need for
the two parameters:
nk
(number of radicals per initiator molecule) and

fk
(radical efficiency). However,

these parameters are provided and defaulted to a value of 1 to provide additional handles for the user to
fit their model to plant data.
Absorption and Desorption

In addition, there is an exchange of radicals between the aqueous phase and the polymer phase.
Radicals generated in the aqueous phase are absorbed by the micelles during micellar nucleation and by
the particle during nucleation and subsequent growth. Radicals in the polymer phase can desorb from the
particle and enter the aqueous phase. The kinetics of absorption and desorption are described as follows:
Absorption by particles:
R
j+Ni
- -
k
ap
N
i
+
1
R ap =
k ap aC p N
i
C
R
j
Absorption by micelles:
Rj+Nm
- -
k
am
N
1
R am =
k am a m C N
m
C
R
j
Desorption:
Ni
k
Ni
1
R

R de =
k de iC
N
i
Where: a
m
- - de
-
+
= Area of a single micelle
a
p
= Area of a single particle

N
m
= Number of micelles with i radicals per cubic meter of

aqueous phase N
i
= Number of particles with i radicals per cubic meter of

aqueous phase
Reaction Rate Constant

The rate constant for each reaction in the built-in kinetics is calculated at the reaction temperature and
pressure using the modified Arrhenius equation with user specified parameters for frequency factor,
activation energy, activation volume, and reference temperature:
kk =
exp
-
R Ea
-
VP
11
-
ref
Where:
k
o
o
TTR
= Pre-exponential factor in l/sec for first order reactions,

and m 3 / kmol - s for second order reactions
Ea = Activation energy in mole-enthalpy units
V = Activation volume in volume/mole units
P = Reaction pressure
T = Reaction temperature
T ref
= Reference temperature
The second term in the exponential function contains the activation volume and is important for high
pressure polymerization systems. For detailed
information of the reactions, see the free-radical Reaction Kinetic Scheme section on page 165.
Rate constants related to absorption by particles, absorption by micelles and desorption from particles are
given by the Arrhenius expression as:
k=
k
o
exp
Ea RT -
assuming zero activation volume.

Following are the model features and assumptions used in the emulsion polymerization model available
in Aspen Polymers.
Model Assumptions
The emulsion polymerization process is extremely complex and involves phenomena for which a
complete theoretical understanding has not been reached. Important assumptions are made in the
emulsion polymerization model:
The reaction mixture is perfectly mixed
Particles are formed by the micellar or the homogeneous mechanism
No agglomeration or breakage of particles occurs
No secondary nucleation occurs
All particles have the same average number of radicals and hence the same volumetric growth rate
The particle size distribution is unimodal, with moments of PSD sufficient to describe the PSD
There are no mass transfer limitations on the polymerization reactions
Molecular weight is controlled by chain transfer reactions
Thermodynamics of Monomer Partitioning

Modeling of the kinetics involved in emulsion polymerization is complicated by the fact that the reaction
mixture is multiphase. It is important to account for partitioning of the components among various phases.
Up to four coexisting phases may be present in the reaction mixture. After the consumption of the
monomer droplets, only three phases will remain in the system.
A short-cut partition coefficient methodology was used to handle the four phases. One benefit of using
this approach is that NRTL parameters are not required for the polymer or its segments. The method
assumes the polymer solubility is zero in the monomer, aqueous, and vapor phases and performs a
rigorous 3-phase flash calculation to yield:
Vapor phase - if present, contains water and monomers
Dispersion phase - contains water, initiators, emulsifiers, activators and some dissolved monomer
Monomer phase - contains monomer and some dissolved water
The user provides a partition coefficient for each component that may be present in the polymer phase.
Following the rigorous 3-phase flash, an iterative algorithm calculates the amount of each component to
transfer from the monomer phase, if present, and the aqueous phase to the polymer phase in order to
satisfy the partition coefficient constraints. As monomer is transferred to the polymer phase, water is
transferred from the monomer phase to the aqueous phase so that its concentration in the monomer
phase is the saturation concentration calculated by the rigorous flash.
The user-supplied partition coefficients are provided as either:
Monomer (L1) basis
xkx
pi
=
1 i * 1 i Aqueous (L2) basis
xkx
pi
=
i 2 * 2 i In either case, the partition coefficients are on a mass basis.
This scheme works equally well for monomer starved or monomer saturated situations. When the
monomer phase collapses, the algorithm transfers monomer from the aqueous phase to the polymer
phase. If the user provided partition coefficients on a monomer basis, the partition coefficient with respect
to the aqueous phase is calculated as:
kkk i
2=
1 i / LL i k i
LL
values are only available when there is sufficient monomer present in the swollen polymer particles
to form a separate monomer phase if polymer were removed. If the 3-phase flash does not detect a
separate monomer phase, k i
LL
values will not be available, and the algorithm will transfer all monomer from the aqueous phase to
the polymer phase.
In addition, there are two rigorous phase equilibrium approaches to handle the thermodynamics of
monomer partitioning. The first rigorous approach assumes the presence of two liquid phases. The
distribution of water, monomers, and polymers is determined by isofugacity relationships, and the
fugacities of various species are computed by the physical property option set chosen for the system. The
second approach performs rigorous four phase (vapor-liquid-liquid-polymer) flash calculations based on a
newly available flash algorithm.
Polymer Particle Size Distribution

Polymer particle size and size distribution, among other factors, determine the rheological properties of
the latex . Although actual particle size distribution is important, it is often measured in terms of certain
averages such as number average and weight average diameters. Further, rigorous tracking of the
particle size distribution by discrete methods is computationally expensive.
In conventional emulsion polymerization where unimodal distributions are normally encountered, the
moments of the particle size distribution give sufficient information about the nature of the particle size
distribution. The particle size distribution can be described in terms of different independent variables
such as diameter or volume of the particle. Since volumetric growth rate of the particle in emulsion
polymerization remains almost constant in Stage I and Stage II of the process, the population balance
equation is formulated in terms of the volume of the particles.
General Population Balance Equation

The general population balance equation for the emulsion polymerization is given as follows:
F(v,t)t
+
(vqF(v
,
t
))
v
= k am AN m a
[R
]w
(v-v)+R
homo
(v-v
)
(3.15)
In Equation 3.15 the right-hand side represents the nucleation of particles from miceller and
homogeneous nucleation. Refer to the table on page 208 for an explanation of the variables used. The
volumetric growth rate is qv for a single unswollen particle (Equation 3.5):
qv =
mh
kpMp
n
MW
mN
a
d
p
(3.16)
The general population balance equation can be converted to the equivalent moment equations. The j-th
moment of the particle size distribution is given as:
j
=
jF ( , j )
d
(3.17)
0
Applying moment definition in Equation 3.17 to the general population balance equation in Equation 3.15,
the first four moments of the particle size distribution are given as:
d
0 dt
= k am AN m a [ R ]
w
+R
homo
(3.18)
d
1 dt
=vq0
+ v m k am AN m a [ R ] w + v
h
R
homo
(3.19)
d
2 dt
=2vq1
+ v 2 m k am AN m a [ R ] w + v
2h
R
homo
(3.20)
d
3 dt
=3vq2
+ v 3 m k am AN m a [ R ] w + v
3h
R
homo
(3.21)
Where:
k
am
= Kinetic constant for the absorption of the oligomeric

radicals into the micelles
A
m
= Area of the micelles

R
homo
= Rate nucleation
of particle formation by homogeneous
Polymer Particle Properties Calculated

The emulsion model is designed to generate the following results that are of interest for the emulsion
polymerization process:
Copolymer composition
Number average molecular weight
Particle size distribution averages for unswollen particles
The results are available as component attributes under the names listed here:
Name Symbol Description Class Units
PSDZMOM
0
Zeroth moment of the particle size distribution (volume)
2 no./s
PSDFMOM
1
0 m3/s
PSDSMOM
2
First moment of the PSD (volume)
2 m6/s
PSDTMOM
3
Second moment of the PSD (volume)
2 m9/s
VOLN V
n
Third moment of the PSD (volume)
0 m3
VOLV V
v
Number average volume of the particles
0 m3
VOLZ V
z
Volume average volume of the particles
0 m3
DIAV D
v
Z-average volume of the particles Volume average diameter
0m
PDV PD
v
Polydispersity for PSD (Volume)
0 ---
SFRAC --- Copolymer
composition
0 ---
MWN --- Number average
molecular weight
0 kg/kmol
User Profiles
In addition to the polymer properties reported through the component attributes, other model calculations
are reported through User Profile variables. The following user profile variables may be requested from
the model:
Glass transition temperature of the polymer (C)
Average number of radicals per particle
% Soap coverage of the polymer particles
Volume of the monomer droplet phase (m3)
Concentration of monomers in the monomer droplets (kmol/m3)
Volume of the aqueous phase (m3)
Monomer concentration in the aqueous phase (kmol/m3)
Volume of the polymer particle phase (m3)
Monomer concentration in the polymer particles (kmol/m3)
Monomer conversion
One profile is reported for each monomer.
User profiles are only accessible if the reaction model is called from a batch reactor (RBatch) or a plug
flow reactor (RPlug). The user profiles are returned in the order shown. A label must be provided to
differentiate the profile variables. For the monomer concentrations in the aqueous, monomer, and
polymer phases one profile is returned for each monomer.
Specifying Emulsion Polymerization

Kinetics
Accessing the Emulsion Model
To access the Emulsion polymerization kinetic model: 1 From the Data Browser, click Reactions. 2 From
the Reactions folder, click Reactions. The Reactions object manager appears. 3 If the kinetic model
necessary, change the default ID for the reaction. 5 Select Emulsion as the reaction type and click OK.
Specifying the Emulsion Model

The Emulsion model input forms are divided into two folders: Specifications and Phases.
Use the Specifications forms to define reacting species and enter reaction rate constant parameters. Use
the following options:
Use this sheet To
Summarize rate constant parameters
Options Select additional options Gel Effect Gel-effect correlation parameters
Use the Phases forms to enter information related to phase partitioning and particle growth. Use the
following options:
Use this sheet To
Phase Equilibria Specify component phase split Particles Specify emulsifiers and define particle radical
exchange information

You must specify the reacting species in the Specifications Species sheet: 1 In the Polymer field, specify
the polymer produced. Also specify
Dispersant and the Redox couple (ferrous salt and reductant) if redox initiation is used. 2 In the
Monomers field list the reacting monomers. For each monomer, in
the goes to field, specify the polymer segment that the monomer converts to. 3 Continue listing other
types of reacting species, e.g. initiators, transfer
agents, etc. 4 Select the Generate Reactions option if you want the reactions to be
Listing Reactions
The Emulsion model generates reactions based on the list of reacting species. You can view the system-
generated reactions, then assign rate constant parameters to these reactions.
You can view a list of the system-generated reactions on the Specifications Reactions sheet. In the
Reaction summary listing for each reaction, the first column indicates the reaction type. The second
column lists the reactants, and the last column lists the products. The Data Browser window can be
resized to better view the reaction listing. Use the following options:
Click To
reactions
Click To
Hide/Reveal
a reaction from the
Delete
Adding Reactions
To add a new reaction to the scheme, click New to open the Add Reaction subform: 1 In Reaction type,
select a type for the new reaction. The Reaction scheme for that type is displayed. 2 In other reactant (for
example, Initiator, Catalyst) fields, enter the
reactants of the categories allowed for that reaction type. 3 Click Cancel to discard the new reaction
Editing Reactions

subform: 1 In the Pre-Exp (k_ref) field, enter the pre-exponential factor. 2 In the Act-Energy (Ea) field,
enter the activation energy. 3 In the Act-Volume (V) field, enter activation volume. 4 In the Ref. Temp.
(Tref) field, enter reference temperature. 5 In the Efficiency field, enter initiator efficiency for initiation
reactions.
6 In the No. radicals field, enter the number of primary radicals formed in
initiation reactions. 7 Click the stoichiometry list and select a new reaction. Enter rate constants
list. 8 Click the Summary tab to see a listing of all the rate constant
parameters.
Selecting Calculation Options

You can select additional simulation options for the model, such as gel-effect, on the Options sheet.
For Gel effect, you need to specify parameters on the Gel Effect sheet.
Adding Gel-Effect
Use the Gel-Effect sheet to add gel effect to reactions: 1 Enter a unique integer identifier in No. 2 In the
Reaction field, specify the reaction to which you would like to
apply gel effect. 3 In the Corr. No. field, specify a gel effect correlation number. 4 In Parameters, list
the parameters for the gel effect correlation.
Specifying Phase Partitioning

Use the Phases Phase Equilibria sheet to specify phase partitioning for the components in the emulsion
system: 1 If you select a Rigorous approach, specify a Method. 2 If you select the Partition Coefficients
approach, in the Basis field
select the phase partitioning basis, for example, MONOMER or AQUEOUS 3 For each component
present in the polymer phase (except the polymer),
specify the split fraction using the Component and Coefficient fields.
Specifying Particle Growth Parameters
Use the Phases Particles sheet to specify data for particle generation and particle related events: 1
Define Emulsifier, and specify critical micelle concentration, CMC, and
surfactant Area. 2 For homogeneous nucleation, specify Aggregation number and Critical
length.
You must specify radical absorption and desorption rate constant parameters for micelles and particles.
References
Barton, J., & Capek, I. (1994). Radical Polymerization in Disperse Systems. New York: Ellis Harwood.
Blackley, D. C. (1975). Emulsion Polymerization: Theory and Practice. London: Applied Science
Publishers Ltd.
Gilbert, R. G. (1995). Emulsion Polymerization: A Mechanistic Approach. Boston: Academic Press.
Hamielec, A. E., & Tobita, H. (1992). Polymerization Processes. In Ullmans Encyclopedia of Industrial
Chemistry, A21, 305. New York: VCH Publishers.
Harkins, W. D. (1945). J. Chem. Phys., 13, 301.
Odian, G. (1991). Principles of Polymerization, 3rd. Ed. New York: John Wiley & Sons.
OToole, J. T. (1965). Kinetics of Emulsion Polymerization. J. Appl. Polym. Sci., 9, 1291.
Poehlein, G. W. (1986). Emulsion Polymerization. In H.F. Mark, N. M. Bikales, C. G. Overberger, and G.
Menges, (Eds.). Encyclopedia of Polymer Science & Technology, 6, 1. New York: Wiley-Interscience.
Ponnuswamy, S. R., & Hamielec, A. E. (1997). Emulsion Polymerization: Theory and Practice. Lecture
notes for intensive short course on polymer reaction engineering held at Burlington, ON, Canada, April
28-30.
Smith, W. V., & Ewart, R. H. (1948). J. Chem. Phys., 16, 592.
11 Ziegler-Natta Polymerization
Model
This section covers the Ziegler-Natta polymerization kinetic model available in Aspen Polymers (formerly
known as Aspen Polymers Plus). The term Ziegler- Natta polymerization is used here to describe a
variety of stereospecific multi- site and single site catalyzed addition polymerization systems including the
traditional Ziegler-Natta catalyzed systems, chromium based catalyzed systems (Phillips type) and the
more recent metallocene based catalyzed systems.
Ziegler-Natta Processes, 226
Specifying Ziegler-Natta Polymerization Kinetics, 244
Several example applications of the Ziegler-Natta polymerization model are given in the Aspen Polymers
Examples & Applications Case Book. Additionally, the Examples & Applications Case Book provides
process details and the kinetics of polymerization for specific monomer-polymer systems.
The Ziegler-Natta polymerization model is applicable to processes utilizing coordination catalysts for the
production of stereospecific polymers.
Some examples of applicable polymers are:
Linear low density polyethylene - Ethylene is copolymerized with an alpha- olefin, such as 1-butene, 1-
hexene, or 1-octene. Commercial processes include low pressure, slurry-phase processes, solution-
phase processes, low pressure, gas phase processes.
High density polyethylene - Ethylene homopolymers or copolymers with high alpha olefins with density
0.940 g / cm3
and higher. Commercial
11 Ziegler-Natta Polymerization Model 225
processes include solution, slurry or suspension, and gas phase polymerization.
Ethylene-propylene elastomers - Polymerization proceeds by solution or slurry processes. Both are
operated continuously in liquid-phase back- mixed reactors.
Polypropylene - Commercial processes include liquid pool, diluent slurry, and gas phase polymerization.
Ziegler-Natta Processes
Ziegler-Natta polymerization accounts for a significant fraction of the polyethylene polymers and all the
polypropylene homopolymers and copolymers produced commercially. The commercial production of
these polyolefins is done exclusively by continuous processes using several different processes and
reactor types operating over a wide range of conditions.
High density polyethylene (HDPE) and linear low density polyethylene (LLDPE) are produced via
catalyzed polymerization processes. The operating conditions for the catalyzed processes are relatively
less severe compared to the high pressure processes for LDPE production. The pressure generally
ranges from 10-80 atm while the temperatures range from 80-110C. The pressure and temperature may
be as high as 200 atm and 250C in some of the solution polymerization processes.
Catalyst Types
There is a variety of catalysts used for ethylene polymerization including supported and unsupported
heterogeneous catalyst systems and homogeneous catalyst systems. The Ziegler-Natta transition metal
(Ti) based catalysts are the most widely used.
However, there are numerous variations of these catalysts. Some vanadium based catalysts are also
used. Chromic oxide on silica catalysts are used in the Phillips loop reactor process, while the Union
Carbide Unipol process may use either Ziegler-Natta (Ti) or chromium compounds on silica catalysts.
More recently, several manufacturers have been developing commercial processes using metallocene
based catalysts, mainly zirconium and titanium. These catalysts are believed to be single site catalysts
that are capable of producing high yields, combined with narrow molecular weight and copolymer
composition distributions.
All commercial isotactic polypropylene homopolymer (PP) is manufactured using heterogeneous Ziegler-
Natta catalyst systems. The catalyst consists of a solid transition metal halide, usually TiCl
3
, with an organoaluminum compound cocatalysts, such

as diethylaluminum chloride (DEAC), or a MgCl
2 supported TiCl 4
. AlEt
3
catalyst.
226 11 Ziegler-Natta Polymerization Model
Ethylene Process Types
There are three types of catalyzed ethylene polymerization processes in commercial use today:
Liquid slurry
Solution
Gas-phase
A partial list of HDPE and LLDPE processes, along with a summary of their characteristics is shown here:
Process Reactor Diluent /
Solvent
Catalyst Temp.
(C)
Press. (atm)
Residence Time (hr)
Company
Liquid slurry
Loop i-butane
n-hexane
Supported Ti or Cr
80-100 30-35 1.5-2.5 Phillips Solvay
CSTR n-hexane Supported
Ti
80-90 8-35 2.0-2.7 Dow
Hoechst Nissan Mitsubishi Montedison Solution CSTR n-hexane
cyclohexane
Ti/V 130-
250
30-200 0.08-0.17 Dow
Dupont Stamicarbon Gas Stirred
bed
--- Supported
Ti or Cr
70-110 20-35 3-5 AMOCO
BASF Fluidized bed
--- Supported
Ti or Cr
85-100 20-30 3-5 BP
Union Carbide
In the slurry process, a hydrocarbon diluent is used, typically a C 4 -
C
7 paraffin, isoparaffin or
cycloparaffin. Under the conditions used the polyethylene is essentially insoluble in the diluent. As a result
a slurry is formed.
In the solution process, the conditions used are such that the polyethylene is completely dissolved in the
solvent.
In gas-phase processes, gaseous ethylene and comonomers are contacted with a polymer-catalyst
powder. Polymerization occurs in the monomer- swollen polymer particles which contain embedded
catalyst fragments with active sites.
Ethylene polymerization processes have been reviewed extensively. More detailed descriptions of these
processes are available in the open literature (Albright, 1985; Choi & Ray, 1985a; Nowlin, 1985; Short,
1983).
Propylene Process Types
There are three types of catalyzed polypropylene homopolymerization processes in commercial use
today:
Liquid slurry
Liquid pool (bulk)
Gas-phase
A partial listing of propylene homopolymerizatio processes, along with a summary of their characteristics
is shown here:
Process Reactor Diluent /
Solvent
Catalyst Tacticit
y (%)
Temp. (C)
Press. (atm)
Residenc e Time (hr)
Company
Bulk (Liquid Pool)
Loop Liquid
monomer
Supported Ti Up to 99 60-80 30-40 1-2 Himont
Mitsui
CSTR Liquid
monomer
Unsupported or supported Ti
Up to 98 60-75 30-40 2 Dart
El Paso Montedison Sumitomo Diluent Slurry
CSTR n-hexane, n-heptane
Unsupported or supported Ti
Up to 98 60-80 15-20 3-4 Montedison
Gas Fluidized bed N2 Supported Ti Up to 98 60-80 20 3-5 Sumitomo
Union Carbide Vertical stirred bed
--- Unsupported or supported Ti
Up to 98 70-90 20 4 BASF
ICI USI Horizontal compartment- ed stirred bed
Up to 98 70-90 20 4 AMOCO
In the slurry process, a hydrocarbon diluent, typically butane, hexane or heptane, is used at operating
temperatures of 70-90C. Under these conditions the isotactic polypropylene is essentially insoluble in the
diluent. As a result a slurry is formed.
In the liquid pool process, liquid propylene is used in place of the diluent. In this process also, the
polypropylene is insoluble in the liquid propylene and a slurry is formed. The higher monomer
concentrations in this process allow for smaller reactors and lower operating temperatures compared to
the slurry process.
In the gas-phase processes, gaseous propylene is contacted with a polymer- catalyst powder.
Polymerization occurs in the monomer-swollen particles which contain embedded catalyst fragments with
active sites.
Propylene polymerization processes have been reviewed extensively in the literature. More detailed
descriptions of these processes are available in the open literature (Albright, 1985; Brockmeier, 1983;
Choi & Ray, 1985b).
Besides polypropylene homopolymer (PP), high impact polypropylene (HIPP) and some ethylene-
propylene (EP) copolymers are produced by including an additional reaction stage to the polypropylene
homopolymerization process. A summary of catalyst processes for propylene copolymerization is shown
here:
Process Reactor
Press. (atm) Resi-
Stage
Stage
dence Time 1
2
(hr)
Bulk (Liquid Pool)
+ Second Stage
Diluent / Solvent Catalyst
Temp. (C)
Co- monomers Company
Loop - fluid bed
--- Supported Ti 60-80 30-40 20 1-2 Ethylene &
others
Himont Mitsui
CSTR - CSTR
--- Supported Ti 60-75 30-40 30-40 2 Ethylene Sumitomo
CSTR - stirred horizontal bed
40-75 30-40 20 2-5 Ethylene Dart
El Paso
Diluent Slurry
CSTR Liquid
monomers & diluents
Ti/V 0-20 5-20 --- 1 Ethylene,
Butene, dienes
Montedison Dutral
Multistage Gas
Fluid bed - fluid bed
--- Supported Ti 60-80 20 20 3-5 Ethylene &
others
Sumitomo Union Carbide Vertical stirred bed - stirred bed
--- Unsupported of supported Ti
70-90 20 20 4 Ethylene &
others
BASF ICI USI
Horizontal stirred bed - horizontal stirred bed
--- Supported Ti 70-90 20 20 4 Ethylene &
others
AMOCO Chisso
In the EP process, last reaction stage is designed to introduce the desired amount of EP copolymer into
the PP product. For example, the Himont spheripol process uses liquid pool loop reactors followed by a
gas-phase fluidized bed reactor for the copolymerization stage. The residence time distribution of the
polymer particles leaving each stage should be as narrow as practical to ensure that the weight ratio of
EP to PP for particles leaving the second stage is as uniform as possible. The Amoco/Chisso process has
largely met this requirement.
The built-in catalyst/polymerization kinetic scheme represents the typical scheme described in the open
literature (Xie et al., 1994). Although a number of reaction mechanisms have been proposed to describe
stereospecific Ziegler-Natta polymerization, there is still no definitive reaction mechanism to completely
describe the kinetic behavior of these complex catalyst/polymerization systems.
Most of the proposed mechanisms include a detailed set of reactions. However, not all of these reactions
apply to every catalyst system nor can they be verified. The kinetic scheme for chromium and
metallocene catalyzed systems can be considered to be a subset of a comprehensive Ziegler-Natta
kinetic scheme.
Reaction Steps
There are a few key elementary reactions that apply to almost all catalyzed addition polymerization
systems. These include the three basic reaction steps:
Chain initiation
Propagation
Chain transfer (spontaneous and to small molecules such as monomer, solvent and chain transfer
agents)
For chromium and metallocene catalyst systems, additional reactions for long chain branching via
terminal double bond polymerization must also be included.
In addition to the polymerization reactions, there are reactions affecting the catalyst active sites on which
the polymerization reactions take place. These include catalyst site activation, inhibition and deactivation.
The catalyst reactions and the polymerization reactions occur simultaneously during the polymerization.
A comprehensive kinetic scheme for the catalyzed multi-site homo- and copolymerization of any number
of monomers has been built into Aspen Polymers.
Catalyst States
The multi-site catalyst states and the types of reactions affecting them are shown here:
In setting up a simulation, the user specifies the catalyst flow rate for the feed streams, and a catalyst
parameter, the moles of sites per unit mass of catalyst. This parameter together with the catalysts flow
rate is used to compute the total moles of sites.
The total moles of sites are made up of potential sites, active sites of different reactivities, and dead sites.
Site activation reactions convert potential sites to active sites, while site deactivation reactions convert
active sites to dead sites. There are several different site activation/deactivation reactions built into the
kinetic scheme and these are discussed later in this section.
Site Types
In the figure, potential sites and dead sites are considered to be independent of site type. The user
specifies the number of site types to be included for a particular simulation.
A vacant site is an active site that does not have a polymer or other molecule attached to it.
A propagation site has a growing polymer molecule attached to it.
Inhibited sites have small molecules such as hydrogen or poisons attached, temporarily blocking it from
becoming propagation sites. The small molecule may dissociate from an inhibited sited, which then
becomes a vacant site once again. Therefore, the site inhibition reaction is considered reversible.
When a vacant site is involved in a chain initiation reaction it is converted to a propagation site. When a
propagation site is involved in a chain transfer reaction, a vacant site and a dead polymer molecule are
formed.
The built-in scheme includes most of the reactions commonly used for modeling Ziegler-Natta
polymerization. Reactions such as depropagation, internal double-bond polymerization with diene
comonomers, and site transformation reactions (Debling et al., 1994; Xie et al., 1994) have not been
included in the current model. These reactions may be added to the built-in scheme in the future. The
current built-in Ziegler-Natta catalyst and polymerization kinetic scheme is shown here:
Built-In Ziegler-Natta Catalysts and Polymerization Kinetic Scheme (continued)
continued
Kinetic Scheme Nomenclature

The nomenclature used in the Ziegler-Natta polymerization kinetic scheme is given here:
Symbol Description
A
m
Cocatalysts m
E
m
Electron donor m
Symbol Description
C
ds
Dead catalyst sites
C
ps
Potential catalyst sites
C
is k Inhibited catalyst sites of type k
D
n k Dead polymer chain of length n ( = n 1 , n 2 , ..., n
m
) for copolymerization produced from a catalyst site of type k H
2
Hydrogen
M
j
Monomer j
N
m
Number of monomers
N
sites
Number of active site types
Ok Reaction order for the non-polymer component at site
type k Pk 0
Vacant catalyst sites of type k
P
nk,
i
Live polymer chain of length n having an active segment of type i attached to a active site of type k S
m
Solvent m (for solution or slurry polymerization)
T
m
Chain transfer agent m
X
n
Inhibitor n
k
0,i
Zeroth moment of live polymer with respect to active segment of type i and active site of type k
In the following discussion:
A polymer chain is considered to be made up of monomer units or segments derived from the
propagating monomers
Live chain ( P
nk,
i
)
refers to growing polymer chains containing n segments or monomer units, with an
active segment of type i attached to a catalyst active site of type k
Dead chain ( D
nk
) refers to a terminated polymer chain

The superscript k refers to the active site type from which the dead polymer chain was formed
The subscript n refers to the chain length in terms of the number of segments or monomer units
incorporated in the polymer chain
Live chains are reactive and can participate in the polymerization reactions while dead chains are usually
considered inert, except in cases where long chain branching reactions are important.
Polymerization Mechanism
The catalyst active site is attached to one end of a live polymer chain via a metal-carbon bond. It is
generally accepted that polymerization proceeds via
a two-step mechanism. In the first step, monomer is complexed to the transition metal site. The second
step is the coordinated insertion of the monomer into the metal-carbon bond. As a result, the polymer
chain and the previously added segments grow away from the active site with every addition of a
monomer molecule.
It is believed that the chain microstructure will not have a strong influence on the mode of monomer
addition. For this reason, the built-in kinetic model assumes that the reactivity of a live polymer chain
depends only on the active segment and the active site type, and is independent of the polymer chain
length and other structural properties. Meaning in the propagation reaction, the rate of propagation R
pk,
ij
is independent of the polymer chain length. It

depends only on the concentration of monomer j, and the concentration of live polymer chains with active
segments of type i attached to an active site of type k. Models using this assumption are referred to as
terminal models in the polymerization literature.
Copolymerization Mechanism
For copolymerization, the built-in kinetic scheme allows the user to specify the number of monomer types
used. Similarly the user has the flexibility to specify the number of each type of reactive species present
in the polymerization: catalysts, cocatalysts, chain transfer agents, solvents, etc. The user is able to tailor
the built-in kinetics to model a specific catalyzed polymerization system by selecting a subset of the
reactions shown in the Built-In Ziegler-Natta Catalysts and Polymerization Kinetic Scheme figure on page
232. However, it is important that the subset include a chain initiation, propagation, and at least one chain
transfer or active site deactivation reaction to produce dead polymer.
Rate Expressions
The rate expression for each reaction is generally written as a product of the rate constant and the
concentrations of the reacting species. In many of the reactions, one of the reacting species is a polymer
chain while the other is a small molecule such as monomer, chain transfer agent, cocatalyst, etc. A
reaction order with respect to the small reacting molecule is included for some of the reactions. This
reaction order has a default value of one.
The rate constants for each reaction at sites of type k are calculated at the reaction temperature using the
Arrhenius equation shown below. The user specified rate constant parameters are pre-exponential factor
(k
ok
) , activation energy ( Eak

) at sites of type k, and the reference temperature.
Rate Constant
11 -

ref
Where:
kk
k
=kok
-exp
aE
TTR

k
o
= Pre-exponential factor in 1/sec for first order reactions

and m 3 / kmol - sec for second order reactions
Ea = Activation energy in mole enthalpy units
T ref
= Reference temperature in Kelvin
Catalyst Pre-Activation
Some of the chromium catalysts used in these processes exhibit slow activation with induction period.
This slow activation can be modeled by catalyst preactivation reaction. The precatalyst goes to catalyst
that further undergoes site activation, initiation and propagation.
Catalyst Site Activation

The catalyst site activation step involves the generation of reactive vacant active sites from potential sites.
Depending on the catalysts system, the activation may be done before the catalyst is fed to the reactor or
within the reactor.
There are several different site activation reactions included in the built-in kinetic scheme. They include
site activation by cocatalyst, by electron donors, by hydrogen, by monomer, and spontaneous site
activation. Different catalyst systems tend to be activated by a different subset of the reactions in this
scheme. For example, TiCl
3
catalyst systems are usually activated with an organoaluminum

cocatalyst such as diethylaluminum chloride (DEAC), in the reactor. Chromic oxide catalysts are calcined
by heating with air for several hours at temperatures of 400C to 975C and cooled in dry air. Some of
these catalysts may be activated with a reducing agent before introduction into the reactor, while others
are activated within the reactor.
Site Activation Reactions

Some of the site activation reactions (activation by monomer, electron donor, hydrogen) have been
proposed to explain the observed rate enhancement behavior in different catalyst systems. For example,
the activation of additional sites by comonomer has been proposed to explain the rate enhancement
observed with the addition of a comonomer to ethylene and propylene homopolymerization reactors.
Chain Initiation
Chain initiation involves the reaction of a monomer molecule at a vacant active site to form a live polymer
molecule of unit length at that site. This reaction converts a vacant active site to a propagation site. The
chain initiation reaction is shown below:
(Po
k
+Mi
P1i
R ci k
=
k ci k
Po
k
C
Mi
)
O
k Mi
The rate of chain initiation at site type k ( R

ci k
) is dependent on the concentration of vacant sites of

type k and the concentration of monomer i. The user can also specify the reaction order with respect to
the monomer concentration. The live polymer chains grow by successive addition of monomer molecules
to form long polymer molecules.
Propagation
The live polymer at each active site type grow or propagate through the addition of monomer molecules
to form long polymer chains. The propagation reaction is represented by:
PMP
in k ,
+
j
k
jn +
,1 PCkR ijp
k
,=k
ijp
,k
inMj
, (main propagation)
Where monomer j is being added to a polymer chain of length n, with an active segment of type i at an
active site of type k. The resulting polymer chain will be of length n+1 and the active segment will be of
type j. The active segment type usually represents the last monomer type incorporated into the polymer
chain.
For copolymerization, there will be N m * N m * N
site
propagation reactions that may have different

reactivities. For example, with two monomers and three site types, the monomer being added could be
monomer 1 or monomer 2 while the active segment type could be segments from monomer 1 or
monomer 2 at each site type.
As a result, there will be twelve rate constants ( k ,
)
, where the subscript i
refers to the active segment type while the second subscript j refers to the propagating monomer type.
The superscript k refers to active site type. For the terminal model the rate of propagation is dependent
only on the concentration of live polymer with active segment i at active site k and the concentration of the
propagating monomer j.
In Aspen Polymers Version 3.0 and higher, another propagation reaction has been added to account for
formation of atactic polymer. This reaction has the same form as the main propagation reaction:
()k
paMi
k
p ij
PMP
in k ,
+
j
k
iin +
, R paij
k
= k paij
k
,0 k
j
C Mi
O
(atactic propagation)
but uses a different rate constant ( k
paij k
) . When the atactic propagation

reaction is included in the simulation, the main propagation reaction should be considered to account for
the formation of all polymer whether it is isotactic or atactic. Hence the main propagation reaction is also
termed the total propagation. The atactic propagation reaction only accounts for the formation of atactic
polymer. The atactic content of the polymer is then calculated from the ratio of atactic to total polymer.
Chain Transfer to Small Molecules
Chain transfer to small molecules such as monomer, solvent or chain transfer agent usually involves the
extraction of hydrogen from the small molecule by the active site and leads to the termination of the live
chain. At the same time, a new vacant site is formed which can undergo chain initiation to start
polymerization. The effect of chain transfer on the polymerization kinetics depends on the reactivity of the
transfer sites.
When the transfer site is very reactive, as is the case when the chain initiation rate constant is greater
than the propagation rate constant, chain transfer will not lower the polymerization rate or conversion, but
will reduce the molecular weight of the polymer. However, if the transfer site is less reactive, as in the
case of low chain initiation rate constant, both the conversion and molecular weight of the polymer will be
lowered.
In the built-in kinetics, chain transfer to hydrogen, cocatalysts, solvent, transfer agent, electron donor,
monomer and spontaneous chain transfer are included as shown in the Built-In Ziegler-Natta Catalysts
and Polymerization Kinetic Scheme figure on page 232.
Chain Transfer to Monomer

For chain transfer to monomer a new polymer chain of unit length is generated while for the other transfer
reactions a vacant site of that type is generated. The dead polymer chain formed by some of the chain
transfer reactions will have an end-group with a terminal double bond. In addition to the rate constant
parameters and the reaction order, the user may also specify a parameter to track the fraction of dead
polymer chains with terminal double bonds that are generated from the chain transfer reactions. The
default value for this parameter is zero.
Site Deactivation
The catalyst site deactivation step involves the deactivation of active sites, vacant and propagation, to
form dead sites. Depending on the catalyst system and operating conditions, the deactivation rate may be
high or low.
There are several different site deactivations reactions included in the built-in kinetic scheme. They
include site deactivation by cocatalyst, by electron donors, by hydrogen, by monomer, by poisons, and
spontaneous site deactivation. Different catalyst systems tend to be deactivated by a different subset of
the reactions.
The deactivation rate constants are assumed to be dependent only on the site type and not on the
polymer segment attached to a site. Therefore, the same rate constant is applied to both vacant and
propagation sites of the same type. Note that deactivation rates shown in the Built-In Ziegler-Natta
Catalysts and Polymerization Kinetic Scheme figure on page 232 are per unit of active (vacant and
propagation) site concentration.
Site Inhibition
Inhibited sites have small molecules such as hydrogen or poisons attached. As a result, inhibited sites are
temporarily blocked from becoming propagation sites. The site inhibition reaction is considered reversible.
Therefore, the small molecule may dissociate from an inhibited site which then becomes a vacant site
once again. The user must specify rate constant parameters for both the forward (inhibition) and reverse
(dissociation) reactions.
Cocatalyst Poisoning
For some catalyst systems, additional amounts of cocatalysts are fed to the reactor to counteract the
effect of any poisons present . This is modeled as a cocatalyst poisoning reaction in the built-in kinetics.
The product of this reaction is designated as a byproduct in the list of reactive species. The byproduct is
considered to be inert and does not participate in any reaction.
Terminal Double Bond Polymerization

For some catalyst systems, primarily metallocene, polymer chains with long chain branches are formed.
However, the long chain branching frequency is usually small. The long chain branches are believed to
be due to propagation reactions involving a live chain and a terminal double bond on a dead polymer
chain. Polymer chains with terminal double bonds are formed by some of the chain transfer reactions. To
form long chain branches, the metal center must be open to provide a favorable reactivity ratio for the
macromonomer.
The concentration of terminal double bond (TDB) end-groups on the dead polymer chains are tracked
through an additional segment called the TDB- Segment. TDB-Segments are generated through the
chain transfer reactions and are consumed through the TDB polymerization reaction. When the TDB
reaction is used, one additional segment needs to be defined in the Components form for the TDB-
Segment. Typically, for a copolymerization system with N monomers, N repeat segments would be
defined in the Components form. However, with the TDB polymerization reaction, N repeat segments and
one end segment should be defined in the Component form. The end segment must be specified as the
TDB-Seg species in the Species folder of the Ziegler-Natta kinetics.
Example for Terminal Double Bond Polymerization

This example starts with the delivered example file Polymers\pp.bkp. 1 Include a segment to represent
the terminal double bond. The segment
database includes several preconfigured TDB segments (each containing one less hydrogen than the
corresponding monomer). Be sure to select Type Segment.
2 Declare the TDB segment an END segment on the Components |
Polymers | Characterization | Segments sheet.
3 Specify the segment in the T.D.B. segment field on the Ziegler-Natta
Reactions | Species sheet.
4 Reactions are not generated automatically for TDB polymerization
reactions. On the Reactions sheet, click New and add as many reactions of type TDB-POLY as you need
to account for multiple sites and active segments.
5 In addition, you need reactions to generate the TDB segment. On the
Rate Constants sheet, set Tdb Frac to a value greater than 0 to cause the TDB segment to form. Tdb
Frac is the fraction of reaction events that lead to terminal double bond formation. Also on this sheet
specify the preexponential factor and activation energy for the TDB-POLY reactions.
Following are the model features and assumptions used in the Ziegler-Natta polymerization model
available in Aspen Polymers.
Phase Equilibria
Rate Calculations
The Ziegler-Natta polymerization kinetic model supplies to the reactor models the reaction rates for the
components and the rate of change of polymer attributes (e.g. the chain length distribution moments) .
The component reaction rates are computed from the kinetic scheme by summing over all reactions that
involve the component. The site based moment rates are derived from a population balance and method
of moments approach similar to that described in the Calculation Method section on page 185.

selected, and the subset of the built-in kinetics used for a specific simulation:
Zeroth, first and second moments for the composite and site based combined polymer
Zeroth and first moments for the composite and site based live polymer
Number and weight degree of polymerization and polydispersity index for the composite and site based
bulk polymer (DPN, DPW, PDI and SDPN, SDPW, SPDI)
Number and weight average molecular weight for the composite and site based bulk polymer (MWN,
MWW and SMWN, SMWW)
Copolymer segment composition for composite and site based bulk polymer (SFRAC and SSFRAC
segment mole fractions)
Total number long chain branches (LCB)
Long chain branching frequencies (FLCB)
Mole fraction of live bulk polymer chains (LPFRAC and LSPFRAC)
Number average degree of polymerization for live polymer (LDPN and LSDPN)
Copolymer segment composition for live polymer (LSFRAC and LSSFRAC)
Live polymer active segment composition (LEFRAC and LSEFRAC)
These variables are stored as component attributes (See Chapter 2). It is assumed that attributes needed
for the kinetic scheme are selected. The specification of the Ziegler-Natta Model is described later in this
section.
In many cases, users may need to know polymer product properties related to the above structural
properties. For example, users may be interested in melt flow rate or melt index, viscosity, density, etc.
These properties can be calculated in user-supplied Fortran subroutines which take the polymer moments
and structural information and return the desired property. An example use of a user supplied subroutine
to return melt index is shown in the HDPE section of the Aspen Polymers Examples & Applications Case
Book.
Specifying Ziegler-Natta Polymerization

Kinetics
Accessing the Ziegler-Natta Model
To access the Ziegler-Natta polymerization kinetic model: 1 From the Data Browser, click Reactions. 2
necessary, change the default ID for the reaction. 5 Select Ziegler-Nat as the reaction type and click OK.
Specifying the Ziegler-Natta Model

The Ziegler-Natta model input forms are as listed below. Use these forms to define reacting species and
enter reaction rate constant parameters.
Use this sheet To
Summarize rate constant parameters Options Specify the reacting phase
You must specify the reacting species on the Species sheet: 1 In the Polymer field, specify the polymer
produced. 2 In the Monomers field list the reacting monomers. For each monomer, in
the goes to field, specify the polymer segment that the monomer converts to. 3 If you select the
terminal double bond polymerization reaction, in the
T.D.B.-Seg field, list TDB segment that is formed by the chain transfer reactions and is consumed by the
terminal double bond polymerization reaction. Otherwise, go to step 4.
Note: The TDB segment should be of type end segment and should not be used as a repeat segment for
a particular monomer (see Step 2). 4 Continue listing other types of reacting species, for example,
solvents,
transfer agents, etc. 5 Select the Generate Reactions option if you want the reactions to be
Listing Reactions
The Ziegler-Natta model generates reactions based on the list of reacting species. You can view the
system-generated reactions, then assign rate constant parameters to these reactions.
You can view a list of the system-generated reactions on the Reactions sheet. In the Reaction summary
listing for each reaction, the first column indicates the reaction type. The second column lists the
reactants, and the last column lists the products. The Data Browser window can be resized to better view
the reaction listing. Use the following options:
Click To
reactions
Click To
Hide/Reveal
a reaction from the
Delete
Adding Reactions
example, Initiator, Catalyst) fields, enter the
Editing Reactions

subform: 1 In the Site No. field, enter the site number. 2 In the ko field, enter the pre-exponential factor. 3
In the Ea field, enter the activation energy. 4 In the Order field, enter the order for component in reaction.
5 In the Fraction field, enter terminal double bond fraction. 6 In the Tref field, enter reference temperature.
7 Click the stoichiometry list and select a new reaction. Enter rate constants
parameters.
References
Albright L. F. (1985). Processes for Major Addition-Type Plastics and Their Monomers, 2nd Ed. Florida:
Krieger Pub.
Brockmeier, N. F. (1983). Latest Commercial Technology for Propylene Polymerization. In R.P. Quirk
(Ed.), Transition Metal Catalyzed Polymerizations - Alkenes and Dienes. New York: Academic Pub.
Choi, K-Y, & Ray, W. H. (1985a). Recent Developments in Transition Metal Catalyzed Olefin
Polymerization - A Survey. I. Ethylene Polymerization. J. Macromol. Sci. Rev. Macromol. Chem. Phys.,
C25 (1), 1.
Choi, K-Y, & Ray, W. H. (1985b). Recent Developments in Transition Metal Catalyzed Olefin
Polymerization - A Survey. II. Propylene Polymerization. J. Macromol. Sci. Rev. Macromol. Chem. Phys.,
C25 (1), 57.
Debling, J. A., Han, G. C., Kuijpers, F., Verburg, J., Zacca, J., & Ray, W. H. (1994). Dynamic Modeling of
Product Grade Transition for Olefin Polymerization Processes. AIChE J., 40, No. 3, 506.
Nowlin, T. E. (1985). Low Pressure Manufacture of Polyethylene. Prog. Polym. Sci., 11, 29.
Short, J. N. (1983). Low Pressure Ethylene Polymerization Processes. In R.P. Quirk (Ed.), Transition
Metal Catalyzed Polymerizations - Alkenes and Dienes. New York: Academic Pub.
Xie, T., McAuley, K.B., Hsu, J. C. C., & Bacon, D. W. (1994). Gas Phase Ethylene Polymerization:
Production Processes, Polymer Properties, and Reactor Modeling. Ind. Eng. Chem. Res., 33, 449.
12 Ionic Polymerization Model
This section covers the ionic polymerization kinetic model available in Aspen Polymers (formerly known
as Aspen Polymers Plus). The cationic, anionic and group transfer addition polymerization kinetics can be
modeled using this model.
Ionic Processes, 250
Specifying Ionic Polymerization Kinetics, 260
Some examples of applicable polymers are given in below:
Polystyrene - Anionic polymerization is used to produce narrow molecular weight distribution
polystyrenes in small quantities. Cationic polymerization is used to produce low molecular weight
polystyrenes for coatings and glues. Block copolymers of styrene and butadiene are produced
commercially with anionic polymerization.
Polyisobutylene - Low-to-medium molecular weight poly isobutylene is produced commercially by
polymerization of high purity isobutylene in isobutane or hexane diluent using aluminum chloride or
hexane trifluoride as a catalyst.
Polybutene - Polybutenes are produced in solution by copolymerizing isobutylene and n-butene using
aluminum chloride or hexane trifluoride as a catalyst.
Polybutadiene - Block copolymers of styrene and butadiene are produced commercially with anionic
polymerization.
Polyoxides - Examples are poly ethylene oxide (PEO) and poly propylene oxide (PPO). Continuous
tubular or column reactors or semibatch
12 Ionic Polymerization Model 249
autoclaves are used. The polymerization can be carried out with different mechanisms: anionic (base
catalysis), cationic (acid catalysis), or coordinate.
Ionic Processes
Many specialty polymers are manufactured by ionic polymerization processes. For the description of a
specific ionic process, refer to the References section. Ionic polymers fall in the category of addition
polymers, i.e., the reactive species grow in length by continuous addition of monomer units. However,
there are several features that distinguish the ionic polymerization processes from other addition
polymerization processes like free-radical and Ziegler- Natta:
Different propagating species are often present in ionic processes. These species may be free ions,
tight ion pairs, loose ion pairs, dormant esters, etc. Moreover the propagating species are often in
equilibrium.
Association or aggregation phenomena is common in BuLi type of initiators for anionic polymerization.
The associated initiator is not reactive and is in equilibrium with its dissociated form. The association
phenomena also takes place with growing polymer chains, which reduces the actual number of chains
growing at any given time. This phenomena affects both the conversion and polymer properties.
Exchange reaction takes place between live and dormant polymer. The active species transfer from one
polymer to another. This reaction controls the molecular weight distribution of the final polymer. If the
exchange reaction rate constant >> propagation rate constant, then for increasing monomer conversion
the polydispersity approaches a limiting value of 1.0.
Ionic reactions are a strong function of solvent, initiator and operating conditions and are susceptible to
poisons.
Chain transfer and termination reactions may be negligible or absent in certain polymerization
processes thus leading to formation of living polymers.

In the following sections, the general chemistry of ionic polymerization and the built-in initiator /
polymerization kinetic scheme are described. The kinetic scheme is based on literature survey of ionic
polymerization mechanisms. Ionic kinetic scheme can model either cationic, anionic or group-transfer
polymerization. The ionic kinetic scheme in Aspen Polymers is a super-set of all the above mentioned
reactions.
Reaction Steps
There are a few key elementary reactions that apply to all ionic polymerization systems. These include
the three basic reaction steps:
Formation of active species
Chain initiation
250 12 Ionic Polymerization Model
Propagation
There is almost no chain transfer in living polymerization. There are additional reactions for each
chemistry which will be discussed later. There can be different forms of propagating species, e.g., free-
ions, ion-pairs, and dormant esters. A given ionic polymerization system can have different combinations
of these propagating species.
To account for different propagating species, the same framework is used as the Ziegler-Natta multi-site
kinetics model. In the ionic model, each site refers to a unique type of active species. To model three
propagating species for an initiator, the model will have three sites with each site corresponding to the
unique propagating active species type. In this framework, the polymer produced by dormant esters will
be stored in live polymer attributes for the selected dormant ester site.
Polymer Molecules Tracked

There are three different types of polymer molecules tracked by ionic kinetic scheme:
P
n,k i
- live polymer molecule chains of length n with active segment k attached to the active center of type
i. For example, free-ions can be site 1, ion-pairs as site 2 and dormant esters as site 3. The propagation
rate constant for dormant esters ( k
p
for
site 3) may be zero.
Qni
- associated (or aggregate) polymer molecule chains of length n formed by association of

propagating species of type i. The site based aggregate polymer attributes contain the information about
polymer formed by association of different propagating species. For example, only the ion pairs
propagating species may associate in case of BuLi type of initiators.
Dni
- dead polymer molecule chains of length n formed by active propagating species of type i. The site
based bulk polymer attributes contain information about the bulk polymer which is a sum of live,
aggregate and dead polymer.
Initiator Attributes
The initiator in ionic model has three attributes which are solved along with moment equations:
P 0 i = P0FLOW; P 0
t,
i
= PT0FLOW; C I i = CIONFLOW These variables are provided as attributes so that they can be used in
user kinetics to add side reactions. For example, a transfer species ( Pt, 0
i
) may undergo a side

reaction with other components; addition of a salt with same counter ion ( C
Ii
) may tilt the polymerization in one direction by allowing counter-ion to be in equilibrium with ion
concentrations from other salts. The initiator decomposition reactions (involving Pi 0
or I
m
) can also be modeled in

Aspen Plus as user reactions which can be solved simultaneously with built-in ionic kinetics in Aspen
Polymers.
The built-in initiator and polymerization kinetic scheme is shown in here :
Built-In Ionic Polymerization Kinetic Scheme
The nomenclature used in the ionic polymerization kinetic scheme is shown here:
Symbol Description
A
m
Chain transfer agent, m
AI
m
Associated initiator, m
b
FC
Coefficient (= 0 when catalyst does not participate in the reaction) b
TCI
Coefficient (= 0 when C-ion does not participate in the reaction) C
I i Counter ion (C-ion) corresponding to active species of
type i C
n
Catalyst, n
D
n i Dead polymer chain length of n produced by active
species of type i d
EQL
Coefficient (= 0 when C-ion does not participate in the reaction) d
EXA
Coefficient (= 0 when Po does not participate in the reaction) d
FC
Coefficient (= 0 when C-ion does not participate in the reaction) d
I2
Coefficient (= 0 when C-ion is not formed in the reaction)
I
p
Initiator, p
M
j
Monomer, j
nm,p Association number for initiator dissociation reaction
Pi 0
Active species of type i (chain length 0)
Pt,i 0
Transfer active species of type i (chain length 0)
Pi
j,j
Active species of type i with active segment j (chain length 1)
P
n,k
i Growing species chain of length n of type i with active
segment k Q
n, i k
Associated polymeric species of chain length n with active segment k T
m
Terminating agent, m
X
m
Exchange agent, m
The ionic model is a terminal model, implying that the rate constants are functions of only terminal
segment of the polymer chain.
Copolymerization
For copolymerization, the built-in kinetic scheme allows the user to specify the number of monomer types
used. Similarly the user has the flexibility to specify the number of each type of reactive species present
in the polymerization:
Associated initiators
Initiators
Catalysts
Exchange agents
Chain transfer agents
Termination agents
The user is able to tailor the built-in kinetics to model a specific polymerization system by selecting a
subset of the reactions shown in the Built-in Ionic Polymerization Kinetic Scheme figure on page 252.
The rate constants for each reaction for active species of type i are calculated at the reaction temperature
using the Arrhenius equation shown below. The user specified rate constant parameters are pre-
exponential factor ( k
oi
) and the activation

energy ( Eai
) at active species of type i:
Rate Constant
i
o
11
Where:
k
o
k=ki
exp
-
Ea
iR
T-
T
ref
= Pre-exponential factor in 1/sec for first order reactions

and m3/kmol-sec for second order reactions
Ea = Activation energy in mole enthalpy units
R = Universal constant
T = Reaction temperature in Kelvin T
ref
= Reference 1E38)
reaction temperature in Kelvin (default is
Formation of Active Species

The active species are the initiator in dissociated form:
AI m
n m,p
I
p
The association and dissociation of initiator is observed in alkyl-Lithium type of initiators in nonpolar
solvents for anionic polymerization. n-butyl-Li exists as hexamer whereas s-BuLi and t-BuLi exist as
tetramers for styrene polymerization. The dissociated initiator further reacts with monomer to form
growing polymer with unit chain length in chain initiation step. This reaction can also be used to represent
self-ionization of some strong acids
in (AlCl 3 , AlBr 3 , TiCl 3
)
cationic polymerization, with nm,p
being the degree of
ionization:
I m +b FC C n
P0i
+d C i FC I
The active species Pi 0

is formed by this reaction. Several initiators (KNH 2 , NaNH
2
) decompose to form an active species (or dissociate into ions) in anionic

polymerization ( b FC = 0 , d
FC
= 1 ) . Polystyrene is manufactured using KNH

2
initiator.
With no reverse reaction, the electron transfer initiation with light (electrochemical initiation) is also a
special case of the above scheme for anionic polymerization. Initiator and catalyst are used in cationic
polymerization with no counter-ion ( d
FC
= 0 ) . In case of anionic polymerization, a starter may be

used to generate an active species.
For polyether polyols (polypropylene oxide), initiator is ROH and catalyst is KOH (weak base) and the
reaction is only in forward direction.
The above scheme can also represent donar-accepter equilibria and self dissociation of acids in cationic
initiation ( A+B A - +B + ) .
Chain Initiation
The active species incorporate monomer to form propagating species with unit chain length:
P0i
+Mj
Pi
j,j
The initiator (in dissociated form) directly reacts with monomer to form propagating species with unit chain
length. A counter-ion may be formed ( d
I2
=1):
I m +M j
Pi
j,j
+d I 2
C
I i The transfer active species incorporate monomer to form propagating
species with unit chain length:
P0
t,i
+Mj
Pi
j,j
Propagation
The growing polymer with an active species at the end of the chain may grow or propagate through the
addition of monomer molecules to form long polymer chains. The propagation reaction is represented by:
P n,k i
+Mj
P
n+ i
j,j
where monomer j is being added to a polymer chain of length n, with an active segment of type k and
active species of type i. The resulting polymer chain will be of length n+1 and the active segment will be
of type j. The
active segment type usually represents the last monomer type incorporated into the polymer chain.
Copolymerization
For copolymerization, there will be N m * N m * N
site
propagation reactions that may have different

reactivities. For example, with two monomers and three site types, the monomer being added could be
monomer 1 or monomer 2 while the active segment type could be segments from monomer 1 or
monomer 2 at each site type. As a result, there will be twelve rate constants ( k
ip,
kj
)
, where the subscript k refers to the active segment type while the
second subscript j refers to the propagating monomer type. The superscript i refers to active species type.
For the terminal model the rate of propagation is dependent only on the concentration of live polymer with
active segment k on active species i and the concentration of the propagating monomer j.
Association or Aggregation
The propagating species initiated by alkyl-Lithium type of initiators in anionic polymerization also exhibit
the association phenomena like the initiator. The association of live polymeric species is usually dimeric
in nature. The associated polymer Q
ni
+
m,k
is tracked as a separate polymer and does not participate in any other

reactions:
P n, i
k
+P m, i
k
Q
ni+
m,k
Exchange
Exchange reactions exchange the growing active species between two different growing polymers. If both
free ions and ion pairs are growing, then the counter-ion can exchange between the two polymeric
species. There can be exchange reaction between dormant polymer (with ester as growing species which
does not propagate) and ion pairs/free ions. The exchange reaction can also take place between an
exchange agent (e.g., alcohol end group in solvent or starter) and a growing polymer. If exchange
reaction with a small molecule does not produce a P 0
species, then d
EXA
= 0. The exchange between growing

species and dormant species takes place in polyether polyols (propylene oxide). The dormant species
can be an alcohol:
P n,k i
+P m,p
j
P n,k
j
+P
m,p i P n,k
i
+ X m P n,k
+
d EXA
P 0 i Equilibrium with Counter-Ion

The following reaction represents the equilibrium between free ions and ion pairs, hence the name
equilibrium with counter-ion ( d
EQL
= 1 ) . The
spontaneous ionization reaction can also be represented by this reaction when d
EQL
= 0:
P n,k i
P n,k
j
+
d EQL C
I j Chain Transfer
There are four types of chain transfer reactions:
Spontaneous
Monomer
Dormant polymer formation
Chain transfer agent
Spontaneous chain transfer can lead to formation of a dead polymer molecule and an active species
caused by proton loss, e.g., cationic polymerization of poly isobutylene:
Spontaneous P n,k
i
Dn
i + P 0 i Chain transfer to monomer can take place with hydride abstraction from an olefin, for example,
cationic polymerization of polyisobutylene and butyl rubber:
Monomer P n,k
i
+Mj
Dni
+P
i j, j
Chain transfer to monomer in polyethers (propylene oxide) can form dormant species (alcohol) . The
dormant species is modeled as a live polymer with a different site type but it does not have the usual
chain initiation and propagation reactions. This dormant polymer can participate in exchange reactions:
Form dormant polymer P n,k
i
+M p
P n,k
j
+P
i p, p
The growing polymer chain can also be transferred to a chain transfer agent, A, leading to formation of a
transfer active species of the same type, i. The reaction rate order wrt. to chain transfer agent can be
specified by the user:
Chain transfer agent P n,k
i
+Am
Dn
i + P 0 t,i Chain Termination

The growing polymer chain with ion pairs as active species can be spontaneously terminated by
combination with counter ion ( b
TCI
= 0 ) , e.g., cationic
polymerization of polystyrene, tetrahydrofuran, polyisobutylene. A growing free ion active species can
terminate by reacting with its own counter ion ( b
TCI
=1):
Counter-ion P n,k
i
+b TCI C I i
D
n i The chain can terminate after reacting with a chain terminating
agent to form a dead polymer. Any small molecule can act as a chain terminating agent.
The reaction rate order wrt. to terminating agent can be specified by the user:
Terminating agent P n,k
i
+T m
D
n i Coupling
Coupling reactions are encountered in thermo-plastic elastomer production. For example, to make
styrene-butadiene-styrene (SBS) TPE, styrene is added first, and then half of the butadiene is added.
Introducing a coupling agent to this reaction system will form SBS polymer. In this example i=j=1 and k=2.
PPP
ni
+
jm
k
mn +
Another mechanism represented by this reaction is higher order association of polymeric chain. Dimeric
association can be modeled by the association reaction, but the coupling reaction should be used to
model higher order association of polymer chains. In a given simulation, the coupling and association
reactions are mutually exclusive.

Following are the model features and assumptions used in the ionic polymerization model available in
Aspen Polymers.
Phase Equilibria
Rate Calculations
The ionic polymerization kinetic model supplies to the reactor models the reaction rates for the
components and the rate of change of polymer attributes (e.g. the chain length distribution moments) :
The component reaction rates are computed from the kinetic scheme by summing over all reactions that
involve the component.
The site based moment rates are derived from a population balance and method of moments approach
similar to that described in the Calculation Method section on page 185.
Additionally, the moment definitions are modified to include the aggregate polymer as separate and as a
part of bulk polymer. The attributes calculate and report up to third moments of live, aggregate and bulk
polymer. The moment definitions are:
Polymer Moment Definition
Live Polymer,
P
n,k i
fk

Aggregate Polymer,
i,=
nf
Pni,
kn
i
fk

Dissociated Aggregate
Polymer,
Q
n,k
i,=
nf
Q
ni,
kn
Q
ni
+ mk
,
if,k
=

nf
Qni
+
mk , n m Bulk Polymer
if
{}k
nf

Nseg k
Pni
,k
+Qni,
k
+
D
ni
= Nseg
i
f,k
+ Nseg
f,
k

nf
D
nk
i
k

i
n

selected, and the subset of the built-in kinetics used for a specific simulation:
Zeroth, first and second moments for the composite and site based bulk polymer
Zeroth and first moments for the composite and site based live polymer and aggregate polymer
Number and weight degree of polymerization and polydispersity index for the composite and site based
bulk polymer (DPN, DPW, PDI and SDPN, SDPW, SPDI)
Number and weight average molecular weight for the composite and site based bulk polymer (MWN,
MWW and SMWN, SMWW)
Copolymer segment composition for composite and site based bulk polymer (SFRAC and SSFRAC
segment mole fractions)
Mole fraction of bulk polymer chains that are live (LPFRAC and LSPFRAC)
Mole fraction of bulk polymer chains that are aggregated (APFRAC and ASPFRAC)
Number average degree of polymerization for live polymer (LDPN and LSDPN)
Number and weight average degree of polymerization for aggregate polymer (ADPN, ADPW, ASDPN
and ASDPW)
Copolymer segment composition for live and aggregate polymer (LSFRAC, ASFRAC, LSSFRAC and
ASSFRAC)
Live polymer active segment composition (LEFRAC and LSEFRAC)
These variables are stored as component attributes. See Chapter 2 for a description of these component
attributes. It is assumed here that attributes needed for the kinetic scheme are selected. For each live
polymer attribute, there is also a corresponding aggregate polymer attribute.
Specifying Ionic Polymerization Kinetics

Accessing the Ionic Model
To access the Ionic polymerization kinetic model: 1 From the Data Browser, click Reactions. 2 From the
Reactions folder, click Reactions. The Reactions object manager appears. 3 If the kinetic model already
exists, double-click the desired Reaction ID in
necessary, change the default ID for the reaction. 5 Select Ionic as the reaction type and click OK.
Specifying the Ionic Model

The Ionic model input forms are as listed below. Use these forms to define reacting species and enter
reaction rate constant parameters:
Use this sheet To
Summarize rate constant parameters Options Specify the reacting phase

You must specify the reacting species on the Species sheet: 1 In the Polymer field, specify the polymer
produced. 2 In the Monomers field, list the reacting monomers.
For each monomer, in the goes to field, specify the polymer segment that the monomer converts to. 3
Continue listing other types of reacting species, for example, solvents,
transfer agents, etc.
Listing Reactions
You can build a list of reactions on the Reactions sheet. In the Reaction summary listing for each
reaction, the first column indicates the reaction type. The second column lists the reactants, and the last
column lists the products. The Data Browser window can be resized to better view the reaction listing.
Use the following options:
Click To
reactions
Click To
Hide/Reveal
a reaction from the
Delete
Adding Reactions
example, Initiator, Catalyst) fields enter the
Editing Reactions
To add or edit a reaction, click Edit to open the Edit Reaction subform: 1 Modify the Reaction type as
needed.

subform: 1 In the ko(fwd) or (rev) field, enter the pre-exponential factor for
forward or reverse reaction. 2 In the Ea(fwd) or (rev) field, enter the activation energy for forward or
reverse reaction. 3 In the Tref field, enter reference temperature. 4 In the Order field, enter the order.
5 In the Asso. No. field, enter the polymer association number. 6 In the Coeff. b and Coeff. d fields, enter
coefficients b and d. 7 Click the stoichiometry list and select a new reaction. Enter rate constants
parameters.
References
Wiley.
Bikales, M., Overberger, & Menges. (1985). Encyclopedia of Polymer Science and Engineering, 2nd Ed.
New York: Wiley Interscience.
Chang, C. C., Miller, J. W., & Schorr, G. R. (1990). Fundamental Modeling in Anionic Polymerization
Processes. J. of Appl. Pol. Sci., 39, 2395-2417.
Chang, C. C., Halasa, A. F., & Miller, J. W. (1993). The Reaction Engineering of the Anionic
Polymerization of Isoprene. J. of Appl. Pol. Sci., 47, 1589-1599.
Compton, R. G. (Ed.). (1992). Mechanism and Kinetics of Addition Polymerizations. Comprehensive
Chemical Kinetics, 31.
Fathi, H., Hamielec, A. E., & Davison, E. J. (1996). Modelling of Anionic Solution Polymerization of
Butadiene - The Effects of Chain Termination and Long Chain Branching on Molecular Weight
Distribution Development. Polymer Reaction Eng., 4, No. 4.
Kennedy, J. P., & Squires, R. G. (1967). Contributions to the Mechanism of Isobutene Polymerization I.
Theory of Allylic Termination and Kinetic Considerations. J. Macromol. Sci., A1(5), 805-829.
Kirk-Othmer. (1991). Encyclopedia of Chemical Technology, 4th Ed. New York: Wiley Interscience.
Moore, J. G., West, M. R., & Brooks, J. R. (1979). The Anionic Solution Polymerization of Butadiene in a
Stirred-Tank Reactor. ACS Symp. Ser., 104.
Muller, et. al. (1995). Kinetic-analysis of Living Polymerization Processes exhibiting slow equilibria.
Application to group transfer and cationic polymerizations. 5th International Workshop on Polymer
Reaction Engineering, 131, 9-11 October, Berlin: DECHEMA.
Odian, G. (1981). Principles of Polymerization, 3rd Ed. New York: Wiley Interscience.
Pepper, G. C. (1957). Cationic Polymerization. Proc. of the Intl. Symp. on Macromol. Chemistry. Prague.
Szwarc, M. (1996). Ionic Polymerization Fundamentals. New York: Hanser.
Treybig, M. N., & Anthony, R. G. (1979). Anionic Styrene Polymerization in a Continuous Stirred-Tank
Reactor. ACS Symp. Ser., 104.
13 Segment-Based Reaction Model
This section describes the segment-based power-law reaction model available in Aspen Polymers
(formerly known as Aspen Polymers Plus).
Segment-Based Model Allowed Reactions, 267
Specifying , 285
The segment-based power-law reaction model can be used to simulate polymerization reactions using a
simple power-law type rate expression. This may be useful when simulating new processes that do not fit
well into the other built-in models in Aspen Polymers, or when a very detailed mechanistic reaction model
is not necessary.
The segment-based power-law model is the best choice for simulating step- growth addition processes
for example, the production of polyurethane.
This model may also be used to represent processes involving changes to polymer segments. The
underlying kinetics are basic power law reactions in which segments and monomeric components may
participate. Some examples of applicable polymers are:
Polyvinyl alcohol (PVA) - Alcoholysis of polyvinylacetate
Chlorinated polyethylene (CPE) - Chlorination of polyethylene
Polymethylmethacrylate (PMMA) - Recovery of methylmethacrylate from PMMA
Polyisobutylene - Chain scission of polyisobutylene
13 Segment-Based Reaction Model 265
Step-Growth Addition Processes
Step-growth addition processes involve reactions between two functional groups to produce a new
functional group without the loss of low molecular weight condensates. For example, in the production of
polyurethane polymers a diol is reacted with a diisocyanate to produce an alternating copolymer with
urethane linkages between the monomer units:
HO R OH O=C=N
X N=C=O O
O
+ R OCNH
X NHCO diol diisocyanate
polyurethane
These reactions are usually irreversible. The individual reaction steps can be simulated using the
segment-based power-law model.
Polymer Modification Processes

The conventional route for synthesizing commercial polymers is through the polymerization of a
monomeric compound. These polymerization reactions fall under different categories depending on the
nature of the monomer and its growth mechanism.
However, once synthesized, polymers may undergo further reactions. In some instances, these reactions
may be undesirable side reactions, in which case they may be considered as degradation reactions. In
other cases, the only mechanism for producing certain polymers may be through the modification of a
starting polymer. Typically, this situation occurs if a monomer is not readily available for that polymer. For
example, polyvinyl alcohol is produced by alcoholysis of polyvinyl acetate.
Modification reactions are often used to improve polymer properties such as oil resistance
(chlorosulfonation of polyethylene), heat resistance (chlorination of polyethylene), solubility ("-cellulose),
and flammability (natural rubber). There are also a few cases where it is economically desirable to react
scrap polymer for monomer recovery (methyl methacrylate from polymethyl methacrylate) (Rodriguez,
1989).
Reaction Categories
Regardless of the end effect of the polymer modification reaction, the events taking place fall into one of
two categories based on the site where they occur on the polymer chain. The reactions may take place
on:
Side groups
Polymer backbone: scission, depolymerization, cross-linking, or bond changes
There are some fundamental issues that distinguish reacting polymers from their low molecular weight
counterparts. One obvious characteristic of reacting polymers is the potential for steric hindrance. A
reacting side group may be too close to the polymer chain, for example. There may also be changes in
solubility as reaction progresses.
Furthermore, crystallinity has an effect on the polymer reactivity; in general, for a semicrystalline polymer,
only the amorphous region is able to react.
266 13 Segment-Based Reaction Model
Finally, an important difference that characterizes polymers is the fact that a higher local concentration of
reacting functional groups is observed than that indicated by the overall polymer concentration (Odian,
1991).
Segment-Based Model Allowed Reactions

The reaction categories allowed in the segment-based reaction model, along with a brief summary of the
conditions where each of these reactions may occur, is shown here:
Segment Based Model Reaction Categories
Conventional Species
Reactions involving all non polymeric species fall under this category. Monomeric components may react
among themselves to produce intermediate species. These reactions are represented as Category I in
the Segment Based Model Reaction Categories figure on page 268.
Side Group or Backbone Modifications
Polymer modification reactions aimed at altering end properties involve in most cases side group or
backbone modifications. In such reactions, groups attached to the polymer chain are substituted. One
example is that of the alcoholysis of polyvinyl acetate to produce polyvinyl alcohol:
CH
3C
OO
OH CH
CH
2
+ CH
3
OH CH CH
2
+ CH
3
CO
2
CH
3
Another example is the chlorination of polyethylene to produce chlorinated polyethylene (CPE):
CH
2
+ Cl
2
CHCl + HCl
Side group and backbone reactions are illustrated as reaction Category II in the Segment Based Model
Reaction Categories figure on page 268.
Chain Scission
A common polymer degradation reaction is chain scission. In this case, bonds are broken along the
polymer chain resulting in shorter polymer molecules with lower molecular weight. Chain scission may be
induced by several factors. One example is the scission of polyisobutylene upon oxidation:
CH
2
Some scission reactions may involve a monomeric component, such as an acid or base:
Chain scission reactions are represented as Category III reactions in the Segment Based Model Reaction
Categories figure on page 268.
Depolymerization
Depolymerization is the reverse of the propagation step of a polymerization reaction. In such reactions,
monomer molecules are lost from the polymer chain. Depolymerization is often considered a degradation
reaction. There are, however, cases where it is brought on by design to recover monomer from scrap
polymer. An example depolymerization reaction is that of polymethyl methacrylate to regenerate methyl
methacrylate:
CH
3
CH
2
CH
3 C CH
2
CH
2
C
+ CH
2 CH
2
CH
2
CH
2
+ HCl CH
2
Cl + CH
3
CH
3
+ CH
2
CH
3
CH
3
C O O CH
3
CH
3
C O O CH
3
CH
2
C
CH
3
CH
2
C CH
2
C
C
OC
C O O CH
3
O
Depolymerization is illustrated as Category IV in the Segment Based Model Reaction Categories figure
on page 268.
Propagation
Propagation reactions involve the addition of monomers to the end of a growing polymer chain.
Propagation is illustrated as Category V in the Segment Based Model Reaction Categories figure on page
268.
Combination
There are other mechanisms through which polymer segments react with each other. Some of these
reactions, grouped as combination reactions, include kinetic events where two polymer molecules
combine into one. These reactions are represented as Category VI in the Segment Based Model
Branch Formation
Branch formation occurs when a polymer molecule attaches to another polymer chain, converting a
repeat unit to a branch point. Monomers can also react with repeat units to initiate branch formation.
Branch formation is illustrated as Category VII in the Segment Based Model Reaction Categories figure
on page 268.
Cross Linking
Cross linking occurs when a repeat unit in one chain reacts with a repeat unit in another chain, forming a
cross link (branch 4) segment. Cross linking is illustrated as Category VIII in the Segment Based Model
Kinetic Rate Expression

The segment-based reaction model uses a modified power-law rate expression where the rate of reaction
is calculated as the product of the reacting species concentrations with a rate constant representing the
specific reactivity of the reaction. The kinetic rate expression in the segment-based model is described
below:
Equation
T
ref
k
inet
,
=
Catalyst i i
ek o i - Ea i TTR
11
-
b
ref
T
ref
i[]
(i
)
T
ref
specified
T
flagU
Ea unspecified *
k
inet
,
ioi-=[
Catalyst ] i
ek i
Ti
flagU ( i
)
Assign User Rate Constants is used:
RT b rate m
=
activity m
j
Ca
j mj
i
k inet
,
Assign User Rate Constants is not used:
j
mnet
Nomenclature
Symbol Description
m User reaction number i Rate constant set number j Component number Product operator C
j
rate m
=
kC a j mj
,
Concentration* of component j, mol/L
i
Catalyst order term for catalyst i (default = 1)
mj
Power-law exponent for component j in reaction m
k
o
Pre-exponential factor in user-specified inverse-time and concentration units**
k i,net
Net rate constant for set i assigned to reaction m
k
mnet
,
Net rate constant for reaction m
ref
Optional reference temperature. Units may be specified, they are converted to K in the model. Defaults to global
reference temperature (Global T
ref
) specified on the Specs sheet. flag
User flag for rate constant set i. This flag points to an element of the user rate constant
array. U User rate constant vector calculated by the optional user rate constant subroutine. The user
flag indicates the element number in this array which is used in a given rate expression. When the user flag is not
specified, or when the user rate constant routine is not present, this parameter is set to 1.0.
* The concentration basis may be changed to other units using the Concentration basis field on the
Specs sheet or using the optional concentration basis subroutine. ** The reference temperature may be
specified globally on the Specs sheet or locally for each rate
constant set on the Rate-Constants sheet. If global and local reference temperatures are both unspecified then this
form of the equation is applied.
Customizing the Rate Expression; User Rate Constant Subroutine
You can modify the standard rate expression using the optional user rate constant feature. The rate
constant form includes a parameter called the user flag that identifies an element in an array of user rate
constants. This array is calculated by a user-written Fortran subroutine. The standard rate expression is
multiplied by the user rate constants as shown above. See Program Files\Aspen Plus
<version>\engine\user\USBRCN.f for a template for this routine.
Concentration Basis for Rate Calculations

Component concentrations depend on the calculation basis: molarity, mole fraction, mass fraction, mass
concentration, etc. The polymer mole fraction is converted into its segment mole fractions according to
the following equation:
Frac s ,
i=
Frac p
* SFRAC ( i
)* Mw
p Mwseg
avg
Where:
Frac
s i,
= Segment mole fraction

SFRAC i( ) = Polymer segment fraction (component attribute)
Mw
p
= Polymer molecular weight

Mwseg
avg
=
Average segment molecular weight = Nseg
SFRAC i Mw i
User Concentration Basis Subroutine
Alternately, a user basis subroutine can be used to calculate the component concentrations and the
reacting-phase holdup basis used in the component and attribute conservation equations. Use this
subroutine when rate constants are available in unusual concentration units not found in Aspen Polymers,
or when the reacting phase volume or area calculated by the reactor model is not consistent with the real
reactor (for example, in plug flow reactors with fixed liquid level). The segment-based model and step-
growth model can use the same basis routine. See Program Files\Aspen Plus
<version>\engine\user\USRMTS.f for a template for this routine.
The following assumptions are built into the segment-based reaction model:
All reactions between two segments are intermolecular; ring formation reactions are specifically
excluded unless the ring molecules are tracked as separate oligomer components
( )*
1
Reactions may occur anywhere in the polymer chain
Mass balance holds for components involved in the reactions on segment basis
Moment of chain length distribution calculations cover up to the first moment (ZMOM, SFLOW, FMOM).
Higher moments (SMOM, TMOM) are not predicted by the current version of the model
Since higher moments not covered, segment-based model should be last in reaction block sequencing

The segment-based reaction model calculates and returns the following information:
Rate of change for all components involved in reaction scheme, and rate of change for all segments
Polymer segment composition (SFLOW, SFRAC, EFRAC)
Zeroth moment of chain length distribution (ZMOM)
First moment of chain length distribution (FMOM)
Number average degree of polymerization (DPN)
Number average molecular weight (MWN)
When the Reacting Site is specified on the Specifications form, the model will calculate rates for the
zeroth moment, first moment, and segment flow rates at the specified site (attributes SZMOM, SFMOM,
and SSFLOW for the specified site number). These attributes are used to calculate the composite
attributes listed above.
This information is returned through the stream compositions for the component rate of change, and
through the polymer component attributes for the segment rate of change and moment calculations.
The rate of change of polymer mass is calculated as follows:
R
Nseg
Rs,
i*
Mw i
p
=
1
Mw
p
This is the sum of the rates of change of segment masses.

Each segment type is assigned a value , which indicates the number of points of attachment
connecting the segment to other segments in the polymer chain:
Segment Type
End 1 Repeat 2 Branch-3 3 Branch-4 4
The rate of change of the zeroth moment (
0
) is calculated from the rate of change of the first
moment (
1
) and the segment type ():
0
t=
t 11 - 2
t The factor of 12 accounts for the fact that each connection links two segments (without this
correction the points of connection are counted twice). This method is best illustrated through these
examples:
Valid Reaction Type Stoichiometry
1
12
0
Yes Initiation
PMM + 2
M+M E + E +2 +1 +1
No Initiation
PM 1
M R +1 +1 0
Yes Propagation
(addition)
E+M R + E +1 +1 0
Yes Propagation
(insertion)
PMP
n
+
1n +
PMP
n*
+
*
1n +
M R +1 +1 0
Yes Combination
PPP
n
+
m mn +
E+E R + R 0 +1 -1
Yes Combination
PPP
n
+
m mn +
E+E R -1 +0 -1
Yes Branching
PMP
n
+
1n +
R+M B3 + E +1 +1 0
Yes Branching
PPP
n
+
m mn +
R+E B3 + R 0 +1 -1
Yes Cross linking
PPP
n
+
m mn +
R+R B4 -1 +0 -1
M = Monomer; E = End group segment; B3 = Branch-3 segment; B4 = Branch-4 segment
This method lets you specify most classes of reactions, however special care must be taken to ensure
that the reaction is defined in a manner that is consistent with the previous equation. In particular, the
segment-based model does not allow initiation reactions of the type
PM 1
since the equation does not account
for the initial formation of polymer molecules through this mechanism. Note, however, that this
mechanism is valid since the same reaction can represent an insertion type propagation step in which the
active polymer end group is conserved.
User Subroutines
The segment-based power-law model can be customized by applying user- written subroutines. There
are two types of subroutines available. The concentration and holdup basis for the model can be changed
through a user basis subroutine. A user rate-constant subroutine can be used to extend the standard
reaction rate expression. These routines can be used together in any combination.
User Basis Subroutine
The user basis subroutine can be used to calculate the component concentrations and the reacting-phase
holdup (typically volume in a CSTR or batch reactor or active area in a PFR). This routine can also be
used to calculate rates of change of components and component attributes. Use this subroutine when
rate constants are available in unusual concentration units not found in Aspen Polymers, or when the
reacting phase volume or area calculated by the reactor model is not consistent with the real reactor (for
example, in plug flow reactors with fixed liquid level).
This subroutine can be used in conjunction with Fortran blocks and user component attributes to calculate
mass-transfer rates and to account for the influence of mass-transfer limitations on the component
concentrations in the reacting phase.
The argument list for the user basis routine is provided here. This argument list is prepared in a Fortran
template called USBBAS.F, which is delivered with Aspen Polymers.
SUBROUTINE USBBAS
INTB, NREALB, REALB, NINTM, 4 INTM, NREALM, REALM, NIWORK, IWORK, 5 NWORK,
WORK, NCPM, IDXM, X, 6 X1, X2, Y, DUM1, FLOWL, 7 FLOWL1, FLOWL2, FLOWV,
FLOWS, VLQ, 8 VL1, VL2, VV, VSALT, VLIQRX, 9 VL1RX, VL2RX, VVAPRX, VSLTRX,
RFLRTN, * IFLRTN, CRATES, NTCAT, RATCAT, CSS, 1 VBASIS, IPOLY, NSEG, IDXSEG,
AXPOS, 2 TIME )
SOUT Input REAL*8 (1) Stream vector NSUBS Input INTEGER Number of substreams in stream
vector IDXSUB Input INTEGER NSUBS Location of substreams in stream
vector ITYPE Input INTEGER NSUBS Substream type
vector
weights IDSCC Input HOLLERITH 2,NCC Conventional
component ID array NPO Input INTEGER Number of property methods NBOPST Input INTEGER 6, NPO Property
method array
NIDS Input INTEGER Number of reaction model IDs NINTB Input INTEGER User-specified length of INTB array
INTB Retention INTEGER NINTB Reactor block integer parameters (See
Integer and Real Parameters, page 154) NREALB Input INTEGER User-specified length of REALB array
REALB Retention REAL*8 NREALB Reactor block real parameters (See Integer and Real Parameters, page 154)
NINTM Input INTEGER User-specified length of INTM array INTM Retention INTEGER NINTM User subroutine
integer parameters
(See Integer and Real Parameters, page 154) NREALM Input INTEGER User-specified length of REALM array
REALM Retention REAL*8 NREALM User subroutine real parameters (See
Integer and Real Parameters, page 154) NIWORK Input INTEGER Length of user subroutine integer work
Packed Vectors, page 155) X Input REAL*8 NCPM
Overall liquid mole fractions X1 Input REAL*8 NCPM First liquid mole fractions X2 Input REAL*8 NCPM Second
liquid mole fractions Y Input REAL*8 NCPM Vapor phase mole fractions Dum1 Dummy REAL*8 (1) Argument
reserved for future
application FLOWL Input REAL*8 Total liquid flow rate,
kmol/sec FLOWL1 Input REAL*8 First liquid flow rate, kmol/sec FLOWL2 Input REAL*8 Second liquid flow rate,
kmol/sec FLOWV Input REAL*8 Vapor flow rate, kmol/sec FLOWS Input REAL*8 Salt flow rate, kmol/sec VL Input
REAL*8 Total liquid molar volume, m3/ kmol VL1 Input REAL*8 First liquid molar volume, m3/ kmol VL2 Input
REAL*8 Second liquid molar volume, m3/ kmol VV Input REAL*8 Vapor molar volume, m3/ kmol VSALT Input
REAL*8 Salt molar volume, m3/ kmol
VLIQRX Input REAL*8 Volume* of liquid in reactor, m3 VL1RX Input REAL*8 Volume* of first liquid in reactor, m3
VL2RX Input REAL*8 Volume* of second liquid in reactor, m3 VVAPRX Input REAL*8 Volume* of vapor in reactor,
m3 VSLTRX Input REAL*8 Volume* of salt in reactor, m3 RFLRTN Retention REAL*8 (1) Real retention for FLASH
IFLRTN Retention INTEGER (1) Integer retention for FLASH CRATES Output REAL*8 NCC Component rates of
change, kmol/m3-
sec NTCAT Input INTEGER Number of component
attributes RATCAT Output REAL*8 NTCAT Component attribute rates of change,
cat/m3-sec CSS Output REAL*8 NCC Concentration vector for the active
phase VBASIS Output REAL*8 Holdup basis used to calculate reaction
rates* IPOLY Input INTEGER Reacting polymer
component index NSEG Input INTEGER Number of segment components IDXSEG Input INTEGER NSEG Segment
component index vector AXPOS Input REAL*8 RPlug only: axial position, m TIME Input REAL*8 RBatch only: time,
sec
* When using molar concentrations, this parameter is volume of the reacting phase in 3m
in RCSTR and RBatch or the cross-sectional area of the reacting phase in 2m in RPlug.
Note: The argument lists for the segment-based user basis routine and step- growth user basis routine
are identical. Both types of models can reference the same basis routines.
Example 1 illustrates how to use the user basis routine to convert the concentration basis from the
standard molar concentration basis (mol/L) to a mass concentration basis (mol/kg). (Note: the current
version of Aspen Polymers supports several concentration basis through the BASIS keyword located on
the Specs sheet. This example is a demonstration). Using these units, the reaction rates are calculated in
units of mol/kg-sec. These rates are multiplied by the holdup basis (VBASIS) for the reactor in the
segment-based power-law model. The holdup basis must be consistent with the concentration basis, e.g.,
in this case it must be in kg. The holdup basis pertains to the reacting phase, it does not include the
phases that do not react.
Example 1: A User Basis Routine For the Mass-Concentration Basis
Ci
=
X
i M Liquid
C
i
= Mass-concentration of component i
X
i
= Mole fraction of component i

M
Liquid
= Average liquid phase

molecular weight of components in the
CALL PPMON_VOLL( TEMP, PRES, X, NCPMX, IDXM, 1 NBOPST, GLOBAL_LDIAG, 1, VLQ,
DVS, KER) C-unpack the mole fraction vector into the molar concentrations...
CALL SHS_UNPACK ( X , NCPMX, IDXM, CSS ) C --------------------------
------------------------------------- C C concentration (mole/kg)=(mole I /
mole liquid )*( mole liquid/kg) C C -----------------------------------------
----------------------
CSS(I) = CSS(I) * 1.D3 / STWORK_XMWL 10 CONTINUE C -----------------
---------------------------------------------- C C reacting phase basis must
be consistent with concentration basis (kg) C liquid mass inventory = liquid
volume * density C C --------------------------------------------------------
-------
VBASIS = VLIQRX * STWORK_XMWL * 1.D-3 / VLQ RETURN
The plug flow reactor model in Aspen Plus assumes that the vapor and liquid move at the same velocity
through the reactor (e.g., no-slip conditions). This assumption is not consistent with the physical reality of
polymer finishing reactors or wiped-film evaporators. The subroutine in Example 2 circumvents the no-slip
assumption in RPlug, allowing you to specify the volume occupied by the liquid phase. In this example,
you specifiy the first integer argument in the RPlug block as 1 and the first real argument as the volume
fraction of the reactor occupied by the liquid phase.
Example 2: A User Basis Routine to Specify Liquid Volume in RPlug
UFRAC = 1.D0 IF ( REALB(1) .NE. RGLOB_RMISS ) UFRAC = REALB(1) IF (
INTB(1).EQ.1 ) THEN C - unpack the mole fraction vector into the
molar concentrations... CALL SHS_UNPACK ( X , NCPMX, IDXM, CSS ) C -
concentration = mole fraction divided by molar
volume of phase DO 20 I = 1, NCOMP_NCC
CSS(I) = CSS(I) / VLQ 20 CONTINUE C - multiply total reactor volume by
user-specified
volume fraction - VBASIS = ( VLIQRX + VVAPRX ) * UFRAC
C - this line makes RPlug calculate liquid residence
time (not L+V) SOUT(NCOMP_NCC+8)=(SOUT(NCOMP_NCC+9)/ SOUT(NCOMP_NCC+6)) / VLQ
RETURN END IF
User Rate-Constant Subroutine

The user rate constant subroutine can be used to modify rate constant parameters for model-generated
and user-specified reactions. Use this routine to modify the standard power-law rate expression for non-
ideal reaction kinetics.
The user rate constant feature can be used to modify the standard power-law rate expression. This
subroutine returns a list of real values, which are stored in an array RCUSER. The length of this array is
defined by the keyword NURC (number of user rate constants) in the user rate constant subroutine form
(USER-VECS secondary keyword). Each of the elements in the user rate constant array can store a
different user rate constant. The USER-FLAG keyword in the Rate Constants form is used to specify
which user rate constant is used with a particular set of rate constants.
Elements 1 through NURC of RCUSER are calculated by a user rate-constant subroutine. The standard
rate expression is multiplied by the USER-FLAGth element of the user rate constant vector RCUSER. For
example, if the USER-FLAG field contains the number 4, the power-law rate term will be multiplied by
the fourth element of array RCUSER. By default, the USER-FLAG keyword is set to zero. The zeroth
element of the RCUSER array is set to a value of 1.0, so the rate expression remains unmodified unless
the USER- FLAG keyword is specified.
The argument list for the subroutine is provided here. This argument list is prepared in a Fortran template
called USBRCN.F, which is delivered with Aspen Polymers.
SUBROUTINE USBRCN
INTB, NREALB, REALB, NINTR, 4 INTR, NREALR, REALR, NIWORK, IWORK, 5 NWORK,
WORK, NCPM, IDXM, X, 6 X1, X2, Y, DUM1, VL, 7 VL1, VL2, VV, VSALT, IPOLY, 8
NSEG, IDXSEG, NCC, CSS, TEMP, 9 PRES, NURC, 1 RCUSER, CATWT )
SOUT Input REAL*8 (1) Stream vector NSUBS Input INTEGER Number of substreams in stream
vector IDXSUB Input INTEGER NSUBS Location of substreams in stream
vector ITYPE Input INTEGER NSUBS Substream type
vector
NPO Property method array (used by
FLASH) NIDS Input INTEGER Number of reaction
model IDs IDS Input HOLLERITH 2,NIDS Reaction model ID list:
i,1 reactor block ID i,2 reactor block type i,3 reaction block ID i,4 reaction block type NINTB Input INTEGER User-
specified length of INTB array INTB Retention INTEGER NINTB Reactor block integer parameters
(See Integer and Real Parameters, page 154) NREALB Input INTEGER User-specified length of REALB
array REALB Retention REAL*8 NREALB Reactor block real parameters (See Integer and Real Parameters, page
154) NINTR Input INTEGER User-specified length of INTM array INTR Retention INTEGER NINTR User subroutine
integer parameters
(See Integer and Real Parameters, page 154) NREALR Input INTEGER User-specified length of REALM
array REALR Retention REAL*8 NREALR User subroutine real parameters
(See Integer and Real Parameters, page 154) NIWORK Input INTEGER Length of user subroutine integer
work vector IWORK Work INTEGER NIWORK User subroutine integer work vector
(See Local Work Arrays, page 155)
NCPM Input INTEGER Number of components present in
the mixed substream (See Packed Vectors, page 155) IDXM Input REAL*8 NCPM Component sequence numbers
(See Packed Vectors, page 155) X Input REAL*8
NCPM Overall liquid mole fractions X1 Input REAL*8 NCPM First liquid mole fractions X2 Input REAL*8 NCPM
Second liquid mole fractions Y Input REAL*8 NCPM Vapor phase mole fractions Dum1 Dummy REAL*8 (1)
Argument reserved for future
application VL Input REAL*8 Total liquid molar volume,
m3/kmol VL1 Input REAL*8 First liquid molar volume, m3/kmol VL2 Input REAL*8 Second liquid molar volume,
m3/kmol VV Input REAL*8 Vapor molar volume,
m3/kmol VSALT Input REAL*8 Salt molar volume, m3/kmol IPOLY Input INTEGER Reacting polymer component
index NSEG Input INTEGER Number of segment components IDXSEG Input INTEGER NSEG Segment component
index vector NCC Input INTEGER Number of components (unpacked) CSS Input REAL*8 NCC Concentration vector
for reacting
species TEMP Input REAL*8 Temperature, K PRES
Input REAL*8 Pressure, Pa NURC Input INTEGER Number of user rate constants (See
User Rate-Constant Subroutine, page 144) RCUSER Output REAL*8 NURC User rate constant vector (See User
Rate-Constant Subroutine, page 144) CATWT Input REAL*8 Catalyst weight, kg (in RPLUG,
weight/length)
Example 3 illustrates how to use this subroutine to implement complex rate expressions in the segment-
based power-law model.
Example 3: Implementing a Non-Ideal Rate Expression
Suppose a side reaction QZ is first order with respect to component Q and first order with respect to a
catalyst C. The effectiveness of the catalyst is reduced by inhibitor I according to the following equation: [
C
eff
]
=
1+([aC
+ actual bT ] )
[I]
Where:
[C
eff
] = Effective catalyst concentration, mol/L

[C
actual
] = Actual catalyst concentration, mol/L

[ ]I = Inhibitor concentration, mol/L
T = Temperature, K
a,b = Equation parameters
The net rate expression can thus be written as:
[]
[ ] rate =
[Q
]
1
+(aC
+ actual
bT )
I
ko
e-
RE
*
T1-
T
1 ref
Where:
k
o
= Pre-exponential factor, (L/mol)/sec

E* = Activation energy
R = Gas law constant T
ref
= Reference temperature for k
o

The standard rate expression for side reactions is:
rate k o
e-
RE
*
T1-
T
1
Ci
*U(j
)i
Where:
= Product operator C i
=
ref
= Concentration of component i
= Power-law exponent for component i

U = User rate constant
j = User rate-constant flag
Suppose the rate constant for the uninhibited reaction is 3 10 -
3 (L/mol)/min at 150C, with an
activation energy of 20 kcal/mol, and the inhibition rate constants are A=0.20 L/mol, B=0.001 L/mol-K.
The stoichiometric coefficients and power-law exponents are specified directly in the Stoic and PowLaw-
Exp keywords. The Arrehnius rate parameters and reference temperature are also specified directly in the
model.
The parameters for the user rate constant equation can be specified using the optional REALRC list.
Including the parameters in the REALRC list allows the model user to adjust these parameters using the
standard variable accessing tools, such as Sensitivity, Design-Specification, and Data-Regression.
The resulting model input is summarized below:
USER-VECS NREALRC=2 NUSERRC=1
REALRC VALUE-LIST=0.2D0 0.001D0 STOIC 1 Q -1.0 / Z 1.0 POWLAW-EXP 1 Q 1.0 / C
1.0 RATE-CON 1 3D-3<1/MIN> 20.000<kcal/mol>
TREF=150.0<C> URATECON=1
The power-law term from this equation is:
rate =
ko
e-
RE
*
T1-
T
1 ref [ C ][ Q
Where:
[C] = Catalyst concentration, mol/L k
o
= Pre-exponential factor
Thus, the required user rate constant is:
U(j
=1
)
=
1(1
+(a+
bT )[ I
]
Where:
[I] = Inhibitor concentration, mol/L
T = Temperature, K
a, b = Equation parameters
An excerpt from the user rate constant subroutine for this equation is shown
below: C - Component Name - INTEGER ID_IN(2) DATA ID_IN /'INHI','BITO'/ C
====================================================================== C
EXECUTABLE CODE C
====================================================================== C -
find location of inhibitor in the list of components -
IF ( IDSCC(1,I).EQ.ID_IN(1).AND.IDSCC(2,I).EQ.ID_IN(2) ) I_IN=I 10
CONTINUE C - get the concentration of the inhibitor -
C_IN = 0.0D0 IF ( I_IN .GT.0 ) C_IN = CSS( I_IN ) C -------------------------
--------------------------------------------- C Parameters: each REALR
element defaults to zero if not specified C ---------------------------------
-------------------------------------
A = 0.0D0 IF ( NREALR .GT. 0 ) A = REALR( 1 ) B = 0.0D0 IF ( NREALR .GT. 1 )
B = REALR( 2 ) C ------------------------------------------------------------
---------- C User rate constant #1 U(1) = 1 / ( 1 + (A+BT)[I] ) C -----------
-----------------------------------------------------------
IF ( NURC.LT.1 ) GO TO 999
RCUSER(1) = 1.0D0 / ( 1.0D0 + ( A + B*TEMP ) * C_IN )
END IF 999 RETURN
Integer and Real Parameters

Each user model has two sets of integer and real parameters. The first set comes from the subroutine
form of the reactor block. The second set comes from the subroutine form of the step-growth reactions
model. Each of these parameters are retained from one call to the next, thus these parameters can be
used as model inputs, outputs, or retention.
The reactor block integer and real parameters can be used to specify data which are specific to a
particular unit operation, such as reactor geometry, mass transfer coefficients, etc. The integer and real
parameters in the subroutine forms can be used to specify global parameters, such as rate constants or
Local Work Arrays

You can use local work arrays by specifying the model workspace array length on the Subroutine forms.
These work areas are not saved from one call to the next. Both user subroutines share a common work
area. User subroutines are responsible for initializing the work space at the start of each subroutine.
Packed Vectors
Aspen Plus frequently uses a technique called packing to minimize simulation time. The user models
previously described use packed vectors to track the mole fractions of each phase (vectors X, X1, X2,
and Y). These vectors contain NCPM elements (Number of Components Present in the Mixed
substream). The component index associated with each element is listed in the vector IDXM. All other
vectors used by the model, including the rates vectors and the component concentration vectors, are
unpacked.
Calculating Unpacked Component Concentrations
Calculate unpacked component concentrations of the first liquid phase given the packed mole fractions of
the first liquid phase and the molar volume of the first liquid phase. IF ( VL1 .GT. 0.D0 .AND.
FLOWL1.GT.0.D0 ) THEN
DO 10 I = 1, NCPM
CSS(I) = X1( IDXM( I ) ) / VL1 10 CONTINUE END IF
Note: NCPM steps were required to load the concentration vector. Since NCPM is always less than or
equal to NCC (total number of conventional components), there is a reduction in the required number of
steps to perform the operation. Using packed arrays for calculations reduces overhead by eliminating the
need to check for zero values when carrying out mathematical operations.
Specifying Segment-Based Kinetics
Accessing the Segment-Based Model
To access the Segment-based power-law kinetic model: 1 From the Data Browser, click Reactions. 2
necessary, change the default ID for the reaction. 5 Select Segment-Bas as the reaction type and click
OK.
Specifying the Segment-Based Model

The Segment-Based model input forms are as listed below. Use these forms to specify reaction
conditions and build a reaction scheme.
Use the Specifications forms to define reaction stoichiometry, enter reaction rate constant parameters,
assign rate constants to reactions, and to specify the concentration, reacting phase, reacting site, and
other model options.
Use this sheet To
Specs Define reacting phase, concentration basis, and reacting
polymer Reactions Define reaction stoichiomerty and enter reaction rate constant
parameters Rate Constants Specify reaction rate parameters and catalysts Assign Rate
Constants
Associate each reaction with one or more sets of rate constants
Use the User Subroutines forms to specify the names and parameters for optional user basis and rate
constant subroutines.
Use this sheet To
Rate Constants Specify the name of the user kinetics routine, the number of
user rate constants calculated by the routine, and to give the integer and real arguments for the user arrays for this
routine Basis Specify the name of the user concentration and holdup basis routine and give the integer and real
arguments for the user arrays for this routine
Specifying Reaction Settings

Use the Specs sheet to define the reaction model settings: 1 In the Reacting polymer field, specify the
reacting polymer.
2 In the Reference temperature field, specify the default global reference
temperature for rate constant parameters. 3 In the Phase field, specify the phase in which reactions
occur.
If the specified phase is Liquid phase 1 or Liquid phase 2 you may also choose to specify additional
options (under the Options frame) to control how calculations are performed when the phases collapse
into a single liquid phase. For details, see Selecting the Reacting Phase next. 4 In the Basis field, specify
the basis for component concentrations in the
reaction rate calculation. Optionally, you can apply a user subroutine to calculate the concentration and
holdup basis. For details, see User Basis Subroutine on page 275. 5 If desired, specify a site number in
the Reacting Site field, and specify which method to use in the Segment concentration basis frame. For
details, see Selecting the Reacting Site on page 286.
Selecting the Reacting Phase

The Specs form lets you specify the phase in which the reactions occur.
Select the appropriate phase from the list in the Reacting Phase field. All of the reactions in the segment-
based reaction object are assumed to take place in the same phase. You can use two (or more) segment-
based models in the same reactor to account for simultaneous reactions in multiple phases.
ensure the specified reacting phase exists.
If the Reacting Phase option is set to Liquid phase 1 or Liquid phase 2 the model assumes two liquid
phases exist. When the named phase is not present, the model prints a warning message and sets the
reaction rates to zero. There are two options for handling phase collapse:
collapse.
These options are especially convenient when modeling simultaneous reactions in two liquid phases
using two step-growth models. In this situation, one would typically select the Use bulk liquid option for
one phase and not the other (to avoid double-counting reactions when one phase collapses).
Selecting the Reacting Site

The segment-based power-law reaction model can be used in conjunction with other Aspen Polymers
reaction models to define side reactions. When combining the segment-based model with a Ziegler-Natta
or ionic polymerization model, use the Reacting Site field on the Specs form to assign the reaction rates
to a particular active site.
Note: The Segment Concentration Basis field lets you select the calculation method for the
concentrations used within the reaction model.
When you select Use composite segment concentration the segment mole fractions used to calculate
the reaction rates are calculated from the following equation:
Frac s ,
i=
Frac p
* SFRAC ( i
)* Mw
p Mwseg
avg
When you select Use segment concentration at specified site the following equation is applied:
Frac is ,
=
Frac p *
SSFRAC *),( ji Mw
avg p Mwseg
Where j refers the specified reacting site number.
In both cases the attribute rates of change are mapped to the component attributes associated with the
user-specified reacting site number (e.g., SSFLOW(i,j), SZMOM(i,j), etc.)
Building A Reaction Scheme

You can build a list of reactions on the Reactions sheet. To do this you must specify a reaction
stoichiometry. The Data Browser window can be resized to better view the reaction listing. Use the
following options:
Click To
reactions
Click To
Hide/Reveal
Activate or de-activate a set of reactions. Inactive reactions are highlighted with a gray background.
Delete
Adding or Editing Reactions
To add a new reaction to the scheme or to edit an existing reaction, click New or Edit to open the Edit
Stoichiometry subform:
Note that in the Reaction no. field, a unique number is assigned to the reaction being added.
1 Specify the Component ID and stoichiometric Coefficient for the
reactants. Reactants must have a negative coefficient. 2 Specify the Component ID and stoichiometric
Coefficient for the
products. Products must have a positive coefficient.
Specifying Reaction Rate Constants

The rate constants are summarized in a grid on the Rate Constants sheet:
1 In the
k
o field, enter the pre-exponential factor.
Note: Reaction rates are defined on a molar basis (moles per volume per time). The time units for the pre-
exponential factors are specified directly on the Rate Constant form. By default, the concentration units
are assumed to be in SI units (kmole/m3 or mole/L). You can change the concentration basis to other
units using the Concentration Basis field of the Specs sheet. Alternately, you may apply a user basis
subroutine.
2 In the field, enter the activation energy. 3 In the b field, enter the temperature exponent.
4 In the
T
ref field, enter the reference temperature. If this field is left blank the reference temperature will
default to the user-specified global reference temperature on the Specs form. 5 If desired, specify a
Catalyst Species and Catalyst Order. 6 If desired, specify a user rate constant element number on the
User Flag
field (For details, see the User Rate-Constant Subroutine on page 144).
Note: Use the Catalyst Species field to associate a rate constant with a particular catalyst. If you leave
this field blank (empty) the model drops the catalyst concentration term from the rate expression. Use the
Catalyst Order field to specify the reaction order with respect to the catalyst (the model assumes first
order by default).

There are two options for assigning rate constants to reactions. By default, the model assumes there is
exactly one set of rate constants for each reaction (for example, rate constant set i is used for reaction
i).
Alternately, you may use the Assign User Rate Constant sheet to assign one or more sets of rate
constants to each reaction. This feature is convenient in two situations:
E
a
Models with a large number of user side reactions when the rate constants of the various reactions are
equal or are related to each other algebraically.
Reactions catalyzed by several catalysts simultaneously.
The assignment option is recommended for two reasons:
You can enter several sets of rate constants for each reaction without re- entering the reaction
stoichiometry.
You can assign a set of rate constants to multiple reactions, reducing the number of adjustable
parameters in the model, which makes it easier to fit against data.
When several rate constants are assigned to a reaction the model calculates a net rate constant by
summing all of the listed rate constants and multiplying the sum by a specified activity.
To assign rate constants to reactions: 1 On the Assign User Rate Constants form, use the Activity field to
specify the activity factor (default value is unity). 2 In the Rate Constant Sets field, select from the list
of pre-defined rate
constant sets for each reaction. These numbers refer to the row numbers on the Rate Constants form.
Including a User Rate Constant Subroutine

Use the User Subroutines Rate Constants form to specify parameters for user rate constants calculations:
1 In subroutine Name, enter the name of the Fortran subroutine. 2 Specify the size of vectors for Integer,
Real and No. const. in Number
of parameters. 3 Specify the size of vectors of Integer and Real in Length of work
arrays. 4 Enter integer and real parameter values in Values for parameters
columns.
Including a User Basis Subroutine

Use the User Subroutines Basis form to specify parameters for basis calculations: 1 In subroutine Name,
enter the name of the Fortran subroutine. 2 Specify the size of vectors for Integer and Real in the Number
of
parameters and Length of work arrays. 3 Enter integer and real parameter values in Values for
parameters
columns.
References
Wiley.
Kroschwitz, J. (Ed.). (1990). Concise Encyclopedia of Polymer Science and Engineering. New York:
Wiley.
Odian, G. (1991). Principles of Polymerization, 3rd Ed. New York: Wiley.
Rodriguez, F. (1989). Principles of Polymer Systems. New York: Hemisphere.
Rudin, A. (1982). The Elements of Polymer Science and Engineering. New York: Academic Press Inc.
14 Steady-State Flowsheeting
Aspen Polymers (formerly known as Aspen Polymers Plus) allows you to model polymerization processes
in both steady-state and dynamic mode. In this chapter, flowsheeting capabilities for modeling processes
in steady-state mode are described.
Polymer Manufacturing Flowsheets, 291
Modeling Polymer Process Flowsheets, 293
Steady-State Modeling Features, 294
Following this introduction, Aspen Polymers flowsheeting capabilities for modeling steady state processes
are discussed in several sections.
Steady-State Unit Operation Models, 295
Plant Data Fitting, 339
User Models, 359
Application Tools, 375
Polymer Manufacturing Flowsheets

Polymer production processes are usually divided into the following major steps:
Monomer synthesis and purification
Polymerization
Recovery/separation
Polymer processing
The modeling issues of interest in each of these steps were discussed in Chapter 1, and are summarized
in the following figure. The focus here is on the various unit operations required in these processing
steps.
14 Steady-State Flowsheeting 291
Monomer Synthesis
During monomer synthesis and storage the engineer is concerned with purity since the presence of
contaminants, such as water or dissolved gases, may adversely affect the subsequent polymerization
stage by poisoning catalysts,
292 14 Steady-State Flowsheeting
depleting initiators, causing undesirable chain transfer or branching reactions which would cause less
effective heat removal. Another concern is the prevention of monomer degradation through proper
handling or the addition of stabilizers. Control of emissions, and waste disposal are also important factors.
Polymerization
The polymerization step is the most important step in terms of capital and operating costs. The desired
outcome for this step is a polymer product with specified properties (e.g. molecular weight distribution,
melt index, viscosity, crystallinity) for given operating conditions. The obstacles that must be overcome to
reach this goal depend on the type of polymerization process.
Polymerization processes may be batch, semi-batch, or continuous. In addition, they may be carried out
in bulk, solution, suspension, or emulsion. Bulk continuous systems provide better temperature and
molecular weight control at the expense of conversion; batch systems offer less control over molecular
weight. In addition, they may result in a high viscosity product and require high temperatures and
pressures. Solution systems also provide good temperature control but have associated with them the
cost of solvent removal from the polymer.
In summary, for the polymerization step, the mechanisms that take place during the reaction introduce
changes in the reaction media which in turn make kinetics and conversion, residence time, agitation, and
heat transfer the most important issues for the majority of process types.
Recovery / Separations
The recovery/separation step is the step where the desired polymer produced is further purified or
isolated from by-products or residual reactants. In this step, monomers and solvents are separated and
purified for recycle or resale. The important issues for this step are phase equilibrium, heat and mass
transfer.
Polymer Processing
The last step, polymer processing, can also be considered a recovery step. In this step, the polymer slurry
is turned into solid pellets or chips. Heat of vaporization is an important issue in this step (Grulke, 1994).
Modeling Polymer Process Flowsheets

The obvious requirement for the simulation of process flowsheets is the availability of unit operation
models. Once these unit operation models are configured, they must be adjusted to match the actual
process data. Finally, tools must be available to apply the fitted model to gain better process
14 Steady-State Flowsheeting 293
understanding and perform needed process studies. As a result of the application of the process models,
engineers are able to achieve goals such as production rate optimization, waste minimization and
compliance to environmental constraints. Yield increase and product purity are also important issues in
the production of polymers.
Steady-State Modeling Features

Aspen Polymers has tools available for addressing the three polymer process modeling aspects.
Unit Operations Modeling Features

A comprehensive suite of unit operations for modeling polymer processes is available in Aspen Polymers.
These include mixers, splitters, heaters, heat exchangers, single and multistage separation models,
reactors, etc. For more information on available unit operation models, see Steady-State Unit Operation
Models on page 295.
Plant Data Fitting Features

Several tools are available for fitting process models to actual plant data. Property parameters may be
adjusted to accurately represent separation and phase equilibrium behavior. This can be done through
the Data Regression System (DRS). See the Aspen Plus User Guide for information about DRS.
Another important aspect of fitting models to plant data has to do with the development of an accurate
kinetic model within the polymerization reactors. The powerful plant data fitting feature (Data-Fit) can be
used for fitting kinetic rate constant parameters. For more information, see Plant Data Fitting on page
339.
Process Model Application Tools

The tools available for applying polymer process models include capabilities for performing sensitivity, for
performing optimizations, and for applying design specifications. For more information, see Application
Tools on page 375.
References
Dotson, N. A, Galvn, R., Laurence, R. L., & Tirrell, M. (1996). Polymerization Process Modeling. New
294 14 Steady-State Flowsheeting
15 Steady-State Unit Operation
Models
This section summarizes some typical usage of the Aspen Plus unit operation models to represent actual
unit operations found in industrial polymerization processes.
Summary of Aspen Plus Unit Operation Models, 295
Distillation Models, 301
Reactor Models, 302
Mass-Balance Reactor Models, 302
Equilibrium Reactor Models, 304
Kinetic Reactor Models, 304
Treatment of Component Attributes in Unit Operation Models, 335
Summary of Aspen Plus Unit Operation

Models
Aspen Plus includes a number of basic unit operation models that are typically used to represent one or
more unit operations found in real processes. These models may be used alone to represent equipment
such as pumps, heaters, valves, mixers, etc., or they may be used as generic tools to build models of
more complex unit operations.
The following table summarizes the available unit operation models:
Basic Unit Operation Models and Stream Manipulators
Dupl Copies inlet stream to any number of outlet streams Flash2 Performs two-phase (vapor-liquid) or three-phase
(vapor-liquid-solid)
phase equilibrium calculations Flash3 Performs three-phase (vapor-liquid-liquid) phase equilibrium
calculations FSplit Splits inlet stream to any number of outlet streams
15 Steady-State Unit Operation Models 295
Basic Unit Operation Models and Stream Manipulators
Heater Represents heaters, coolers, or mixers with known heat duty or
specified temperature Mixer Adiabatic mixing of any number of feed streams Mult Multiplies stream
flow rates by a constant Pipe Calculates pressure drop through pipelines Pump Represents pumps or liquid
standpipes (pressure must be specified)
Distillation and Fractionation Models
Sep Mass-balance model for separation operations with any number of
product streams Sep2 Mass-balance model for separation operations with two product
streams RadFrac Predictive multistage distillation model MultiFrac Predictive model for complex
distillation operations with multiple
columns
Reactor Models
RStoic Mass-balance model based on specified conversion for any number of
stoichiometric reactions RYield Mass-balance model based on specified product yield for any number of
stoichiometric reactions REquil Chemical equilibrium calculated from user-specified equilibrium
constants RGibbs Chemical equilibrium calculated by Gibbs free-energy minimization RCSTR
Predictive, reaction rate-based model to simulate continuous stirred
tank reactors RPlug Predictive, reaction rate-based model to simulate continuous plug-flow
reactors RBatch Predictive, reaction rate-based model to simulate batch and semi-batch
stirred tank reactors
Dupl
The Dupl block copies one inlet stream to two or more outlet streams. By design, the mass flow rate and
attribute rates out of this block will be greater than the flow rates into the block, violating mass and
attribute conservation principles.
Frequently, the Dupl block is used as a shortcut to reduce the simulation time required to model a
process consisting of two or more parallel process lines. For example, consider the process shown here:
Operating Conditions
R1A R1B R2A R2B R3A R3B
Temperature, C
250 250 260 260 270 265
Pressure, torr 760 760 1200 1200 1500 1700
Volume, liter 2000 2000 1500 1500 1000 1200
296 15 Steady-State Unit Operation Models
The second unit (R2A and R2B) in the A and B lines consist of identical unit operations operating at
the same conditions. The third unit (R3A and R3B) operates differently in the two lines. Since the
process lines are identical up to the third unit, there is no need to include both process lines in the model.
Instead, we can consider one line, such as A and duplicate the outlet stream at the point where the
process conditions diverge from each other.
Another application of the Dupl model is to carry out simple case studies. For example, assume there are
two proposed scenarios for carrying out a given reaction. In the first scenario, the reaction is carried out at
a high temperature in a small reactor with a short residence time. In the second scenario, the reaction is
carried out at a low temperature in a large reactor
with high residence times. The two reactors can be placed in a single flow sheet model. The duplicator
block is used to copy one feed stream to both reactors. The two cases can be compared by examining
the stream summary.
Flash2
The Flash2 block carries out a phase-equilibrium calculation for a vapor-liquid split. The chemistry
feature of this block can be used to extend the phase equilibrium to vapor-liquid-solid systems. The free-
water option can be used to extend the phase equilibrium calculations to include a free water phase in
addition to the organic liquid phase.
The Flash2 model can be used to simulate simple flash drums with any number of feed streams. The
model is also a good tool for representing spray condensers, single-stage distillations, knock-back
condensers, decanters, and other types of equipment which effectively operate as one ideal stage.
The Flash2 model assumes a perfect phase split, but an entrainment factor can be specified to account
for liquid carryover in the vapor stream. The entrainment factor is specified by the user, it is not calculated
by the model. If a correlation between the vapor flow rate and the entrainment rate is available, this
correlation can be applied to the model using a Fortran block which reads the vapor flow rate calculated
by the Flash block, calculates the entrainment rate, and writes the resulting prediction back to the Flash
block. Note that this approach creates an information loop in the model which must be converged.
The Flash2 block does not fractionate the polymer molecular weight distribution. Instead, the molecular
weight distribution of the polymer in each product stream is assumed to be the same as the feed stream.
Flash3
The Flash3 block carries out phase-equilibrium calculations for a vapor-liquid- liquid splits. The liquid
phases may be organic-organic (including polymer- monomer) or aqueous-organic. For aqueous-organic
systems, the Flash3 model is more rigorous than the Flash2/free water approach described above. The
key difference is that the Flash3 model considers dissolved organic compounds in the aqueous phase
while the free water approach assumes a pure water phase.
Generally, three-phase flashes are more difficult to converge than two-phase flashes. Three-phase flash
failures may indicate bad binary interaction parameters between the components. The problem may also
stem from bogus vapor pressures or heats of formation. In general, it is a good idea to study two-phase
splits for the system in question before attempting to model a three-phase decanter or reactor.
As with the two-phase flash, the three-phase flash is more stable if temperature and pressure are
specified. Other options, such as duty and vapor fraction, are more difficult to converge. Temperature
estimates may aid convergence in duty-specified reactors.
The Flash3 block does not fractionate the polymer molecular weight distribution. Instead, the molecular
FSplit
The flow splitter block, FSplit, is used to represent valves or tanks with several outlets. The outlet flow
rates can be specified on a mass, mole, or volume basis, or they can be specified as a fraction of the feed
stream. In general, the fraction specifications are best because they are independent of the feed stream
flow rates. This makes the model more flexible and reliable when using tools like SENSITIVITY or
DESIGN-SPEC which might directly or indirectly manipulate the stream which is being split. The FSplit
block can also be used with reactor models to account for back-mixing.
The FSplit block assumes that the class 2 polymer attributes split according to mass mixing rules. For
example, if the outlet stream is split 60:40, then the class 2 attributes, such as the segment flow rates, are
also split 60:40. This approach is identical to assuming that the properties of the polymer in each outlet
stream are the same as the properties of the polymer in the inlet stream.
Heater
Heater can be used to represent heaters, coolers, mixers, valves, or tanks. The Heater block allows you
to specify the temperature or heat duty of the unit, but does not carry out rigorous heat exchange
equations. Any number of feed streams can be specified for the Heater block. This block follows the same
mixing rules as the Mixer model.
Mixer
The mixer block, Mixer, is used to mix two or more streams to form a single mixed outlet. The mixer block
can be used to represent mixing tanks, static mixers, or simply the union of two pipes in a tee. The Mixer
model assumes ideal, adiabatic mixing. The pressure of the mixer can be specified as an absolute value
or as a drop relative to the lowest feed stream pressure.
The Mixer model is functionally equal to the Heater model, except it only allows adiabatic mixing. For this
reason, the Heater model may be a better choice for modeling mixing tanks.
The Mixer block assumes that the class 2 polymer attributes are additive. For example if stream A and
B are mixed to form stream C, and the zeroth moments of a polymer in stream A and B are 12
kmol/sec and 15 kmol/sec, then the polymer in the product stream has a zeroth moment of 12+15=27
kmol/sec.
Mult
The Mult block is used to multiply the flow rate of a stream. A common application of this block is to
collapse two parallel process line models into a
single line to avoid unnecessary duplicate calculations. For example, consider the process shown here:
In this process, the A and B lines consist of identical equipment with the same operating conditions.
The Mult blocks HALF and TWICE are used to divide the feed stream flow rate by two after R1,
representing the split between lines, and to double the product flow rate, representing the junction of the
parallel lines into a single line at R3. This technique avoids the duplicate calculations for R2 A and B
reactors, which should give the same results. This technique can save a great deal of simulation time.
Pump
The Pump block changes the pressure of a stream. This block can be used to represent an actual pump,
or it can be used to represent pressure increases due to liquid head in standpipes.
Pipe
The Pipe model is used to calculate pressure drops in pipelines. The algorithms in this model are not
designed for non-ideal fluids such as polymers, so the pipe model should be used with caution in polymer
process models. A better option to calculate pressure drops in polymer pipelines is to use RPlug with a
user-written pressure-drop subroutine.
Sep
The Sep block is a generic separation model that allows component fractionation between two or more
product streams. The products can be split according to flow rate or fractional specifications. The Sep
block is commonly used to represent distillation columns or other separation equipment when the product
stream purity is well known and the details of the separation process are not important.
The Sep block does not fractionate the polymer molecular weight distribution. Instead, the molecular
Sep2
The Sep2 block is a generic separation model that allows component fractionation between two product
streams. The products can be split according to flow rate or fractional specifications. The Sep2 block is
commonly used to represent distillation columns or other separation equipment when the product stream
purity is well known and the details of the separation process are not important. Compared to the Sep
block, the Sep2 block has more flexible input options, but it only allows two outlet streams.
The Sep2 block does not fractionate the polymer molecular weight distribution. Instead, the molecular
Distillation Models
Aspen Plus includes several shortcut distillation models (DISTL, SFRAC, etc.) which can be used to
represent distillation columns. These blocks do not fractionate the polymer molecular weight distribution.
Instead, the molecular weight distribution of the polymer in each product stream is assumed to be the
same as the feed stream. The class-2 component attributes in each product stream are set proportional
to the mass flow rate of the attributed component in each product stream.
With the exception of the RadFrac model, the rigorous distillation models in Aspen Plus do not account
for component attributes.
RadFrac
The RadFrac block is a rigorous multistage distillation model for two- and three-phase systems. RadFrac
allows polymer feed streams at any tray, but it does not account for polymerization reaction kinetics. The
molecular weight distribution and other polymer properties are not fractionated between the phases.
Instead, the class-2 component attributes of the polymer components are split at each stage in proportion
to the polymer component mass fractions. For example, if 90% of the polymer fed to a given tray goes to
the liquid phase leaving that tray, then 90% of the zeroth moment and other class-2 attributes are
assigned to the liquid phase on that tray.
Reactor Models
Aspen Plus includes three classes of reactor models which include various levels of rigor and predictive
capability. These classes are: (1) mass-balance models; (2) equilibrium models; and (3) rigorous kinetic
models.
The least predictive models, RStoic and RYield, calculate output flow rates based on user-specified input
flow rates. If polymer components are involved in the reactions, then the component attributes associated
with the polymer components must be specified for the product stream. These models calculate the mass
and energy balances, but they do not perform rigorous kinetic calculations.
The RGibbs and REquil models assume chemical and phase equilibrium. When polymer components are
involved in the reactions, then the specified stoichiometry must be consistent with the reference molecular
weight of the polymer component. In addition, the component attribute values for the polymer product
must be specified by the user. Since the solution algorithms for these models do not consider the
influence of the segmental composition of polymer components, they cannot be applied to copolymers.
Rigorous kinetic models include RCSTR (continuous stirred tank reactor), RPlug (plug-flow reactor
model), and RBatch (batch stirred tank reactor). Each of these models can consider one, two, or three
reacting phases. These reactor models are with the reaction kinetic models to predict product stream
composition and flow rates based on calculated reaction rates.
Mass-Balance Reactor Models

RStoic
The RStoic reactor model is used to represent reaction equipment when reaction kinetics are unknown or
are unimportant, for example when reactions are very fast and proceed until the limiting reagent is
exhausted. RStoic requires knowledge of the net reaction stoichiometry, and the extent of reaction or
conversion of a key component.
RStoic calculates the product stream flow rates based on user-specified reaction stoichiometries and
extent of reaction or conversion of a key component. The reaction stoichiometry statements may include
monomers, oligomers, or polymers, but may not include segments. Instead, the segment information
(SFLOW or SFRAC) must be specified as component attributes in the COMP-ATTR sentence.
Reactions Involving Polymers

If polymer components are involved in any of the reactions, use the COMP- ATTR form to specify
molecular weight values (MWN, MWW or PDI) or degree of polymerization (DPN, DPW or PDI ) for the
polymer products. Specify the SFRAC attribute for homopolymers or copolymers with a known product
polymer composition. For copolymers with product compositions which
depend on the feed flow rates of monomers or polymer segments, specify dummy values for the SFLOW
attribute and use a user-written Fortran block to predict product segment flow rates which are consistent
with the calculated product flow rates. Write the calculated results into the product stream of the RStoic
block.
When some of the specified reactions involve polymers, the reaction stoichiometry must be written in a
manner consistent with the reference molecular weight of the polymer component. Otherwise, the mass
and energy balance calculations will not be consistent.
Simulating Polymer Phase Change

The RStoic model may be used with the substream feature to simulate phase changes in polymers. For
example, the user may define a reaction to convert polymer from the liquid or amorphous state (in the
MIXED substream) to crystalline polymer (in the CISOLID) substream. Conversely, melting can be
simulated as a reaction that converts polymer in the CISOLID substream to polymer in the MIXED
substream.
When RStoic is used in this manner, the model automatically fractionates the component attributes
between the product substreams. If the user does not specify the product component attributes, the
model sets the values of the class-2 attributes in each substream proportional to the flow rate of the
attributed component in the substream. In effect, the model assumes that there is no selectivity of
properties between the product phases. The polymer in each product phase will have the same
characteristics (segment composition, mole weight, etc) as the polymer in the feed stream.
RYield
The RYield reactor model is used to represent reaction equipment when reaction kinetics are unknown or
are unimportant, and the reactions result in a product distribution with a known yield.
RYield calculates the product stream flow rates based on user-specified reaction stoichiometries and
yield distributions. The reaction stoichiometry statements may include monomers, oligomers, or polymers,
but may not include segments. Instead, the segment information (SFLOW or SFRAC) must be specified
as component attributes in the COMP-ATTR sentence.
If polymer components are involved in any of the reactions, use the COMP- ATTR form to specify
molecular weight values (MWN, MWW or PDI) or degree of polymerization (DPN, DPW or PDI ) for the
polymer products. Specify the SFRAC attribute for homopolymers or copolymers with a known product
polymer composition. For copolymers with product compositions which depend on the feed flow rates of
monomers or polymer segments, specify dummy values for the SFLOW attribute and use a user-written
Fortran block to predict product segment flow rates which are consistent with the calculated yield. Write
the calculated results into the product stream of the RYield block.
When some of the specified reactions involve polymers, the reaction stoichiometry must be written in a
manner consistent with the reference
molecular weight of the polymer component. Otherwise, the mass and energy balance calculations will
not be consistent.
Equilibrium Reactor Models

REquil
The REquil model calculates product stream flow rates using equilibrium constants determined from
Gibbs free energy. The equilibrium constants are based on user-specified reaction stoichiometries and
yield distributions. The reaction stoichiometry statements may include monomers or oligomers, but may
not include polymers or segments. If the feed stream includes polymer components, the attributes of the
polymer components will be copied to the outlet stream.
RGibbs
The RGibbs model uses the Gibbs free energy minimization technique to determine the composition of
each phase. This algorithm cannot predict the product of equilibrium polymerization reactions. Polymer
phase equilibrium, however, can be predicted by the model. The RGibbs phase equilibrium algorithm
assumes that the composition and molecular weight distribution of a polymer component is equal in each
of the product phases. The class-2 component attributes of the polymer component are set in proportion
to the mass flow of the polymer component in each of the product phases. The mass flow rates in the
product phases are set by the Gibbs free energy minimization algorithm.
To properly split component attributes among the RGibbs solution phases, use the "Phase equilibrium
only" option. With this the model can predict multiple liquid phases such as three liquid phases. Surface
tension effects are not considered. If you are certain that there will be no vapor phase, uncheck the
"Include vapor phase" box to speed up calculations. Use one outlet stream for each predicted phase, to
separate out the component attributes of that phase.
Kinetic Reactor Models

RCSTR
The RCSTR model represents a continuous stirred tank reactor with one or more phases.
The model assumes perfect mixing within and between the phases, phase equilibrium, and isothermal,
isobaric operation. Non-ideal mixing can be represented using a network of RCSTR models.
Temperature
The CSTR model allows you to specify duty or temperature. If duty is specified, it is a good idea to
provide a temperature estimate, T-EST, to improve the convergence of the model. The maximum
temperature step size, T-STEP, may also influence the CSTR convergence. This parameter defaults to
50C, which results in substantial changes in reaction rates for reactions with typical activation energies.
The temperature/duty iteration loop is referred to as the Energy Balance or EB-LOOP in the CSTR
diagnostics.
Pressure
Pressure can be specified as an absolute value or as a pressure drop relative to the feed stream with the
lowest pressure. In Aspen Plus, pressure drops are expressed as non-positive pressure specifications
given in absolute pressure units.
Residence Time
The RCSTR model allows you to specify the effective hold-up in several different ways. For single-phase
reactors, you can specify the total reactor volume or the total residence time. If the residence time is
specified, then the estimated reactor volume should be specified to improve the residence- time/volume
loop convergence (RT-LOOP).
When two or more condensed phases are present, the RCSTR model assumes that each condensed
phase has the same residence time. This no-slip assumption implies that the volume ratios of the
condensed phases in the reactor are equal to the volume flow ratios of the condensed phases exiting the
reactor.
For multiphase reactors, specify the condensed phase volume or residence time in addition to the total
reactor volume. Do not specify the total residence time, as this residence time is the average of the vapor
and liquid phases. If the reacting phase residence time is specified, provide an estimate for the reacting
phase volume. This will improve the reactor convergence. If residence time convergence is troublesome,
try adjusting the volume step size.
Multiphase Reactors
The RCSTR model can be used to simulate single- or multiple-phase reactors. The valid-phases keyword
is used to define the number and type of fluid phases present in the reactor.
Amorphous solid polymers are treated as a liquid phase in Aspen Polymers (formerly known as Aspen
Polymers Plus). Crystalline solids can be addressed by defining a CISOLID substream to track the flow
rate of each inert crystalline solid.
Dissolving or crystallizing solids can be captured using the Chemistry feature to define chemical
equilibrium reactions between the solid and fluid phases. Note, however, that the current version of
RCSTR does not allow components to appear in both kinetic reactions and in chemistry equilibrium
reactions.
The user may attach multiple outlet streams directly to the reactor model. The phase or phases flowing to
these streams are identified on the streams form. When solids are present the solid phases will be added
to the liquid outlet.
In older releases of Aspen Plus, the RCSTR model had one process fluid outlet stream containing all of
the phases exiting the reactor. This option is still supported in the current release for upward compatibility.
As shown in the following figure, a Flash2 or Flash3 block can be used to split the mixed outlet stream of
the reactor:
Reactors with Non-Ideal Mixing

Networks of RCSTR and RPlug blocks can be used to account for non-ideal mixing found in industrial
reactors. For example, many industrial reactors are divided into zones by vertical or horizontal baffles. In
addition, some reactors have poor mixing characteristics which result in dead zones. The figures that
follow demonstrate ways to model some types of real reactors.
Since many of the network models involve recycle loops, they may require substantially more simulation
time than a single RCSTR block. In addition, the recycle loop convergence may make the model more
difficult to converge. For these reasons, the simplest model that agrees with process data is always the
best choice.
This figure shows a two-phase CSTR with horizontal partitions:
This figure shows a two-phase CSTR with vertical partitions:
This figure shows a two-phase CSTR with an external heat exchanger:
This figure shows a two-phase CSTR with a dead-zone:
RCSTR Algorithm
The RCSTR model uses a trial-and-error technique to solve the mass and energy balance equations.
Trial-and-error solutions are difficult to reach when the reaction rates are high, the variables cover several
orders of magnitude, when many equations must be solved simultaneously, and when the variables are
strongly related to each other. All of these conditions are found in polymerization reaction kinetics, making
reactor convergence especially challenging.
A good understanding of the design of the RCSTR model is required in order to troubleshoot
convergence problems. Otherwise, it may be difficult to
understand how to apply the various convergence parameters to improve the reliability of the model.
The RCSTR algorithm consists of a series of nested loops, as shown in the following figure. The loops
are solved from the inside to the outside using various trial-and-error solver algorithms. Some
convergence parameters are associated with each of these loops.
The outer-most loop involves the volume and residence time of the CSTR. There are many options for
specifying the characteristic volume of a multiphase CSTR. The following table shows the various
calculations for volume and residence times in RCSTR:
Specifications: Total reactor volume (Vol)
=
FV
Rvjf
j
V
j
fjfvkjv
k
=
V
j Ff j v
jj
k
Specifications: Total residence time (Res-time)
VRRFvjf
jj
R
**
V
fjv
jfkv
k
V Ff v
k
=
j
jj
Specifications: Total reactor volume (Vol), key phase volume (Ph-vol)
R
j
V
R
=
FV
Rvjf
jj
Vj
= specifed
*
j
=
V
j Ff j v
j
Specifications: Total reactor volume (Vol), key phase volume fraction (Ph- vol-frac)
=
FV
Rvjf
j
V j = rV
jR
j
=
V
j Ff j v
j
Specifications: Total reactor volume (Vol), key phase residence time (Ph- res-time)
=
FV
Rvjf
j
V j = j Ff j v
j
**
j
= specified j
Specifications: Total residence time (Res-Time), key phase volume fraction (Ph-vol-frac)
VR=
RF
vjf
j ** j
V j = rV
jR
=
V
j Ff j v
j
VR
= Total reactor volume;
Vj
= Volume of phase j;
vj
= Molar volume of
phase j
rj
= Volume fraction of phase j;
R
= Total residence time;
j
= Residence
time of phase j F = Total molar flow rate at reactor outlet;
fj
= Molar fraction of phase j
* If more than one condensed phase is present, and the key phase is liquid, then the specified volume applies to the
sum of the condensed phase volumes. ** This equation is solved by trial-and-error technique.
When residence time is specified instead of volume, the RCSTR model adjusts the volume to satisfy the
residence time specification.
Convergence problems in the residence time loop can be alleviated by providing initial volume estimates
in the ESTIMATES form. If convergence problems persist, then the maximum volume step size (Max-
Vstep) should be reduced. If the key phase residence time is specified, then the RCSTR model uses the
specified reactor volume as an upper limit for the key phase volume.
EB LOOP
The second loop is the energy balance conservation equation (EB-LOOP). In this loop, the reactor
temperature is adjusted to match the specified reactor duty. If the temperature is specified instead of the
duty, this loop is by- passed.
Since the reaction rates are very sensitive to temperature, large changes in the reactor temperature
between energy-balance iterations (EB-ITER) may cause the mass-balance loop (MB-LOOP) to diverge.
This problem can be solved by providing a good temperature estimate (T-EST) in the ESTIMATES form.
If the problem persists, the maximum temperature step size (Max- Tstep) should be reduced (the default,
50C, is rather large).
MB-LOOP
The next loop is the mass-balance loop (MB-LOOP). This loop uses a multivariable solver to converge the
conservation equations for component mole flow and for the class two component attributes.
Two solvers are available: Broyden and Newton. The Broyden algorithm tends to be relatively fast, but it
may be unstable if the number of components and attributes is large and the reaction rates are high. The
Newton algorithm tends to be slower, but more stable for many classes of problems. The Newton
algorithm calculates the response of each variable to each other variable by perturbing the variables one
at a time by a very small amount. These perturbation steps require lots of simulation time, which makes
each iteration of the Newton algorithm slow.
The number of mass-balance iterations (MB-Maxit) is defined on the convergence form. By default, the
model allows 50 mass-balance iterations. This default is sufficient for the Newton algorithm, but is usually
too small for the Broyden algorithm. For polymer reaction kinetics, the number of required mass-balance
iterations may be as high as 500.
Using a Damping Factor

The stability of the Broyden algorithm can be adjusted using a damping factor (DAMP-FAC) defined on
the Convergence form. Decreasing the damping factor decreases the step-size, resulting in a larger
number of smaller, more stable steps. Thus, the maximum number of iterations should be increased as
the damping factor is decreased.
The damping factor is sensitive on a log scale. If the Broyden algorithm appears unstable, try setting the
damping factor to 0.5, 0.3, 0.1, 0.05 etc. Optimum damping factors for polymerization kinetics typically fall
between 0.1 and 0.001.
The conservation equations have the form: accumulation = input - output + Generation For the
component mole balance equations:
RiS
i
F
in
S
i
F
out
Si
j
Gi,
jV
jS
i
For the class-2 component attributes equations:

=i
-i
'
,
Where:
Ri
RiSi
= A i in
S
i
-Ai
out
S
i
+
j
GijV
jS
i
= Residual value for equation i, kmol/sec

Fi
in = Molar flow rate of component i into the reactor, kmol/sec

Fi
out = Molar flow rate of component i out of the reactor, kmol/sec

G
i,
j = Molar sec
generation rate of component i in phase j, kmol/m3
A i in = Flow rate of attribute i into the reactor, kmol/sec or
particle/sec
A i out = Flow rate of attribute i out of the reactor, kmol/sec or
particle/sec
G i ,
j = Generation rate of attribute i in phase j, kmol/m3 sec or

particle/m3 sec V
j
= Volume of phase j in the reactor

S
i
= Scaling factor for equation i

The mass-balance loop is converged when the maximum scaled residual of the conservation equations
falls below the specified tolerance (MB-TOL):
Maximumerror = MAX i
RS
ii
< MB -
TOL
A secondary criteria is the root-mean-square scaled error, or RMS error:
RMS Error =
1N
i
i
Ri
2
S
i
The CSTR mass-balance algorithm iterates until the maximum error falls below the specified mass-
balance tolerance or the maximum number of mass- balance iterations is reached. If the maximum error
criteria is reached, and the RMS error is decreasing by a factor of ten on each iteration, the CSTR model
continues to iterate until the RMS error reaches the specified function tolerance (FUNC-TOL). This allows
the model to reach very tight convergence tolerances when the convergence behavior is good.
Scaling Factors
The scaling factors play an important role in the convergence behavior of the model. If the scaling factors
are large, and the variables are small, then the model will be loosely converged. If the scaling factors are
small, and the variables are large, the convergence criteria will be unacceptably tight, and the model will
not converge. There are two scaling options in the RCSTR model, as shown here:
Variable Type Component Scaling Substream Scaling
Enthalpy Estimated outlet stream enthalpy 105 Component Mole Flows The larger of:
Estimated component mole flow in outlet stream (or retention value if available) (Trace) x (Substream flow rate)
Total estimated outlet stream mole flow rate
Class 2 Attributes The larger of:
Estimated attribute value in outlet stream (or retention value if available) (Attribute scaling factor from the TBS table)
x (Estimated mole flow rate of the attributed component) (Trace) x (Total estimated outlet mole flow rate) x (Attribute
scaling factor from the TBS table) 10 - 11 Note: If the estimated component flow or attribute value is zero or missing,
the default scaling factor is applied.
(Attribute scaling factor from the TBS table) x (Substream flow rate)
By default, the component scaling option is used. With this option, the minimum scaling factors depend
on the value of the TRACE parameter. The trace scaling factor is effectively a minimum mole fraction.
For components with concentrations below the trace level, the scaling factors are set to a minimum value.
The default scaling factors for component attributes are defined as constants in an Aspen Plus Table
Building System (TBS) data file, COMPATTR.DAT. Although the default scaling factors are set to
appropriate values for most classes of reaction kinetics, the optimal values for a particular type of kinetics
may be different than the defaults. The default attribute scaling factors can be adjusted using the
Components Scaling form.
The scaling factors should make the scaled values as close to unity as possible. For this reason, the
scale factors are set to the predicted values from previously converged passes through the RCSTR block.
On the first pass through the flowsheet, the scaling factors will be set to the estimated value for the
variable. Thus, component flow and component attribute estimates can be used to set the initial scale
factors.
The scaling factors for component attribute values are normalized with the total mole flow rate of the
outlet stream. This keeps the scaling factors reasonable for models of any type of process, from bench
scale to production scale units.
The inner-most loop is the phase equilibrium loop, or flash equations. For this reason, it is essential to
have accurate physical properties over the entire range of temperatures and pressures found in the
process.
The flash calculations start from retention values once the mass-balance error falls below the retention
threshold (Ret-Thresh) specified in the convergence form. If the retention threshold is set very high, then
the flash may fail, resulting in step-size cuts in the mass balance loop. If the retention threshold is
reduced, the reactor calculations may require more time. For most simulation problems, setting the
retention threshold to 1 1010 results in fast flash convergence without errors. If errors occur, try using
the default value, 1 105 . If errors persist, the most likely cause is a physical property problem.
Initialization Options
The convergence behavior of the RCSTR model depends on how the model is initialized. There are three
initialization options for the RCSTR model.
Solver InitializationDo not use integration By default, the solver algorithm initializes itself using
previously saved simulation results (retention). This saves time if the RCSTR block is inside a flowsheet
recycle loop, where the block will be run several times in succession. It also saves time if the block is
inside a sensitivity, optimization, design-spec, or data-fit study. Alternately, the user can force the model
to restart from estimates every time by checking the restart flag on the block-options form. When retention
is not available, or when the restart option is active, the model uses user-specified estimates to initialize
the solver algorithm. Estimates can be provided for the reactor volume, phase volume, reactor
temperature, component flow rates, and component attribute values. The component attribute estimates
can be specified using class-2 or class-0 attribute values. If estimates are not provided, the model
initializes the variables using the mixed feed stream (for example, the initial value of a component flow
rate may be set to the total flow rate of that component in all feed streams to the reactor).
Integration InitializationAlways use integration In the integration algorithm, the RCSTR is treated as a
dynamic stirred- tank reactor. The conservation equations are numerically integrated from an initial
condition to the steady-state condition. The initial compositions in the reactor are set equal to those in the
feed stream. If temperature is specified in the reactor, then the temperature profile during initialization can
be ramped from the feed stream temperature to the specified temperature over the interval of several
residence times. If duty is specified, then the duty can be ramped from adiabatic conditions to the
specified duty. Ramping allows the reactor to cold-start for improved integration performance. The
numerical integration carries forward until the residual terms (accumulation terms) drop below the
specified mass-balance tolerance. At this point, the model enters the solver and continues until the model
converges.
Note that initial guesses for component flow rates and component attributes should not be provided when
using the integration initialization option unless the reactor exhibits multiple steady-state solutions. In this
case, initial estimates may be used to force the reactor towards a particular solution.
Hybrid InitializationInitialize using integration The hybrid option takes advantage of the robust
integration algorithm to initialize the reactor during the first pass. On subsequent passes, when a
previously converged solution is available, the solution algorithm bypasses integration and jumps directly
into the trial-and-error solver. Since the solver algorithm is much faster than the integration algorithm, the
hybrid option offers improved performance for most problems.
Note: By default, the RCSTR model does not use integration (e.g., the trial and error solution algorithm
starts directly from the user-specified initial guesses or from retention values). Optionally, the RCSTR
model can be initialized using an integration approach or a hybrid approach that uses integration only
when retention values are not available.
Troubleshooting Convergence Problems

To diagnose RCSTR convergence problems, set the terminal reporting level to 7 in the Block-Options
form. This causes the RCSTR model to report the residence time iterations (RT-ITER), energy balance
iterations (EB-ITER), and mass-balance iterations (MB-ITER) to the control panel. In addition, the model
reports the maximum and root-mean-square errors for each loop.
The Simulation diagnostic reporting level controls the diagnostic messages written to the history file (.HIS
file). The maximum mass-balance error is reported at level 5. At level 6, the model reports the value of
each reacting component flow rate and each component attribute. At level 7, the model reports values
and rates of change (reaction rates) for components and attributes. At level 8, the model reports the
values, rates, and residuals (error) of each solved variable.
When troubleshooting convergence problems, simplify the problem by specifying temperature and volume
instead of duty and residence time. If convergence problems persist, they must be related to the mass-
balance loop, the reaction kinetic model or rate constants, or the underlying physical property
calculations.
Numerical integration is much more reliable than trial-and-error solvers. If the RCSTR mass-balance fails
to converge, try running the same kinetics in an RPlug model. If possible, set the phase criteria liquid-
only to eliminate physical property problems from the list of possible sources of error. If the RPlug model
cannot converge with the specified kinetics, then the problem is almost certainly related to reaction
kinetics.
Possible sources of error in the reaction kinetics include:
Errors in the molecular weight of a product or reactant
Errors in the specified stoichiometry of a reaction (mass balance is violated)
Unreasonable rate constants, especially activation energies (verify the units)
Reactions with zeroth-order reactants which are not present
Unreasonable concentrations of catalysts or inhibitors (put the feed stream in a flash block and verify
that the concentrations in the reacting phase make sense).
Errors in user-written Fortran subroutines.
If these sources of error are eliminated, and convergence problems persist, try simplifying the model by
removing unnecessary side reactions or trace components from the model. Convergence is much easier
if the number of equations is reduced, the speed of most convergence algorithms varies with the cube of
the number of equations (the number of equations equals the number of reacting components plus the
number of class-2 component attribute elements).
Common Problems
The following table summarizes solutions for some common problems encountered when using RCSTR:
Problem Solution
Initial flash failure This is usually a physical property problem. Check the heat of formation (DHFORM) and ideal gas
heat capacity parameters (CPIG) of the polymer and oligomer components. If supercritical components are present,
consider treating them as Henrys law components Verify that the property method you are using is appropriate for
the specified temperature and pressure Verify the specified phases are consistent with the specified temperature and
pressure Verify the specified local and global flash tolerance Mass balance not converged in maximum number of
iterations, but the error is decreasing from one iteration to the next.
Increase the maximum number of iterations. If more than 500 iterations are required for the Broyden algorithm, try
adjusting the damping factor. Provide better initial guesses. Mass balance not converged in maximum number of
iterations, the maximum error is varying erratically between iterations, and the history file shows reasonable rates.
If using the Broyden algorithm, try decreasing the damping factor by logarithmic steps (0.5, 0.3, 0.1...0.0001) until the
problem converges. If the problem persists, try using the Newton algorithm. Provide better initial guesses. Mass
balance is not converging, the maximum error appears to oscillate between values or gets stuck and does not
change.
If using Newton algorithm, change the stabilization strategy from dogleg to line search. This works especially well
for ionic and Ziegler-Natta kinetics.
Problem Solution
Mass balance not converged in maximum number of iterations, the maximum error is varying erratically between
iterations, and the history file shows some reaction rates or attribute rates are much larger than others (or are erratic
between iterations).
Check the specified rate constants in the kinetic models, especially activation energies. Verify the units of the
activation energies. Verify flow rates of catalysts and initiators in the feed streams to the reactor. If using user
kinetics, check your subroutine for errors. Verify the reactor volume (residence time). Mass balance not converged in
maximum number of iterations. Reaction rates are very high, as expected.
Try using the Newton algorithm with good initial guesses. If this fails, delete the initial guesses and try using the
integration initialization. Mass balance not converged in maximum number of iterations. Some reacting components
(catalysts, initiators) are present in very small quantities.
Try adjusting the trace parameter in order-of- magnitude steps from the default (1 10 - 3 ) down to the
concentration of the trace components. If this fails, reset trace to the default value and try integration initialization.
Energy balance loop does not converge, or mass-balance loop does not converge after the second energy balance
loop iteration, or temperature step-size cutting (T-CUT) iterations appear in the diagnostic messages
Verify that the reactor converges with the temperature specified. If not, see items listed above, otherwise, provide a
better temperature estimate (T-Est). If the problem persists, try adjusting the maximum temperature step-size (Max-
Tstep) from 50C to 10C or even 5C. Residence time loop does not converge, or mass-balance loop does not
converge after the second residence-time loop.
Verify that the reactor converges with the residence time specified. If not, see items listed above, otherwise, provide
better volume estimates. If the problem persists, try adjusting the maximum volume step-size (Max-Vstep). Verify that
the correct residence time is specified (condensed-phase residence time for two-phase reactors). Verify two phases
exist if the reactor valid phases=vapor-liquid. Flash failures appear during the mass-balance loop; the step-size
cutting (X-CUT) diagnostic message appears.
This may be a physical property problem; it may reflect overly-tight flash tolerances; or the flash may be unstable
when starting from retention values Loosen the local and global flash tolerance levels or increase the maximum
number of flash iterations. Reactor converges but an error message says that the mass-balance does not close
Check the molecular weights of each reactant and product. Verify that reaction stoichiometry is correct.
RPlug
The RPlug model represents an ideal plug-flow reactor with one or more phases. The model assumes
perfect radial mixing within and between the phases, phase equilibrium, and no-slip conditions between
the phases (e.g., the phases all have the same residence time). Dead zones, back-mixing, and other
types of non-ideal plug-flow behavior can be represented using RPlug in combination with other blocks.
The RPlug model does not allow multiple feed
streams. A mixer block must be used in conjunction with the RPlug block to account for multiple feed
streams.
Temperature
RPlug allows many options for specifying the reactor duty or temperature:
Type Specifications Calculations
ADIABATIC None Temperature is calculated at each
axial position based on the enthalpy balance. T-SPEC Process stream temperature as a
function of axial position (linear interpolation between the points)
Duty is integrated along the length of the reactor. The model reports the net duty across the reactor T-COOL-SPEC
Heat transfer routine optional
Heat media stream temperature (assumed constant along length of reactor). Overall heat-transfer coefficient. Area is
determined from length, diameter , and number of tubes: A=NBDL
Duty is integrated along the length of the reactor. The temperature of the process stream is determined from the
energy balance. The model reports the net duty across the reactor CO-COOL Thernal fluid stream required Heat
transfer routine optional
Thermal fluid stream temperature, composition, and flow rate. Overall heat-transfer coefficient. Area is determined
from length, diameter, and number of tubes: A=NBDL.
Duty is integrated along the length of the reactor and is reported as a net value. The temperature of the process and
thermal fluid streams are determined from the energy balance.
COUNTER-COOL Thermal fluid stream required Heat transfer routine optional
Thermal fluid composition, flow rate and effluent temperature. Overall heat-transfer coefficient. Area is determined
from length, diameter, and number of tubes: A=NBDL.
Duty is integrated along the length of the reactor and is reported as a net value. The temperature of the process and
thermal fluid streams are determined from the energy balance. A design specification may be used to fit thermal fluid
feed temperature by adjusting thermal fluid outlet temperature.
RPlug allows one process stream and one heat media stream. Reactions can occur only in the process
stream. Heat transfer calculations are carried out between the process stream and the heat media
stream. The heat media stream represents a thermal fluid stream or a heating stream and the heat media
stream flows co- or counter-current to the process stream.
If a heat media stream is not specified, the model assumes a constant heat media temperature and solve
for the process fluid temperature.
The heat transfer rate or heat transfer coefficient value is calculated as a function of axial position, stream
conditions, etc., by a user-written Fortran subroutine. This feature is used to develop rigorous models
non-reactive heat exchangers.
Pressure
The pressure at the reactor entry can be specified as an absolute value or as a pressure drop relative to
the feed stream. In Aspen Plus, pressure drops are expressed as non-positive pressure specifications
given in absolute pressure units.
The pressure drop across the reactor can be specified as a constant or calculated in a user-written
Fortran subroutine. If the pressure drop is specified, the model assumes it is linear along the length of the
reactor.
Residence Time
The RPlug model assumes a cylindrical geometry. The length, diameter, and number of tubes are
specified. The process fluid is assumed to move through the tubes, and the thermal fluid is assumed to
flow on the outside of the tubes.
The total reactor volume cannot be specified, but the aspect ratio (length/diameter) has no influence on
the model predictions. Thus, the diameter can be set to 1.12838 units, which corresponds to an area of
1.0000 units2
. With this area, the length in units and volume in units3
have the same numerical value,
thus the specified length is equal to the volume.
The phase volumes cannot be specified independently. Instead, the RPlug model assumes that the
phases move through the reactor without slipping past each other. This assumption is valid for situations
where one phase is dispersed as droplets or bubbles in a second, continuous phase, such as dew in a
vapor phase or small gas bubbles in a liquid phase. This assumption is not valid for multiphase plug flow
reactors with controlled levels.
With this assumption in place, the reactor residence time is equal to the residence time of each phase
present in the reactor. The residence time is calculated by numerical integration.
One work-around for the no-slip assumption is to write a user kinetic subroutine (or a step-growth mass-
transfer routine) which calls the flash model directly. Then, specify the reactor as liquid-only and set the
diameter to the hydraulic diameter of the reactor.
Calculating Residence Time
Equation to Calculate Residence Time in RPlug:
D2
N4
=zzFzL=
0
dz
j f jz , v
jz ,
Where:
= Reactor residence time
D = Tube diameter
N = Number of tubes
Z = Axial position in reactor of length L
F
z
= Total molar flow rate of process stream at axial location z

f
j z,
= Molar fraction of phase j at axial location z

v
j z,
= Molar volume of phase j at axial location z
Multiphase Reactors
The RPlug models have one process fluid outlet stream that contains all of the phases exiting the reactor.
As shown here, a flash block is used in conjunction with these blocks to split the liquid and vapor phases
from the mixed outlet stream of the reactor:
In this application, it is good practice to specify PRES=0 (no pressure drop) and DUTY=0 in the flash
block to ensure that the phase split occurs at conditions which are consistent with the reactor outlet.
Another option is to specify temperature and to use a transfer block to copy the RPlug outlet stream
temperature to the flash specifications.
Reactors with Non-Ideal Mixing

Back-mixed plug flow reactors can be modeled using a recycle stream or by breaking the reactor down
into a series of RCSTR blocks. For example:
The recycle-stream approach has the advantage of RPlugs profile-based input and output plotting, but it
requires a flowsheet convergence loop that may be difficult to converge, especially if the circulation ratio
is large. The series-of- CSTRs approach does not require recycle loop convergence, but the results are
not as easily interpreted as the RPlug model.
Reactors with dead zones can be represented using parallel plug-flow reactors, as shown here:
The dead zone is represented by a plug-flow reactor with a large residence time. The active zone is
represented as a plug-flow reactor with a shorter residence time. The volumes of the two reactors sum to
the total volume of the real reactor. This approach assumes the dead zone reaches steady state.
As always, the simplest model which agrees with process data is the best choice.
The following figure shows a reactor with injection ports:
To diagnose numerical problems in RPlug, set the terminal reporting level to 7 in the Block-Options
form. With this setting, the RPlug block will report the normalized axial location, residence time (in
seconds), pressure (in Pascal), temperature (in K), and vapor molar fraction at each converged step.
file). The maximum mass-balance error is reported at level 5. At level 6, the model reports reacting
component flow rates and component attribute values. At level 7, the model also reports the rates of
change of these variables. At level 8, the model also reports initial scale factors for all variables.
First, simplify the problem by specifying temperature instead of duty or heat- transfer parameters (thermal
fluid temperature, U, or thermal fluid stream). Specify the reactor as liquid-only. This will eliminate many
possible sources of error and help focus the problem on kinetics and integration parameters.
Scaling Factors
RPlug uses Gears variable-step-size algorithm to numerically integrate the mass, energy, and attribute
conservation equations along the axial dimension of the reactor. At each axial step, the conservation
equations are solved by a trial-and-error technique.
Like RCSTR, RPlug solves the conservation equations using scaling factors to normalize the variables.
The values of these scaling factors can have a strong influence on the speed and reliability of the
integration.
The Gear integrator in Aspen Plus offers three error scaling options (ERR- METHOD in RPlug):
Static scaling
Dynamic scaling
Hybrid scaling
The RPlug static and dynamic scaling options are summarized in the following table:
Variable Type Static Scaling Dynamic Scaling
Enthalpy 105 (SI units) x total mass flow The larger of: Enthalpy at 2 Cutoff Component Mole Flows
The scaling factor at z = 0 to 1.0 is set to
The scaling factor at z = z + z is 0.1 x total mass flow
set to the larger of: Component mass flow at z Cutoff Scaling factors are updated at each step
Class 2 Attributes The scaling factor at z = 0 to 1.0 is set to
the larger of: Attribute value in inlet stream (Attribute scaling factor from the TBS table) x (mole flow rate of the
attributed component in the inlet) (Cutoff) x (total mole flow rate at the inlet) x (Attribute scaling factor from the TBS
table) Scaling factors are held constant
The scaling factor at z = z + z is set to the larger of: Attribute value at z Cutoff Scaling factors are updated at each
step
The static scaling method uses a constant set of scaling factors throughout the reactor. The dynamic
scaling method updates the scaling factors based on the previously converged step. The scaling factors
are never set lower than the specified minimum scale factor.
The static scaling method may result in faster integration for many types of problems, but there are
potential numerical problems when using this method. Consider an irreversible reaction A B in a plug-
flow reactor in which component B is not present in the feed. The scaling factor for component A will
be set very large and the scaling factor for B will be set to the minimum scaling factor. This will result in
relatively loose tolerance for the mass balance in A and tight tolerance for the mass balance in B.
Further, as the reaction approaches completion the component B will have a large flow rate but a small
scaling factor. This makes the conservation equation for B difficult to solve, which will result in small
integration steps.
Consider the same situation with dynamic scaling. The initial scaling factors are the same as the static
case. With each new step, however, the scaling factors are updated to the variable values from the
previous step. This keeps the scaled variables close to one throughout the integration. For example:
One pitfall of dynamic scaling, however, occurs when a variable value decreases and approaches zero.
As the value and the scaling factor get
progressively smaller, small absolute errors become large scaled errors. This also makes the solution
difficult, and leads to small steps in the integrator. This problem can be controlled by setting the minimum
scaling factor to a reasonable value. The default value, 10-10
is much too small for most problems. A value of 10-5
is reasonable for most situations, and will result in better model
performance.
The hybrid option uses static scaling for all variables except enthalpy, which is scaled dynamically. This
option may be the best choice when the stream enthalpy is far from the default scale factor,
10 5 .
In general, the dynamic scaling method results in tighter convergence, but it requires more simulation
time than the static scaling method. This does not apply to every case, however, and it may also depend
on the solver algorithm. It is a good idea to experiment with these parameters to find the most reliable
convergence strategy for each reactor in each model. When component attributes are present, as in
polymerization kinetics, dynamic scaling is used by default.
Solver Method
At each step during the integration, the energy, mass, and attribute conservation equations are solved by
trial-and-error. One of the two corrector algorithms, direct substitution or Newtons method, can be
selected. The Newton algorithm perturbs each variable to determine the slope, resulting in a smaller
number or larger steps compared to the Direct algorithm. Since the perturbation passes require some
time, it is difficult to predict if the Newtons method or the Direct method is best for a given problem. In
general, the Newtons method appears to give the best performance with polymerization kinetics, but it is
a good idea to try using each algorithm with both dynamic and static scaling to determine the best
combination of convergence parameters for a particular problem.
The corrector tolerance is set as a ratio from the integration tolerance (Corr- Tol-Ratio). By default, the
corrector tolerance is ten times tighter than the integration tolerance (the corrector tolerance ratio is 0.1).
For some problems, especially those involving reactors with heat transfer calculations, the optimal
corrector tolerance ratio may be higher than 0.1, but this ratio should not be set larger than 1.0. The flash
tolerance should be tighter than the corrector tolerance. Otherwise, round-off errors in the flash
calculations make the corrector tolerance difficult to achieve. The model always uses the smaller of the
specified RPlug flash tolerance (in the convergence form) or the global flash tolerance.
Other Integration Parameters
By default, the initial step size in RPlug is set to one percent of the reactor length (Hinit=0.01). If the
solver cannot converge the equations with this step size, it will cut the step size by a factor of ten. This
process will repeat up to six times. If the solver still cannot converge, the reactor calculation fails with an
error message solver cannot converge with minimum step size.
Frequently, reaction rates or heat transfer rates are much faster near the entrance of the reactor than at
the exit of a reactor due to step changes in temperature or pressure or due to the high concentrations of
reactants at the inlet of the reactor. For these types of problems, the minimum step size may
need to be reduced. For step-growth kinetics, try using an initial step size of 1 10-4 . Smaller initial step-
sizes may be required for addition kinetics, especially if quasi-steady-state approximations are not
applied.
The maximum number of integration steps defaults to 1000. For very stiff kinetics, e.g., kinetics with fast
reaction rates involving trace components, the maximum number of steps may need to be increased,
especially if the corrector is using direct substitution. If more than 5000 steps are required, try changing
the corrector method, scaling method, or increase the cutoff level.
RPlug stores many types of results at regular intervals (printing points). The number of intervals defaults
to ten, but the number of print points can be increased to get smoother plots. Since the integration steps
do not necessarily correspond to the print points, the model uses polynomial interpolation to determine
the results for a print point based on the steps before and after this point. If the integration step sizes are
very large, the interpolation algorithm may give strange results, such as sine waves. This problem can be
fixed by reducing the maximum step size (Max-StepSize) to a value smaller than the increments between
print points (this forces the model to use linear interpolation). By default, the maximum step size is much
larger than the reactor length.
When hybrid scaling is used, the tolerance of the energy balance is controlled by the energy balance
tolerance ratio.
Common Problems
The following table summarizes common problems encountered when using the RPlug unit operation
block:
Problem Solution
Solver cannot converge for initial step
Try reducing the initial step size by orders of magnitude from the default (10-2) to 10-8. If the problem persists, try
increasing the cutoff parameter from 10-10 to 10-5. If the problem still persists, verify the values and units of the rate
constants in the kinetic model. Verify the heat-transfer coefficient if applicable. Verify the temperature, composition,
and flow rates of the feed streams. Check the history file diagnostics for unusually high reaction rates. Integration
error: non- negativity violation.
This problem is usually related to infeasible reaction kinetics. If using a user kinetic routine, verify the code,
otherwise, a zeroth-order reactant may be completely consumed. Check the history file diagnostics; look for the
component flow rate or attribute element which has a value of zero and a negative rate of change. Integration error:
maximum number of steps is reached
Try increasing the cutoff parameter from 10-10 to 10-5. If the problem persists, try different combinations of scaling
method and corrector method. As a last resort, try increasing the number of steps to 5000. If the problem still
continues, search for errors in the kinetics; check the diagnostics for unreasonable reaction rates. Integration error:
corrector tolerance cannot be achieved
Tighten the flash tolerance to a value below the corrector tolerance. Loosen the integration tolerance to 1 10-3 .
Increase the corrector tolerance ratio to 0.2, 0.3, 0.5. If the problem continues, verify the kinetics and heat-transfer
parameters. Check history diagnostics. Flash failures appear during the integration
This may be a physical property problem; it may reflect overly-tight flash tolerances, loosen the local and/or global
flash tolerance levels or increase the maximum number of flash iterations.
Reactor converges but an error message says that the mass-balance does not close
Check the molecular weights of each reactant and product. Verify that reaction stoichiometry is correct.
RBatch
RBatch is a rigorous model for batch and semi-batch reactors. Any number of continuous feed streams
can be specified in addition to a batch charge stream. Optionally, a vapor vent may be considered. The
RBatch model does not have a vent condenser option; Aspen Custom Modeler is required to rigorously
model batch polymerization reactors with vent condensers or overhead columns.
The RBatch model assumes feed and product accumulator holding tanks with continuous outlets. The
accumulator concept provides a bridge between the continuous steady-state modeling environment in
Aspen Plus and the inherently dynamic nature of batch reactors. The conversion between continuous
streams and discreet charges and dynamic product accumulations is controlled by specified cycle times
and continuous feed stream profiles specified in the reactor.
Temperature
RBatch allows many options for specifying the reactor duty or temperature, as summarized here:
Type Specifications Calculations
T-SPEC Reactor temperature The model reports the temperature profile, and
the instantaneous and cumulative duty profiles. T-PROFILE
Reactor temperature as a
function of time. Linear interpolation is used to determine temperatures between specified points.
The model reports the temperature profile, and the instantaneous and cumulative duty profiles.
T-COOL- SPEC
Heat media stream temperature. Overall heat-transfer coefficient. Heat exchange surface area.
The temperature of the reactor is determined from the energy balance at each time step. The model reports the
temperature profile, and the instantaneous and cumulative duty profiles. DUTY- SPEC
Instantaneous heat duty (assumed constant for entire cycle). Set the duty to zero to model an adiabatic reactor.
temperature profile.
DUTY- PROFILE
Instantaneous heat duty as function of time. Linear interpolation is used to determine duty between specified points.
temperature profile, and the instantaneous and cumulative duty profiles. USER- DUTY
Heat transfer subroutine name The user routine returns the instantaneous heat
duty at each time step. The temperature of the reactor is determined from the energy. The model reports the
temperature profile, and the instantaneous and cumulative duty profiles.
The temperature or duty can be specified as a time-varying function. Heat transfer can be accounted for
by assuming a constant thermal fluid temperature, heat transfer area, and heat transfer coefficient, or by
writing a Fortran routine that returns the instantaneous duty at each time step.
If the temperature or temperature profile is specified, RBatch assumes a temperature controller. If the
reactor is single-phase, or if the reactor volume is specified, the model assumes perfect temperature
control, otherwise, the model uses a proportional-integral-derivative (PID) controller equation to represent
a temperature controller:
Qt=Mt
K(T-T)
()(+K
I
t
--)
0
+
dTT
s dt
Where: Q t
reactor
stt
TtTt
s dt KD
tt
= Instantaneous heat duty (J/sec)

M
t reactor = Mass in reactor at time t (kg)
Tt
= Temperature in reactor at time t (K)

Tt
s = Temperature setpoint at time t (K)

t = Time (sec)
K = Proportional gain (J/kg-K)
I = Integral time (sec)
D = Derivative time (sec)
By default, the proportional gain is 2500 J/kg-K, which results in very tight control at the expense of
excessive simulation time. The speed of the model can be increased by reducing the gain (try a value of
25 J/kg-K).
Pressure
If the reactor volume is not specified, the RBatch model assumes the reactor operates as a closed
system with a variable volume. The pressure at the reactor is specified as constant value or as a time-
varying profile.
If the reactor volume is specified, and there is a vent stream attached to the reactor, the flow rate of the
vent stream is determined from the specified pressure or pressure profile. The vent flow is positive when
the calculated reactor pressure exceeds the specified reactor pressure.
If the reactor volume is specified, there is no vent stream attached to the reactor, and the pressure profile
is not specified, then the pressure is determined by the temperature and molar volume of the material
inside the reactor.
If the reactor volume is controlled, a pressure controller model can be linked to a continuous feed stream.
The flow rate of the feed stream is adjusted to maintain a constant pressure inside the vessel. The
continuous feed stream flow rate can decrease to zero, but it cannot reverse direction if the pressure
exceeds the specified setpoint. The model uses a proportional-integral- derivative (PID) controller
equation to represent the pressure controller:
Ft=
K(
Pt-Pt
)+KI
t(0
)
(-)
-+
dPtPt
s
dt
Where:
Ft
s
PtPt
s
dt KD
= Instantaneous flow rate (kmol/sec)

Pt
= Pressure in reactor at time t (Pa)

Pt
s = Pressure setpoint at time t (Pa)

t = Time (sec)
K = Proportional gain (kmol/sec)/Pa
I = Integral time (sec)
D = Derivative time (sec)
Reactor Volume
If the reactor pressure is not specified, then RBatch will predict the reactor pressure based on a specified
reactor volume. The pressure will be manipulated by a trial-and-error algorithm to satisfy the specified
volume.
If pressure and volume are both specified, you must either attach a vent stream to the reactor or attach a
continuous make-up stream and pressure controller to the reactor.
Residence Time
The residence time of the reactor is controlled by user-specified stop criteria. You can specify whether
RBatch should halt the reaction when the stop criterion variable is approached from above or below. If
several stop criteria are specified, RBatch stops at the first stop criteria it reaches.
In addition to stop criteria, you must specify a maximum time for the reactor. This prevents runaway
calculations in the event that none of the stop criteria are feasible.
The stop criteria may include one or more of the following:
A maximum reaction time
A maximum or minimum component mole or mass fraction in the reactor
The amount of material (mass, moles, or volume) in the reactor or vent accumulator
A maximum vent flow rate
A maximum or minimum reactor temperature, pressure, or vapor fraction
The value of a Prop-Set property (includes user Prop-Set properties or system properties such as
viscosity, etc.)
Batch Operations
RBatch can represent batch or semi-batch reactors, depending on what streams are connected to it in the
flowsheet. If a vent stream or time-varying continuous feed stream is connected to the RBatch block, then
the model operates in semi-batch mode.
The batch reactor model is interfaced into the Aspen Plus continuous flow, steady-state modeling
environment through the concept of holding tanks, as shown here:
The holding tanks convert the:
Continuous batch charge stream to a discreet batch charge
Final vent accumulator inventory to a continuous, time-averaged vent stream
Final reactor inventory to a continuous, time-averaged reactor product stream
Four types of streams are associated with RBatch:
Continuous Batch Charge
Time-Varying Continuous Feed
Time-averaged Continuous Reactor Product
Time-averaged Continuous Vent Product
Continuous Batch Charge: The material transferred to the reactor at the start of the cycle. The mass of
the batch charge equals the flow rate of the batch charge stream, multiplied by the batch cycle time. The
mass of the batch charge is equivalent to accumulating the batch charge stream in a holding tank during
a reactor cycle. The contents of the batch charge holding tank are instantaneously transferred to the
reactor at the start of each batch cycle.
Time-Varying Continuous Feed: Streams that are fed to the reactor over some discreet interval during the
batch cycle. The composition, temperature, pressure, component attribute values, and time-averaged
flow rate of the
stream are specified in the flowsheet. The flow rate of the continuous feed streams can be specified as a
constant value, a time-varying profile, or manipulated by the pressure controller model to meet a time-
varying pressure setpoint.
Time-averaged Continuous Reactor Product: This stream is determined by dividing the final reactor
inventory by the cycle time. This is analogous to instantaneously dumping the reactor contents to a large
holding tank at the end of the cycle, and continuously draining the tank throughout each cycle.
Time-averaged Continuous Vent Product: This stream is determined by dividing the final vent
accumulator inventory by the cycle time. During the batch cycle, the time-varying continuous vent stream
is accumulated in the vent accumulator. The model assumes the vent accumulator contents are instantly
drained to a large holding tank at the end of the cycle, and the holding tank contents are continuously
removed throughout the cycle.
Cycle Time
RBatch is a dynamic batch reactor model that is interfaced into the Aspen Plus continuous steady-state
modeling environment. The interface requires converting batch charges and accumulator inventories into
continuous stream flow rates. The cycle time is used to convert the batch charge flow rate into the initial
reactor inventory. The cycle time is also used to convert the vent accumulator inventory and the reactor
inventory into vent and reactor product streams.
For example, assuming a reactor has a cycle time of two hours and that no continuous feed streams are
specified, then:
If the batch charge stream is set to 50 kg/hour, the initial reactor inventory is 100 kg.
If at the end of the reaction cycle, the vent accumulator contains 30 kg of material, the time-averaged
continuous vent stream flow rate is 15 kg/hr. The composition of the time-averaged vent stream will be
the same as the final composition in the vent accumulator.
The final reactor inventory will be 70 kg, and the time-averaged reactor product flow rate will be 35
kg/hr.
RBatch allows you to specify a feed time and down time instead of the cycle time. In this case, the time-
averaged batch charge stream is divided by the feed time to calculate the initial batch inventory. The
time-averaged product flow rates are based on the cycle time, which is calculated from the sum of the
feed time, the down time, and the reaction time. This option is not recommended unless it is used to
correct the mass balance for the influence of time-varying continuous feed streams.

To diagnose numerical problems in RBatch, set the terminal reporting level to 7 in the Block-Options
form. With this setting, RBatch reports the time (in seconds), pressure (in Pascal), temperature (in K), and
vapor mole fraction at each converged integration step.
file). The maximum mass-balance error is reported at level 5. At level 6, the model reports reacting
component flow rates and component attribute values. At level 7, the model also reports the rates of
change of these variables. At level 8, the model reports initial scale factors for all integrated variables.
First, simplify the problem by specifying temperature instead of duty or heat- transfer parameters (thermal
fluid temperature, U, or heat transfer subroutine). Specify the reactor as liquid-only. Specify the reactor
pressure, but not the reactor volume. This will eliminate many possible sources of error and help focus
the problem on kinetics and integration parameters. Once the model works with these settings, then
revert the settings to duty, volume, and so on, making sure the model converges with each new
specification.
Scaling Factors
RBatch uses Gears variable-step-size algorithm to numerically integrate the mass, energy, and attribute
conservation equations for the reactor and the mass-balance equations for the vent condenser (if
applicable). At each time step, the conservation equations are solved by a trial-and-error technique.
RBatch solves the conservation equations using scaling factors to normalize the variables. The values of
these scaling factors have a strong influence on the speed and reliability of the integration.
The Gear integrator in Aspen Plus offers three error scaling options (ERR- METHOD):
Static scaling
Dynamic scaling
Hybrid scaling
The RBatch static and dynamic scaling factors are summarized here:
Enthalpy 105 (SI units) x mass holdup Enthalpy at previous time step Component Mass Inventory In Reactor and
Vent Accumulator
The scaling factor at t = t + t is set to the larger of: Component mass flow at t Cutoff Scaling factors are updated at
each step Class 2 Attribute Inventory in Reactor and Vent Accumulator
The scaling factor for each component inventory equation is set to:
0.1 * (mass of batch charge stream) Scaling factors are held constant
The scaling factor of each component attribute is set to: (Attribute scaling factor from the TBS table) x (cycle time)
(this is the attribute inventory at time = 0) Scaling factors are held constant
The scaling factor at t = t + t is set to the larger of: Attribute inventory at time = t Cutoff Scaling factors are updated
at each step
The static scaling method uses a constant set of scaling factors throughout the reactor. The dynamic
scaling method updates the scaling factors based on the previously converged step. The cutoff
parameter is the minimum scaling factor used in dynamic scaling.
The static scaling method may result in faster integration for many types of problems, but there are
potential numerical problems when using this method. Consider an irreversible reaction A B in a plug-
flow reactor in which component B is not present in the feed. The scaling factor for component A will
be set very large and the scaling factor for B will be set to the minimum scaling factor. This will result in
relatively loose tolerance for the mass balance in A and tight tolerance for the mass balance in B.
Further, as the reaction approaches completion the component B has a large flow rate but a small
scaling factor. This makes the conservation equation for B difficult to solve, which will result in small
integration steps.
The hybrid option uses static scaling for all variables except enthalpy, which is scaled dynamically. This
option may be the best choice when the stream enthalpy is far from the default scale factor,
10 5 .
Consider the same situation with dynamic scaling. The initial scaling factors are the same as the static
case. With each new step, however, the scaling factors are updated to the variable values from the
previous step. This keeps the scaled variables close to unity throughout the integration. For example:
One pitfall of dynamic scaling, however, occurs when a variable value decreases and approaches zero.
As the value and the scaling factor get progressively smaller, small absolute errors become large scaled
errors. This also makes the solution difficult, and leads to small steps in the integrator. This problem can
be controlled by setting the minimum scaling factor (cutoff in the convergence form) to a reasonable
value. The default value, 10-10
is much too small for
most problems. A value of 10-5
is reasonable for most situations, and results in
better model performance.
In general, the dynamic scaling method results in tighter convergence, but it requires more simulation
time than the static scaling method. This does not apply to every case, however, and it may also depend
on the solver algorithm. It is a good idea to experiment with these parameters to find the most reliable
convergence strategy for each reactor in each model. When component attributes are present, as in
polymerization kinetics, dynamic scaling is used by default.
Solver Method
At each step during the integration, the energy, mass, and attribute conservation equations are solved by
trial-and-error. Two corrector algorithms, direct substitution and Newtons method, can be selected. The
Newton algorithm perturbs each variable to determine the slope, resulting in a smaller number or larger
steps compared to the Direct algorithm. Since the perturbation passes require some time, it is difficult to
predict if Newtons method or the Direct method is best for a given problem. In general, Newtons method
appears to give the best performance with polymerization kinetics, but it is a good idea to try using each
algorithm with both dynamic and static scaling to determine the best combination of convergence
parameters for a particular problem.
The corrector tolerance is set as a ratio from the integration tolerance (Corr- Tol-Ratio). By default, the
corrector tolerance is ten times tighter than the integration tolerance (the corrector tolerance ratio is 0.1).
For some problems, especially those involving reactors with heat transfer calculations, the optimal
corrector tolerance ratio may be higher than 0.1, but this ratio should not be set larger than 1.0. The flash
tolerance should be tighter than the corrector tolerance. Otherwise, round-off errors in the flash
calculations make the corrector tolerance difficult to achieve. The model always uses the smaller of the
specified RPlug flash tolerance (in the convergence form) or the global flash tolerance.
Other Integration Parameters
By default, the initial step size in RBatch is set to one tenth of a second (Hinit=0.1). If the solver cannot
converge the equations with this step size, it will cut the step size by a factor of ten. This process will
repeat up to six times. If the solver still cannot converge, the reactor fails with an error message solver
cannot converge with minimum step size.
Frequently, initial reaction rates or heat transfer rates are very fast, so the minimum step size may need
to be reduced. For step-growth kinetics, the default value should be sufficient. Smaller initial step-sizes
may be required for addition kinetics, especially if quasi-steady-state approximations are not applied.
The maximum number of integration steps defaults to 1000. For very stiff kinetics, e.g., kinetics with fast
reaction rates involving trace components, the maximum number of steps may need to be increased,
especially if the corrector is using direct substitution. If more than 5000 steps are required, try changing
the corrector method, scaling method, or increase the cutoff level.
RBatch stores many types of results at regular intervals (printing points). The number of intervals
depends on the reaction time. Since the integration steps do not necessarily correspond to the print
points, the model uses polynomial interpolation to determine the results for a print point based on the
steps before and after this point. If the integration step sizes are very large, the interpolation algorithm
may give strange results, such as sine waves. This problem can be fixed by reducing the maximum step
size (Max-StepSize) to a value smaller than the increments between print points (this forces the model to
use linear interpolation). By default, no maximum step size is enforced.
RBatch has the option to stop exactly at print points and vent accumulator points instead of interpolating
these points. When the exact option is set to
yes, the model adjusts the integration steps to exactly match these points. This requires extra steps in
the integrator that may slow down the model, but it results in more accurate simulations.
When hybrid scaling is used, the tolerance of the energy balance is controlled by the energy balance
tolerance ratio.
Common Problems
The following table summarizes common problems encountered when using RBatch:
Problem Solution
Solver cannot converge for initial step
Try reducing the initial step size by orders of magnitude from the default (10-1) to 10-8. If the problem persists, try
increasing the cutoff parameter from 10-10 to 10-5. If the problem still persists, verify the values and units of the rate
constants in the kinetic model. Verify the heat-transfer coefficient if applicable. Verify the temperature, composition,
and flow rates of the feed streams. Check the history file diagnostics for unusually high reaction rates. Integration
error: non- negativity violation.
This problem is usually related to infeasible reaction kinetics. If using a user kinetic routine, verify the code,
otherwise, a zeroth-order reactant may be completely consumed. Check the history file diagnostics; look for the
component flow rate or attribute element that has a value of zero and a negative rate of change. Integration error:
maximum number of steps is reached
Try increasing the cutoff parameter from 10-10 to 10-5. If the problem persists, try different combinations of scaling
method and corrector method. As a last resort, try increasing the number of steps to 5000. If the problem still
continues, search for errors in the kinetics; check the diagnostics for unreasonable reaction rates. Integration error:
corrector tolerance cannot be achieved
Tighten the flash tolerance to a value below the corrector tolerance. Loosen the integration tolerance to 1 10-3 .
Increase the corrector tolerance ratio to 0.2, 0.3, 0.5. If the problem continues, verify the kinetics and heat-transfer
parameters. Check history diagnostics. Flash failures appear during the integration
This may be a physical property problem; it may reflect overly-tight flash tolerances, loosen the local and/or global
flash tolerance levels or increase the maximum number of flash iterations. Reactor converges but an error message
says that the mass-balance does not close
Set the cycle time instead of the feed time. Check the molecular weights of each reactant and product. Verify that
reaction stoichiometry is correct.
Treatment of Component Attributes in Unit

Operation Models
As described in previous chapters, Aspen Polymers includes two classes of component attributes. Class-
2 attributes are primary conserved quantities and always have flow-type units (attribute value / unit
time). These attributes include the zeroth moment of the polymer (polymer molecule flow rate), the
segment flow rates, etc. Class-0 attributes are secondary quantities that can be derived from the primary
quantities.
The class-2 attributes follow flow-based mixing rules. In other words, if two streams are mixed, the
product stream class-2 attributes are equal to the sum of the feed stream class-2 attributes. These mixing
rules apply to each unit operation that allows multiple feeds of the same type (for example, multiple
process fluid feeds). In the distillation models, these mixing rules apply on a tray-by-tray basis (e.g., if two
or more feed streams enter the same tray).
The blocks with more than one outlet (Flash2, Flash3, Sep, etc.) assume that the class 2 polymer
attributes split according to mass mixing rules. For example, if 90% of the mass of the polymer flows to
the liquid phase, then 90% of the polymer molecules also flow with the liquid phase. This approach is
identical to assuming that the properties of the polymer, such as the molecular weight distribution, are not
fractionated in any way; instead, the molecular weight distribution of each polymer component in each of
the product phases is identical to that of the polymer in the feed stream.
The following table summarizes the attribute handling for the different models:
Block Component Attribute Handling
Basic Unit Operation Models
Dupl All attributes in feed stream are copied to each outlet stream. FSplit SSplit Sep Sep2
Class 2 attributes divide in proportion to flow rate of attributed component. Class 0 attributes are recalculated for each
outlet stream.
Equation to calculate outlet stream attributes:
A
out
=
FF
out
in
A
F = Flow rate of attributed component (in = mixed feed, out = outlet) A = Class-2 component attribute value (in =
mixed feed, out = outlet) Flash2 Flash3
in
Class 2 attributes divide in proportion to flow rate of attributed component. Class 0 attributes are recalculated for each
outlet stream. Polymer components are not fractionated by the phase equilibrium models used by these blocks.
A
out
=
FF
out
in
A
mixed feed, out = outlet) When multiple substreams exist, the model distributes polymer attributes between
substreams using the same rule. Mult Class 2 attributes multiply in proportion to flow rate of attributed component.
Class 0
attributes are recalculated for each outlet stream.
in
A
out
=
FF
out
in
A
in
mixed feed, out = outlet)
Mixer Heater*
Class 2 attributes are summed across all feed streams. Class 0 attributes are recalculated for the outlet stream.
A = Class-2 component attribute value (in = mixed feed, out = outlet)

Distillation Models
RadFrac Component attribute conservation equations are included in this model at the tray-by- tray level. The class-2
attributes are calculated at each tray by the following equation:
A
A out =
A
in feeds
out
=
FF
out
in
A
F = Flow rate of attributed component (in = mixed feed to tray, out = outlet from tray) A = Class-2 component attribute
value (in = mixed feed to tray, out = outlet from tray) The RadFrac model does not allow polymer reaction kinetics.
MultiFrac This unit operation block does not consider component attributes. Polymers must be
converted to oligomer components if polymer fractionation is to be considered in this model.
Reactor Models
RStoic RYield
in
If user specified attributes in the COMP-ATTR form, they are used for the product stream. Otherwise, class 2
attributes divide in proportion to the flow rate of the attributed component. Class 0 attributes are recalculated for each
outlet stream.
A
out
=
FF
out
in
A
mixed feed, out = outlet) RGibbs REquil
in
Polymer and heterogeneous catalyst components may not participate in the reactions in these blocks. The class 2
attributes divide in proportion to the flow rate of the attributed component. Class 0 attributes are recalculated for each
outlet stream.
A
out
=
FF
out
in
A
mixed feed, out = outlet) RCSTR RPlug RBatch
in
When using Aspen Polymers reaction kinetics, these models calculate the class-2 component attributes using
standard conservation equations. These models can be used with a user-written Fortran subroutine through the
USER reaction option. If the user kinetics include component attributes, then the COMP-ATTR field in the user
kinetics form of the reactor model must be set to yes. In RCSTR, initial guesses for the outlet attribute values can be
specified in the COMP-ATTR form.
* This also applies to any block that allows multiple feed streams and uses an implied mixer to
calculate the net feed stream.
References
Chan, W.-M., Gloor, P. E., & Hamielec, A. E. (1993). A Kinetic Model for Olefin Polymerization in High-
Pressure Autoclave Reactors. AIChE J., 39, No. 1.
Chaudhari, R. V., & Shah, Y. T. (1986). Recent Advances in Slurry Reactors, Concepts and Design of
Chemical Reactors. S.A. Whitaker & A. Cassano (Eds.). Switzerland: Gordon and Breach Science
Publishers.
Henderson, J. N., & Bouton, T. C. (Eds.). (1979). Polymerization Reactors and Processes. ACS Symp.
Ser.
Rodriguez, F. (1996). Principles of Polymer Systems. New York: Taylor & Francis.
Trambouze, P., van Landeghem, H., & Wauquier, J. P. (1988). Chemical Reactors:
Design/Engineering/Operation. Paris: Editions Technips.
Walas, S. M. (1988). Chemical Process Equipment Selection and Design. Boston: Butterworths.
16 Plant Data Fitting
Aspen Polymers (formerly known as Aspen Polymers Plus) simulation models can be fit to plant or
laboratory data using Data-Fit. One or more sets of measured data are provided which may include
model inputs or results. Data- Fit adjusts or estimates input parameters to find the best match between
the model predictions and data. Data-Fit can also reconcile measured data against the model.
Data-Fit minimizes the weighted sum of square errors, where each error is the difference between a
reconciled input or calculated output and the data. In statistical terms, Data-Fit performs either ordinary
least squares or maximum likelihood (errors-in-variables) estimation.
Data Fitting Applications, 339
Data Fitting For Polymer Models, 340
Steps for Using the Data Regression Tool, 345 (including troubleshooting tips)
This section emphasizes using the Data-Fit tool to fit process reaction kinetic parameters. A more general
description of this tool is available in the Aspen Plus User Guide.
Data Fitting Applications

The data regression tool in Aspen Plus can be used to fit model parameters and reconcile process data.
These applications may be carried out simultaneously.
Parameter regression usually involves adjusting model parameters to improve the agreement between
model predictions and process data. For example, reaction rate constants may be manipulated to match
the measured polymer molecular weight and monomer conversion. Manipulated parameters may include
reaction rate or equilibrium constants, physical property constants, or equipment specifications. Fitted
parameters may include model predictions such as reactant conversion, product yield, by-product
content, polymer component attributes, stream compositions or flow rates, or equipment heat duty,
temperature, pressure, or holdup.
16 Plant Data Fitting 339
Data reconciliation runs involve manipulating one or more sets of model inputs to match model
predictions to process data. For example, the average feed rate of a makeup stream can be estimated
based on the flow rate and composition of the feed and product streams. Manipulated data typically
includes feed stream flow rates and compositions, equipment operating conditions, heat transfer
coefficients, etc.
The Data-Fit model can be used to reconcile input data and fit model parameters simultaneously.
Simultaneous regression and reconciliation is typically used to fine-tune models which already match
process data and trends relatively well.
Data Fitting For Polymer Models

Polymer process models frequently include non-ideal phase equilibrium, reaction kinetics, and
complicated unit operations. Fitting these complex models against process and laboratory data is not a
trivial task. A great deal of consideration must be given to the way this problem is approached.
A detailed example describing how to fit a free-radical reaction kinetics problem is included in the Aspen
Polymers Examples & Applications Case Book.
A general procedure for fitting complex models is given below.
Step 1. Process Data Review
Collect data for the process. Sources of data include process information management system (PIMS),
process design documents (PDDs), process flow diagrams (PFDs). Verify reproducibility / standard
deviations of data by collecting multiple data sets for each case. Verify steady state by collecting data at
regular intervals over several plant residence times. Verify data feasibility against mass and energy
balance calculations.
Step 2. Literature Search
Collect information about the process. Sources of data include in-house lab data, databanks, trade
journals, conference notes, polymer handbooks, online electronic databases, experimental designs, etc.
Step 3. Preliminary Model Fitting
Carry out physical property data regression, property constant parameter estimation runs. Test the
parameters against all pertinent data from steps 1 and 2. To the extent possible, verify pure component
physical properties and phase equilibrium predictions using Property Analysis tools.
Step 4. Preliminary Model Development
Develop a basic model of the process, ignoring details such as non-ideal mixing, heat transfer, etc.
Specify temperature instead of duty, volume instead of residence time. Use parameters from steps 1-3.
340 16 Plant Data Fitting
Step 5. Trend Analysis
Use the sensitivity feature to evaluate trends between model outputs (conversion, polymer attributes, etc.)
and model inputs (rate constants, operating conditions, etc.) Compare the predicted trends against
available process or lab data. If the trends are not well matched, adjust specific model parameters to
improve the predicted trend. Model fitting may be carried out using Sensitivity, Design-Specification,
Data-Fit, or by trial and error.
Step 6. Model Refinement
Use the Data-Fit tool to carry out simultaneous parameter estimation and data reconciliation. Relax model
assumptions, such as perfect mixing, as needed. Bring model up to the appropriate level of detail, fitting
key parameters at each development step.
Data Collection and Verification

The first step in fitting a model is to collect and review data. Sources of data may include process
information management system (PIMS), process design documents (PDDs), and process flow diagrams
(PFDs), shift log sheets, and laboratory analysis reports. It is important to verify the reproducibility of the
data by collecting several duplicate sets of each datum. Duplicate data are especially important for
analytical measurements such as melt flow index and intrinsic viscosity.
For continuous processes, it is a good idea to verify that the process operates under steady-state
conditions by collecting data at regular intervals. The data should be collected at regular intervals over a
period that exceeds the cumulative residence time of the key unit operations in the process.
Verify data feasibility against mass and energy balance calculations. It is impossible to force a rigorous
model to match data that violates the fundamental conservation equations.
When possible, obtain calibration data for unit operating conditions, especially level calibration data for
reactors and flow rate calibration data for flow meters. The method and assumptions used to calibrate
these instruments must be taken into consideration for data reconciliation runs.
Literature Review
Before you regress process data, it is a good idea to collect information about the process. Sources of
data include in-house lab data, databanks, trade journals, conference notes, polymer handbooks, on-line
electronic databases, experimental designs, and so on.
The open and in-house process literature may contain a wealth of information about key model
parameters. Further, these sources may provide additional sources of fundamental data which can be
used to independently evaluate model parameters.
Simulation studies described in trade journals are an excellent source of insight and know-how related to
model development. These studies frequently point out which assumptions are valid and which
parameters are
important. In addition, these papers may elucidate reaction mechanisms or physical phenomena that
should be considered in a rigorous process model.
The physical property and rate constant data reported in the open literature are never perfect, but they do
serve as a good starting point for fitting the model.
Preliminary Parameter Fitting

It is important to determine as many of the model parameters as possible early in the model development
process. Try to decouple the parameters from each other whenever possible. For example, find ways to
establish phase equilibrium parameters independently of reaction equilibrium constants. Make simplifying
assumptions to reduce the number of unknown parameters.
Physical property parameters should be firmly established before fitting rate constants. When data are
available, use the physical property data regression system (DRS) to fit the density, enthalpy, heat
capacity, and vapor pressure of pure components. If phase equilibrium data are available, use DRS to
regress phase equilibrium parameters.
When property data are unavailable for a component, the property constant estimation system (PCES)
can be used to estimate property parameters from molecular structure. These estimations, however,
should be checked against process data. If data are available for components with similar structures, they
can be used to estimate the properties of components that are not found in the databank.
The following table lists some of the key physical property parameters in Aspen Polymers and describes
how they influence polymerization kinetics:
Property Parameters Influence on Polymerization Reaction Kinetics
Density DNLRKT,
DNLVK
Concentration is proportional to density. Reaction kinetics depend on component concentrations. Vapor pressure
PLXANT, HENRY
The vapor pressure controls phase equilibrium of volatile components in vapor-liquid systems. The phase equilibrium
strongly influences concentrations, which controls kinetics. Enthalpy DHFORM,
DHFVK, DHFVKM, DHSUB, DHCON, DHFMDP
The component enthalpies influence the predicted heat duties and temperatures in the model.
Heat capacity CPIG, CPL,
CPLVK, CPCVK
The heat capacity controls the influence of temperature on enthalpy.
Transition temperatures
TMVK, TGVK Phase transitions occur at the melting point and
glass point. Predicted enthalpy, density, and heat capacity for polymer and oligomer components depend on the
phase regime. Phase equilibrium
In multiphase reactors the phase equilibrium determines the component concentrations in each phase, which
influences the reaction rates.
Property Parameters Influence on Polymerization Reaction Kinetics
Solubility (of a solid)
K-SALT The solubility parameter influences the
concentration of partially soluble solids in the liquid phase. When catalysts, inhibitors, or monomers are fed as solids,
this parameter controls their concentration, which in turn controls their reaction rate.
If reaction kinetic parameters are unavailable from in-house or open literature, it may be necessary to
carry out experiments to determine the magnitude of the rate constants. Carry out the reactions under
controlled conditions to isolate the influence of reaction kinetics from phase equilibrium, mass transfer,
heat transfer, etc. For example, carry out the experiments in sealed tubes so the liquid phase
concentrations are unaffected by phase equilibrium.
Reaction experiments should be performed over a range of temperatures to allow determination of the
activation energies.
Preliminary Model Development

Once the preliminary parameter fitting is complete, these parameters can be used to develop a
preliminary model. At this stage of the model development process, it may be best to use simplified
models for some of the ancillary operations that are not directly involved in the polymerization reactors.
For example, it may be more convenient to represent distillation columns using the non-predictive Sep or
Sep2 models instead of the RadFrac or MultiFrac rigorous distillation models.
The most important rule for model development is to keep it simple. Model development must be carried
out in several stages. Add detail to the model one step at a time. Each generation of the model can yield
valuable insights into the process and can provide substantial benefit to the model developer. At each
stage in the process, fit the appropriate model parameters and validate the model against all sources of
available data. Verify the predicted trends against process data, operator experience, and engineering
know-how. Over time, the level of detail and power of the model can be increased.
During the preliminary development, use the most basic specifications possible. For example, in the
RCSTR model specify temperature and reacting phase volume instead of duty and residence time. This
approach will make the model run faster and will help to isolate the influence of property parameters from
reaction kinetic parameters.
Once the preliminary model is complete, it can be tested against process data. Major discrepancies
between the data and the model predictions should be addressed during this step.
Trend Analysis
Use the preliminary model to carry out trend evaluation studies. The sensitivity feature can be used to
examine the influence of process variables on the model predictions. Compare these trends against
process data. If the
predicted trends are not consistent, adjust the appropriate model parameters to improve the match. For
example, if the predicted slope of the monomer conversion versus temperature curve is less than the
measured slope, the activation energy of the polymerization reaction may be too low.
Use the sensitivity tool to examine the influence of the model parameters on the model predictions and to
determine which parameters are important in the model. Parametric studies can be carried out by
manipulating two or more variables in a sensitivity study.
It is good practice to include as many model predictions as possible in each sensitivity study. The
simulation runs take the same amount of time regardless of the number of defined variables. It is much
easier to understand the predicted trends when the sensitivity results are detailed.
Once you know which parameters are critical to the model predictions, the data regression tool can be
used to adjust these parameters to match specific trends. Keep the number of manipulated parameters to
a minimum until all of the key parameters are established independently.
Model Refinement
The Data-Fit tool is the best choice for refining the fit between the model predictions and the process
data, especially when several sets of data are available. Data-Fit can adjust several model parameters
simultaneously, capturing subtle interactions among the parameters to get the best overall match
between the process data and model predictions.
When the model predictions cannot match the process data, the assumptions in the model may be too
broad. Perhaps the process is limited by heat- or mass-transfer, or a reactor is not ideally mixed. Maybe
there are additional side reactions that should be considered in the model, or the rate expression needs
to be modified to account for some unusual aspect of reaction kinetics. These issues can be addressed
during the model refinement process by adding new layers of detail to the model. Avoid adding more
detail than necessary, however, because model fitting is a process of diminishing returns.
Model refinement is an open-ended process. The model parameters can be tuned more accurately as
more data become available from the process. Bad data points are easier to spot when there are more
sets of data to compare.
It is impossible for a simulation model to match process data perfectly. There are several sources of error
that lead to differences between the model results and process data, including:
Variations in process operating conditions due to disturbances, excursions from steady state, control
system actions, etc.
Imperfect calibration of flow meters, level controllers, etc.
Analytical error in lab measurements
Simplifications and assumptions in the model, such as ideal mixing, isothermal and isobaric vessels,
phase equilibrium, etc.
Errors in the model parameters.
Steps for Using the Data Regression Tool
There are three steps involved in using the data regression tool:
Creating a base-case model
Entering lab or process data and operating conditions into data sets
Defining regression cases
Step 1. Creating a base-case model
If the regression tool is being used to fit reaction kinetic parameters from lab batch reactor data, use the
RBatch model with an appropriate reaction kinetic model.
If the model parameters are being regressed from process data, develop a model of the process. Before
setting up the data fit run, make sure the model predictions are reasonable and that the model is robust
(converges without errors) over the ranges of each manipulated parameter. You can use sensitivity
blocks to screen the model for accuracy and to test how robust the model is.
The rate constants and property parameters entered into the base case model become the initial
estimates for the regression.
Step 2. Entering lab or process data and operating conditions into data sets
There are two types of data sets used with the regression tool, Point-Data and Profile-Data:
Use To specify
Point-Data Operating conditions for steady-state unit operation models.
Feed streams for continuous processes or batch charge streams. Analytical data, measured flow rates, or
composition data for product streams. Polymer or catalyst component attribute data for product streams. Profile-Data
Operating profiles for batch reactors or plug-flow reactors, including
temperature, pressure, and duty profiles, continuous feed stream profiles, etc. Time-series measured data for a batch
reactor or data along the axial profile of a plug-flow reactor. Note: Component attribute profiles and user variable
profiles are not available as profile data in this release of Aspen Polymers. To fit profile data for these types of
variables, treat each data point in the profile as a point datum, and specify the coinciding stop-time (RBatch) or length
(RPlug) of the reactor as another point datum in the same data set.
Step 3. Defining regression cases
For each case, specify the parameters to be adjusted and the data sets to be fitted. Several regression
cases can be included in the same simulation run. The cases are run sequentially; a prompt will appear
on the screen that lets
you specify which cases to include in the run, and the sequence order of the cases. Each successive
case uses the fitted parameters and reconciled data from the previous case. If the data regression is run
again, the previously fit values are used as initial estimates unless the simulation is reinitialized.
Identifying Flowsheet Variables

You must identify each measured and manipulated variable considered in the regression. Most types of
variables, such as stream flow rates, equipment operating conditions, and component attribute values can
be accessed directly using the variable accessing system.
In the data regression and data set forms, you cannot access vector data, such as the stream vector and
component attribute vector. You must access each stream variable or component attribute element as a
separate scalar variable.
When specifying feed stream data, avoid using mole, mass, or volume fractions as variables in the data
set. If the composition of the feed stream changes from one validation case to another, specify the flow
rates of the components in the stream. If the composition is constant but the flow rate changes, specify
the composition and base-case flow rate in the model, and specify the total stream flow rate as a point-
data variable. This avoids problems with normalizing fractions and reduces the number of variables
handled by the data-fit algorithm.
Some unit operation models have both input and results variables for the same operating condition. For
example, in the RCSTR model you can access the specified heat duty (DUTY), or the calculated reactor
duty (QCALC). If a variable is an INPUT variable in the regression it must be specified in the unit
operation model.
For example, if the reactor duty is a manipulated INPUT variable in the regression, it must be specified as
an input variable (DUTY), and the reactor duty must be specified in the reactor model. If the reactor duty
is a measured RESULTS variable, it must be specified as a results variable (QCALC), and is usually not
specified in the model (the temperature is specified instead).
The following table provides a cross-reference of commonly-used INPUT and RESULTS variables for key
specifications related to several unit operation models:
Model Operating Condition Input Variable Results Variable
RBatch Cumulative reactor duty DUTY QCALC RCSTR with one phase
Duty Pressure Temperature Reactor volume Reactor residence time
DUTY PRES* TEMP VOL RES-TIME
QCALC use outlet stream pressure TCALC VOL-CALC RT-CALC RCSTR with multiple phases
Reacting phase volume REACT-VOL VOLL-CALC for liquid volume
VOLV-CALC for vapor volume VOLLS-CALC for total liquid+solid volume
Model Operating Condition Input Variable Results Variable
Reacting phase residence time
PH-RES-TIME VOLL-CALC for liquid residence
time RTV-CALC for vapor residence time RTLS-CALC for liquid or solid residence time RPlug Duty
Pressure (process fluid) Temperature (process fluid) Residence time (process fluid)
DUTY PRES* (feed) SPEC-TEMP** RES-TIME
QCALC REAC-PRES** REAC-TEMP** RT-CALC (entire reactor) REAC-RESTIM** (residence time at a profile point)
Flash2 and Flash3
Duty Pressure Temperature
DUTY PRES* TEMP
QCALC use outlet stream pressure use outlet stream temperature RadFrac and MultiFrac
Condenser duty Reboiler duty Reflux ratio Boilup ratio Stage temperature Stage pressure Design specification
setpoint
Q1 QN basis-RR*** basis-BR*** STAGE-TEMP STAGE-PRES VALUE
COND-DUTY REB-DUTY RR BR TEMP PRES various - it depends on the specification
* The pressure variable is treated as a pressure drop if the specified value is non-
positive. ** Specify location (RPlug) or stage number (RadFrac / MulitFrac) *** Basis can be MOLE, MASS, or
STDVOL - the variable specified in the data set
must match the variable specified in the column .
Some measured data, such as polymer melt index and intrinsic viscosity, are not predicted by the
standard property sets in Aspen Polymers. The best way to include these properties in a data regression
is to write a user Prop-Set property subroutine. Each user property can be linked to a property set.
Property sets can be accessed as stream-property variables.
Manipulating Variables Indirectly

In-line Fortran blocks can be used to enforce assumptions in the model or to manipulate variables
indirectly. Using these techniques to reduce the number of manipulated variables can greatly enhance the
speed and reliability of the regression.
Example 1: Using Fortran Blocks to Enforce Modeling Assumptions
Suppose:
Your process involves a catalyst and an initiator.
The key variables involved in the regression cases are the process operating conditions and the
monomer feed rate. The catalyst and initiator flow rates are always proportional to the monomer feed
rate.
Create a Fortran block and define the monomer, catalyst, and initiator flow rates as flowsheet variables.
Specify the monomer flow rate as a read variables and the catalyst and initiator flow rates as write
variables as shown below: FORTRAN SETCAT
DEFINE FLOMON MASS-FLOW STREAM=FEED COMPONENT=MONOMER DEFINE FLOINI MASS-FLOW
STREAM=ADDITIVE COMPONENT=PEROXIDE DEFINE FLOCAT MASS-FLOW STREAM=CATALYST
COMPONENT=METAL READ-VARS FLOMON WRITE-VARS FLOINI FLOCAT C Specify the base-
case flow rates in kg/hr below F BCMON = 1200.0 F BCCAT = 20.0 F BCINI = 5.0
C Calculate the flow rates of initiator and catalyst F FLOINI = FLOMON *
BCINI / BCMON F FLOCAT = FLOMON * BCCAT / BCMON
Define the monomer flow rate as a variable in a point-data set. During the data regression run, the
regression model will write the monomer flow rate for each case. The Fortran block will be executed each
time the regression block manipulates the monomer flow rate. The Fortran block will read the new
monomer flow rate, calculate the initiator and catalyst flow rates, and write their values.
Using this technique to indirectly manipulate the additive flow rates reduces the number of variables in the
regression, making the regression faster and more reliable. The cost of this approach is that the indirectly
manipulated variables (catalyst and initiator flow rates) cannot be reconciled (the model has no
information regarding the standard deviations of these variables).
Example 2: Using Parameters and Fortran Blocks to Indirectly Manipulate Process Variables
Suppose:
Your polymerization process uses two monomers.
The key variables involved in the regression cases are the monomer ratio and the polymer production
rate. You want to vary these parameters in the data regression.
In the base-case model, define the monomer ratio and production rate as parameter variables in a
Fortran block. Specify the base-case monomer ratio and production rate in the same Fortran block.
Specify this block to sequence first, as shown below: FORTRAN INITIAL
DEFINE RATIO PARAMETER 1 DEFINE PRODRT PARAMETER 2 SEQUENCE FIRST C specify
monomer mole ratio F RATIO = 1.05 C specify polymer production rate, kg/hr F
PRODRT = 2000.0
Create a second Fortran block. Define the monomer flow rates as flowsheet variables. Access the
monomer mole ratio and production rate parameters. Specify the parameter variables as read variables
and the monomer flow rate variables as write variables. After solving the algebra, the Fortran block can
be defined as shown below: FORTRAN ADJUST
DEFINE RATIO PARAMETER 1 DEFINE PRODRT PARAMETER 2 DEFINE FLOM1 MOLE-FLOW
STREAM=FEED COMPONENT=MONO-1 DEFINE FLOM2 MOLE-FLOW STREAM=FEED
COMPONENT=MONO-2 READ-VARS RATIO PRODRT WRITE-VARS RATEM1 RATEM2 C w = mole
weight of each monomer F WM1 = 150.23 F WM2 = 230.30 C calculate average
molecular weight of monomers F RATINV = 1.0 / RATIO F WMAVG = ( 1.0 + RATINV
) * ( WM1 + WM2*RATINV ) C calculate monomer flow rates in kmol/hr F FLONET =
PRODRT / WMAVG F FLOM1 = FLONET / ( 1.0 + RATINV ) F FLOM2 = FLONET - RATEM1
The production rate and mole ratio parameters can be accessed as parameter variables in the data-set.
The standard deviation for the production rate and mole ratio variables may be specified; the units of the
standard deviations are the same as the units of the parameters.
Entering Point Data

There are two types of point data: input variables and result variables. Input variables include feed stream
flow rates, equipment operating conditions, and other parameters that are inputs to the simulation model.
Result variables include product stream flow rates or composition, polymer or catalyst component
attributes, stream properties, or any other simulation calculation that can be compared to measured
process data.
If some results data are missing from one or more sets of data, they can be left blank on the input forms.
The model will estimate the values of these results and tabulate them after the regression run.
Unknown input data may also be estimated. Leave the input field blank and specify large standard
deviations (for example, 50%) for each missing datum. Supply a realistic initial guess and make sure the
standard deviation results in reasonable bounds for each missing variable.
The upper and lower bounds for reconciled unknown input variables are determined from the specified
standard deviation and the bound factor, which defaults to ten:
Lower bound = Measured value - (Bound Factor)*(Standard Deviation)
Upper bound = Measured value + (Bound Factor)*(Standard Deviation)
Make sure these limits are reasonable. In particular, the limits for a stream flow rate must not allow the
stream flow rate to become zero or negative.
Entering Profile Data

The plug-flow reactor model (RPlug) predicts results at various points along its length axis. The batch
reactor model (RBatch) predicts results at various points in time during the batch cycle. You can define
profile data sets to specify the operating profiles as input data, or to fit the model to measured results
data.
To do this, specify the time and value for each datum in the profile. You can specify standard deviations
for results variables. Data reconciliation is not allowed for input profile data.
The following table lists the profile data sets that are currently available for these reactor models.
Model Variable
Type
Description Profile Name
RBatch, RPlug
Input Temperature of process fluid TEMPERATURE
Pressure of process fluid PRESSURE Instantaneous reactor duty DUTY Results Partial pressure of a component
PARTIAL-PRES
Molar concentration of a component in the liquid phase
MOLECONC-L
Molar concentration of a component in the vapor phase
MOLECONC-V
Mole fraction of a component in the liquid phase MOLEFRAC-L Molar fraction of a component in the vapor phase
MOLEFRAC-V Mass concentration of a component in the liquid phase
MASSCONC-L
Mass concentration of a component in a slurry phase MASSCONC-LS Mass fraction of a component in the liquid
phase MASSFRAC-L Cumulative reactor heat duty CUM-DUTY RBatch Input Feed stream component flow rates not
applicable
Results Instantaneous vent mole flow rate VENT-MOLFLOW Instantaneous vent volume flow rate VENT-VOLFLOW
Property Set property in the reactor REACTOR-PROP Property Set property in the accumulator ACCUM-PROP
Property Set property in the vent VENT-PROP RPlug Results Property Set property in the reactor PROP-VALUE
If you are fitting component attribute or user Prop-Set property profiles, you must treat the measured
variables as point data for the reactor outlet stream. Use the reactor length or stop-time as an additional
point data. Each profile point must be treated as a separate data case in the data set.
If some results data are missing from one or more sets of profile data, they can be left blank on the input
forms. The model will estimate the values of these results and tabulate them after the regression run.
Entering Standard Deviations

Standard deviations may be specified for input and result variables. The standard deviation is the level of
uncertainty in the measurement. You can enter the value as an absolute or percent error (append a
percentage sign, %, to the value). Statistically determined standard deviations may be available from an
on-line process information management system (PIMS), from lab databases, or from other information
resources. When the standard deviations are not available, you can enter your best estimate of the
expected error based on your experience or the specifications of the instrument.
The objective function of the data regression is to minimize the sum of weighted square errors. For results
variables, each error is defined as the difference between the reconciled or specified datum and the value
calculated by the model. Each error is scaled against the square of the standard deviation:
Objective function =
i
Measurement i -
Prediction
i (Standard deviation) 2 i
If the specified standard deviation of a variable is too small, the model over- emphasizes the importance
of the variable during the fitting process. This may cause the model to make unreasonable adjustments in
some parameters to force good fits to variables with small standard deviations.
You must be careful to consider both the precision and accuracy of each variable. For example, a
variable may have a low standard deviation because it is very precise (it reproduces well in successive
trials), but the measurement may be inaccurate (it may not reflect the true value of the measured
parameter). Consider the case where a level controller may show little deviation in the liquid volume in a
reactor, but the calibration of the level transducer may not be accurate to within ten percent of the real
liquid volume. In this case, the standard deviation of the specified liquid volume should be large enough
to reflect the accuracy of the volume, not the deviation of the liquid level.
If standard deviations are specified for input variables, the model reconciles these variables. If you do not
specify the standard deviation of an input variable, the model assumes the specified values are exact.
Reconciling input variables accounts for measurement errors in the operating conditions and can lead to
better models, but it can substantially increase how long the run takes to complete.
Standard deviations must be specified for each of the result variables. Specify reasonable standard
deviations to keep the model from forcing a match by making wild adjustments to the parameters. The
specified standard deviations are probably too small (or the data quality is poor) if several of the
parameters reach their upper or lower bounds.
Defining Data Regression Cases
You can fit any number of data sets in the same regression case. Point-Data and Profile-Data may both
be included. Each regression case must involve at least one estimated parameter and at least one
reconciled input variable. There are no upper limits to the number of estimated parameters and reconciled
inputs, however the required simulation time is very sensitive to the number of variables included in each
regression case.
Each input variable with a non-zero standard deviation is reconciled (adjusted). The reconciled inputs are
tabulated in the regression results.
Each estimated parameter must be defined in the base case, or have a default value (such as a physical
property parameter). The specified values for the base case run are used as the initial guesses for the
regression. If the base- case value lies outside the specified bounds, the boundary condition closest to
the base case value is used.
Sequencing Data Regression Cases

For data fit problems, Aspen Plus will:
Run the base-case simulation
Execute the data regression
Replace the base-case parameter values with the estimated parameter values and rerun the base-case
simulation
If Sensitivity blocks are present, Aspen Plus runs them after the regression is complete. The estimated
parameter values are used to calculate the results for these blocks.
Flowsheet convergence loops and Design-Specification loops are used in the preliminary and final base-
case simulations and they are sequenced inside the data regression loop. The sequencing of Fortran
blocks and Transfer blocks depends on which variables are accessed.
If more than one regression is included in a simulation, the regressions can be affected sequentially.
Each successive regression uses the estimated parameters from the previous regression.
Regression blocks can be manually sequenced if the automatic sequence does not meet the needs of a
particular run, however automatic sequencing is usually the best choice.
Interpreting Data Regression Results

The key results of the data regression tool are:
The Chi-square statistic and critical Chi-square value for the fit.
Estimates and standard deviations for each estimated parameter.
A table of the measured values, estimated values, and normalized residuals for each data set.
The Chi-square value is an indicator of the quality of the fit. A model is considered well fit if the Chi-
square value falls below the critical Chi-square value. The reliability of different fits or different modeling
approaches can be
tested by comparing the Chi-square values of the fits. For example, suppose a reactor is thought to have
non-ideal mixing. This assumption can be evaluated by developing two models, one which assumes ideal
mixing (one CSTR stage) and one which assumes non-ideal mixing (a series of CSTR stages). The two
models can be fit against the same data using the same parameters. The model with the lower Chi-
square statistic represents the data more accurately, and can be considered the most realistic.
Ideally, the standard deviations of the estimated parameters are small, and the confidence interval of
each parameter is narrow. In practice, however, the standard deviation of the parameters may be
relatively large. This does not necessarily indicate a poor fit. For example, if the activation energy and
preexponential factor for a reaction are both included as estimated parameters in the data regression,
then the standard deviation of the estimated preexponential factor will be large. In this example, small
differences in one parameter (the activation energy) requires large differences in another parameter (the
pre-exponential factor) to keep the model predictions relatively constant.
The residual values are indicative of the difference between the measured data and model predictions.
For fitted data, the residuals are defined as:
Residual i = (Measuredvalue i - Predictedvalue i
) (Standarddeviation
2
/i
)
For reconciled data, the residuals are defined as:
Residual i = (Measured value i - Estimated value i
)2
/ (Standard deviation
i
)
Review the residual values to verify they are sensible. Large residual values may indicate a major
problem with the model or data, or may reflect an unreasonably tight standard deviation. Never specify
extremely tight standard deviations. This causes the data regression algorithm to waste time attempting
to obtain tight fits on some variables. If some data are considered extremely accurate, they should be
assigned standard deviations of zero.
The regression results may be plotted against the initial estimates and measured data. Plots of this type
include a 45 dotted line that indicates a perfect fit, e.g., each prediction is exactly equal to the
measured data. Points which fall far from this line are the least well fit. Verify these outliers to make sure
the data is correctly entered into the model and that the units of measurement are consistent.

If the data regression tool fails to converge, check the objective function. A large objective function value
indicates a poor fit between the model predictions and measured data. If the objective function is large,
review the residual values for each type of measured data. Large residual values may indicate a very
basic error in the data entry. For example, the data may be entered in the wrong units or there may be
typing errors in the specified values. Always review the model thoroughly to eliminate these types of
problems before adjusting convergence parameters or making other major changes to the regression.
Convergence errors can occur for a number of reasons. When a problem occurs, ask:
Does the base case model converge well and give reasonable results?
Is the base case model formulated to handle data that may be out of mass or energy balance?
Are the initial estimates of the parameters good enough?
Are the specified standard deviations reasonable?
Do the model inputs completely determine the measured results?
Do the specified bounds allow the regression to take the model into infeasible regions, causing the unit
operation blocks or flowsheet convergence to fail?
Are the assumptions and simplifications in the model reasonable?
Regression runs with many variables and runs for highly non-linear models may still be difficult to
converge. In some cases, the convergence criteria may be unnecessarily tight.
The following table summarizes several convergence parameters that can be used to tune a regression
run. It is not necessary to adjust the convergence parameters for most regressions.
Parameter Description
ALG-ITERATION Maximum number of algorithm iterations. The default value is
sufficient for nearly all problems MAX-PASSES Maximum number of flowsheet passes. This parameter may need
to be increased for regressions involving a large number of variables. SSQTOL Convergence tolerance for sum of
weighted square errors (Absolute objective function tolerance) This is the absolute tolerance for the objective
function. The default tolerance is very tight, so regressions that converge to this tolerance should be reviewed
thoroughly. Verify that the specified standard deviations are sensible. Change the default value of this parameter if
you which to fit the model to achieve a particular objective function value. RFCTOL Relative objective function
tolerance. The problem is considered
converged if the model predicts that the maximum possible objective function is less than the product of the relative
function tolerance and the current value of the objective function. For example, if RFCTOL is 0.1, then the model is
converged when the predicted change in the objective function is less than ten percent of the objective function value
for the current iteration. XCTOL Minimum variable step-size tolerance. The problem is converged if
the relative step size in the variables falls below XCTOL and the objective function is decreasing slowly (less than
50% per iteration). XFTOL Minimum objective step-size tolerance INIT-STEP Factor used to determine initial step
sizes. This factor can
profoundly affect the performance of the algorithm. If the initial steps are too large or too small, the model must adjust
the step size until appropriate step sizes are determined. PERT-FACTOR During the regression, the model
determines the response of each
variable to each other variable by making small adjustments, or
Parameter Description
pertubations, to the variables. The size of these adjustments is determined by the algorithm, this parameter is used to
determine the maximum pertubation step sizes for each variable. You may need to increase this value when the fitted
data are not very sensitive to the manipulated parameters, or decrease this value when the sensitivity is very strong.
BOUND- FACTOR
Factor used to determine lower and upper bounds for reconciled inputs. If the value is too large, the model may enter
an infeasible region, for example a stream flow rate may go to zero. If the value is too small, the parameter ranges
may be too narrow to fit the data. INIT-METHOD Method used to initialize the regression. Specify BASE-CASE to use
the base case values to initialize the reconciled input parameters. Specify MEASUREMENTS to use the measured
data to initialize the reconciled inputs.
Ensuring Well-Formulated Regressions

Poorly formulated regressions may result in large residual values and a large objective function. Before
starting a regression run, use sensitivity studies to test the model. Verify that the manipulated parameters
have a strong influence on the measured data. Dont try to fit parameters which have only a weak impact
on the model predictions.
Make sure the parameter ranges are sensible. It is a waste of time to fit a parameter within a narrow
range (less than 5%). On the other hand, if the range is too large, the regression algorithm may push the
model into an infeasible region. For example, if the distillate to feed ratio in a column is allowed to
decrease to zero, the column model will fail.
The way the data regression is formulated has a major influence on how quickly and easily the problem
converges. De-couple the manipulated variables as much as possible. For example, dont fit the rate
constants and phase equilibrium parameters at the same time if the two sets of parameters can be fit
independently in two smaller data regression runs.
Use the weighing factors if some sets of data are more reliable than others. A larger weight may be
assigned to a set of data that are based on long-term averages from the process information
management system, lower weights might be assigned to data based on poorly kept records from the
distant past.
Make sure the manipulated parameters can be determined from the available data. For example, the
activation energy of a reaction cannot be determined from isothermal data.
The base-case file needs to be formulated in a robust manner. If the base case model does not converge
reliably away from the base case condition, then it is likely that the regression run will fail. Use the
sensitivity tool to verify that the model is stable over the entire range of each manipulated parameter and
to verify that the model is sensitive to each parameter.
Where possible, use relative or normalized inputs instead of absolute inputs. For example, in column
models use the distillate to feed ratio (D:F) instead of
distillate flow rate. Use pressure drop specifications instead of pressure. These specifications make the
model more reliable and help to avoid problems that occur if the measured data are inconsistent.
Fitting Activation Energy

It is tempting to try to fit activation energies and pre-exponential factors in the same regression run. This
can lead to significant headaches if the problem is not approached right. Consider, for example, the
standard Arrehnius rate expression:
k net =
k
o
exp
-
RT E
act
Using this expression, the net rate constant, k

net
, is sensitive to the activation energy, E

act
. If the activation energy is adjusted a little bit, a large adjustment must be made to the pre-
exponential factor to offset this difference. In other words, the activation energy controls the magnitude of
the reaction rate as well as the temperature sensitivity of the reaction rate.
A better approach is to use the modified Arrehnius expression:
k net =
k
o
exp
-
E R act
T1-
T
ref 1
The parameter T
ref
is a reference temperature that typically represents the

middle of the temperature range used to estimate the activation energy. Using this formula, the net rate
constant, k
net
, remains constant at the reference temperature

regardless of the value of the activation energy. With this approach, the pre-exponential factor, k
o
, controls the magnitude of the reaction rate at the

reference temperature. The activation energy, E
act
, controls the
temperature sensitivity of the rate constant. This makes it much easier to fit the model.
Scaling the Fitted Parameters

When several types of parameters are adjusted in the same run, the magnitude of the manipulated
parameters may influence how well the data regression converges. Ideally, the manipulated parameters
should be within several orders of magnitude of each other.
Suppose, for example, the manipulated parameters include rate constants for several different types of
reactions. These expected values of the rate constants may differ by several orders of magnitude. In this
situation, the regression procedure may over-emphasize the manipulated variables with the smallest
magnitude.
You can get around this problem using two CALCULATOR blocks as shown in Example 3. Use one
CALCULATOR block to define a PARAMETER variable for each manipulated variable in the regression.
Initialize each parameter to one. Use a second CALCULATOR block to READ these parameter values, to
multiply them by base case values, and then WRITE the results to the manipulated variables. In the data
regression block, manipulate the PARAMETER variables.
This technique allows the data regression to operate on normalized variables instead of absolute
variables which makes it much easier for the regression algorithm to choose appropriate step sizes and
ensures that the variables are given equal weighting by the algorithm.
Example 3: Using Fortran Blocks to Scale Manipulated Parameters
Problem Description: Suppose two pre-exponential factors are adjusted to match conversion and intrinsic
viscosity, which are defined as user Prop-Set properties. The pre-exponential factors have very different
magnitudes, so scaling is required to get a good fit.
Instead of manipulating the rate constants directly, use PARAMETER variables to define and manipulate
correction factors for the rate constants. Use a CALCULATOR block to initialize these correction factors
to unity. Manipulate these PARAMETER variables in the regression. Use a second CALCULATOR block
to adjust the pre-exponential factors using the correction factors manipulated by the data regression
model.
USER-PROPERTY INT-VISC SUBROUTINE=USRPSP FLASH=YES USER-PROPERTY CONVERSN
SUBROUTINE=USRPSP FLASH=YES PROP-SET INT-VISC INT-VISC PROP-SET CONVERSN
CONVERSN
DATA-SET DS-1
DEFINE CAT MASS-FLOW STREAM=CATALYST SUBSTREAM=MIXED COMPONENT=CAT DEFINE
TEMP BLOCK-VAR BLOCK=CSTR1 SENTENCE=PARAM VARIABLE=TEMP DEFINE VISC STREAM-
PROP STREAM=PRODUCT PROPERTY=INT-VISC DEFINE CONV STREAM-PROP STREAM=PRODUCT
PROPERTY=CONVERSN USE STD-DEV 0.001 0.1 0.002 0.0050 / DATA 0.025 290.0 0.844
0.8550 / DATA 0.023 295.0 0.842 0.8700 / DATA 0.055 280.0 0.850 0.9050 / DATA
0.033 292.0 0.835 0.9000
STEP-GROWTH MYMODEL
RATE-CON 1 PRE-EXP=9.67D14 ACT-ENERGY=41.0 RATE-CON 2 PRE-EXP=3.25D0 ACT-
ENERGY=0.0 etc...
CALCULATOR INITIAL
DEFINE P1 PARAMETER 1 DEFINE P2 PARAMETER 2 P1 = 1.0D0 P2 = 1.0D0 EXECUTE
FIRST
CALCULATOR ADJUST
DEFINE P1 PARAMETER 1 DEFINE P2 PARAMETER 2 DEFINE EXP1 REACT-VAR
REACTION=MYMODEL VAR=PRE-EXP SENT=RATE-CON ID1=1 DEFINE EXP2 REACT-VAR
REACTION=MYMODEL VAR=PRE-EXP SENT=RATE-CON ID2=2 C specify base case pre-
exponential factors for side rxn 1 and 2 F BASE1 = 9.67D14 F BASE2 = 3.25D0 C
calculate pre-exponential factors using correction factors
C manipulated by the data regression block F EXP1 = BASE1 * P1 F EXP2 = BASE2
* P2
READ-VARS P1 P2 WRITE-VARS EXP1 EXP2
REGRESSION FIT-1
DATA DS-1 VARY PARAMETER 1 LABEL=CORRECT FACTOR RXN #1 LIMITS 0.1 10.0
VARY PARAMETER 2 LABEL=CORRECT FACTOR RXN #2 LIMITS 0.1 10.0
17 User Models
This section discusses the features available in Aspen Polymers (formerly known as Aspen Polymers
Plus) for incorporating user modules into a simulation model.
User Unit Operation Models, 359
User Kinetic Models, 365
User Physical Property Models, 370
Note: For more information on user models, see your Aspen Plus User Models documentation.
User Unit Operation Models

There are cases where users may need to create special models to represent a process. Usually these
models can be configured by combining several of the standard unit operation building blocks. For more
complex reactor geometries or in order to represent highly non-ideal systems users may need to provide
their own model as a Fortran subroutine.
There are two user unit operation blocks available: USER and USER2. The first allows a limited number
of inlet and outlet streams. The second allows multiple inlet and outlet streams. Both unit operations take
full advantage of the Aspen Plus flowsheeting capabilities. The required Fortran subroutine must process
the feed streams and return the condition and composition of the outlet streams.
User Unit Operation Models Structure

There are three stages to the execution of Aspen Plus unit operation models: input processing, simulation
calculations, and report writing. Normally, the implementation of a new model requires that all three
stages be accounted for. However, in the case of USER2 models, a generic framework handles the input
setup and processing stage. A Fortran subroutine must be written to perform the simulation calculations
and for writing the report. If no report
17 User Models 359
writer is provided Aspen Plus automatically echoes the input data in the report.
The following figure summarizes the simulation sequence of a unit operation model:
User Unit Operation Model Calculations

A user unit operation model can be programmed to represent any unit operation. Most applications would
include combinations of the following: separations, reactions, heat transfer, mass transfer, mixing and
splitting. There are some common steps that are found in the simulation calculations within unit operation
models, including user models. These steps include:
Feed processing
Physical properties and phase equilibrium calculations
Unit operation calculations (kinetics, heat transfer, mass transfer, etc)
Results storage and outlet stream initialization
Utilities are available to facilitate each of these steps. The available Fortran utilities and monitors are:
Stream Handling
NPHASE Determines number of substreams LPHASE Finds the location of a substream within a stream SSCOPY
Copies a substream from one stream to another NSVAR Determines the size of the stream vector
360 17 User Models
Component Attribute Handling
GETDPN Find the number average degree of polymerization GETMWN Find the number average molecular weight
GETPDI Find the polydispersity GETSMF Find the segment mole fractions GETSWF Find the segment weight
fractions CAUPT Load attributes into physical property system LCATT Finds the location of a component attribute in
the
stream vector
Component Handling (See Aspen Plus User Models)
CPACK Packs out trace components ISPOLY Determines if a component is a polymer ISSEG Determines if a
component is a segment ISOLIG Determines if a component is an oligomer ISCAT Determines if a component is a
catalyst ISINI Determines if a component is an ionic initiator KCCID Finds the component index (position in stream
vector)
Property Monitors (See Aspen Plus User Models)
KVL Calculates vapor-liquid equilibrium ratio (K-value) KLL Calculates liquid-liquid equilibrium ratio ENTHL
Calculates liquid mixture enthalpy VOLV Calculates liquid mixture molar volume FUGLY Calculates liquid mixture
fugacity coefficient IDLGAS Performs ideal gas calculations VISCL Calculates liquid mixture viscosity
Flash Routine (See Aspen Plus User Models)
FLASH Flash monitor
Error Handling (See Aspen Plus User Models)
IRRCHK Function to check diagnostic level ERRPRT Error printing routine WRTTRM Writer to terminal file or control
panel
Report Writer (See Aspen Plus User Models)
RPTHDR Report pagination /header writer
Stream Processing
In order to perform its calculations the user model must be able to read and process the Aspen Plus
stream structure. The stream structure is documented in Aspen Plus User Models. Example 1 shows a
USER2 model routine.
Note: The data in the streams coming in and out of the model are stored in SI units.
17 User Models 361
There are several utilities available for stream processing. These perform functions such as finding the
number of stream variables, i.e. the size of the stream vector, copying one stream to another, finding the
total number of substreams, and finding specific substreams within a stream. Several stream handling
utilities are documented in Chapter 4 of Aspen Plus User Models.
In addition to the standard composition and state information found in the stream structure, there are also
component attributes. If the user model processes polymers, then component attributes must be
processed and their outlet stream values must be calculated and stored. The attributes available include
polymer properties such as degree of polymerization, molecular weight, polydispersity, and copolymer
composition. These are documented in the Polymer Structural Properties section of Chapter 2. In order to
process attributes, there are Fortran utilities available that perform functions such as copying attributes
from one stream to another, retrieving number average molecular weight and degree of polymerization,
retrieving copolymer composition, locating specific component attributes within the stream vector, and
determining the size of a vector component attribute. The component attribute handling utilities are
documented in Chapter 4 of Aspen Plus User Models .
There are also utilities for processing components: for excluding trace components, for determining
component type (polymer, oligomer, segment, catalyst), etc. These can be found with the component
attribute processing utilities.
Example 1: USER2 Model Routine
C----------------------------------------------------------------------
SUBROUTINE USRMOD (NMATI, SIN, NINFI, SINFI, NMATO, 2 SOUT, NINFO, SINFO,
IDSMI, IDSII, 3 IDSMO, IDSIO, NTOT, NSUBS, IDXSUB, 4 ITYPE, NINT, INT, NREAL,
REAL, 5 IDS, NPO, NBOPST, NIWORK, IWORK, 6 NWORK, WORK, NSIZE, SIZE, INTSIZ,
LD) C---------------------------------------------------------------------- C
IMPLICIT NONE C C DECLARE VARIABLES USED IN DIMENSIONING C
INTEGER NMATI, NINFI, NMATO, NINFO, NTOT, + NSUBS, NINT, NPO, NIWORK,NWORK,
+ NSIZE C #include "ppexec_user.cmn"
EQUIVALENCE (RMISS, USER_RUMISS) EQUIVALENCE (IMISS, USER_IUMISS) C #include
"dms_plex.cmn"
EQUIVALENCE (IB(1), B(1)) REAL*8 B(1) C #include "dms_rglob.cmn" C #include
"dms_global.cmn" C
362 17 User Models
#include "dms_ipoff1.cmn" C #include "dms_ncomp.cmn" C C DECLARE FUNCTIONS C
INTEGER SHS_LCATT, DMS_KCCIDC INTEGER XMW, LMW C C DECLARE ARGUMENTS C
INTEGER IDSMI(2,NMATI), IDSII(2,NINFI), + IDSMO(2,NMATO), IDSIO(2,NINFO), +
IDXSUB(NSUBS),ITYPE(NSUBS), INT(NINT), + IDS(2,3), NBOPST(6,NPO), +
IWORK(NIWORK),INTSIZ(NSIZE),NREAL, LD, I
INTEGER KH2O REAL*8 SIN(NTOT,NMATI), SINFI(NINFI), + SOUT(NTOT,NMATO),
SINFO(NINFO), + WORK(NWORK), SIZE(NSIZE) C C DECLARE LOCAL VARIABLES C
INTEGER IMISS REAL*8 REAL(NREAL), RMISS, WATER C
INTEGER IDXP, LZMOM, LMWN, IMWN(2), IZMOM(2) REAL*8 AMWP, ZMOM C INITIALIZE
ARRAY OF ATTRIBUTE NAMES
DATA IZMOM / "ZMOM"," " / DATA IMWN / "MWN "," " / C C-----------------------
----------------------------------------------- C C BEGIN EXECUTABLE CODE C
C---------------------------------------------------------------------- C
OFFSETS TO COMPONENT MOLECULAR WEIGHTS
XMW(I) = DMS_IFCMNC('MW') + I C C FIRST COPY FIRST INLET TO FIRST
OUTLET C
DO 100 I = 1, NTOT
SOUT(I,1) = SIN(I,1) 100 CONTINUE C C INITIALIZE THE SECOND OUTLET C
DO 200 I = 1, NCOMP_NCC+1
SOUT(I,2) = 0D0 200 CONTINUE C
DO 300 I = NCOMP_NCC+2, NCOMP_NCC+9
SOUT(I,2) = RMISS 300 CONTINUE C C FIND LOCATION OF COMPONENT
ATTRIBUTES
17 User Models 363
C IDXP is position of polymer component in component list. C Can be obtained
with ispoly function C find location of attributes in stream
LZMOM = SHS_LCATT( 1, IDXP, IZMOM ) LMWN = SHS_LCATT( 1, IDXP, IMWN ) IF
(LZMOM .NE. 0) ZMOM = SOUT(LZMOM+1,1) C C EXAMPLE OF FINDING A COMPONENT
POSITION BY NAME C
KH2O = DMS_KCCIDC ( 'H2O' ) C C CAN ALSO PASS POSITION AS PARAMETER IN
INT VECTOR C E.G. KH2O = INT(2)
IF ( KH2O .EQ. 0 ) GO TO 999 C C PUT COMPONENT (WATER) IN THE SECOND
OUTLET C
WATER = SIN(KH2O,1) SOUT(KH2O,1) = 0D0 SOUT(NCOMP_NCC+1,1) =
SIN(NCOMP_NCC+1,1) - WATER SOUT(KH2O,2) = WATER SOUT(NCOMP_NCC+1,2) = WATER C
999 RETURN
END
Physical Property Calculations

Physical properties and phase equilibrium calculations can be performed within a user model. Property
methods, models, and parameters specified in the input either through a built-in or a user-defined
property method, can be used for the user model calculations. This can be done through property
monitors. The user model requests the property of interest by calling a specific monitor, sets the state
information and calculation codes in the call to the monitors, and in turn obtains thermodynamic
properties such as fugacity coefficients, enthalpies, entropies, molar volumes, etc. A flash calculation
routine is also available. See the table on page 360 for a listing of frequently used property monitors. The
FLASH routine and the property monitors are documented in Aspen Plus User Models. See also User
Physical Property Models on page 370.
Unit Operation Calculations

The purpose of a user unit operation block is to allow the flexibility to program user correlations or
algorithms to represent a process. Independently from the physical property calculations for which
monitors are provided, users can take advantage of the Fortran subroutine structure to incorporate the
calculations needed to represent their process. Aspen Plus System Management documents
programming guidelines to be followed when defining the model calculations. The calculations performed
within a user unit operator model for a polymer system are similar to those that could be performed within
a kinetic model. See User Kinetic Models on page 365.
364 17 User Models
Diagnostics
Throughout the simulation calculations, a user model may call the Aspen Plus error handler to issue
diagnostic messages ranging from fatal errors to warnings and information. The error handler is
documented in Aspen Plus User Models. These diagnostics can be written to the terminal or the control
panel. The USER labeled commons contains output file numbers through which the terminal, control
panel and simulation files can be accessed. See Aspen Plus User Models for a description of the USER
labeled common.
User Unit Operation Report Writing

A report section can be included for a user model in the Aspen Plus simulation report. This requires a
Fortran report writer subroutine. To write the report a report pagination utility is available. This utility is
documented in Aspen Plus User Models. Note that in the user interface the integer and real arrays for the
user model are displayed on the results screen of the user model.
User Kinetic Models

User kinetic models are primarily intended for situations where the polymerization phenomena taking
place are highly complex and cannot be represented by the built=in models. Users can write their own
equations for the rate of change of components and the attributes of the polymer that they are intending
to track. This is done through a USER reaction block. The USER block can be used in conjunction with
built-in models. The user model gives the basic framework for specifying the reaction stoichiometry and
the rate constant parameters. The user kinetic model requires a Fortran subroutine which performs all the
computations that are required for computing the rates of change for components in the reactive phase
and rates of change for polymer attributes. The structure of this subroutine is documented in Aspen Plus
User Models. For polymerization kinetics user model, there are specific calculations that are typically
performed. These include:
Locating the polymer component attributes within the stream vector. This is done through the utility
routine SHS_LCATT. Users need to determine and provide IDXP which is the component index for the
polymer. LDPN = SHS_LCATT( 1, IDXP, ICATYP( 1, IDPN ) ) LZMOM = SHS_LCATT( 1, IDXP,ICATYP(
1, IZMOM ) )
Retrieving the polymer attribute values from the stream vector SOUT. The following code shows how to
retrieve DPN from SOUT. Other attributes can be similarly obtained. IF( LDPN .GT. 0 .AND.
SOUT(LDPN+1) .GT. 0D0) DPN = SOUT(LDPN+1)
Calculating the specific volume of the reacting phase from the stream vector SOUT. From the stream
vector, calculate the total number of moles and volume of the reacting phase. This example assumes that
the reacting phase is a single liquid phase. CALL SHS_CPACK (SOUT, NCK, IDXX, XX, TOTFLO)
CALL PPMON_VOLL (
17 User Models 365
+ TEMP, PRES, XX, NCK, IDXX, NBOPST, 4, 1, + SVOL, DV, KER)
VFLOW1 = SLIQRX VFLOW = SVOL * SOUT(NCK+1)
Calculating molar concentration of each component and class 2 attributes in the reacting phase. This is
obtained by dividing the mole fraction of the component in the reacting phase by the molar volume of the
reacting phase. It is also shown how to compute concentration of ZMOM, a class 2 attribute for the
polymer. DO 50 I = 1, NC
CONC(I) = XX(I)/SVOL 50 CONTINUE
IF(LZMOM .GT. 0 .AND. VFLOW .GT. RGLOM_RMIN)
ZMOM=SOUT(LZMOM+1)/VFLOW
Loading the rate constants for each reaction in the reacting phase. The vector REALR will hold the
values of the kinetic constants. DO 200 I = 1, NR
AK(I) = REALR(I) 200 CONTINUE
Calculating the rate of reaction for each component and returning that information to the reactor. The
rate equations are user derived. For example assume that the following user reactions are to be included
in the user kinetics:
A 1 + A 2 - - k
1
A3+
Waste 1 k
1
A 3 - -
k
2
Waste
2
The rate constants for user reactions are obtained as: AK(1) = k1 AK(2) = k2
The reaction rate for the components ( 1=A1, 2=A2, 3=A3 ) are calculated as:
RATES(1) = -AK(1)*CONC(1)*CONC(2)*VFLOW RATES(2) = -
AK(1)*CONC(1)*CONC(2)*VFLOW RATES(3) = (AK(1)*CONC(1)*CONC(2) -
AK(2)*CONC(3))*VFLOW
Calculating rate of change for Class 2 attributes for the polymer. The user is responsible for deriving the
expression for the rate of change of attribute values. DO 400 I = 1, NTCAT
RATCAT(I) = 0D0 400 CONTINUE C
The following example code explains the above steps in greater detail.
Note: The data coming in and out of the model are stored in SI units.
Example 2: User Kinetic Subroutine
366 17 User Models
C------------------------------------------------------------------------
SUBROUTINE USRKIP (SOUT, NSUBS, IDXSUB, ITYPE, NINT, 2 INT, NREAL, REAL,
IDS, NPO, 3 NBOPST, NIWORK, IWORK, NWORK, WORK, 4 NC, NR, STOIC, RATES,
FLUXM, 5 FLUXS, XCURR, NTCAT, RATCAT, NTSSAT, 6 RATSSA, KCALL, KFAIL, KFLASH,
NCOMP, 7 IDX, Y, X, X1, X2, 8 NRALL, RATALL, NUSERV, USERV, NINTR, 9 INTR,
NREALR, REALR, NIWR, IWR, * NWR, WR, NRL, RATEL, NRV, 1 RATEV) C-------------
-----------------------------------------------------------
IMPLICIT NONE C C DECLARE VARIABLES USED IN DIMENSIONING C
INTEGER NSUBS, NINT, NPO, NIWORK,NWORK, + NC, NR, NTCAT, NTSSAT,NCOMP, +
NRALL, NUSERV,NINTR, NREALR,NIWR, + NWR C #include "ppexec_user.cmn"
EQUIVALENCE (RMISS, USER_RUMISS) EQUIVALENCE (IMISS, USER_IUMISS) C C C
C.....RCSTR... #include "rcst_rcstri.cmn" #include "rxn_rcstrr.cmn" C
C.....RPLUG... #include "rplg_rplugi.cmn" #include "rplg_rplugr.cmn"
EQUIVALENCE (XLEN, RPLUGR_UXLONG) EQUIVALENCE (DIAM, RPLUGR_UDIAM) C
C.....RBATCH... #include "rbtc_rbati.cmn" #include "rbtc_rbatr.cmn" C
C.....PRES-RELIEF... #include "prsr_presri.cmn" #include "rbtc_presrr.cmn" C
C.....REACTOR (OR PRES-RELIEF VESSEL OR STAGE) PROPERTIES... #include
"rxn_rprops.cmn"
EQUIVALENCE (TEMP, RPROPS_UTEMP) EQUIVALENCE (PRES, RPROPS_UPRES) EQUIVALENCE
(VFRAC, RPROPS_UVFRAC) EQUIVALENCE (BETA, RPROPS_UBETA) EQUIVALENCE (VVAP,
RPROPS_UVVAP) EQUIVALENCE (VLIQ, RPROPS_UVLIQ) EQUIVALENCE (VLIQS,
RPROPS_UVLIQS) C C INITIALIZE RATES
17 User Models 367
C C C DECLARE ARGUMENTS C
INTEGER IDXSUB(NSUBS),ITYPE(NSUBS), INT(NINT), +
IDS(2),NBOPST(6,NPO),IWORK(NIWORK), + IDX(NCOMP), INTR(NINTR), IWR(NIWR), +
NREAL, KCALL, KFAIL, KFLASH,NRL, + NRV, I
REAL*8 SOUT(1), WORK(NWORK), + STOIC(NC,NSUBS,NR), RATES(1), + FLUXM(1),
FLUXS(1), RATCAT(NTCAT), + RATSSA(NTSSAT), Y(NCOMP), + X(NCOMP), X1(NCOMP),
X2(NCOMP)
REAL*8 RATALL(NRALL),USERV(NUSERV), + REALR(NREALR),WR(NWR), RATEL(1), +
RATEV(1), XCURR C C DECLARE LOCAL VARIABLES C
INTEGER IMISS, IDPN(2), IZMOM(2), XMW REAL*8 REAL(NREAL), RMISS, XLEN, DIAM,
TEMP, + PRES, VFRAC, BETA, VVAP, VLIQ, + VLIQS
DATA IDPN / "DPN ", " " / DATA IZMOM / "ZMOM", " " / C BEGIN EXECUTABLE CODE
C ASSUME WE ARE USING A BATCH REACTOR. FOR OTHER REACTORS THE C PROCEDURE IS
SIMILAR C OFFSETS TO COMPONENT MOLECULAR WEIGHTS
XMW(I)=DMS_IFCMNC('MW')+I C C FIND INDEX OF SPECIES BY NAME
IDXP=DMS_KCCIDC('POLY') C C C DETERMINE POINTERS TO POLYMER ATTRIBUTES
LDPN = SHS_LCATT( 1, IDXP, IDPN ) LZMOM = SHS_LCATT( 1, IDXP, IZMOM ) C C GET
POLYMER ATTRIBUTES VALUES FROM SOUT C
IF( LDPN .GT. 0 .AND. SOUT(LDPN+1) .GT. 0D0) DPN = SOUT(LDPN+1)
C------------------------------------------------------------------ C GET
REACTING PHASE SPECIFIC MOLAR VOLUME, SVOL ASSUMING IT IS C LIQUID C
CALL SHS_CPACK (SOUT, NCK, IDX, X, TOTFLO) CALL PPMON_VOLL ( + TEMP, PRES, X,
NCK, IDX, NBOPST, 4, 1, SVOL, DV, KER)
VFLOW1 = SLIQRX C C C GET VOLUME OF REACTING PHASE, VFLOW
368 17 User Models
C
VFLOW = SVOL * SOUT(NCK+1) C
C----------------------------------------------------------------- C
C.....CALCULATE MOLAR CONCENTRATIONS OF COMPONENTS AND CLASS 2 C ATTRIBUTES
DO 50 I = 1, NC
CONC(I) = XX(I)/SVOL 50 CONTINUE IF(LZMOM .GT. 0 .AND. VFLOW .GT.
RGLOM_RMIN)
ZMOM=SOUT(LZMOM+1)/VFLOW
C------------------------------------------------------------------ C
INITIALIZE THE RATES FOR COMPONENTS TO ZERO C
DO 100 I = 1, NC RATES(I) = 0D0 100 CONTINUE C C-----------------------------
------------------------------------- C LOAD REACTION RATE CONSTANTS FROM THE
REALR
DO 200 I = 1, NR
AK(I) = REALR(I) 200 CONTINUE C C-----------------------------------
------------------------------- C CALCULATE REACTION RATES FOR COMPONENTS C
DO 300 I = 1, NC DO 310 J = 1, NC
M = COMPUTE CORRECT INDEX RATES(I) = RATES(I) - AK(M) *
CONC(I)*CONC(J)*VFLOW 300 CONTINUE
C C C CALCULATE RATES FOR CLASS-2 ATTRIBUTE EXAMPLE C------------------------
------------------------------------------
DO 400 I = 1, NTCAT
RATCAT(I) = 0D0 400 CONTINUE
C C INITIALIZE ATTRIBUTES OF INTEREST IN THIS WAY C FOR ARRAY ATTRIBUTES THIS
GIVES FIRST LOCATION IN ARRAY C RACAT(LZMOM - (NC+9) + 1) = 0
RETURN END
17 User Models 369
User Physical Property Models
There is often a need among industrial users to calculate one or more physical properties based on in-
house or literature correlations and expressions that are not available in Aspen Polymers. In such cases,
users can take advantage of physical property user models.
A user subroutine needs to be supplied for each user model that will calculate the desired property. For
each physical property, a fixed subroutine name and argument list exists; these can be found in Aspen
Plus User Models. An example of a simple user subroutine that calculates and returns the liquid molar
enthalpy of a mixture (HLMX) is provided below. For instructions on how to use user physical property
models from the graphical user interface, see Volume 2 of this User Guide, Aspen Polymers Physical
Property Methods and Models.
User model development in polymer simulation is very similar to that in the simulation of standard
components. In case some polymer attributes are needed for the calculation of a user property, these can
be retrieved by calling the appropriate utility routine (see the table on page 360 for a summary of the
utilities available). The following can be helpful while developing a physical property user model in Aspen
Polymers:
The index vector, IDX, contains the indexes of the components present in the current calculation run.
For example, if the first component present currently is listed third in the component list, then: IDX(1) = 3.
Parameter values are retrieved using the utility DMS_IFCMNC. For example, suppose you want to pick
up the molecular weight of a component. You need to define an integer array with elements the locations
of the molecular weights of all the components in the component list on the plex vector, B: XMW(I) =
DMS_IFCMNC('MW') + I
Then, the molecular weight of the component listed third in the component list is B(XMW(3)).
In polymer user models, it is often necessary to identify whether a particular component is polymer,
oligomer, or segment. This is done by the utility logical functions SHS_ISPOLY, SHS_ISOLIG, and
PPUTL_ISSEG. For instance, suppose you want to perform a certain manipulation on the polymer
components present in your run: IF (SHS_ISPOLY(I)) GO TO 10
Which will send the calculation to line number 10 if the component with index I is a polymer component.
The mole fraction vector X (or Z) is based on the apparent molecular weight of the polymer components.
If you need to perform calculations for a polymer run where the mole fractions are needed, then you must
use the true mole fractions (which are based on the true molecular weight of the polymer) rather than the
apparent mole fractions X. This is done by a conversion utility routine called POLY_XATOXT: CALL
POLY_XATOXT( N, IDX, XMW, X, XTRUE)
Where: XMW is the vector of the apparent molecular weights, IDX is the index vector, X is the stream
apparent mole fraction vector, and XTRUE is
370 17 User Models
the vector that contains the mole fractions based on the true molecular weight of the polymer.
Polymer attributes needed for calculations in user physical property models are retrieved using utility
subroutines. For a list of available utilities see the table on page 360. As an example, to get the number
average degree of polymerization, DPn, for a particular component you must give: CALL
POLY_GETDPN( 1, 1, I, DPN )
Where I is the component index. For a detailed description of all the polymer utilities available see
Chapter 4 of Aspen Plus User Models.
Users can call several Aspen Plus subroutines to perform specific tasks. For example, routine IDLGAS
will return the ideal-gas properties of the components and their mixture, while PL001 will return the vapor
pressure of the desired components (see Aspen Plus User Models).
After calculating a molar property, the appropriate conversion must be made so that the returned
property is based on the apparent mole basis. For instance, after the calculation of the liquid enthalpy of a
polymer component based on the true molecular weight, the following conversion should be made:
HL_app = HL_true * MW_app / MW_true
A sample user subroutine that calculates and returns the mixture liquid enthalpy is given in the Example
3.
Note: The data coming in and out of the model are stored in SI units.
Example 3: User subroutine for mixture liquid enthalpy calculation
C----------------------------------------------------------------------
SUBROUTINE HL2U (T ,P ,Z ,N ,IDX , 1 IRW ,IIW ,KCALC ,KOP ,NDS , 2 KDIAG
,QMX ,DQMX ,KER ) C C--------------------------------------------------------
-------------- C HV2U IS A USER MIXTURE ENTHALPY SUBROUTINE C C THIS USER
SUBROUTINE CALCULATES THE LIQUID ENTHALPY OF A BINARY C MIXTURE CONTAINING
ONE POLYMER AND ONE SOLVENT. C C C NAME OF MODULE: HL2U C C
IMPLICIT NONE C
DIMENSION Z(N), IDX(N), KOP(10) DIMENSION D(15)
C... USER DIMENSION
DIMENSION XTRUE(10) C C
17 User Models 371
#include "dms_ncomp.cmn" #include "ppexec_user.cmn" #include "dms_plex.cmn" C
EQUIVALENCE (IB(1), B(1)) INTEGER XMW, DHFORM, CPIG, II, DMS_IFCMNC INTEGER
IMON, IPOL, IIMON, IIPOL, I, N, J, ISEG REAL*8 DELT1, DELT2, DELT3, DELT4,
H_MON, H,POL, * HM_MIX, AVG_MW, T, TREF, QMX C C-----------------------------
----------------------------------------- C C STATEMENT FUNCTIONS FOLLOW C
XMW(I) = DMS_IFCMNC('MW') + I DHFORM(I) = DMS_IFCMNC('DHFORM') + I CPIG(I,J)
= DMS_IFCMNC('CPIG') + 11*(J - 1) + I C C *** NOTE
******************************************* C C PARAMETERS ARE LOCATED USING
THE UTILITY DMS_IFCMNC C AND THE NAME OF THE PARAMETER. FOR EXAMPLE, C
DMS_IFCMNC('MW') RETRIEVES THE LOCATIONS WHERE THE C COMPONENT MOLECULAR
WEIGHTS ARE STORED. C C ****************************************************
C
DO 100 I=1,10 XSEG(I) = 0.D0 100 CONTINUE C
TREF = 298.15 C C------------------------------------------------------
---------------- C C *** NOTE ******************************************* C
COMPONENT ID FOR MONOMER *HARD-WIRED* AT POSITION 2 C COMPONENT ID FOR
POLYMER *HARD-WIRED* AT POSITION 3 C
**************************************************** C
IMON = 2 IPOL = 3 ISEG = 4 C C C## BOTH Z AND XSEG ARE PACKED: XSEG(IPOL)
CONTAINS MOLE FRAC OF SEGMENT C
CALL XATOXT(N, IDX, B(XMW(1)), Z, XTRUE) C C POLYMERIC SPECIES PROP-SET
PROPERTIES C
DELT1 = T - TREF DELT2 = (T**2 - TREF**2)/2.D0 DELT3 = (T**3 - TREF**3)/3.D0
DELT4 = (T**4 - TREF**4)/4.D0 H_MON = B(DHFORM(IMON)) + B(CPIG(1,IMON))*DELT1
+ + B(CPIG(2,IMON))*DELT2 + B(CPIG(3,IMON))*DELT3 + B(CPIG(4,IMON))
372 17 User Models
+*DELT4
H_POL = B(DHFORM(IPOL)) + B(CPIG(1,IPOL))*DELT1 + + B(CPIG(2,IPOL))*DELT2 +
B(CPIG(3,IPOL))*DELT3 + B(CPIG(4,IPOL)) +*DELT4 C C *** NOTE
******************************************* C IN CASE A COMPONENT ATTRIBUTE
WAS NEEDED FOR THE C CALCULATION OF THE POLYMER ENTHALPY, THE APPROPRIATE C
UTILITY ROUTINE SHOULD BE CALLED. C C FOR EXAMPLE, SUPPOSE THE NUMBER-AVERAGE
DEGREE OF C POLYMERIZATION (DPn) OF THE POLYMER WAS NECESSARY. C THE UTILITY
ROUTINE GETDPN CAN BE USED TO RETURN C THE DESIRED ATTRIBUTE: C C CALL
POLY_GETDPN (1, 1, IPOL, DPN) C C THE ARGUMENTS HAVE THE FOLLOWING MEANING: C
C 1 = CONVENTIONAL SUBSTREAM C 1 = DPN FOR 1 COMPONENT IS REQUESTED (NCP=1) C
IPOL = POLYMER COMPONENT INDEX C DPN = RETURNED VALUE OF THE NUMBER AVERAGE C
DEGREE OF POLYMERIZATION C C
**************************************************** C
IIMON = 0 IIPOL = 0 DO 10 I=1,N II = IDX(I) IF (II.EQ.IMON) IIMON = I IF
(II.EQ.IPOL) IIPOL = I 10 CONTINUE C
HM_MIX = H_MON*XTRUE(IIMON) + H_POL*XTRUE(IIPOL) AVG_MW =
B(XMW(IMON))*Z(IIMON) + B(XMW(IPOL))*Z(IIPOL) C C C CONVERT FROM TRUE TO
APPARENT MOLE BASIS
QMX = HM_MIX * AVG_MW / B(XMW(ISEG)) C C
999 CONTINUE
RETURN END
References
Aspen Plus System Management. Burlington, MA: Aspen Technology, Inc.
17 User Models 373
374 17 User Models
18 Application Tools
This section discusses the tools available for applying Aspen Polymers (formerly known as Aspen
Polymers Plus) features to solve real-life problems.
The topics covered include:
Example Applications for a Simulation Model, 375
Application Tools Available in Aspen Polymers, 376
Model Variable Accessing, 378
Example Applications for a Simulation

Model
The main purpose of a simulation model is to provide the engineer with a deeper understanding of the
molecular and macroscopic processes which are vital to a polymer manufacturing process. This
understanding will eventually lead to improvements in various aspects of the process related to safety,
productivity, and polymer product quality. These are some typical scenarios in which a simulation model
is used to meet this objective.
A model may be used to:
Identify superior grade transition policies and better plant startup and shutdown procedures which
minimize offspec polymer product
Reduce the number of lengthy and costly experiments on bench, pilot, and plant scale for polymer
product and polymerization process development
Train process engineers, chemists, plant operators
Identify sources of variance in polymer product quality
Provide data for the design of rupture discs and vent lines
Find optimal temperature profiles for a continuous reactor train which minimize reaction medium
viscosity while meeting product specifications
Investigate monomer feed policies for a semi-batch copolymerization process for keeping the chemical
composition distribution narrow
Design a free-radical initiator mix to maximize productivity under the constraints of safe reactor
operations
18 Application Tools 375
Application Tools Available in Aspen
Polymers
Several analysis and flowsheeting tools are available in Aspen Polymers to configure a model for
performing analyses and studies of a process. These include:
CALCULATOR - used to incorporate Fortran or Microsoft Excel calculations in the simulation
DESIGN-SPEC - used to apply specifications on process variables
SENSITIVITY - used to examine the effect of varying one or more process variables
OPTIMIZATION - used to perform optimization calculations
For each of these tools, with the exception of CALCULATOR, Aspen Plus sets a loop around a model,
flowsheet section, or entire flowsheet. Within this loop, selected operating variables are manipulated and
key process variables are sampled.
The calculation procedure for analysis and flowsheeting tools is illustrated here:
The categories of accessible flowsheet variables are described in Model Variable Accessing on page 378.
Note that in most cases Aspen Plus automatically generates the calculation sequence. You can also
specify a sequence manually. For details on how use these tools in your simulations, see the Aspen Plus
User Guide. Example uses of these features are given in the Aspen Polymers Examples and Applications
Case Book.
CALCULATOR
Calculator blocks provide a mechanism for you to incorporate Fortran statements or Microsoft Excel
spreadsheets into the flowsheet calculations. This can be used to calculate and set input variables based
on special user inputs. For this reason, calculator blocks can be used as feed-forward
376 18 Application Tools
controllers. You can also use calculator blocks to calculate and write results to the Aspen Plus report,
control panel, or external file.
Calculator blocks can be used to display charts, tables, or graphs through Excel.
To use this block you must specify which model variables to sample or manipulate, enter the Fortran
statements or create the Excel sheet, and set the sequence in which the block must be executed during
the flowsheet calculations.
An example use of a calculator block as a feed-forward controller would be to hold the flowrate of a
catalyst proportional to a monomer flow for a situation where that monomer flow varies.
DESIGN-SPEC
Design-Spec blocks allow you to set a process variable that is normally calculated during the simulation.
For each specification, you must identify which process variable can be adjusted to meet that
specification. For this reason, Design-Spec blocks can be used as feedback controllers.
To use this block you must specify which model variables must be fixed, what values they must be fixed
at, and which model input variables can be manipulated. You can include Fortran statements in Design-
Spec blocks.
An example use of a Design-Spec block would be to set a maximum amount for impurities in a product
stream.
SENSITIVITY
Sensitivity blocks provide a mechanism for you to analyze the effect of operating variables, which you
select on the process. This block generates a matrix of manipulated variables versus sampled variables.
If there is more than one manipulated variable, the sensitivity analysis is performed for each combination
of manipulated variables. It is recommended that you use multiple Sensitivity blocks if you do not want to
combine the manipulated variables.
To use this block you must specify which are the manipulated variables, which are the sampled variables,
and how they must be tabulated. You can include Fortran statements in Sensitivity blocks.
An example use of a Sensitivity block would be to determine the effect of reactor temperature or pressure
on the polymer product properties.
OPTIMIZATION
Optimization blocks provide a mechanism for you to minimize or maximize an objective function
calculated using key process variables. To define the objective function you would use Fortran
statements.
To use this block you must define the objective function, specify manipulated variables, and define
constraints, if any.
An example use of Optimization would be to find the optimal reactor temperature to meet polymer product
property specifications while minimizing reaction medium viscosity.
Model Variable Accessing

When using the various model analysis tools to perform sensitivity studies, optimization studies, or data
fitting, or when applying design specifications, or adding calculator blocks to a simulation model, users
must access many different flowsheet variables. These flowsheet variables are grouped by type:
Unit operation block variable
Stream variable (including polymer component attributes)
Reaction variable
Physical property variable
A partial list of accessible variables is given here:
Variable Type
Identifier Description
Block BLOCK-VAR Unit operation block variable
Unit operation block vector Stream STREAM-VAR Non component dependent stream variable
MOLE-FLOW Component mole flow MOLE-FRAC Component mole fraction MASS-FLOW Component mass flow
MASS-FRAC Component mass fraction STDVOL-FLOW Component standard volume flow STDVOL-FRAC
Component standard volume fraction STREAM-PROP Stream Prop-Set property STREAM-VEC Entire stream vector
SUBSTRM-VEC Entire substream vector Stream COMPATTR-VAR Component attribute element (Notes 1-4)
COMPATTR-VEC Component attribute (Notes 1-4) SUBSATTR-VAR Substream attribute element SUBSATTR-VEC
Substream attribute Reaction REACT-VAR Reaction variable (Note 5) Physical UNARY-PARAM Unary physical
property parameter Properties BI-PARAM Binary physical property parameter
Notes:
1. Component attributes may be accessed in several ways. They may be
accessed through STREAM-VEC or through SUBSTRM-VEC. In this case, users are responsible for
locating the desired attribute and attribute element within the stream or substream vector. See the table
that follows for the MIXED substream vector structure.
2. Component attributes may also be accessed with COMPATTR-VAR. With COMPATTR-VAR, users
must provide the element number for attributes
having more than one element. See the Polymer Structural Properties section of Chapter 2 to find out the
dimensions of polymer component attributes. If the attribute is dimensioned by number of polymer
segments, NSEGS, (e.g. SFLOW, or SFRAC polymer attributes), the ordering of elements follows the
order in which the list of polymer segments was specified (See the Component Classification section of
Chapter 2). For component attributes dimensioned by number of catalytic sites, each element represents
a site number, i.e. site no. 1, no. 2, etc. For two- dimensional component attributes dimensioned by
number of segments and number of catalytic sites (NSEGS*NSITES), the first dimension is NSEG,
therefore, the ordering of elements is as follows: the list of specified segments is repeated for each site
beginning with site no. 1.
3. Component attributes may also be accessed with COMPATTR-VEC. In this
case, users are not required to provide an element number since the whole component attribute is
returned as a vector having one or more elements. The ordering of elements within the attribute vector
follows the description given in Note 2.
4. COMPATTR-VAR and COMPATTR-VEC are equivalent for component
attributes having only one element.
5. REACT-VAR may be used to access kinetic constant parameters for reaction kinetic models, including
free-radical, step-growth and Ziegler-Natta. The type of information required to access these parameters
is model dependent. For free-radical, the reaction type (INIT-DEC, for example), and the reacting species
are required, in addition to the name of the parameter to be accessed. The same is true for Ziegler-Natta
which also requires a catalyst site type number. For step-growth, a reaction number is required. For the
standard Aspen Plus reaction models, a reaction number, and/or substream identifier may be needed to
locate the parameters.
The MIXED substream structure is summarized here:
Array Index Description
1, ..., NCC Component mole flows (kgmole/sec) NCC + 1 Total mole flow (kgmole/sec) NCC + 2 Temperature (K)
NCC + 3 Pressure (N/m2) NCC + 4 Mass enthalpy (J/kg) NCC + 5 Molar vapor fraction NCC + 6 Molar liquid fraction
NCC + 7 Mass entropy (J/kg-K) NCC + 8 Mass density (kg/m3) NCC + 9 Molecular weight (kg/kgmole) NCC + 10
value
1
Values for component attribute 1 of component 1

value
ncat1
(polymer or other attributed component)

value value
1
ncat1
Values for component attribute 2 of component 1 (polymer or other attributed component)

value
1
Values for component attribute 1 of component 2

value
ncat1
(polymer or other attributed component)
Note: NCC is the number of conventional components (including polymers, segments and oligomers)
entered on the Components Specifications Selection sheet. This parameter is stored as NCOMP_NCC in
labeled common DMS_NCOMP (See Aspen Plus User Models, Appendix A).
References
Convergence and Optimization in Aspen Plus, Course notes. Burlington, MA: Aspen Technology, Inc.

19 Run-Time Environment
This chapter discusses various topics related to working in the Aspen Polymers (formerly known as
Aspen Polymers Plus) environment.
The topics covered include:
Aspen Polymers Architecture, 381
Installation Issues, 382
Configuration Tips, 382
User Fortran, 383
Troubleshooting Guide, 383
Aspen Polymers Architecture

Aspen Polymers is a layered product. In other words, this product works in conjunction with a main
program. This main program is Aspen Plus for steady-state simulation and Aspen Dynamics or Aspen
Custom Modeler for dynamic simulation. Aspen Polymers brings to these simulators the polymer process
technology in the form of component characterization, physical property models and databanks, kinetic
models, and the associated input forms.
As a result of this layered architecture the installation and configuration of Aspen Polymers is closely tied
to that of Aspen Plus for steady-state simulation and that of Aspen Dynamics and Aspen Custom Modeler
for dynamic simulation. In this chapter we will focus on topics related to the Aspen Plus environment.
The overall Aspen Polymers architecture is shown here:
19 Run-Time Environment 381
Installation Issues
Hardware Requirements
Aspen Polymers is available on all the hardware platforms supported by Aspen Plus. For the user
interface and engine, these are Windows 2000 with Service Pack 1 and Windows XP. Consult the Aspen
Engineering Suite Installation Guide for the hardware requirements.
Installation Procedure
Refer to the Aspen Engineering Suite Installation Guide, Aspen Polymers chapter for information on how
to install Aspen Polymers on your system.
Configuration Tips
Startup Files
The information needed to launch the main Aspen Plus application window is recorded in startup files.
These files define the type of simulation, default settings for the user interface, hosts for the simulation
engine, run settings, etc. One type of startup file is used to define defaults for the type of simulation. This
is the simulation template.
Simulation Templates
Simulation templates are available to help you get started setting up your model. These templates
typically contain options such as unit sets, physical property method selection, and Table File Format
(TFF) selection for stream result tables. Polymer simulation templates are available. You can create your
own personal template to allow faster definition of a new simulation model.
382 19 Run-Time Environment
To use a simulation template, after starting Aspen Plus, on the startup box select the template startup
option. Then choose one of the polymer simulation templates. This will automatically setup a global unit
set, an appropriate polymer property method, and a polymer TFF for the stream tables.
To learn more about TFF files see the Aspen Plus System Management.
User Fortran
User Fortran Templates
There are several ways for you to customize your models by adding calculations in Fortran. The End-Use
Properties section of Chapter 2 described how to setup a user Prop-Set for calculating end-use
properties. Chapter 4 described how to setup user unit operation models, user kinetic models, and user
property models. Templates are available for your use in creating the Fortran files used in these features.
You will find these templates in the following location:
Version Location
Windows %asptop%\user
User Fortran Linking

User Fortran calculations in the form of user routines are linked dynamically to Aspen Polymers during a
simulation. Within user Fortran, you will often access utilities located within Aspen Polymers. In order to
access these utilities, you will need to know the name of the object libraries where they are located. This
applies to the utilities described in Chapter 4 of Aspen Plus User Models. The name of the utility as
shown in the example call sequence includes the name of the object library where it is located.
You can also create your own dynamic link libraries to hold your user Fortran files. The Aspen Plus
System Management guide describes how to work with Fortran code modifications.
Troubleshooting Guide
Following are tips to help you diagnose and resolve problems you may run into while setting up or running
Aspen Polymers.
User Interface Problems

A list of symptoms relating to problems you may encounter when using the user interface is provided
below. Possible causes and solutions are given for each symptom.
Symptom Cause Solution
The polymer input forms cannot be found on the GUI.
The installation was not complete.
You must locate your installation CD and do an incremental installation of Aspen Polymers. Select Aspen Polymers
from the product list and chose the subcomponents button to select the Aspen Polymers steady state installation
option. Aspen Polymers is installed but not enabled.
Enable Aspen Polymers. From the Tools menu, select Options. On the Startup tab there is a box entitled Enable
forms for layered products. Make sure you select Aspen Polymers A file created without using polymer features
appears incomplete in the components record.
You visited the polymer record while creating the file, then later switched off Aspen Polymers.
You must enable Aspen Polymers (From the Tools menu, Select Options, click on the Startup tab). In the Data
Browser, select Polymers (Polymers will appear as incomplete), right mouse click, select Delete. Windows crashes
during input specifications.
An invalid operation was performed either by the Aspen Plus program or by another program running simultaneously.
Usually, when you crash, a backup file is created. Startup Aspen Plus again, then you should be able to recover your
file. If the invalid operation was caused by Aspen Plus, repeat the input steps that lead to the crash, verify that it is
reproducible, and submit the problem to Technical Support. Windows crashes during simulation calculations.
The simulation engine encountered an error that could not be transferred to the GUI.
Export an input summary. Run the input summary alone, then examine the run history for simulation errors. Change
the input specifications associated with the error and rerun. Aspen Plus ran out of resources to create run files. This
can happen especially for large simulations. You may see error messages referring to the amount of virtual memory
available.
Free-up some disk space and run again. Also, consult the Aspen Plus System Management reference manual. An
entire section is devoted to managing virtual memory on Win95/98 and WinNT.
Aspen Plus ran out of memory to load dynamic link libraries.
Make some disk space available or increase the amount of memory available to the application, then run again.
Windows crashes after simulation is complete.
Aspen Plus could not load the simulation results.
If you are running on a remote hosts, there may have been a communication failure at the end of the simulation
calculations. You can submit the run again or you can manually load the results file (.SUM) from the remote host. If
you are running on a local PC host, Aspen Plus may have run out of memory to load the results. Make some disk
space available or increase the amount of memory available to the application and run again. If the load failure was
not due to any of the above, there may be some information recorded in the results file (.SUM) that is causing the
problem. Contact Technical Support and be prepared to supply the results file and/or your saved simulation file.
Simulation Engine Run-Time Problems
A list of symptoms relating to problems you may encounter with the simulation engine at run-time are
provided below. Possible causes and solutions are given for each symptom.
During simulation calculations an error message occurs for a license failure.
The application could not find a valid free license to complete the simulation.
If the license error message refers to "Feature 10". This means that you do not have a license for Aspen Plus itself. If
you are using a licensed installation, then this could be a temporary license failure. This can happen for multi-user
sites, or if you are using a license manager located on a network. In that case, you simply need to try again later. If
you are using an installation with a single activator, then your license key file may be corrupted, the port where the
activator is plugged in could be damaged, or the activator could be damaged. To correct your license key files,
perform a license key installation again. If the problem is your activator, contact Technical Support to have it
replaced. If the license error message refers to another feature number, you may still have run into a temporary
license failure (see above). In that case, try again. If this was not a temporary license failure, then you created a
simulation file which uses features for which you are not licensed. If the message refers to "Feature 15", then you are
trying to use Aspen Polymers without a valid license. Other feature numbers refer to specific add-on products. You
must contact AspenTech to obtain a valid Aspen Polymers license. A message box comes up stating that an error
occurred in the Aspen Plus engine.
See "Windows crashes during simulation calculations" under User Interface Problems. See also "After one run a
subsequent run following an input change crashes" later in this section.
See "Windows crashes during simulation calculations" under User Interface Problems. See also "After one run a
subsequent run following an input change crashes" later in this section.
A run history message appears referring to a dynamic load module error.
Aspen Plus ran out of resources to load dynamic link libraries.
See "Windows crashes during simulation calculations" under User Interface Problems.
You are referencing user Fortran and do not have the compiled object file in your working directory. The working
directory is the location from which you opened an existing file. If you created a file from a template or opened an
existing file from a floppy or a write protected area (e.g. \xmp or \app) the working directory is as specified in Tools
Options Startup.
Compile the user Fortran and place it in your run directory.
A run history message appears which refers to "Virtual Memory Exhausted".
You ran out of virtual memory space to load the run files.
See the Aspen Plus System Management, which discusses virtual memory management.
After one run a subsequent run following an input change crashes.
The problem size has changed as a result of the input or for other reasons Aspen Plus unsuccessfully tried to reuse
the previous run data space. Usually an error message appears which states that a "Fatal error has been
encountered".
Usually after the crash you should be able to recover your file and run with the input change. To prevent this from
happening for the same run, reinitialize the simulation before making repeated runs. This is still a problem that should
be reported to Technical Support.
References
Aspen Engineering Suite Installation Guide for Windows. Burlington, MA: Aspen Technology, Inc.
Aspen Plus System Management. Burlington, MA: Aspen Technology, Inc.
A Component Databanks
This appendix documents the Aspen Polymers (formerly known as Aspen Polymers Plus) component
databanks. There are currently two databanks available:
POLYMER Databank - containing polymer pure component parameters
SEGMENT Databank - containing segment pure component parameters
In addition users may retrieve parameters from the Aspen Plus databanks.
Pure Component Databank

The pure component databanks contain pure component data for over 1500 species. Typically
components such as monomers, solvents, catalysts, initiators, etc. would be retrieved from the pure
component databanks. The parameters in these databanks include those listed in POLYMER Property
Parameters on page 387.
POLYMER Databank
POLYMER contains property parameters for polymers.
Note that a generic polymer component is available in the databank for custom designed polymers.
POLYMER Property Parameters

The following table shows the parameters stored in the POLYMER databank:
Parameter No. Elements Description
CPIG 11 Ideal gas heat capacity DGFVK 1 Free energy of formation, ideal gas reference state DHFVK 1 Heat of
formation, ideal gas reference state DHVLWT 5 Heat of vaporization MW* 1 Polymer reference molecular weight
OMEGA 1 Acentric factor PC 1 Critical pressure
A Component Databanks 387
PLXANT 9 Antoine coefficient TC 1 Critical temperature VC 1 Critical volume VLTAIT 9 Tait molar volume model
coefficients ZC 1 Critical compressibility factor
* MW is a reference molecular weight calculated as the average
segment molecular weight using:
MW
=
NSEG MWSEG
For the generic polymer component MW is set to 1.
POLYMER Databank Components

The following table shows the polymers contained in the POLYMER databank:
Alias Polymer Name
ABS Acrylonitrile-butadiene-styrene BR-1 Poly(butadiene) CA-1 Cellulose-acetate Cellulose Cellulose Chitosan
Chitosan CPE Chlorinated-Poly(ethylene) CTA Cellulose-triacetate Dextran Dextran EVA Ethylene-vinyl-acetate EEA
Ethylene-ethyl-acrylate EPR Ethylene-propylene HDPE High-density-Poly(ethylene) Heparin Heparin Hyaluronic
Hyaluronic-Acid I-PB Isotactic-Poly(1-butene) I-PMMA Isotactic-Poly(methyl-methacryl) I-PP Isotactic-Poly(propylene)
Keratan Keratan-Sulfate LDPE Low-density-poly(ethylene) LLDPE Linear-low-density-poly(ethylene) NBR Nitrile-
butadiene-rubber NYLON6 Nylon-6 NYLON66 Nylon-66 PAA Poly(acrylic-acid) P(ACA&S) Poly(acrylamide-styrene)
388 A Component Databanks
Alias Polymer Name
PALA Poly(alanine) PAMIDE Poly(amide) PAMS Poly(alpha-methylstyrene) P(AMS&AN) Poly(a-methylstyrene-AN)
PAN Poly(acrylonitrile) PARA Poly(acrylamide) PARG Poly(arginine) PASN Poly(asparagine) PASP Poly(aspartic-
acid) PB-1 Poly(1-butene) PBA Poly(n-butyl-acrylate) PBMA Poly(n-butyl-methacrylate) P(BMA&S) Poly(n-butyl-
methac-styrene) PBS-1 Poly(butadiene-styrene) PBT Poly(butylene-terephthalate) PC-1 Poly(carbonate) P(C&DMS)
Poly(carbonate-dimet-siloxane) PCHMA Poly(cyclohexyl-methacrylate) PCYS Poly(cysteine) PD-1 Poly(decene-1)
PDMA Poly(decyl-methacrylate) PDMS Poly(dimethylsiloxane) P(DMS&S) Poly(dimethylsiloxane-styrene) PE
Poly(ethylene) PEA Poly(ethyl-acrylate) PEEK Poly(ether-ether-ketone) PEG Poly(ethylene-glycol) P(EG&PG)
Poly(eth-glycol-prop-glycol) PEMA Poly(ethyl-methacrylate) PEO Poly(ethylene-oxide) P(EO&POX) Poly(eth-oxide-
prop-oxide) P(E&P) Poly(ethylene-propylene) PET Poly(ethylene-terephthalate) P(E&VAC) Poly(ethylene-vinyl-
acetate) PGLN Poly(glutamine) PGLU Poly(glutamic-acid) PGLY Poly(glycine) PH Poly(heptene-1) PHA Poly(n-
hexyl-acrylate) PHENOXY Phenoxy PHIS Poly(histidine) PHMA Poly(n-hexyl-methacrylate) PI Poly(imide)
Alias Polymer Name
PIB Poly(isobutylene) PIBMA Poly(isobutyl-methacrylate) PILE Poly(isoleucine) PIP-1 Poly(isoprene) PLEU
Poly(leucine) PLYS Poly(lysine) PMA Poly(methyl-acrylate) P(MAA&MMA) Poly(methac-acid-met-methac)
P(MAA&S) Poly(methac-acid-styrene) P(MAA&VAC) Poly(methac-acid-vin-acetate) PMET Poly(methionine) PMMA
Poly(methyl-methacrylate) PMMS Poly(m-methylstyrene) PMP Poly(4-methyl-1-pentene) PMVPD Poly(2-methyl-5-
vinylpyridine) PNA Poly(sodium-acrylate) POCS Poly(o-chlorostyrene) POE Poly(oxyethylene) POLYMER Generic
polymer component POM Poly(oxymethylene) POMS Poly(o-methylstyrene) POP Poly(oxypropylene) PP
Poly(propylene) PPA Poly(n-propyl-acrylate) PPBRS Poly(p-bromostyrene) PPEMA Poly(n-pentyl-methacrylate) PPG
Poly(propylene-glycol) PPHE Poly(phenylalanine) PPO Poly(phenylene-oxide) PPMA Poly(n-propyl-methacrylate)
PPMOS Poly(p-methoxystyrene) PPMS Poly(p-methylstyrene) PPOX Poly(propylene-oxide) PPRO Poly(proline) PPS
Poly(phenylene-sulfide) PS-1 Poly(styrene) PSBMA Poly(sec-butyl-methacrylate) PSER Poly(serine) PSF
Poly(sulfone) P(S&VP) Poly(sytrene-vinylpyrrolidone) P(S&VPD) Poly(styrene-4-vinylpyridine) PT-1
Poly(tetrahydrofuran) PTFE Poly(tetrafluoroethylene)
Alias Polymer Name
PTHR Poly(threonine) PTRP Poly(tryptophan) PTYR Poly(tyrosine) PU-1 Poly(urethane-fiber) PVA Poly(vinyl-
alcohol) PVAC Poly(vinyl-acetate) P(VAC&VAL) Poly(vin-acetate-vin-alcohol) PVAL Poly(valine) PVAM Poly(vinyl-
amine) PVC Poly(vinyl-chloride) PVCAC Poly(vin-chloride-vin-acetate) PVDC Poly(vinylidene-chloride) PVDF
Poly(vinylidene-fluoride) PVF Poly(vinyl-fluoride) PVI Poly(vinyl-isobutyl-ether) PVME Poly(vinyl-methyl-ether) PVO
Poly(vinylpropionate) PVP Poly(vinylpyrrolidone) PVPD Poly(4-vinyl-pyridine) SAN Styrene-acrylonitrile SBR Styrene-
butadiene-rubber
UF Urea-formaldehyde
SEGMENT Databank
SEGMENT contains property parameters for polymer segments.
Note that a special nomenclature was devised to identify polymer segments. The segment name consists
of the name of the monomer from which it originates, followed by a label to identify it as a repeat unit (-R)
or an end group (-E). In cases where several molecular structures are possible, a numeric subscript is
used to differentiate the isomers. A similar convention is used for assigning component aliases.
SEGMENT Property Parameters

The following table shows the parameters stored in the SEGMENT databank:
ATOMNO 10 Vector of atomic number of chemical elements in
segment (used with NOATOM) CPCVK 6 Crystalline heat capacity CPIG 11
Ideal gas heat capacity*
CPLVK 6 Liquid heat capacity DGFVK 1 Free energy of formation, ideal gas reference state DHCON 1 Enthalpy of
condensation DHFVK 1 Enthalpy of formation, ideal gas reference state DHSUB 1 Enthalpy of sublimation DNCVK 4
Crystalline density DNGVK 5 Glass density DNLVK 4 Liquid density MW 1 Molecular weight NOATOM 10 Vector of
number of each type of chemical
element in segment (used with ATOMNO) TGVK 1 Glass transition
temperature TMVK 1 Melt transition temperature VKGRP 24 Van Krevelen functional groups VOLVW 1 Van der
Waals volume UFGRP 24 UNIFAC functional groups
* Estimated from Joback functional group.
SEGMENT Databank Components

The following table shows the SEGMENT databank components:
Alias Segment Name Molecular Structure
CF2-R Methylene-fluoride-R
CO-R Carbonyl-R
CHF2-E Methylene-fluoride-E
CH2O-R Oxymethylene-R
C2O2-R Oxalic-acid-R
OOCC
C2HO3-E Oxalic-acid-E
C2H2-R-1 cis-Vinylene-R
C2H2-R-2 trans-Vinylene-R
C2H2-R Vinylidene-R
CF
2
OC
CHF
2
OCH
2
OO
C COH
C CH
2
C2H2CL-E Vinyl-chloride-E
C2H2F-E Vinyl-fluoride-E
C2H2CL2-R Vinylidene-chloride-R
C2H2F2-R Vinylidene-fluoride-R
C2H3-E Vinyl-E
C2H3CL-R Vinyl-chloride-R
C2H3F-R Vinyl-fluoride-R
C2H3NO-R Glycine-R
C2H3O-E Acetate-E ~COCH
3
C2H3O-E-1 Oxyvinyl-E
C2H3O-E-2 Vinyl-alcohol-E
C2H4-R Ethylene-R
C2H4N-E Vinylamine-E-1
C2H4NO-E Glycine-E-1
C2H4NO2-E Glycine-E-2
C2H4O-R-1 Ethylene-oxide-R
C2H4O-R-2 Oxyethylene-R
C2H4O-R-3 Vinyl-alcohol-R
C2H4O2-R Ethylene-glycol-R
CH CHCl
CH CHF
CH
2
CCl
2
CH
2
CF
2
CH CH
2
CH
2
CHCl
CH
2
CHF
CH
2
O NH
C
O CH
CH
2
CH CH OH
CH
2
CH
2
CH CH NH
2
NH
2
O CH
2
C
CH
2
O NH
OH
CH
2
C
CH
2
O
O
CH
2
CH
2
CH
2
CH OH
O CH
2
CH
2
O
C2H5-E Ethylene-E
C2H5N-R Vinylamine-R
C2H5O-E-1 Ethylene-oxide-E-1
C2H5O-E-2 Ethylene-oxide-E-2
C2H5O2-E Ethylene-glycol-E
C2H6N-E Ethyleneamine-E
C2H6OSi-R Dimethyl siloxane-R
C2H7OSi-E Dimethyl siloxane-E
C3H2O2-R Malonic -acid-R
C3H2O2Na-E Sodium acrylate-E-1
C3H3N-R Acrylonitrile-R
C3H3NO-R Acrylamide-R-1
CH
2
CH
3
CH
2
CH NH
2
CH
2
CH
2 OH
CH
3
CH
2
O
O CH
2
CH
2
OH
CH
2
CH
2 NH
2
CH
3 Si O CH
3
CH
3 Si OH CH
3
OO
CCH
2
C
CH CH O C
ONa
CH
2
CH C N
CH CH
C O NH
C3H3O2-E Acrylic acid-E-1
C3H3O2Na-R Sodium-acrylate-R
C3H303-E Malonic-acid-E
C3H4NO-E Acrylamide-E-1
C3H4NO-B Acrylamide-B
C3H4N2O-B Urea-formaldehyde-R
C3H4O2-R Acrylic-acid-R
C3H4O2Na-E Sodium-acrylate-E-2
C3H5-E Propylene-E-1
C3H5Cl-R 2-chloropropylene-R
CH CH
C O OH
CH
2
CH C O
ONa
OO
CCH
2
CO
COH
CH CH
NH
2
CH
2
CH C O
NH
ONC
N
CH
2 CH
2
CH
2
O
CH C
OH
CH
2
O
CH
2
CH CH CH
3
CH
2
C
ONa
CHCl CH
2
C3H5NO-R-1 Acrylamide-R-2
C3H5NO-R-2 Acrylamide-R-3
C3H5NO-R-3 Alanine-R
C3H5NOS-R Cysteine-R
C3H5NO2-R Serine-R
C3H5O2-E Acrylic-acid-E-2
C3H6-R Propylene-R
C3H6NO-E-1 Acrylamide-E-2
C3H6NO-E-2 Alanine-E-1
CH
2
O
CH
2
NH
CH
2
C
CH
O
C
NH
2
O CHNH C
CH
3
O CHNH C
CH
2 SH
O CHNH C
CH
2 OH
CH
2
CH
2 C O OH
CH
2
CH CH
3
CH
2
CH
2OC
NH
2
NH
2
O CH C CH
3
C3H6NOS-E Cysteine-E-1
C3H6NO2-E-1 Alanine-E-2
C3H6NO2-E-2 Serine-E-1
C3H6NO2S-E Cysteine-E-2
C3H6NO3-E Serine-E-2
C3H6O-R-1 Oxypropylene-R
C3H6O-R-2 Propylene-oxide-R
C3H6O-R-3 Vinyl-methyl-ether-R
C3H6O2-R Propylene-glycol-R
O NH
2
CH C CH
2 SH
O NH
CH C CH 3
OH
O NH
2
CH C CH 2 OH
O NH
CH C CH 2
OH
SH
O NH
CH C CH 2
OH
OH
O CH
2
CH CH
3
CH
2
CH O CH 3
CH
2
CH O CH
3
O
CH
2
CH O CH 3
C3H6O2-R-1 1,3-Propanediol-R ~O(CH
2
)
3
O~
C3H6O2-R-2 1,2-Propanediol-R
OCHCH
2
O CH
3
C3H7-E Propylene-E-2
CH
2
CH
2 CH
3
C3H7O-E-1 Oxypropylene-E
HO
CH
2
CH CH
3
C3H7O-E-2 Propylene-oxide-E
CH
2
CH CH
3
C3H7O-E-i i-Propanol-E ~OCH(CH
3
OH
)
2 C3H7O-E-n n-Propanol-E ~O(CH
2
)
2
CH
3
C3H7O2-E Propylene-glycol-E
O
CH
2
CH OH CH 3
C3H7O2-E-1 1,3-Propanediol-E ~O(CH
2
)
3
OH
C3H7O2-E-P 1,2-Propanediol-E-P
OCHCH
2
C3H7O2-E-S 1,2-Propanediol-E-S
C4H2O2-R-cis Maleic-acid-R
C4H2O2-R-tra Fumaric-acid-R
C4H3O3-E-cis Maleic-acid-E
C4H3O3-E-tra Fumaric-acid-E
OH
CH
3 OCH
2
CHCH
3 OH O
OC
C
CHH
C
C
OHC
C
HO
C
C
C
O
O
CHH
C
COH
O H COH
C
HO
C
C4H4O2-R Succinic-acid-R
C4H5-B Butadiene-B
C4H5-E-1 Butadiene-E-1
C4H5NO3-R Aspartic-acid-R
C4H5O2-E-1 Methyl-acrylate-E-1
C4H5O2-E-2 Methyl-acrylic-acid-E-1
C4H5O2-E-3 Vinyl-acetate-E-1
C4H5O3-E Succinic-acid-E
C4H6-R-1 Butadiene-R-1
C4H6-R-2 Butadiene-R-2
C4H6NO3-E Aspartic-acid-E-1
OO
C(CH
2
)
2
C
CH
2
CH CH CH
CH CH CH
CH
2
CH
2
CH C
CH
2
O NH CH C
CH
2OC
OH
C
CH
2OC
OCH
3
CH
3 CH
COC
OH
CH CH
O
C
CH
3O
OO
C(CH
2
)
2
COH
CH
2
CH CH CH
2
CH
2
CH CH CH
2
NH
2
CH
C
O
CH
2OC
OH
C4H6NO4-E Aspartic-acid-E-2
C4H6N2O2-R Asparagine-R
C4H6O2-R-1 Methyl-acrylate-R
C4H6O2-R-2 Methyl acrylic-acid-R
C4H6O2-R-3 Vinyl-acetate-R
C4H7-E-1 1-Butene-E
C4H7-E-2 Isobutylene-E
NH
CH
CH
2
C
O
OH
OC
OH
NH
CH
O
CH
2
O
C
NH
2
CH
O
C
C
CH
2
O CH
3
O
CH
3 CH
2
CC
OH
CH
2
CH O
C CH
3O
CH CH
C
2
H
5
CH C
CH
3
CH
3
CH
2
CH
2
CH CH
2
CH
2
CH CH CH
3
C4H7NO2-R Threonine-R
C4H7N2O2-E Asparagine-E-1
C4H7N2O3-E Asparagine-E-2
C4H7O2-E-1 Methyl-acrylate-E-2
C4H7O2-E-4 Vinyl-acetate-E-2
C4H8-R-1 1-Butene-R
NH CH C
O
CHOH CH
3
O NH
2
CH C
CH
2CO
NH
2
O CHNH
OH
NH
2
CH
2
C
CH
2CO
CH
2 C O O CH
3
CH
3 CH
2
CH C O OH
CH
3 C CH
3 C O OH
CH
2
CH
2 C O O CH
3
CH
2
CH C
2
H
5
C4H8-R-2 Isobutylene-R
C4H8NO2-E Threonine-E-1
C4H8NO3-E Threonine-E-2
C4H8O-R Tetrahydrofuran-R
C4H8O2-R Butylene-glycol-R
C4H8O3-R Diethylene-glycol-R
C4H9O-E-1 Tetrahydrofuran-E-1
C4H9O-E-2 Tetrahydrofuran-E-2
C4H9O2-E Butylene-glycol-E
C4H9O3-E Diethylene-glycol-E
C5H6O2-R Glutaric-acid-R
C5H7NO-R Proline-R
C5H7NO3-R Glutamic-acid-R
CH
3 CH
2
C CH
3
NH
2
CH C
O
CHOH CH
3
NH
CH CHOH C
O OH
CH
3
CH
2
CH
2
CH
2
CH
2
O
OC
4
H
8
O
OC
2
H
4
OC
2
H
4
O
C
4
H
8
OH
C
4
H
9
O
OC
4
H
8
OH
OC
2
H
4
OC
2
H
4
OH
OO
C(CH
2
N
)
3
C
OC
O NH CH C C
2
H
4 C O OH
C5H7O2-E-1 Methyl-methacrylate-E-1
C5H7O2-E-2 Ethyl-acrylate-E-1
C5H7O2-E-3 Vinyl-propionate-E-1
C5H7O3-E Glutaric-acid-E
C5H8-R Isoprene-R
C5H8NO-E Proline-E-1
C5H8NO2-E Proline-E-2
C5H8NO3-E Glutamic-acid-E-1
CH
3 CCH C O O CH
3
CH CH
COOC
2
H
5
CH CH
O
CC
2
H
5O
OO
C(CH
2
CH
2
)
3
COH
C CH CH
2 CH
3
HN
O
O
N
C
C OH
NH
2
O CH C C
2
H
4 C O OH
C5H8NO4-E Glutamic-acid-E-2
C5H8N2O2-R-1 Glutamine-R
C5H8N2O2-R-2 Trimethylene-diisocyanate-R
C5H8O2-R-1 Methyl-methacrylate-R
C5H8O2-R-2 Ethyl-acrylate-R
C5H8O2-R-3 Vinyl-propionate-R
C5H9-E 1-Pentene-E-1
C5H9NO-R Valine-R
O NH
CH C C
2
OH
NH
H
4 C O OH
O CH C C
2
H
4CO
NH
2
CO
O
C NH C
3
C
H
6
NH
CH
3 CH
2 C O OCH
3
CH
2
CH C O O C
2
H
5
CH
2
CH O
O
C
C
2
CH CH
C
3
H
5
H
7
NH CH C
O
CH CH
3
CH
3
C5H9NOS-R Methionine-R
C5H9N2O2-E Glutamine-E-1
C5H9N2O3-E Glutamine-E-2
C5H9O2-E-3 Ethyl-acrylate-E-2
C5H9O2-E-4 Vinyl-propionate-E-2
C5H10-R 1-Pentene-R
O NH CH C C
2
H
4S
CH
3
O NH
2
CCH C
2
H
4 C O NH
2
CH
3 CH
2
CH
O CH
3
O
CO
CH
3CC
CH
3
OCH
3
CH
2
CH
2COOC
2
H
5
CH
2
CH
2O
CO
CH
2
C
2
H
5
CH C
3
H
7
C5H10NO-E Valine-E-1
C5H10NOS-E Methionine-E-1
C5H10NO2-E Valine-E-2
C5H10NO2S-E Methionine-E-2
C6H4S-R Phenylene-sulfide-R
C6H5O-E Phenol-E
C6H5S-E-1 Phenylene-sulfide-E-1
C6H5S-E-2 Phenylene-sulfide-E-2
C6H6N2-R-M m-Phenylene-diamine-R
C6H6N2-R-O o-Phenylene-diamine-R
C6H6N2-R-P p-Phenylene-diamine-R
O NH
2
CH C C
2
H
4S
CH
3
NH CH C
O
CH
OH
CH
3
CH
3
NH CH C
O
H
4
OH
S
CH
3
S
O
S
SH
NH
C
2
NH
NH NH NH
NH
C6H7N2-E-M m-Phenylene-diamine-E
C6H7N2-E-O o-Phenylene-diamine-E
C6H7N2-E-P p-Phenylene-diamine-E
C6H7N3O-R Histidine-R
C6H8NO-E Vinylpyrrolidnone-E-1
C6H8N3O-E Histidine-E-1
C6H8N3O2-E Histidine-E-2
C6H8O2-R Adipic-acid-R
C6H9NO-R Vinylpyrrolidnone-R
C6H9O2-E-1 Ethyl-methacrylate-E-3
NH
NH
NH
2
CHCH
O CN
O O C (CH
2 C CH
2
)
4
CH
O CN
CH C CH
3
O
C
OC
2
H
5
NH
NH
2
NH
2
C6H9O2-E-2 n-Propyl-acrylate-E-1
C6H9O3-E Adipic-acid-E
C6H10-R 1,4-Hexadiene-R
C6H10NO-E Vinylpyrrolidnone-E-3
C6H10O2-R-1 Ethyl-methacrylate-R-1
C6H10O2-R-2 n-Propyl-acrylate-R
C6H10O3-R Amylose-R
C6H10O5-R-1 Cellulose-R
CH CH
O
C
OC
3
H
7
O O C (CH
2 C OH CH
2
)
4
CH
CH
2
CH
CH
CH
3
CH
2
CH N 2
C
O
CH
2
CH
3
CH
2
C
O
C
OC
2
H
5
CH
O
C
OC
3
H
7
CH
2
O OH
O
CH
2
O OH
O
OH OH
C6H10O5-R-2 Dextran-R
C6H11-E-1 4-Methyl-1-pentene-E-1
C6H11-E-2 1-Hexane-E-1
C6H11NO-R-1 Caprolactam-R
C6H11NO-R-2 Isoleucine-R
C6H11NO-R-3 Leucine-R
C6H11O-E Vinyl-isobutyl-ether-E-1
O
CH
2
CH CH CH
2
O HO
OH OH
CH
3 CH
3
CH CH
C
4
CH
H
9
NH (CH
2
)
5
C
O
NH CH
C
O
CH C
2
H
5 CH
3
NH
CH
C
O
CH
2 CH
CH
3 CH
3
CH CH
O
CH
2
CH
3
CH
3
CH
2
CH
CH
3 CH C O O C
2
H
5
C6H11O2-E-3 n-Propyl-acrylate-E-2
C6H11O3-E Amylose-E
C6H11O5-E Cellulose-E-1
C6H11O6-E-1 Cellulose-E-2
C6H11O6-E-2 Dextran-E-2
C6H12-R-1 1-Hexane-R
C6H12-R-2 4-Methyl-1-pentene-R
C6H12NO-E-1 Caprolactam-E-1
CH
3 CCH 3
COOC
2
H
5
CH
2
CH
2COOC
3
CO
H
7
CH
2
OH
HO
CH
2
O OH
HO
OH OH
CH
2
O OH
O
OH
OH OH
CH
2
O
O
HO
OH
OH OH
CH
2
CH C
4
H
9
CH
2
CH CH
2
CH
3
CH
3
NH
2
CH
O (CH
2
)
5
C
C6H12NO-E-2 Isoleucine-E-1
C6H12NO-E-3 Leucine-E-1
C6H12NO2-E-1 Caprolactam-E-2
C6H12NO2-E-2 Isoleucine-E-2
C6H12NO2-E-3 Leucine-E-2
C6H12N2O-R Lysine-R
C6H12N4O-R Arginine-R
C6H12O-R Vinyl-isobutyl-ether-R
NH
2
CH C
O
CH CH
3
C
2
H
5
NH
2
CH C
O
CH
2 CH
CH
3 CH
3
NH
(CH
2
)
5
C
O OH
NH CH CH
C
O OH
CH
3
C
2
H
5
NH CH CH
2
C
O OH
CH
3 CH
3
NH CH
CO
C
4
CH
H
8
NH
2
NH CH C
CH
2 CH
2 CH
2 NH C NH NH
2
O
CH
2
CH O CH
2
CH
CH
3
CH
3
C6H12O2-R Hexamethylene-diol-R
C6H13-E-3 1-Hexane-E-2
C6H13N2O-E Lysine-E-1
C6H13N2O2-E Lysine-E-2
C6H13N4O-E Arginine-E-1
C6H13N4O2-E Arginine-E-2
O (CH
2
)
6
O
CH
2
CH
2 CH
2
CH
CH
3
CH
3
CH
3
CH CH
3
CH
3
CH
3
CH
2
CH
CH C
4
H
9
NH
2
O CH C C
4
H
8
NH
2
O NH
CH C OH C
4
H
8
NH
2
O NH
2
CH C CH
2 CH
2 CH
2 NH C NH NH
2
CH C CH
2 CH
2 CH
2 NH C NH NH
2
O NH
OH
C6H13O-E Vinyl-isobutyl-ether-E-2
C6H13O2-E Hexamethylene-diol-E
C6H14N2-R Hexamethylene-diamine-R
C6H15N2-E Hexamethylene-diamine-E
C7H5O-E Benzoic-acid-E
C7H5O2-E Phenylcarbonate-E
C7H6N-E 4-Vinyl-pyridine-E-1
C7H7N-R 4-Vinyl-pyridine-R
C7H8N-E 4-Vinyl-pyridine-E-2
C7H10O2-R Pimelic-acid-R
C7H11O2-E-1 n-Butyl-acrylate-E-1
CH
2
CH
2O
CH
2
CH
3 CH
3
O (CH
2
CH
)
6
OH
NH
(CH
2
)
6 NH NH (CH
2
)
6
NH
2
O
C
C
O
O
CH CH
N
CH
2
CH N
CH
2
CH
2
N
OO
C(CH
2
)
5
C
CH CH
COOC
4
H
9
C7H11O2-E-2 n-Propyl-methacrylate-E-1
C7H11O3-E Pimelic-acid-E
C7H12O2-R-1 n-Butyl-acrylate-R
C7H12O2-R-2 n-Propyl-methacrylate-R
C7H13-E 1-Heptene-E-1
C7H13O2-E-1 n-Butyl-acrylate-E-2
C7H14-R 1-Heptene-R
C7H15-E-1 1-Heptene-E-2
CH C
CH
3
COOC
3
H
7OO
C(CH
2
)
5
COH
CH
2
CH C O O C
4
OOC
3
H
9
CH
3 CH
2
CC
CH CH
C
5
H
7
H
11
CH
2
CH
2COOC
4
OOC
3
H
9
CH
3 CH
2
CH C
OOC
3
H
7
CH
3 CH
3
CC
CH
2
H
7
CH C
5
H
11
CH
2
CH
2C
5
H
11
C7H15-E-2 1-Heptene-E-3
C8H4O2-R Terephthalate-R
C8H4O2-R-1 Phthalate-R
C8H4O2-R-2 Isophthalate-R
C8H5O3-E Terephthalic-acid-E
C8H5O3-E-1 Phthalic-acid-E
C8H5O3-E-2 Isophthalic acid-E
C8H6Br-E p-Bromostyrene-E-1
C8H6Cl-E-1 o-Chlorostyrene-E-1
CH
3
CH C
5
H
11
OOCC
O
C
OC
O
C
OC
OOCC
OH
O
C
O C OH
O
C
C
OH
Br
O
CHCH
CHCH
Cl
C8H6Cl-E-2 p-Chlorostyrene-E-1
C8H7-E Styrene-E-1
C8H7Br-R p-Bromostyrene-R
C8H7Cl-R-1 o-Chlorostyrene-R
C8H7Cl-R-2 p-Chlorostyrene-R
C8H8-R Styrene-R
C8H8Br-E p-Bromostyrene-E-2
C8H8Cl-E-1 o-Chlorostyrene-E-2
CHCH
Cl
CHCH
CH
2
CH
Br
CH
2
CH
Cl
CH
2
CH
Cl
CH
2 CH CH 2
CH
2
Br
CH
2
CH
2
Cl
C8H8Cl-E-2 p-Chlorostyrene-E-2
C8H8N-E 2-Methyl-5-vinylpyridine-E-1
C8H8O-R Phenylene-oxide-R
C8H9-E Styrene-E-2
C8H9N-R 2-Methyl-5-vinylpyridine-R
C8H10N-E 2-Methyl-5-vinylpyridine-E-2
C8H12O2-R Suberic-acid-R
C8H12O6-R Cellulose-acetate-R
CH
2
CH
2
Cl
CH CH
N
CH
3
CH
3
O
CH
3
CH
2
CH
2
CH
2
CH N
CH
3
CH
2
CH
2
N
CH
3
OO
C(CH
2
)
6
C
O CH
2
O C CH
3OO
OH OH
C8H13O2-E-1 n-Butyl-methacrylate-E-1
C8H13O2-E-2 Isobutyl-methacrylate-E-1
C8H13O2-E-3 sec-Butyl-methacrylate-E-1
C8H13O3-E Suberic-acid-E
C8H13O6-E Cellulose-acetate-E
C8H14N2O2-R Hexamethylene-diisocyanate-R
C8H14O2-R-1 n-Butyl-methacrylate-R
C8H14O2-R-2 Isobutyl-methacrylate-R
C8H14O2-R-3 sec-Butyl-methacrylate-R
CH C
CH
3
O
C
OC
4
H
9
CH C
CH
3
O
C
O CH
2
CH
3
CH C
CH CH
3
CH
3
O
C
O CH
3 CH
C
2
H
5
OO
C(CH
2
)
6
COH
O CH
2
O C CH
3 O OH
OH OH
O O C NH (CH
2
CH
2
)
6
NH C
CH
3COC
OC
4
H
9
CH
2
CH
3COC
O CH
3 CH
2
CH
2
CH CH
3
CH
3COC
O CH
3 CH
C
2
H
5
C8H15-E 1-Octene-E-1
C8H16-R 1-Octene-R
C8H17-E-1 1-Octene-E-2
CH CH
C
6
H
13
CH
2
CH
CH
3
OC
OC
4
OOC
4
H
9
CH
3 CCH 3
C
H
9
CH
2
CH
CH
3
OC
O CH
2
CH
3 CH
3
O O CH
2
CH
CH
3 CH
3
CC
CH
CH
3 CH
3
CH
3 CH
2
CH O C
CH
3 O CH C
2
O O CH
H
5
CH
3 CH
3
CC
CH
3
C
2
H
5
CH
2
CH C
6
H
13
CH
2
CH
2C
6
H
13
C8H17-E-2 1-Octene-E-3
C9H7O3-E Dimethyl-terephthalate-E
C9H9-E-1 Alpha-Methylstyrene-E-1
C9H9-E-2 m-Methylstyrene-E-1
C9H9-E-3 o-Methylstyrene-E-1
C9H9-E-4 p-Methylstyrene-E-1
C9H9NO-R Phenylalanine-R
C9H9NO2-R Tyrosine-R
CH
3
CH C
6
H
13
OOCC
O
CH
3
CH
3 CCH
CHCH
CH
3
CHCH
CH
3
CHCH
CH
3
CH
2
O NH
CH C CH 2
O NH
CH C
OH
C9H9O-E p-Methoxystyrene-E-1
C9H10-R-1 alpha-Methylstyrene-R
C9H10-R-2 m-Methylstyrene-R
C9H10-R-3 o-Methylstyrene-R
C9H10-R-4 p-Methylstyrene-R
C9H10NO-E Phenylalanine-E-1
C9H10NO2-E-1 Phenylalanine-E-2
CHCH
CCH 2
OCH
3
CH
3
CH
2
CH CH 3
CH
2
CH
CH
3
CH
2
CH
CH
3
CH
2
O NH
2 CH C CH 2
O NH
CH C OH
C9H10NO2-E-2 Tyrosine-E-1
C9H10NO3-E Tyrosine-E-2
C9H10O-R p-Methoxystyrene-R
C9H11-E-1 alpha-Methylstyrene-E-2
C9H11-E-2 alpha-Methylstyrene-E-3
C9H11-E-3 m-Methylstyrene-E-2
O NH
2
CH C CH 2
OH
CH
2
O NH
CH C
OH
OH
CH
2
CH
OCH
3
CH
3 CH
2
CH
CH
3 CH
3
C
CH
2
CH
2
CH
3
C9H11-E-4 o-Methylstyrene-E-2
C9H11-E-5 p-Methylstyrene-E-2
C9H11O-E p-Methoxystyrene-E-2
C9H12-R Ethylidene-norbornene-R
C9H14O2-R Azelaic-acid-R
C9H15O2-E-1 n-Hexyl-acrylate-E-1
C9H15O2-E-2 n-Pentyl-methacrylate-E-1
C9H15O3-E Azelaic-acid-E
C9H16O2-R-1 n-Hexyl-acrylate-R
CH
2
CH
2
CH
3
CH
3
CH
2
CH
2
CH
2
CH
2
OCH
3
CH
CH
CH
CH
2
CH
CH
2
C
CH
CH
3OO
C(CH
2
)
7
C
CH CH
COOC
6
H
13
CH
3 CH C C O O C
5
H
11
OO
C(CH
2
)
7
COH
CH
2
CH C O O C
6
H
13
C9H16O2-R-2 n-Pentyl-methacrylate-R
C9H17-E 1-Nonene-E-1
C9H17O2-E-1 n-Hexyl-acrylate-E-2
C9H18-R 1-Nonene-R
C9H19-E-1 1-Nonene-E-2
C9H19-E-2 1-Nonene-E-3
C10H12-R Dicyclopentadiene-R
CH CH
C
7
H
15
CH
2
CH
2COOC
6
H
13
CH
3 CH
2
CH C O O C
5
CH
3 CCH 3
COOC
5
CH
2
CH C
7
H
15
CH
2
CH
2C
7
H
15
CH
3
CH C
7
H
15
CH
CH
2
CH
2
CH
CH
CH
CH
CH
CH
CH
H
11
H
11
C10H15O2-E Cyclohexyl-methacrylate-E-1
C10H16O2-R Cyclohexyl-methacrylate-R
C10H16O2-R-1 Sebacic-acid-R
C10H17O2-E-1 Cyclohexyl-methacrylate-E-2
C10H17O2-E-2 Cyclohexyl-methacrylate-E-3
C10H17O2-E-3 n-Hexyl-methacrylate-E-1
C10H17O3-E Sebacic-acid-E
C10H18O2-R n-Hexyl-methacrylate-R
C10H19-E 1-Decene-E-1
CH
3 CCH O C
O
CH
3 CCH 2
COO
OO
C(CH
2
)
8
C
CH
3 CH
2
CH C O O
CH
3 CCH 3
COO
CH
3 CCH C O O
C
6
C(CH
2
H
13 O O
)
8
COH
CH
3 CCH 2
COO
C
6
CH CH
C
8
H
13
H
17
C10H20-R 1-Decene-R
C10H21-E-1 1-Decene-E-2
C10H21-E-2 1-Decene-E-3
C11H10N2O-R Tryptophan-R
C11H11N2O-E Tryptophan-E-1
C11H11N2O2-E Tryptophan-E-2
CH
3 CH
2
CH C O O
C
6
OO
H
13
CH CCH 3
3
C
C
6
CH C
8
H
13
CH
2
CH
2
H
17
CH
2C
8
H
17
CH
3
CH C
8
H
17
NH CH C
CH
2
N
O
CH
2
N
O NH
2 CH C NH CH C CH
2
N
O
OH
C11H21-E 1-Undecene-E-1
C11H22-R 1-Undecene-R
C11H23-E-1 1-Undecene-E-2
C11H23-E-2 1-Undecene-E-3
C12H6O2-R 2,6-Napthalene-diacid-R
C12H7O3-E 2,6-Napthalene-diacid-E
C12H16O8-R Cellulose-triacetate-R
C12H17O8-E Cellulose-triacetate-E
C12H22N2O8-R Chitosan-R
C12H23-E 1-Dodecene-E-1
CH CH
C
9
H
19
CH
2
CH C
9
CH
2
H
19
CH
2C
9
H
19
CH
3
CH C
9
H
19
O
OO
O CH
2
O CCH
3
O
O O CCH
3
CO
CCH 3
O O C CH 3
O CH
2
O CCH
3
HO
O
OOO
OH NH
2
CH
3
CH
2
OH
OH
NH
2
CH
2
O
CH CH
C
10
OH
H
21
O
C12H23N2O8-E Chitosan-E-1
C12H23N2O9-E Chitosan-E-2
C12H24-R 1-Dodecene-R
C12H25-E-1 1-Dodecene-E-2
C12H25-E-2 1-Dodecene-E-3
C13H9O3-E 2,6-Napthalene-dimethylester-E
C14H23NO10-R Heparin-R
C14H24NO10-E Heparin-E-1
C14H24NO11-E Heparin-E-2
CH
2
O OH
OH
NH
2
O
OH O OH NH
2
CH
2
O
O
OH NH
2
OH
CH
2
OH
OH
NH
2
HO
O O CH
2
CH
2
OH
CH C
10
H
21
CH
2
CH
2C
10
H
21
CH
3
CH C
10
H
21
CH
2
OH O HO
O
O OH
CH
2
OH
O
O
O
OH
O
OH NH C CH
3
CH
2
OH
HO
OH
CH
2
OH
O
O
O
OH
O
OH NH C CH
3
CH
2
OH
HO
O
CH
2
OH O
OH O OH NH
C CH
3
C14H25O2-E Decyl-methacrylate-E-1
C14H26O2-R Decyl-methacrylate-R
C14H27O2-E-1 Decyl-methacrylate-E-2
C14H27O2-E-2 Decylmethacrylate-E-3
C15H14O2-R Bisphenol-A-R
C15H15O2-E Bisphenol-A-E
CH
3 CH C
O
C
OC
10
H
21
CH
3 CH
2
C
O
C
OC
10
CH
H
21
CH
3 CH
2
O
C
OC
10
OC
10
H
21
CH
3 CH
3
C
O
C
H
21
CH
3OC
O CH
3
CH
3OC
OH CH
3
B Kinetic Rate Constant
Parameters
This appendix provides decomposition rate parameters for commonly used initiators. Within each group
the initiators are arranged by increasing total number of carbon atoms.
The parameters are grouped as follows:
Water Soluble Azo-nitriles
Solvent Soluble Azo-Nitriles
Diacyl Peroxides
Peroxycarbonates
Alkyl Peroxides
Hydroperoxides
Peroxyesters
C-C Initiators
Sulfonyl Peroxides
Initiator Decomposition Rate Parameters

The table at the end of this section shows the decomposition rate parameters for monofunctional free-
radical initiators. These parameters assume first- order decomposition kinetics. These data are all
included in the INITIATOR database in Aspen Polymers (formerly known as Aspen Polymers Plus).
Initiator decomposition rates depend on several factors including temperature, pressure, solvent type, and
initiator concentration.
Solvent Dependency
Decomposition rates are lowest in solvents that act as radical scavengers, such as poly chlorinated
organic compounds (e.g., TCE). Initiators used for bulk-phase vinyl chloride polymerizations are typically
in these types of compounds since they closely mimic the solvent environment during
B Kinetic Rate Constant Parameters 431
polymerization. Decomposition rates may be increased by a factor of 2-3 in polar solvents such as
chlorobenzene compared to reactions in non-polar solvents such as benzene. Decomposition rates of
water-soluble initiators are typically measured in water. The table that follows lists the solvents in which
the rate parameters are measured. The user may wish to apply correction factors to the rate parameters
when the polymerization solvent environment is different than the measurement basis.
Concentration Dependency
At high initiator concentrations there is an induced initiation effect. Primary radicals attack and split un-
decomposed initiator molecules. This reduces the measured half-life time and efficiency of the initiator. All
of the data reported in the following table are based on measurements at relatively low initiator
concentrations (0.2 molar or less). Although the standard decomposition rate expressions do not account
for induced initiator, the user may modify the rate expression using a gel effect term.
Temperature Dependency
Initiator decomposition rates are reported in several formats including rate constants, half-life times at
specified temperatures, and half-life temperatures at specified times. These data are all related to each
other through the following equations:
k
ref
=
A exp
-
E
ref
kk
T
=
T ref
exp
-
TTR
E
T RT
11 -
ref
k
T=
-
)5.0ln( t
2
,
T
60
=
-
E
3600
A
Where:
A = Pre-exponential factor (1/sec)
ref
1
R
ln
-
)5.0ln(
k = Decomposition rate at reference temperature (1/sec)

= Decomposition rate at temperature T, K
E = Activation energy (J/kmol-K)
f
T
k
T
T
ref
= Reference temperature, K
T = Temperature, K
t
12
,
T
= Half life at temperature T, sec

These equations were applied to the published raw data to allow the rate constants to be published in a
concise format here.
432 B Kinetic Rate Constant Parameters
Pressure Dependency
Most sources do not publish activation volume, which describe the pressure dependency of the reaction
rates. Initiator decomposition reactions are known to exhibit pressure dependence over very wide ranges
of pressure. For example, the half-life of organic peroxides double with a 3000 bar pressure increase
(Degussa, 2004), which implies an activation volume of 1.9x10-5 m 3
/
kmol . This term can be ignored for processes that operate at reasonably low pressures.
The following table shows the decomposition rate parameters for monofunctional free-radical initiators at
a reference temperature of 60C (Tref(K)=333.15). These data are all included in the INITIATOR
database in Aspen Polymers.
Decomposition Rate Parameters
Decomposition Activation Energy
Half Life Temperature, C
ID Long Name Trade Name(s) Formula / Molecular Structure MW CAS No kref (1/s) A (1/sec) kcal/mol GJ/kmol
1 min 1 hr 10 hr Solvent Source
Water Soluble Azo-Nitriles
ABAH 2,2-azo-bis(2-
amidinopropane) dihydrochloride
Vazo 56 (DuPont) V-50 (Wako Chem)
C8H20N6Cl2 271.19264 2997-92-4 3.3436E-05 6.44E+14 29.4 0.12300 110.5 73.7 55.9 Water DuPont
VAZO68 4,4-azo-bis
(4-cyanovaleric acid)
HCl
HN NH HCl H
2
NNN
NH
2
Vazo 68 (DuPont) C12H22N2O4 258.31776 2638-94-0 7.3642E-06 5.12E+12 27.2 0.11380 132.7 88.7 68.0 Water
DuPont
NN
COOH
VA61 2,2-azo-bis[2-(2-
imidazolin-2-yl)propane]
HOOC
VA-061 (Wako Chem) C12H22N6 250.34712 20858-12-2 1.3404E-03 1.00E+15 27.2 0.11400 78.4 45.0 28.9 Acidic
water Wako
NN
VA86 2,2-Azobis[2-methyl-N-(2-
hydroxyethyl)propionamide]
N
NH
N
HN
VA-086 C12H24N4O4 288.34712 61551-69-7 6.7869E-06 7.95E+14 30.6 0.12800 123.9 86.0 67.7 Water Wako
NN
HN CH
2
VAZO44 2,2-azo-bis(N,N-
dimethylene isobutyramidine) dihydrochloride
OO
HOH
2
CH
2
C NH
CH
2 OH Vazo 44 (DuPont)
C12H24Cl2N6 323.26840 27776-21-2 1.3564E-04 8.10E+12 25.6 0.10700 103.3 63.0 44.0 Water
DuPont VA-44 (WakoChem)
NN
VA46B 2,2-azo-bis[2-(2-
imidazolin-2-yl)propane disulfate dihydrate
N
NH
N
2HCl
NN
HN
VA-046B (Wako Chem) C12H30N6O10S2 482.53664 20858-12-2 1.4388E-03 1.18E+17 30.4 0.12700 75.9 46.0
31.4 Water Wako
VA41 2,2-azo-bis[2-(5-methyl-
2-imidazolin-2-yl)propane] dihydrochloride
N
NH
N
H
2
SO
4
HN
H
2
O
VA-041 (WakoChem) C14H26Cl2N6 349.30628 n/a 2.7035E-04 2.53E+15 28.9 0.12100 91.3 57.4 41.0 Water Wako
NN
VA58 2,2-azobis[2-(3,4,5,6- tetrahydropyrimidin-2- yl)propane] dihydrochloride
N
NH
N
HCl
HCl N N 2HCl
HN
NH
VA-058(WakoChem) C14H28Cl2N6 351.32216 102834-39-0 2.5342E-05 1.44E+15 30.1 0.12600 111.8 75.5 58.0
Water Wako
VA57 2,2-azobis[N-(2-
carboxyethyl)-2- methylpropionamidine] tetrahydrate
N N NH
VA-057 (WakoChem) C14H34N6O8 414.45960 n/a 2.8824E-05 5.56E+14 29.4 0.12300 112.0 74.9 57.0 Water Wako
HOOC HN
NN
NH
COOH 4 H
2 HN NH
O
VA85 2,2-Azobis{2-methyl-N-[2-
(1-hydroxybuthyl)] propionamide}
VA-085 (Wako Chem) C16H32N4O4 344.45464 n/a 7.8450E-07 6.41E+13 30.4 0.12700 148.2 105.4 85.0 Water
Wako
VA60 2,2-azo-bis{2-[1-(2-
hydroxyethyl)-2-imidazolin- 2-yl]propane} dihydrochloride
OOH
3
CH
2
C
NN
CH
2
CH
3 NH HN HOH
2
C
CH
2
NN
OH
VA-060 (Wako Chem) C16H32Cl2N6O2 411.37472 11858-13-0 1.9254E-05 9.56E+15 31.5 0.13200 111.7 76.9 60.0
Water Wako
Solvent Soluble Azo-Nitriles
V30 1-cyano-1-methyl-
ethylazofomamide
N
N
2HCl N N CH
2
CH
2
OH
CH
2 OH N N CONH
2
CH
2
V-30(WakoChem) C5H8N4O 140.14488 10288-28-5 4.4161E-08 1.86E+15 34.5 0.14430 164.9 123.9 104.0 Toluene
Wako
AIBN 2,2'-azo-bis-isobutyronitrile Vazo 64 (DuPont)
Perkadox AIBN (AkzoNobel)
CN
C8H12N4 164.21024 78-67-1 1.0464E-05 2.74E+15 31.1 0.13023 118.3 82.0 64.4 Chlorobenzene AkzoNobel
NC N N CN
AMBN 2,2'-azo-bis(2-
Vazo 67 (DuPont)
C10H16N4 192.26400 13472-08-7 8.4357E-06 1.38E+15 30.8 0.12893
121.2 84.0 66.0 Chlorobenzene AkzoNobel methylbutyronitrile)
Perkadox AMBN (AkzoNobel) V-59 (Wako Chem)
C
2
V601 dimethyl 2,2'-azobis (2-
methylpropionate)
CN
NN
CN H
5
C
2
H
5
V-601 (Wako Chem) C10H18N2O4 230.26400 2589-57-3 8.5556E-06 6.99E+14 30.4 0.12700 122.1 84.3 66.0
Toluene Wako
NN
ACCN 1,1-azo-di-(hexa
hydrobenzenenonitrile)
OOH
3
CO
OCH
3
Vazo 88 (DuPont)
C14H20N4 244.33976 2094-98-6 5.4449E-07 1.07E+16 34.0 0.14219 140.2 103.0 84.9
ChlorobenzeneAkzoNobel Perkadox ACCN (AkzoNobel) V-40 (Wako Chem)
N
N CN
AMVN 2,2'-azo-bis(2,4-dimethyl
valeronitrile)
NC
Vazo 52 (DuPont) V-65 (Wako Chem)
C14H24N4 248.37152 4419-11-8 1.0349E-04 1.78E+14 27.8 0.11630 102.1 65.0 47.2 Toluene DuPont
VF096 2,2'-azo-bis[N-(2-
propenyl)-2- methylpropionamide]
VF-096(WakoChem) C14H24N4O2 280.37032 129136-92-1 1.5480E-07 4.67E+14 32.7 0.13700 157.8 116.1 96.0
Toluene Wako
OO
NH
HN N N
AMOMVN 2,2'-azo-bis(4-methoxy-
2,4-dimethyl valeronitrile)
V-70 (Wako Chem) C16H28N4O2 308.42408 15545-97-8 1.1718E-03 1.26E+15 27.5 0.11500 79.4 46.1 30.0
Toluene Wako
VAM110 2,2'-azo-bis(N-butyl-2-
methylpropionamide)
CN
NN
CN H
3
CO
H
2
C
CH
2
OCH
3
Vam-100(WakoChem) C16H32N4O2 312.45584 n/a 2.3941E-08 4.40E+14 33.9 0.14200 174.2 130.9 110.0 Toluene
Wako
NN
HN C
4
VAM111 2,2'-azo-bis(N-cyclohexyl-
2-methylpropionamide)
OO
C
4
H
9
NH
H
9
Vam-110(WakoChem) C20H36N4O2 364.53160 n/a 3.4427E-08 1.71E+13 31.5 0.13200 181.3 133.7 111.0 Toluene
Wako
N N NH HN Diacyl Peroxides
PP dipropionyl peroxide C6H10O4 146.14300 3248-28-0 4.3006E-05 1.14E+15 30.5 0.12760 119.1 81.9 63.9
Benzene Polymer
Handbook
SAP succinic acid peroxide Luperox SAP (Atofina)
SUCP-70-W (Degussa)
OO
O
O
O
O
C8H10O8 234.16260 123-23-9 8.7924E-06 4.89E+10 24.0 0.10043 142.3 91.0 67.4 Acetone Atofina
O
IBP diisobutyryl peroxide Trigonox 187-C30
(AkzoNobel)
O
O
O
O HO
O
O
OH
C8H14O2 142.19796 3437-84-1 2.7220E-03 3.42E+14 26.1 0.10906 72.7 39.0 22.8 Chlorobenzene AkzoNobel
BP dibenzoyl peroxide Luperox AFR40 (Atofina) C14H10O4 242.23100 94-36-0 3.8607E-06 3.40E+14 30.4 0.12721
130.3 91.0 72.1 Benzene Atofina
DCLBP bis(2,4-dichlorobenzoyl)
peroxide
O
O
O
O
O
O
O
DCLBP (Degussa) C16H6Cl2O4 O
O
333.12664 133-14-2 4.2163E-05 3.95E+14 28.9 0.12100 109.1 72.0 54.1 Benzene Degussa
Cl
Cl O
O Cl Cl
OMBP bis(ortho-methylbenzoyl)
peroxide
Perkadox 20 (Akzo Nobel) OMBP (Degussa)
C16H14O4 270.28476 3034-79-5 1.5072E-05 6.85E+13 28.4 0.11900 120.9 81.0 61.9 Benzene Degussa
PMBP bis(para-methylbenzoyl)
peroxide
O
O
O
O
PMBP (Degussa) C16H14O4 270.28476 895-95-2 5.1895E-06 2.06E+14 29.9 0.12500 128.6 89.0 70.0 Benzene
Degussa
O
OP dioctanoyl peroxide Trigonox SE-8
(AkzoNobel)
O
O
O
H
3
INP bis(3,5,5-
trimethylhexanoyl) peroxide
O
C(CH
2
)
6
O
O (CH
2
)
6
CH
3
O
Trigonox 36
C18H34O4 314.46556 3851-87-4 2.0300E-05 2.70E+15 30.7 0.12835 112.8 77.0 59.6
Chlorobenzene AkzoNobel (AkzoNobel) Luperox 219 (AtoFina)
O
DP didecanoyl peroxide Luperox DEC (Atofina)
Perkadox SE-10 (AkzoNobel)
O
OO
C20H38O4 342.51932 762-12-9 1.4646E-05 8.34E+14 30.1 0.12600 117.2 80.0 62.0 Benzene Degussa
O
LP dilauroyl peroxide Luperox LP (Atofina)
Laurox (AkzoNobel)
O
C
9
H
19
O
C
9
O
H
19
O
Peroxycarbonates
BPIC tert-butylperoxy isopropyl
carbonate
O
C
11
H
23
O
C
11
O
H
23
TrigonoxBPIC C8H16O4 O
176.21264 2372-21-6 7.0005E-08 2.44E+16 35.9 0.15015 154.9 117.0 98.5 ChlorobenzeneAkzoNobel
O
OO
IPPC diisopropyl
peroxydicarbonate
IPPC (Degussa) C8H16O6 208.21144 105-64-6 1.6931E-04 7.70E+14 28.4 0.11900 96.3 61.0 44.0 Benzene
Degussa
NPPC di-n-propyl
peroxydicarbonate
O
O
O
O
O
O
Luperox 221 (AtoFina) Trigonox NPP-CK85 (AkzoNobel)
O C8H16O6 208.21144 16066-38-9 1.4752E-04 3.56E+15 29.5 0.12362 96.1 62.0 45.5 Chlorobenzene
AkzoNobel
SBPC di-secbutyl
peroxydicarbonate
O
O
O
O
O
O
Luperox 225 (AtoFina) Trigonox SBP (AkzoNobel)
TBPIC tert-butylperoxy-
isopropylcarbonate
O
O
O
O
O
O
O
Trigonox BPIC (Akzo) Luperox TBIC (AtoFina) TBPIC (Degussa)
C11H20O6 248.27620 2372-21-6 7.0005E-08 2.44E+16 35.9 0.15015 154.9 117.0 98.5 ChlorobenzeneAkzoNobel
TBPEHC tert-butylperoxy 2-
ethylhexyl carbonate
O
O
Trigonox 117
C13H26O4 246.34704 12/4/3443 6.4441E-08 3.95E+16 36.3 0.15172 154.4 117.0 98.7
ChlorobenzeneAkzoNobel (AkzoNobel) Luperox TBEC (AtoFina)
O
O
O
CHPC dicyclohexyl
peroxydicarbonate
C
4
H
9O
C
2
H
5
CHPC (Degussa) C14H22O6 286.32508 1561-49-5 1.9626E-04 3.30E+16 30.8 0.12900 91.9 59.9 44.2
Chlorobenzene AkzoNobel
(Polymer Handbook) O
TAPEHC tert-amylperoxy 2-
ethylhexyl carbonate
O
O
O
O
O
Trigonox 131
C14H28O4 260.37392 70833-40-8 1.2326E-07 2.29E+16 35.5 0.14841 150.5 113.0 94.7
ChlorobenzeneAkzoNobel (AkzoNobel) Luperox TAEC (AtoFina)
O
EHPC di(2-ethylhexyl)
peroxydicarbonate
C
2
H
5
C
4
C
2
HH
9
OO
5
O
Luperox 223 (AtoFina)
C18H34O6 346.46436 16111-62-9 1.1396E-04 1.80E+15 29.3 0.12245 98.9 64.0 47.1
Chlorobenzene AkzoNobel Trigonox EHP
O (AkzoNobel)
O
O
O
O
O
BCHPC Di(4-tert-butylcyclohexyl)
peroxydicarbonate
Perkadox 16 (AkzoNobel)
MYPC Dimyristyl
peroxydicarbonate
O
O
O
O
O
O
O C30H58O6 514.78692 53220-22-7 9.9164E-05 3.06E+15 29.7 0.12430 99.5 65.0 48.3
CEPC dicetyl peroxydicarbonate Perkadox 24 (AkzoNobel)
OC
14
H
29
O
O
O
O
O
C
14
H
29
Alkyl Peroxides
DTBP di-tert-butyl peroxide Trigonox B (AkzoNobel)
Luperox DI (AtoFina)
OC
16
H
33
O
O
O
O
OO
OO
OO
OO
OO
C
16
H
33
DTAP di-tert-amyl peroxide Trigonox 201
(AkzoNobel) Luperox DTA (AtoFina)
BCUP tert-butylcumyl peroxide Trigonox T (AkzoNobel)
BCUP (Degussa)
DCUP dicumyl peroxide Perkadox BC (AkzoNobel) Luperox 500 (AtoFina)
DTBCP di-tert-butyl cumyl peroxide C26H38O2 382.58652 3.6200E-09 3.05E+15 36.5 0.15260 184.4 142.0 121.4
Toluene Warson
(1980)
Hydroperoxides
TBHP tert-butyl hydroperoxide Trigonox A (AkzoNobel)
Luperox TBH (AtoFina) TBHP (Degussa)
TAHP tert-amyl hydroperoxide Trigonox TAHP (Akzo)
TAHP (AtoFina)
O OH
C
2
TMBHP 1,1,3,3-tetramethylbutyl hydroperoxide
H
5
O OH
Trigonox TMBH (AkzoNobel)
C8H18O2 O OH
146.22972 5809-08-5 9.0052E-11 9.13E+18 44.2 0.18500 172.7 153.0 135.0 ChlorobenzeneAkzoNobel
CUHP cumene hydroperoxide Trigonox K (AkzoNobel)
C9H12O2 152.19308 80-15-9 1.8527E-09 1.13E+12 31.7 0.13256 221.8 166.0 139.8
ChlorobenzeneAkzoNobel Luperox CU (AtoFina) CUHP (Degussa)
O OH
IPCHP isopropylcumyl
TrigonoxM(AkzoNobel) C12H18O2 194.27372 26762-93-6 5.6157E-09 2.28E+12 31.4 0.13144
207.1 154.0 129.0 ChlorobenzeneAkzoNobel hydroperoxide
O OH
Peroxyesters
TBPA tert-butyl peroxyacetate Trigonox F (AkzoNobel)
C6H12O3 132.15948 107-71-1 5.7708E-08 1.51E+16 35.7 0.14936 157.5 119.0 100.2
ChlorobenzeneAkzoNobel Luperox 7 (AtoFina)
O
TAPA tert-amyl peroxyacetate Trigonox 133
(AkzoNobel) Luperox 555 (AtoFina)
OO
C
2 O O TBPIB tert-butyl peroxyisobutyrate Trigonox 41
(AkzoNobel)
OH
5
C8H16O3 O
160.21324 109-13-7 1.3027E-06 2.02E+15 32.3 0.13516 136.3 98.0 79.5 Chlorobenzene AkzoNobel
O
O
TBPPI tert-butyl peroxypivalate Trigonox 25 (AkzoNobel) Luperox 11 (AtoFina) TBPPI (Degussa)
TBPEA tert-butyl
peroxydiethylacetate
OOO
Trigonox 27 (AkzoNobel)
OO C10H20O3 188.26700 2550-33-6 2.4603E-06 2.52E+15 32.0 0.13400 130.6 93.0 74.8
TAPPI tert-amyl peroxypivalate Trigonox 125
(AkzoNobel) Luperox 554 (AtoFina) TAPPI (Degussa)
O
OO
TBPB tert-butyl peroxybenzoate Triganox C (AkzoNobel)
Luperox P (AtoFina) TBPB (Degussa)
O
C
2
H
5
O
TBPN7 tert-butyl
peroxyneoheptanoate
OO
Trigonox 257
C11H22O3 202.29388 110-05-4 8.0391E-05 2.17E+14 28.1 0.11756 104.2 67.0 49.1
Chlorobenzene AkzoNobel (AkzoNobel)
OO
TAPB tert-amyl peroxybenzoate Trigonox 127
(AkzoNobel) Luperox TAP (AtoFina) TAPB (Degussa)
O
C
3
H
7
O
TBPEH tert-butylperoxy-2-
ethylhexanoate
O
O
OC
2
H
5
Trigonox 21 (AkzoNobel) Luperox 26 (AtoFina)
TMBPPI 1,1,3,3-tetramethylbutyl
peroxypivalate
OO
C
4
H
9
C
2
H
5
C13H26O3 O
230.34764 22288-41-1 9.0908E-05 2.41E+14 28.1 0.11750 103.0 66.0 48.2 Chlorobenzene AkzoNobel
O
O
TAPEH tert-amyl peroxy-2-
ethylhexanoate
Trigonox 121(AkzoNobel) Luperox 575 (AtoFina) TAPEH (Degussa)
TBPIN tert-butylperoxy-3,5,5-
trimethyl-hexanoate
OO
C
4C
2
HH
5
O
C
2
H
5
9
Trigonox 42S
C13H26O3 230.34764 13122-18-4 1.6062E-07 1.90E+15 33.6 0.14078 154.0 114.0 94.6
ChlorobenzeneAkzoNobel (AkzoNobel)
O
OO
TBPND tert-butyl
Trigonox 23
C14H28O3 244.37452 26748-41-4 1.1742E-04 1.49E+14 27.6 0.11547
101.2 64.0 46.2 Chlorobenzene AkzoNobel peroxyneodecanoate
(AkzoNobel) Luperox 10 (AtoFina) TBPND (Degussa)
OO
DMHBPEH 1,1-dimethyl-3-
hydroxybutyl peroxy-2- ethylhexanoate
O
C
2
H
5
C
2
O
C
4
H
9H
5
Luperox 665 (AtoFina) C14H28O4 260.37392 95732-35-7 1.0997E-05 3.49E+13 28.2 0.11800 125.0 84.0 64.4 TCE
AtoFina
TAPND tert-amyl
peroxyneodecanoate
C
2
H
5
O
OH C
4
H
9
O
Trigonox 123
C15H30O3 258.40140 68299-16-1 1.7016E-04 1.46E+14 27.3 0.11438 97.9 61.0 43.3
Chlorobenzene AkzoNobel (AkzoNobel) Luperox 546 (AtoFina)
OO
CUPN7 cumyl peroxyneoheptanoate Trigonox 197
(AkzoNobel) Luperox 288 (AtoFina)
O
C
2
H
5C
2
H
5
C
4
H
9C
2
H
5
C
2
TMBPEH 1,1,3,3-tetramethylbutyl
peroxy-2-ethylhexanoate
OO
O
O
CO
H
5C
2
H
5
DMHBPND 1,1-dimethyl-3-
hydroxybutyl peroxyneodecanoate
OC
4
H
9
C
2
H
5
Luperox 610 (AtoFina) C16H32O4 C
4
H
9
C
2
H
5 288.42768 95718-78-8 4.0233E-04 1.14E+14 26.6 0.11131 90.4 54.0 36.6 a-
methylstyrene
O
AtoFina
O
O
OH
C
2
H
5
TMBPND 1,1,3,3,-tetramethylbutyl
peroxyneodecanoate
Triganox 423 (AkzoNobel)
CUPND cumyl peroxyneodecanoate Trigonox 99 (AkzoNobel) Luperox 188 (AtoFina) CUPND (Degussa)
C
4
H
9
C
2
C
2
H5H
5
O
O
O
OO
C-C Initiators
DMDPB 2,3-dimethyl-2,3-
diphenylbutane
O
C
2
H
5
C
2
S
C
4
H
9H
5
Sulfonyl Peroxides
ACHSP acetyl
cyclohexanesulphonyl peroxide
Lupersol 228Z (AtoFina) C8H14O5S O
222.26216 3179-56-4 7.3692E-04 7.27E+17 32.0 0.13390 80.1 51.0 36.6 Toluene Warson
(1980)
O
OOO
References
Note: Anonymous data sources from the internet are documented by the vendor name and the year in
which the data were collected.
AkzoNobel (2004). Initiators for Polymer Production, Product Catalog.
AtoFina (2004). Organic Peroxides, General Catalog.
AtoFina (2004). Organic Peroxides, Product Bulletin, Diacyl Peroxides.
AtoFina (2004). Organic Peroxides, Product Bulletin, Dialkyl Peroxides.
AtoFina (2004). Organic Peroxides, Product Bulletin, Peroxydicarbonates.
AtoFina (2004). Organic Peroxides, Product Bulletin, Tertiary Alkyl Hydroperoxides.
AtoFina (2004). Fine Chemicals Technical Data.
Degussa (2004). Technical Information. Half-Life Times of Organic Peroxides.
Dupont (2004). Vazo Free radical initiators. (http://www.dupont.com/vazo/grades.html)
Masson, J.C. (1989). Decomposition Rates of Organic Free Radical Initiators. Polymer Handbook, 3rd
Edition. New York.
Wako Chemical (2004). Water Soluble Azo-Initiator. (http://www.wako-
chem.co.jp/specialty/waterazo/main.htm)
Wako Chemical (2004). Solvent Soluble Azo-Initiator. (http://www.wako-
chem.co.jp/specialty/oilazo/main.htm)
Warson, H. (1980). Per-Compounds and Per-Salts in Polymer Processes. England: Solihull Chemical
Services, 5-17.
C Fortran Utilities
For descriptions of Fortran utilities useful in writing user kinetic subroutines, see Chapter 4 of Aspen Plus
User Models.
C Fortran Utilities 445
446 C Fortran Utilities
D Input Language Reference
This section describes the input language for:
Specifying Components, 447
Specifying Component Attributes, 451
Specifying Attribute Scaling Factors, 453
Requesting Distribution Calculations, 454
Calculating End Use Properties, 454
Specifying Physical Property Inputs, 456
Specifying Step-Growth Polymerization Kinetics, 460
Specifying Free-Radical Polymerization Kinetics, 467
Specifying Emulsion Polymerization Kinetics, 477
Specifying Ziegler-Natta Polymerization Kinetics, 484
Specifying Ionic Polymerization Kinetics, 494
Specifying Segment-Based Polymer Modification Reactions, 501
Specifying Components
This section describes the input language for specifying components.
Naming Components
Following is the input language used to name components.
Input Language for Components
COMPONENTS cid [cname] [outid] / ...
Input Language Description for Components
COMPONENTS cid Component ID. Used to refer to the component in

all subsequent input and is also used to identify the component in the simulation report. Aspen Plus input
language conventions and naming guidelines apply to this keyword.
D Input Language Reference 447
cname The databank name or alias used for that
component. Refer to the documentation for the desired databank to find out the correct databank name or
alias for the desired component. Place an asterisk (*) in the cname position if you do not wish to retrieve
the component from the databank. Note that in this case you are required to provide all necessary
outid Eight-character name used for the component in
reports. (Default=cid)
Input Language Example for Components
DATABANKS PURE13 / POLYMER / SEGMENT / INITIATOR COMPONENTS
INI1 LP INIT / ; INITIATOR STY STYRENE STYRENE / ; MONOMER CAN ACRYLONITRILE
CAN / ; MONOMER XYLENE P-XYLENE XYLENE / ; SOLVENT STYSEG STYRENE-R STY-SEG /
; STYRENE SEGMENT ACNSEG ACRYLONITRILE-R ACN-SEG / ; ACN SEGMENT SAN SAN SAN
; COPOLYMER
Specifying Component Characterization Inputs

A POLYMERS paragraph is used to define polymers, their segments, oligomers, and heterogeneous
catalysts, if any, involved in the polymerization. This paragraph is also used to define the polymer and
catalyst component attributes desired in the simulation. Only the names of the attributes need to be
specified in the POLYMERS paragraph. Initial values for the component attributes may be entered for the
polymer and catalyst components in each stream via the STREAM paragraph. Following is the input
language for the POLYMERS paragraph.
448 D Input Language Reference
Input Language for Polymers, Oligomers, and Catalysts
POLYMERS
PARAM kwd=value SEGMENTS seg-id seg-type / ... OLIGOMERS olig-id seg-id
number / ... POLYMERS poly-id / ... CATALYSTS cat-id mol-site / ...
INITIATORS ini-id/ ... ATTRIBUTES comp-id attr-list / ... DISTRIBUTION polyid
disttype NPOINTS=value FUNCLOG=YES/NO UPPER=value
Input Language Description for Polymers, Oligomers, and Catalysts
PARAM Used to enter special parameters. Keywords are as follows.

NSITE Number of catalyst site types
N-BIFUN- INIT
Number of bifunctional initiators
SEGMENTS Used to specify all the segments used in the simulation. The
information entered through this keyword is used by the system to pass segment property information.
seg-id Name of the segment (must be a valid
component ID)
seg-type Segment type. This information is used to
differentiate segment types. The options are END, REPEAT, BRANCH3, or BRANCH4. The default value
is REPEAT
POLYMERS Used to identify all polymers present in the simulation.
poly-id Name of the polymer (must be a valid component
ID)
OLIGOMERS Used to specify the structure of oligomers present in the
simulation.
olig-id Oligomer component ID
seg-id ID for segment contained in that oligomer. All the
segment names must be valid component IDs (Optional)
number Number of this segment in the oligomer
(Default=1)
POLYMERS Used to identify all polymers present in the simulation.
poly-id Name of the polymer (must be a valid component
ID)
CATALYSTS Used to identify all the heterogeneous polymerization
catalysts present in the simulation and to specify the moles of catalytic sites per mole of catalyst.
cat-id Catalyst component ID
mol-site Moles of catalytic sites per unit mass of that
catalyst
INITIATORS Used to identify all the ionic polymerization initiators present
in the simulation.
ini-id Initiator component ID
ATTRIBUTES Used to specify all the polymer/catalyst component attributes
desired for each polymer/catalyst in the simulation. Only the attribute names need to be specified here.
Values for the component attributes are entered in the COMP-ATTR sentence of the STREAM
paragraph.
comp-id Polymer or catalyst component ID
attr-list List of component attributes. The component
attributes specific to polymers are listed in Polymer Component Attributes in Chapter 2, while those for
catalysts are listed in Site-Based Species Attributes in Chapter 2.
DISTRIBUTION Used to request polymer property distribution plots.
polyid Polymer ID
disttype Distribution type
NPOINTS Number of points
FUNCLOG Calculate distribution as rW(r) vs. r on a log scale.
Default is NO
upper Upper limit
Since component attributes represent a significant feature in Aspen Polymers (formerly known as Aspen
Polymers Plus), a complete subsection has been devoted to their use in the simulator. For more detailed
information regarding component attributes, see the Polymer Structural Properties section of Chapter 2.
Input Language Example for Polymers, Oligomers and Catalysts
POLYMERS
POLYMERS SAN ; DEFINE SEGMENTS IN POLYSTYRENE
SEGMENTS STYSEG REPEAT/
ACNSEG REPEAT ; DEFINE TYPE OF SEGMENTS PRESENT ; DEFINE
ATTRIBUTES FOR POLYMERS
ATTRIBUTES SAN DPN DPW PDI MWN MWW ZMOM FMOM SMOM SFLOW SFRAC &
LDPN LZMOM LFMOM LSFLOW LSFRAC LEFLOW LEFRAC LPFRAC
DISTRIBUTION PS CHAIN-SIZE NPOINTS=100 UPPER=9999
Specifying Component Attributes

This section describes the input language for specifying component attributes..
Specifying Characterization Attributes

See Specifying Component Characterization Inputs on page 448.
Specifying Conventional Component Attributes

To assign user component attributes to a conventional component use the ATTR-COMPS paragraph as
follows:
Input Language for Catalyst Component Attributes
ATTR-COMPS comp-id attr-list CLASS=CV / ...
Input Language Description for Catalyst Component Attributes
comp-id Standard component ID.

attr-list List of attributes. Valid attributes were given in User Attributes in
Chapter 2.
Initializing Attributes in Streams

Following is the input language used to enter attribute values in streams.
Input Language for Material Streams
STREAM sid
SUBSTREAM ssid keyword=value basis-FLOW cid flow / . . . basis-FRAC cid frac
/ . . . COMP-ATTR cname cattrname (value-list) / . . .
Keywords: TEMP PRES basis-FLOW
Optional Keywords: NPHASE PHASE
Input Language Description for Material Streams
SUBSTREAM Used to enter state and flash specifications for substreams.

Ssid Substream ID
TEMP Temperature
PRES Pressure
basis- FLOW
Flow rate on a MOLE, MASS, or VOLUME basis
NPHASE Number of phases
PHASE Used to specify the phase when NPHASE=1
PHASE=V (vapor), L (liquid), or S (solid)
basis-FLOW Used to enter component flows.
cid Component ID
flow Component mole or mass flow
basis-FRAC Used to enter component fractions.
cid Component ID
frac Component mole or mass fraction
COMP-ATTR Used to enter component attribute values.
Cname Component name
cattrname Component attribute name. For polymer
attributes, values must be entered for at least SFRAC or SFLOW, and DPN or both ZMOM and FMOM
value-list List of values for each element in the attribute.
Use * to skip entries
Input Language Example for Material Streams
STREAM FEED
SUBSTREAM MIXED TEMP=70 PRES=1 MASS-FLOW STY 13.5 /ACN 7.27 /XYLENE 79 /SAN
0.1E-5/INI1 0.23 COMP-ATTR SAN DPN (3000) / DPW (6000) / PDI (2) / MWN
(312450) / MWW (624900) / ZMOM (0.39E-10) / FMOM (1.17E-7) / SMOM (7.02E-4) /
SFLOW (0.55E-7 0.55E-7) / SFRAC (0.5 0.5) / LSFLOW (0. 0.) / LEFLOW (0. 0.)
Specifying Attribute Scaling Factors

This section describes the input language used to change the default scaling factors for component
attributes.
Specifying Component Attribute Scale Factors

The ATTR-SCALING paragraph is used to override the default scaling factors and upper bounds for
component attributes. The standard values for these parameters are defined in the Aspen Plus system
definition file through the TBS data table PPCMATTR.DAT.
The component attribute scaling factors are used in flowsheet tear-stream convergence and in reactor
model convergence as described in Component Attribute Scale Factors in Chapter 2.
The model uses one set of scaling parameters for all elements of each component attribute. If one
component attribute is used by more than one component, different scaling factors can be applied for
each instance of the attribute.
Input Language for Attribute Scaling Factors
ATTR-SCALING
SCALING COMP=comp-id ATTR=attr-id
SCALE-FACTOR=scale UPPER-BOUND=upper
Input Language Description for Attribute Scaling Factors
SCALING Used to enter special parameters. Keywords are as follows.

comp-id Attributed component ID
attr-id Attribute ID
scale Number of catalyst site types
upper Upper limit
Input Language Example for Component Attribute Scaling
ATTR-SCALING
SCALING PP LSEFLOW SCALE=1E-008 UPPER=1.E35 SCALING PP LZMOM SCALE=1E-008
UPPER=1.E35 SCALING PP LSZMOM SCALE=1E-008 UPPER=1.E35 SCALING TICL4 CVSFLOW
SCALE=1E-008 UPPER=1.E35 SCALING TICL4 CPSFLOW SCALE=1E-008 UPPER=1.E35
Requesting Distribution Calculations

See Specifying Component Characterization Inputs on page 448.
Calculating End Use Properties

This section describes the input language for calculating end use properties.
Input Language for Prop-Set
PROP-SET propsetid propname-list keyword=value
Optional Keywords:
COMPS PHASE UNITS TEMP PRES
Input Language Description for Prop-Set
Use the Prop-Set paragraph to define a property set. A property set is a collection of thermodynamic,
transport, and other properties. Each property set you define is identified by an ID you supply.
Propsetid Property set ID.
Propname-list List of property names. (See Aspen Physical Property System
Physical Property Data documentation.)
COMPS List of component Ids (applies to all properties listed in Aspen
Physical Property System Physical Property Data documentation). (Default=all components actually
present when the property is calculated.)
PHASE PHASE=V Vapor
PHASE=L Total liquid
PHASE=L1 First-liquid
PHASE=L2 Second-liquid
PHASE=T Total mixture
PHASE=S Solid
Phase compositions are determined at stream conditions. (Default=T, if listed as a valid phase for the
property in Aspen Physical Property System Physical Property Data documentation; otherwise no
default.)
UNITS Units options selected for the units keywords that are listed for the property in Aspen Physical
Property System Physical Property Data documentation. (Default=IN-UNITS if Prop-Set is specified for
design specifications, Fortran blocks, optimization paragraphs and constraint paragraphs. Default=OUT-
UNITS if Prop-Set is specified for reports. If a property has mole, mass, or flow units, the default will be
mole units.)
TEMP Temperatures for property calculations. (Default=stream
temperature. For VVSTD and VVSTDMX, Default=25C.)
PRES Pressures for property calculations. (Default=stream
pressure. For VVSTD and VVSTDMX, Default=1 atm.)
Input Language for USER-PROPERTY
USER-PROPERTY userpropid propname-list keyword=value
Keyword: SUBROUTINE
Optional Keywords: FLASH UNIT-TYPE UNIT-LABEL COMP-DEP LVPCT- DEP CURVE-PROP
DEFAULT-PROP BLEND-METHOD BLEND-OPT EXTRAPOLATE
Input Language Description for USER-PROPERTY
Use the USER-PROPERTY paragraph to define the property. This property can be referenced in the
Prop-Set paragraph in the same way as built-in properties. You must supply a Fortran subroutine to
calculate the value of the user Prop-Set properties.
userpropid User property set ID. This property must be different from
built-in properties. (See Aspen Physical Property System Physical Property Data documentation.)
SUBROUTINE Name of user-supplied subroutine for calculating the
property. For details on writing the user-supplied subroutine, see Aspen Plus User Models reference
manual.
FLASH FLASH=NO Does not flash the stream before the
user-supplied subroutine is called (Default)
FLASH= NOCOMPOSITE
Does not flash the stream for total stream properties (When PHASE=T in the Prop-Set paragraph), but
flashes for any other phase specification
FLASH=YES Always flashes stream before the user-
supplied subroutine is called
UNIT-TYPE Units keyword for the property. If not entered, unit
conversion is not performed on property values returned from the user-supplied subroutine.
UNIT-LABEL Unit label for the property printed in the report. A unit label is
used only when unit conversion is performed by the user- supplied subroutine (that is, when UNIT-TYPE
is not given).
COMP-DEP COMP-DEP=YES Property is component property
COMP-DEP=NO Property is a mixture property (Default)
Specifying Physical Property Inputs

This section describes the input language for specifying physical property inputs. More information on
physical property methods and models is given in Volume 2 of this User Guide.
Specifying Property Methods

Following is the input language used to specify property methods.
Input Language for Property Methods
PROPERTIES opsetname keyword=value /
opsetname [sectionid-list] keyword=value /...
Optional keywords: FREE-WATER SOLU-WATER HENRY-COMPS
HENRY-COMPS henryid cid-list
Input Language Description for Property Methods
The PROPERTIES paragraph is used to specify the property method(s) to be used in your simulation. In
this paragraph properties may be specified for the entire flowsheet, for a flowsheet section, or for an
individual unit operation block. Depending on the component system used, additional information may be
required such as Henry's law information, water solubility correlation, free- water phase properties. The
input language for specifying property methods is as follows.
opsetname Primary property method name
(See the Aspen Polymers User Guide, Volume 2).
sectionid-list List of flowsheet section IDs.
FREE-WATER Free water phase property method name (Default=STEAM-
TA).
SOLU-WATER Method for calculating the K-value of water in the organic
phase.
SOLU-WATER=0 Water solubility correlation is used,
vapor phase fugacity for water calculated by free water phase property method
SOLU-WATER=1 Water solubility correlation is used,
vapor phase fugacity for water calculated by primary property method
SOLU-WATER=2 Water solubility correlation is used with
a correction for unsaturated systems, vapor phase fugacity for water calculated by primary property
method
SOLU-WATER=3 Primary property method is used. This
method is not recommended for water- hydrocarbon systems unless water- hydrocarbon interaction
parameters are available. (Default)
HENRY-COMPS Henry's constant component list ID.
The HENRY-COMPS paragraph identifies lists of components for which Henry's law and infinite dilution
normalization are used. There may be any number of HENRY-COMPS paragraphs since different lists
may apply to different blocks or sections of the flowsheet.
henryid Henry's constant component list ID
cid-list List of component IDs
Input Language Example for Property Methods
HENRY-COMPS HC INI1 PROPERTIES POLYNRTL HENRY-COMPS=HC
Specifying Property Data

Following is the input language used to specify property data.
Input Language for Property Data
PROP-DATA
PROP-LIST paramname [setno] / . . . PVAL cid value-list / value-list / . . .
PROP-LIST paramname [setno] / . . . BPVAL cid1 cid2 value-list / value-list /
. . . COMP-LIST cid-list CVAL paramname setno 1 value-list COMP-LIST cid2-
list BCVAL paramname setno 1 cid1 value-list /
1 cid1 value-list / . . .
Physical property models require data in order to calculate property values. Once you have selected the
property method(s) to be used in your simulation, you must determine the parameter requirements for the
models contained in the property method(s), and ensure that they are available in the databanks. If the
model parameters are not available from the databanks, you may estimate them using the Property
Constant Estimation System, or enter them using the PROP-DATA or TAB-POLY paragraphs. The input
language for the PROP-DATA paragraphs is as follows. Note that only the general structure is given, for
information on the format for the input parameters required by polymer specific models see the relevant
chapter in Volume 2 of this User Guide.
Input Language Description for Property Data
PROP-LIST Used to enter parameter names and data set numbers.

PVAL Used to enter the PROP-LIST parameter values.
BPVAL Used to enter the PROP-LIST binary parameter values.
COMP-LIST Used to enter component IDs.
CVAL Used to enter the COMP-LIST parameter values.
BCVAL Used to enter the COMP-LIST binary parameter values.
paramname Parameter name
setno Data set number. For CVAL and BCVAL the
data set number must be entered. For setno > 1, the data set number must also be specified in a new
property method defined using the PROP-REPLACE paragraph. (For PROP-LIST, Default=1)
cid Component ID
cid1 Component ID of first component of binary
pair
cid2 Component ID of second component of binary
pair
value-list List of parameter values. For PROP-LIST, enter
one value for each element of the property; for COMP-LIST, enter one value for each component in the
cid-list.
cid-list List of component ID
Input Language Example for Property Data
PROP-DATA
IN-UNITS SI PROP-LIST PLXANT / TB PVAL HOPOLY -40.0 0 0 0 0 0 0 0 1D3 /
2000.0 PVAL COPOLY -40.0 0 0 0 0 0 0 0 1D3 / 2000.0
PROP-DATA
IN-UNITS SI PROP-LIST MW PVAL HOPOLY 1.0 PVAL COPOLY 1.0 PVAL ABSEG 192.17
PVAL ASEG 76.09 PVAL BSEG 116.08
PROP-DATA
IN-UNITS SI PROP-LIST DHCONM / DHSUB / TMVK / TGVK PVAL HOPOLY -3.64261D4 /
8.84633D4 / 1.0 / 0.0 PVAL COPOLY -3.64261D4 / 8.84633D4 / 1.0 / 0.0
PROP-DATA
IN-UNITS SI PROP-LIST GMRENB / GMRENC BPVAL MCH ASEG -92.0 / 0.2 BPVAL ASEG
MCH 430.0 / 0.2
Estimating Property Parameters

Following is the input language used to estimate property parameters.
Input Language for Property Parameter Estimation
ESTIMATE [option]
STRUCTURES
method SEG-id groupno nooccur / groupno nooccur /...
Input Language Description for Property Parameter Estimation
The main keywords for specifying property parameter estimation inputs are the ESTIMATE and the
STRUCTURES paragraphs. A brief description of the input language for these paragraphs follows. For
more detailed information please refer to the Aspen Physical Property System Physical Property Data
documentation.
option Option=ALL Estimate all missing parameters (default)
method Polymer property estimation method name
SEG-id Segment ID defined in the component list
groupno Functional group number (group IDs listed in Appendix B of
Volume 2 of this User Guide)
nooccur Number of occurrences of the group
Input Language Example for Property Parameter Estimation
ESTIMATE ALL STRUCTURES
VANKREV ABSEG 115 1 ;-(C6H4)- VANKREV BSEG 151 2 / 100 2 ; -COO-CH2-CH2-COO-
VANKREV ABSEG 115 1 / 151 2 / 100 2 ;-(C6H4)-COO-CH2-CH2-COO-
Specifying Step-Growth Polymerization

Kinetics
Following is the input language for the STEP-GROWTH REACTIONS paragraph.
Input Language for Step-Growth Polymerization
REACTIONS rxnid STEP-GROWTH
DESCRIPTION '...' REPORT REPORT=yes/no RXN-SUMMARY=yes/no RXN-DETAILS=yes/noI
STOIC reactionno compid coeff / ... RATE-CON setno pre-exp act-energy [T-exp]
[T-ref] [USER-RC=number] [CATALYST=compid] [CAT-ORDER=value] POWLAW-EXP
reactionno compid exponent / [ASSIGN reactionno [ACTIVITY=value] RC-
SETS=setno-list] SPECIES POLYMER=polymerid OLIGOMER=oligomer-list REAC-GRP
groupid type /... SPEC-GROUP compid groupid number / groupid number / ...
RXN-SET rxn-setno
[A-NUCL-SPEC=compid] [A-ELEC-GRP=groupid] & [V-ELEC-SPEC=compid] [V-NUCL-
GRP=groupid] & [V-NUCL-SPEC=compid] [V-ELEC-GRP=groupid] & RC-SETS=rc-setno-
list SG-RATE-CON rc-setno
[CAT-SPEC=compid] [CAT-GRP=groupid] & sgpre-exp [sgact-energy] [sgt-exp]
[sgt-ref] [USER-RC=number] SUBROUTINE KINETICS=kinname RATECON=rcname
MASSTRANS=mtname USER-VECS NINTK=nintk NREALK=nrealk NINTRC=nintrc &
NREALRC=nrealc NINTMT=nintmt NREALMT=nrealmt & NIWORK=niwork NWORK=nwork
NURC=nurc INTK value-list REALK value-list INTRC value-list REALRC value-list
INTMT value-list REALMT value-list INCL-COMPS compid-list REAC-TYPE FOR-
CON=yes/no REV-CON=yes/no REARRANGE=yes/no
EXCHANGE=yes/no CONVERGENCE SOLVE-ZMOM=yes/no OLIG-TOL=tolerance
OPTIONS REAC-PHASE=phaseid CONC-BASIS=basis SUPPRESS-WARN=yes/no
USE-BULK=yes/no
The keywords for specifying rate constant parameters for the built-in reactions, and for specifying user
reactions are described here.
Input Language Description for Step-Growth Polymerization
rxnid Unique paragraph ID.

DESCRIPTION Up to 64 characters between double quotes.
REPORT Reaction report options- controls writing of reaction report
in .REP file.
REPORT=YES Print reaction report
REPORT=NO Do not print reaction report
RXN- SUMMARY=YES
Print stoichiometry for each model- generated and user-specified reaction. (Default).
RXN- SUMMARY=NO
Do not print this summary.
RXN-DETAILS=YES Print stoichiometry, rate constants, and
probability factors for each model- generated and user-specified reaction.
RXN-DETAILS=NO Do not print this detailed summary.
STOIC Used to specify stoichiometry for user reactions.
Reactionno Reaction number
compid Component ID
coeff Stoichiometric coefficient (positive for
products, negative for reactants)
RATE-CON Used to specify rate constants for user reactions.
SetNo Rate constant set number
pre-exp Pre-exponential factor in inverse-time
units
act-energy Activation energy in mole enthalpy units
T-exp Temperature exponent
T-ref Reference temperature
number User rate constant flag
CATALYST= compid
Optional catalyst component ID
CAT-ORDER=value Optional reaction order for catalyst
(default=1)
POWLAW-EXP Used to specify power-law exponents for user reactions.
reactionno Reaction number
compid Component ID
exponent Power law exponent
ASSIGN Used to assign rate constant(s) to user reactions.
ACTIVITY= value
Multiplying factor used to calculate net rate constant
RC-SETS = setno-list
List of rate constants (from RATE-CON) which apply to this user reaction
SPECIES Used to specify key components involved in the reactions.
polymerid Component ID for polymer product
oligomer-list List of oligomers to be tracked
REAC-GRP Used to identify the names and types of reacting functional
groups participating in the reaction network.
groupid Functional group ID
type Functional group type
EE-GRP Electrophilic repeat unit
NN-GRP Nucleophilic repeat unit
EN-GRP Mixed electrophilic/nucleophilic repeat unit
E-GRP Electrophilic leaving group
N-GRP Nucleophilic leaving group
EX-GRP Electrophilic modifier (end cap)
NX-GRP Nucleophilic modifier (end cap)
SPEC-GROUP Used to characterize the reacting functional group
composition of the components (segments and monomers) participating in the step-growth reaction
network.
compid Component ID
groupid Reactive functional group ID
number Number of occurrences of group in species
SG-RATE-CON Used to specify rate constants for model-generated step-
growth reactions and to specify which catalyst they apply to (if any).
setno Rate constant set number
CAT-SPEC= compid
Component ID of catalyst species
CAT-GRP= groupid
Group ID of catalyst group
USER-RC= number
User rate expression flag
sgpre-exp Pre-exponential factor in inverse-time units
sgact-energy Activation energy in mole-enthalpy units
sgt-exp Temperature exponent
sgt-ref Reference temperature in temperature units
RXN-SET Used to assign sets of rate constants to model-generated
reactions.
A-NUCL-SPEC= compid
Component ID of reactant which acts as the attacking nucleophile
A-ELEC-GRP= groupid
Group ID of electrophilic leaving group in attacking nucleophilic reactant
V-ELEC-SPEC= compid
Component ID of reactant which acts as the nucleophile. When reactions occur inside polymer molecules,
this may be a segment.
V-ELEC-GRP= groupid
Group ID of electrophilic group in victim species (attached to V-NUCL-GRP)
V-NUCL-SPEC= compid
Component ID of nucleophilic reactant attached to the victim electrophilic reactant at the reacting site
V-NUCL-GRP= groupid
Group ID of nucleophilic group in victim species (attached to V-ELEC-GRP)
RC-SETS = rcsetno-list
List of rate constants (from SG-RATE- CON) which apply to the set of reactions identified by the previous
keywords
SUBROUTINE Used to provide the names of user-supplied Fortran
subroutines. The subroutine argument lists are documented in the User Subroutines section of Chapter 3.
KINETICS= kinname
User kinetic subroutine name
RATECON= rcname
User rate constant subroutine name
MASSTRAN= mtname
User concentration basis / mass-transfer subroutine name
USER-VECS Used to specify the size of vectors for user subroutines.
NINTK=nintk Length of integer array for kinetics
NREALK=nrealk Length of real array for kinetics
NINTRC=nintrc Length of integer array for rate constants
NREALRC= nrealrc
Length of real array for rate constants
NINTMT=nintmt Length of integer array for user basis
routine
NREALMT= nrealmt
Length of real array for user basis routine
NIWORK= niwork
Total length of integer workspace
NWORK=nwork Total length of real workspace
NURC=nurc Number of rate constants calculated by
user subroutine
INTK Used to enter integer parameter for kinetics.
REALK Used to enter real parameters for kinetics.
INTRC Used to enter integer parameters for rate constants.
REALRC Used to enter real parameters for rate constants.
INTMT Used to enter integer parameters for mass transfer.
REALMT Used to enter real parameters for mass transfer.
INCL-COMPS Used to list components which participate in reactions in the
user kinetics model, but which do not appear in model- generated or user-specified reactions.
Compid-list List of additional components to include
in the mass-balance calculations
REAC-TYPE Used to specify which classes of reactions will be generated
by the step-growth model (default is YES for all types of reactions.
FOR-CON= yes/no
Generate forward condensation reactions
REV-CON= yes/no
Generate reverse condensation reactions
REARRANGE= yes/no
Generate re-arrangement reactions
EXCHANGE= yes/no
Generate end-group exchange reactions
CONVERGENCE Used to specify convergence parameters.
SOLVE-ZMOM= yes/no
Explicitly solve zeroth moment (default = no)
OLIG-TOL= tolerance
Specify tolerance for oligomer fractionation calculations (default is 1x10-4)
OPTIONS Used to specify reaction model options.
REAC-PHASE= phaseID
Specify the reacting phase as L, L1, L2, or V (default is L)
CONC-BASIS= basis
Specify concentration units for rate constants as MOL/L (default), MMOL/L, MOL/KG, or MMOL/KG
SUPRESS-WARN= yes/no
YES: do not print warnings when the specified phase is not present
NO: always print warnings when the specified phase is not present (default)
USE-BULK= yes/no
YES: force the model to apply the specified reaction kinetics to the bulk phase when the specified phase
is not present (default)
NO: rates are set to zero when the specified phase is not present
Input Language Example for Step-Growth Polymerization
REACTIONS NYLON STEP-GROWTH
DESCRIPTION NYLON-6 KINETICS: SIMPLE MODEL WITHOUT CYCLICS REPORT RXN-
DETAILS=YES SPECIES POLYMER=NYLON6 REAC-GROUP TNH2 E-GRP / TCOOH N-GRP / BCAP
EN-GRP SPECIES-GRP T-NH2 TNH2 1 / T-NH2 BCAP 1 / T-COOH TCOOH 1 / &
T-COOH BCAP 1 / ACA TNH2 1 / ACA TCOOH 1 / & ACA BCAP 1 / B-ACA BCAP 1 / H2O
TNH2 1 / H2O TCOOH 1 SG-RATE-CON 1 TREF=260 PRE-EXP= 5.461 ACT-ENERGY=23.271
SG-RATE-CON 2 CAT-SPEC=ACA TREF=260 PRE-EXP=40.678 ACT-ENERGY=20.670 SG-RATE-
CON 3 CAT-SPEC=T-COOH TREF=260 PRE-EXP=40.678 ACT-ENERGY=20.670 SG-RATE-CON 4
TREF=260 PRE-EXP=0.0124 ACT-ENERGY=29.217 SG-RATE-CON 5 CAT-SPEC=ACA TREF=260
PRE-EXP=0.0924 ACT-ENERGY=26.616 SG-RATE-CON 6 CAT-SPEC=T-COOH TREF=260 PRE-
EXP=0.0924 ACT-ENERGY=26.616 RXN-SET 1 ELECTRO-GRP=TNH2 NUCLEO-GRP=TCOOH RC-
SETS= 1 2 3
RXN-SET 2 NUCLEOPHILE=H2O RC-SETS= 4 5 6 STOIC 1 CL -1.0 / H2O -1.0 / ACA 1.0
STOIC 2 CL -1.0 / H2O -1.0 / ACA 1.0 STOIC 3 CL -1.0 / H2O -1.0 / ACA 1.0
STOIC 4 ACA -1.0 / CL 1.0 / H2O 1.0 STOIC 5 ACA -1.0 / CL 1.0 / H2O 1.0 STOIC
6 ACA -1.0 / CL 1.0 / H2O 1.0 STOIC 7 CL -1.0 / B-ACA 1.0 STOIC 8 CL -1.0 /
B-ACA 1.0 STOIC 9 CL -1.0 / B-ACA 1.0 STOIC 10 B-ACA -1.0 / CL 1.0 STOIC 11
B-ACA -1.0 / CL 1.0 STOIC 12 B-ACA -1.0 / CL 1.0 STOIC 13 CL -1.0 / ACA -1.0
/ T-NH2 1.0 / T-COOH 1.0 STOIC 14 CL -1.0 / ACA -1.0 / T-NH2 1.0 / T-COOH 1.0
STOIC 15 CL -1.0 / ACA -1.0 / T-NH2 1.0 / T-COOH 1.0 STOIC 16 T-NH2 -1.0 / T-
COOH -1.0 / ACA 1.0 / CL 1.0 STOIC 17 T-NH2 -1.0 / T-COOH -1.0 / ACA 1.0 / CL
1.0 STOIC 18 T-NH2 -1.0 / T-COOH -1.0 / ACA 1.0 / CL 1.0 STOIC 19 CL -1.0 /
B-ACA 1.0 STOIC 20 CL -1.0 / B-ACA 1.0 STOIC 21 CL -1.0 / B-ACA 1.0 RATE-CON
1 PRE-EXP=0.00424 ACT-ENERGY=19.880 TREF=260 RATE-CON 2 PRE-EXP=0.840712 ACT-
ENERGY=18.806 TREF=260 RATE-CON 3 PRE-EXP=0.840712 ACT-ENERGY=18.806 TREF=260
RATE-CON 4 PRE-EXP=1.370519 ACT-ENERGY=17.962 TREF=260 RATE-CON 5 PRE-
EXP=271.7817 ACT-ENERGY=16.888 TREF=260 RATE-CON 6 PRE-EXP=271.7817 ACT-
ENERGY=16.888 TREF=260 RATE-CON 7 PRE-EXP=1.23117 ACT-ENERGY=22.845 TREF=260
RATE-CON 8 PRE-EXP=93.61226 ACT-ENERGY=20.107 TREF=260 RATE-CON 9 PRE-
EXP=93.61226 ACT-ENERGY=20.107 TREF=260 RATE-CON 10 PRE-EXP=0.893159 ACT-
ENERGY=26.888 TREF=260 RATE-CON 11 PRE-EXP=67.83767 ACT-ENERGY=24.151
TREF=260 RATE-CON 12 PRE-EXP=67.83767 ACT-ENERGY=24.151 TREF=260 RATE-CON 13
PRE-EXP=1.23117 ACT-ENERGY=22.845 TREF=260 RATE-CON 14 PRE-EXP=93.61226 ACT-
PRE-EXP=67.83767 ACT-ENERGY=24.151 TREF=260 RATE-CON 18 PRE-EXP=67.83767 ACT-
PRE-EXP=67.83767 ACT-ENERGY=24.151 TREF=260 POWLAW-EXP 1 CL 1.0 / H2O 1.0
POWLAW-EXP 2 CL 1.0 / H2O 1.0 / T-COOH 1.0 POWLAW-EXP 3 CL 1.0 / H2O 1.0 /
ACA 1.0 POWLAW-EXP 4 ACA 1.0 POWLAW-EXP 5 ACA 1.0 / T-COOH 1.0 POWLAW-EXP 6
ACA 2.0 POWLAW-EXP 7 CL 1.0 / T-NH2 1.0 POWLAW-EXP 8 CL 1.0 / T-NH2 1.0 / T-
COOH 1.0 POWLAW-EXP 9 CL 1.0 / T-NH2 1.0 / ACA 1.0 POWLAW-EXP 10 T-NH2 1.0
POWLAW-EXP 11 T-NH2 1.0 / T-COOH 1.0 POWLAW-EXP 12 T-NH2 1.0 / ACA 1.0
POWLAW-EXP 13 CL 1.0 / ACA 1.0 POWLAW-EXP 14 CL 1.0 / ACA 1.0 / T-COOH 1.0
POWLAW-EXP 15 CL 1.0 / ACA 2.0 POWLAW-EXP 16 ACA 1.0 POWLAW-EXP 17 T-COOH 1.0
/ ACA 1.0 POWLAW-EXP 18 ACA 2.0 POWLAW-EXP 19 ACA 1.0 POWLAW-EXP 20 ACA 1.0 /
T-COOH 1.0 POWLAW-EXP 21 ACA 2.0 CONVERGENCE SOLVE-ZMOM=YES OPTIONS REAC-
PHASE=L CONC-BASIS=MOL/KG
Specifying Free-Radical Polymerization

Kinetics
Following is the input language for the FREE-RAD REACTIONS paragraph. The reaction keywords and
rate coefficient parameters for free-radical polymerization are given. Users may select a subset of the
built-in reactions for a given simulation.
Input Language for Free-Radical Polymerization
REACTIONS reacid FREE-RAD
PARAM QSSA=yes/no QSSAZ=yes/no QSSAF=yes/no RAD-INTENS=value SPECIES POLYMER=cid
INITIATOR=cid-list MONOMER=cid-list INHIBITOR=cid-list &
SOLVENT=cid-list BI-INITIATOR=cid-list COINITIATOR=cid-list CHAINTAG=cid-list &
CATALYST=cid-list INIT-DEC cid idpre-exp idact-energy idact-volume ideffic & idnrad
ref-temp [GEL-EFFECT=gelid] [EFF-GEFF=gelid] [COEF1=value BYPROD1=cid] & [COEF2=value
BYPROD2=cid] INIT-CAT cid1 cid2 icpre-exp icact-energy icact-volume iceffic
icnrad ref-temp [GEL-EFFECT=gelid] [EFF-GEFF=gelid] & [COEF1=value BYPROD1=cid]
[COEF2=value BYPROD2=cid] INIT-SP cid1 cid2 ispre-exp isact-energy isact-volume ref-
temp &
[GEL-EFFECT=gelid] [COEF1=value BYPROD1=cid] [COEF2=value
BYPROD2=cid] INIT-SP-EFF cid coeffa coeffb coeffc BI-INIT-DEC cid bdpre-exp bdact-
energy bdact-volume bdeffic
ref-temp [GEL-EFFECT=gelid] [EFF-GEFF=gelid] & [COEF1=value BYPROD1=cid] [COEF2=value
BYPROD2=cid] SEC-INIT-DEC cid sdpre-exp sdact-energy sdact-volume sdeffic
ref-temp [GEL-EFFECT=gelid] [EFF-GEFF=gelid] & [COEF1=value BYPROD1=cid] [COEF2=value
BYPROD2=cid] CHAIN-INI cid cipre-exp ciact-energy ciact-volume ref-temp [GEL-
EFFECT=gelid] PROPAGATION cid1 cid2 prpre-exp pract-energy pract-volume ref-temp [GEL-
EFFECT=gelid] CHAT-MON cid1 cid2 cmpre-exp cmact-energy cmact-volume ref-temp [GEL-
EFFECT=gelid] CHAT-POL cid1 cid2 cppre-exp cpact-energy cpact-volume ref-temp [GEL-
EFFECT=gelid] CHAT-AGENT cid1 cid2 capre-exp caact-energy caact-volume ref-temp [GEL-
EFFECT=gelid] CHAT-SOL cid1 cid2 cspre-exp csact-energy csact-volume ref-temp [GEL-
EFFECT=gelid] B-SCISSION cid bspre-exp bsact-energy bsact-volume ref-temp [GEL-
EFFECT=gelid] TERM-DIS cid1 cid2 tdpre-exp tdact-energy tdact-volume ref-temp [GEL-
EFFECT=gelid] TERM-COMB cid1 cid2 tcpre-exp tcact-energy tcact-volume ref-temp [GEL-
EFFECT=gelid] INHIBITION cid1 cid2 inpre-exp inact-energy inact-volume ref-temp [GEL-
EFFECT=gelid] SC-BRANCH cid1 cid2 scpre-exp scact-energy scact-volume ref-temp [GEL-
EFFECT=gelid] HTH-PROP cid1 cid2 hppre-exp hpact-energy hpact-volume ref-temp [GEL-
EFFECT=gelid] CIS-PROP cid1 cid2 pcpre-exp pcact-energy pcact-volume ref-temp [GEL-
EFFECT=gelid] TRANS-PROP cid1 cid2 ptpre-exp ptact-energy pcact-volume ref-temp [GEL-
EFFECT=gelid] TDB-POLY cid1 cid2 tdpre-exp tdact-energy tdact-volume ref-temp [GEL-
EFFECT=gelid] PDB-POLY cid1 cid2 pbpre-exp pbact-energy pbact-volume ref-temp [GEL-
EFFECT=gelid] GEL-EFFECT gelid CORR-NO=corrno &
MAX-PARAMS=maxparams GE-PARAMS=paramlist / ... SUBROUTINE GEL-EFFECT=subname
OPTIONS REAC-PHASE=phaseid SUPRESS-WARN=yes/no USE-BULK=yes/no
Input Language Description for Free-Radical Polymerization
reacid Paragraph ID.

PARAM Used to specify polymerization mechanism, radiation
intensity, and request the Quasi-Steady-State Approximation (QSSA).
RAD-INTENS= value
Used to specify a value for the radiation intensity to be used for the induced initiation reaction (default is
1.0)
QSSA= YES/NO
Used to request QSSA for all moments (default is NO)
QSSAZ= YES/NO
Used to request QSSA for the zeroth moment only (default is NO)
QSSAF= YES/NO
Used to request QSSA for the first moment only (default is NO)
QSSAS= YES/NO
Used to request QSSA for the second moment only (default is NO)
SPECIES Reacting species identification. This sentence is used to
associate components in the simulation with reactive species in the built-in free-radical kinetic scheme.
The following species keywords are currently valid
INITIATOR List of standard initiators
BI-INITIATOR List of bifunctional initiators
CATALYST List of catalysts
COINITIATOR List of coinitiators
MONOMER List of monomers
POLYMER Reacting polymer ID
CHAINTAG Chain transfer agends
SOLVENT List of solvents which act as chain transfer
agents
INHIBITOR List of inhibitors
MON-RSEG Specifies the pairing between monomers and their
corresponding repeat segments in a polymer.
monomer Monomer ID
r-seg Corresponding repeat segment ID
INIT-DEC Identifier for initiator decomposition reaction.
cid1 Initiator ID
idpre-exp Preexponential factor
idact-energy Activation energy
idact-volume Activation volume (default is 0.0)
ideffic Initiator efficiency (default is 1.0)
idnrad Number of radicals from one initiator
molecule (default is 2.0)
ref-temp Reference temperature
GEL-EFF=gelid Gel effect sentence ID
EFF- GEFF=gelid
Efficiency factor gel effect sentence ID
COEF1=value Stoichiometric coefficient of first by-product
(default=1.0)
BYPROD1=cid Byproduct 1 component ID
COEF2=value Stoichiometric coefficient of 2nd by-product
(default=1.0)
INIT-CAT Identifier for catalyzed initiator decomposition reaction.
cid1 Initiator ID
cid2 Catalyst ID
icpre-exp Preexponential factor
icact-energy Activation energy
icact-volume Activation volume (default=0.0)
iceffic Initiator efficiency (default=1.0)
icnrad Number of radicals from one initiator
molecule (default=2.0)
EFF- GEFF=gelid
(default=1.0)
(default=1.0)
INIT-SP Identifier for thermal and radiation induced initiation
reaction.
cid1 Monomer ID
cid2 Co-initiator ID
ispre-exp Preexponential factor
isact-energy Activation energy
isact-volume Activation volume (default is 0.0)
INIT-SP-EFF Parameters for thermal and radiation induced initiation
reaction.
cid Monomer ID
coeffa Exponent for coinitiator concentration
(default is 0.0)
coeffb Exponent for monomer concentration
(default is 0.0)
coeffc Exponent for radiation intensity (default is
0.0)
BI-INIT-DEC Bifunctional initiator primary decomposition
cid1 Bi-initiator ID
bdpre-exp Preexponential factor
bdact-energy Activation energy
bdact-volume Activation volume (default is 0.0)
bdeffic Initiator efficiency (default is 1.0)
EFF- GEFF=gelid
(default=1.0)
(default=1.0)
SEC-INIT-DEC Bifunctional initiator secondary decomposition
cid1 Bi-initiator ID
sdpre-exp Preexponential factor
sdact-energy Activation energy
sdact-volume Activation volume (default is 0.0)
sdeffic Initiator efficiency (default is 1.0)
EFF- GEFF=gelid
(default=1.0)
(default=1.0)
CHAIN-INI Identifier for chain initiation reaction.
cid1 Monomer ID
cipre-exp Preexponential factor
ciact-energy Activation energy
ciact-volume Activation volume (default is 0.0)
PROPAGATION Identifier for chain propagation reaction.
cid1 Active segment ID
cid2 Monomer ID
prpre-exp Preexponential factor
pract-energy Activation energy
pract-volume Activation volume (default is 0.0)
CHAT-MON Identifier for chain transfer to monomer reaction.
cid1 Monomer corresponding to polymer active
segment ID
cid2 Monomer ID
cmpre-exp Preexponential factor
cmact-energy Activation energy
cmact-volume Activation volume (default is 0.0)
CHAT-POL Identifier for chain transfer to polymer reaction.
cid2 Segment ID on dead chain
cppre-exp Preexponential factor
cpact-energy Activation energy
cpact-volume Activation volume (default is 0.0)
CHAT-AGENT Identifier for chain transfer to transfer agent reaction.
cid2 Transfer agent ID
capre-exp Preexponential factor
caact-energy Activation energy
caact-volume Activation volume (default is 0.0)
CHAT-SOL Identifier for chain transfer to solvent reaction.
cid2 Solvent ID
cspre-exp Preexponential factor
csact-energy Activation energy
csact-volume Activation volume (default is 0.0)
B-SCISSION Identifier for beta-scission reaction.
bspre-exp Preexponential factor
bsact-energy Activation energy
bsact-volume Activation volume (default is 0.0)
TERM-DIS Identifier for chain termination by disproportionation
reaction.
cid1 First polymer active segment ID
cid2 Second polymer active segment ID
tdpre-exp Preexponential factor
tdact-energy Activation energy
tdact-volume Activation volume (default is 0.0)
TERM-COMB Identifier for chain termination by combination reaction.
cid1 Monomer corresponding to first polymer
active segment ID
cid2 Monomer corresponding to second polymer
active segment ID
tcpre-exp Preexponential factor
tcact-energy Activation energy
tcact-volume Activation volume (default is 0.0)
INHIBITION Identifier for chain inhibition reaction.
cid1 Polymer active segment ID
cid2 Inhibitor ID
inpre-exp Preexponential factor
inact-energy Activation energy
inact-volume Activation volume (default is 0.0)
SC-BRANCH Identifier for short chain branching reaction.
cid1 Reactant polymer active segment ID
cid2 Product active segment ID
scpre-exp Preexponential factor
scact-energy Activation energy
scact-volume Activation volume (default is 0.0)
HTH-PROP Head-to-head propagation reaction
cid2 Monomer ID
hppre-exp Preexponential factor
hpact-energy Activation energy
hpact-volume Activation volume (default is 0.0)
CIS-PROP Cis-propagation for diene monomers
cid2 Diene monomer ID
pcpre-exp Preexponential factor
pcact-energy Activation energy
pcact-volume Activation volume (default is 0.0)
TRANS-PROP Trans-propagation for diene monomers
cid2 Diene monomer ID
pract-volume Activation volume (default is 0.0)
TDB-POLY Terminal double bond polymerization
cid2 Terminal double bond segment ID
tbpre-exp Preexponential factor
tbact-energy Activation energy
tbact-volume Activation volume (default is 0.0)
PDB-POLY Pendent double bond polymerization
cid2 Pendent double bond segment ID
pbpre-exp Preexponential factor
pbact-energy Activation energy
pbact-volume Activation volume (default is 0.0)
GEL-EFFECT Gel effect switch and correlation selection. This sentence is
used to:
Modify the reaction rate expression or initiator efficiency factor, typically to account for the gel effect at
high conversion.
Select a gel effect correlation from a list of built-in and user specified gel effect correlations
Specify the maximum number of parameters
Specify the parameter values for the selected correlation
The default action is to not include a gel effect.
gelid Gel effect sentence ID
GETYPE= reactiontype
Used to identify the type of reaction to apply gel effect to. A list of valid reaction types follows
CORR-NO= corrno
Used to select a correlation number. If a correlation number greater than the number of built-in
correlations (currently 2) is specified then the user should supply a Fortran subroutine containing the user
gel effect correlation.
MAX-PARAMS= maxparams
Used to enter the maximum number of gel effect parameters for the correlation selected.
GE-PARAMS= paramlist
Used to enter a list of parameters for the correlation selected.
SUBROUTINE User subroutines sentence.
GEL-EFFECT= subname
Used to specify the name of the subroutine containing user gel effect correlations. The user gel-effect
subroutine argument list was shown in the Gel Effect section in Chapter 3. A Fortran template called
USRGEL.F is available for your use.
REAC-PHASE= phaseID
SUPRESS-WARN= yes/no
USE-BULK= yes/no
Input Language Example for Free-Radical Polymerization
REACTIONS SBD FREE-RAD
DESCRIPTION "test file" PARAM QSSA=yes SPECIES INITIATOR=APS MONOMER=STY BD &
SOLVENT=EB POLYMER=SBD CHAINTAG=DDM COINITIATOR=CINI
INIT-DEC APS 1.6220E+11 1.1530E+08 0.0 EFFIC=.80 NRADS=2 &
BYPROD1=CO2 COEF1=0.1 BYPROD2=CO COEF2=0.2 INIT-SP STY CINI
438000.0 1.1480E+08 0.0 CHAIN-INI STY 2.2E7 3.2E7 CHAIN-INI BD 1.2E8 3.88E7
PROPAGATION STY STY 2.2E7 3.2E7 PROPAGATION STY BD 4.4E7 3.2E7 PROPAGATION BD
BD 1.2E8 3.88E7 PROPAGATION BD STY 8.5E7 3.88E7 HTH-PROP STY STY 2.2E5 3.2E7
HTH-PROP BD BD 1.2E6 3.88E7 CIS-PROP BD BD 1.2E6 3.88E7 CIS-PROP STY BD 4.4E5
3.2E7 TRANS-PROP BD BD 1.2E6 3.88E7 TRANS-PROP STY BD 4.4E5 3.2E7 CHAT-MON
STY STY 2200. 3.2E7 CHAT-MON STY BD 4400. 3.2E7 CHAT-MON BD BD 12000. 3.88E7
CHAT-MON BD STY 8500. 3.88E7 CHAT-AGENT STY DDM 1051.0 2.9590E+07 0.0 CHAT-
AGENT BD DDM 900.0 2.9590E+07 0.0 CHAT-SOL STY EB 1051.0 2.9590E+07 0.0 CHAT-
SOL BD EB 900.0 2.9590E+07 0.0 B-SCISSION STY 1.00E6 4.5E7 TDB-FRAC=1 B-
SCISSION BD 1.00E6 4.5E7 TDB-FRAC=1 TERM-COMB STY STY 1.30E7 9.90E6 GEL-
EFFECT=1 TERM-COMB STY BD 1.30E7 9.90E6 GEL-EFFECT=1 TERM-COMB BD BD 1.30E7
9.90E6 GEL-EFFECT=1 TERM-COMB BD STY 1.30E7 9.90E6 GEL-EFFECT=1 TERM-DIS STY
STY 1.30E6 9.90E6 GEL-EFFECT=1 TERM-DIS STY BD 1.30E6 9.90E6 GEL-EFFECT=1
TERM-DIS BD BD 1.30E6 9.90E6 GEL-EFFECT=1 TERM-DIS BD STY 1.30E6 9.90E6 GEL-
EFFECT=1 TDB-POLY STY STY 2.2E5 3.2E7 TDB-POLY STY BD 4.4E5 3.2E7 TDB-POLY BD
BD 1.2E6 3.88E7 TDB-POLY BD STY 8.5E5 3.88E7 PDB-POLY STY BD 4.4E3 3.2E7 PDB-
POLY BD BD 1.2E2 3.88E7 INIT-SP-EFF STY COEFFA=0.0 COEFFB=3.0 COEFFC=0.0 GEL-
EFFECT 1 CORR-NO=2 MAX-PARAMS=10 &
GE-PARAMS=1 0 2.57 -5.05E-3 9.56 -1.76E-2 & -3.03 7.85E-3 0.0 2
Specifying Emulsion Polymerization

Kinetics
Following is the input language for the EMULSION REACTIONS paragraph. Users are able to select the
phases in which the reactions are occurring and also define the kinetics of particle absorption, desorption,
and termination.
Input Language for Emulsion Polymerization
REACTIONS reacid EMULSION
PARAM KBASIS=monomer/aqueous SPLIT-PM spm-cid kll SPECIES INITIATOR=cid MONOMER=cid
INHIBITOR=cid &
DISPERSANT=cid . . . INIT-DEC phasid cid idpre-exp idact-energy [idact-volume] ideffic
&
idnrad ref-temp INIT-CAT phased cid1 cid2 icpre-exp icact-energy [icact-
volume] iceffic &
icnrad ref-temp INIT-ACT phasid cid1 cid2 iapre-exp iaact-energy [iaact-
volume] iaeffic &
ianrad ref-temp PROPAGATION phasid cid1 cid2 prpre-exp pract-energy [pract-
volume] ref-temp CHAT-MON phasid cid1 cid2 cmpre-exp cmact-energy [cmact-volume] ref-
temp CHAT-POL phasid cid1 cid2 cppre-exp cpact-energy [cpact-volume] ref-temp CHAT-
AGENT phasid cid1 cid2 capre-exp caact-energy [caact-volume] ref-temp TERM-DIS phasid
cid1 cid2 tdpre-exp tdact-energy [tdact-volume] ref-temp TERM-COMB phasid cid1 cid2
tcpre-exp tcact-energy [tcact-volume] ref-temp INHIBITION phasid cid1 cid2 inpre-exp
inact-energy [inact-volume] ref-temp REDUCTION phasid cid1 cid2 rdpre-exp rdact-energy
[rdact-volume] rdeffic &
rdnrad ref-temp OXIDATION phasid cid1 cid2 oxpre-exp oxact-energy [oxact-
volume] ref-temp GEL-EFFECT GETYPE=reactiontype CORR-NO=corrno &
MAX-PARAMS=maxparams GE-PARAMS=paramlist / ... SUBROUTINE GEL-EFFECT=subname ABS-MIC
ampre-exp amact-energy ABS-PART appre-exp apact-energy DES-PART dppre-exp dpact-energy
EMUL-PARAMS emulid cmc-conc area
Input Language Description for Emulsion Polymerization
reacid Paragraph ID.

PARAM Use to enter basis parameters.
KBASIS= monomer/ aqueous
Basis for phase split ratios
SPLIT-PM Used to enter homosaturation solubility of species in the
polymer phase.
spm-cid Component ID of the species
partitioning into the polymer phase
kll Ratio of mass fraction of species in
polymer phase to mass fraction in reference phase. KBASIS determines whether the reference phase is
the monomer of aqueous phase
associate components in the simulation with species in the built-in free-radical kinetic scheme. The
following species keywords are currently valid
INITIATOR CATALYST MONOMER CHAINTAG DISPERSANT INHIBITOR POLYMER EMULSIFIER
ACTIVATOR REDOX-AGENT REDUCTANT
INIT-DEC Identifier for initiator decomposition reaction.
phasid Reaction phase (DISPERSANT)
cid Initiator ID
idpre-exp Preexponential factor
idact-energy Activation energy
idact-volume Activation volume (optional)
ideffic Initiator efficiency
idnrad Number of radicals from one initiator
molecule
INIT-CAT Identifier for catalyzed initiator decomposition reaction.
cid1 Initiator ID
cid2 Catalyst ID
icpre-exp Preexponential factor
icact-energy Activation energy
icact-volume Activation volume (optional)
iceffic Initiator efficiency
icnrad Number of radicals from one initiator
molecule
INIT-ACT Identifier for initiation by activator and initiator.
cid1 Initiator ID
cid2 Activator ID
iapre-exp Preexponential factor
iaact-energy Activation energy
iaact-volume Activation volume (optional)
iaeffic Initiator activation efficiency
ianrad Initiator activation number of radicals
PROPAGATION Identifier for chain propagation reaction.
phasid Reaction phase (POLYMER or
DISPERSANT)
cid1 Monomer corresponding to active
polymer segment ID
cid2 Monomer ID
pract-volume Activation volume (optional)
CHAT-MON Identifier for chain transfer to monomer reaction.
phasid Reaction phase (POLYMER)
polymer segment ID
cid2 Monomer ID
cmpre-exp Preexponential factor
cmact-energy Activation energy
cmact-volume Activation volume (optional)
CHAT-POL Identifier for chain transfer to polymer reaction.
polymer segment ID
cid2 Monomer corresponding to reacting
polymer segment ID or dead chain
cppre-exp Preexponential factor
cpact-energy Activation energy
cpact-volume Activation volume (optional)
CHAT-AGENT Identifier for chain transfer to transfer agent reaction.
polymer segment ID
cid2 Transfer agent ID
capre-exp Preexponential factor
caact-energy Activation energy
caact-volume Activation volume (optional)
TERM-DIS Identifier for chain termination by disproportionation
reaction.
DISPERSANT)
cid1 First active polymer segment ID
cid2 Second active polymer segment ID
tdpre-exp Preexponential factor
tdact-energy Activation energy
tdact-volume Activation volume (optional)
TERM-COMB Identifier for chain termination by combination reaction.
DISPERSANT)
cid1 First active polymer segment ID
cid2 Second active polymer segment ID
tcact-volume Activation volume (optional)
INHIBITION Identifier for chain inhibition reaction.
cid1 Active polymer segment ID
cid2 Inhibitor ID
inpre-exp Preexponential factor
inact-energy Activation energy
inact-volume Activation volume (optional)
REDUCTION Identifier for reduction step of redox initiation.
cid1 Reductant ID
cid2 Redox agent (catalyst) ID
rdpre-exp Preexponential factor
rdact-energy Activation energy
rdact-volume Activation volume (optional)
rdeffic Reduction activation efficiency
rdnrad Reduction activation number of radicals
OXIDATION Identifier for oxidation step of redox initiation.
cid1 Initiator ID
cid2 Redox agent (catalyst) ID
oxpre-exp Preexponential factor
oxact-energy Activation energy
oxact-volume Activation volume (optional)
GEL-EFFECT Gel effect switch and correlation selection. This sentence is
used to
Include a gel effect for any reactions in the built-in kinetic scheme and for the initiator efficiency
Select a gel effect correlation from a list of built-in and user specified gel effect correlations
Specify the maximum number of parameters
Specify the parameter values for the selected correlation
The default action is to not include a gel effect.
GETYPE= reactiontype
Used to identify the type of reaction to apply gel effect to. A list of valid reaction types follows
INITIATION Initiator decomposition
INIT-EFF Initiator efficiency
PROPAGATION Propagation, chain initiation and induced
initiation reactions
CHAT-MON Chain transfer to monomer
CHAT-POL Chain transfer to polymer
CHAT-AGENT Chain transfer to agent
TERMINATION Termination
CORR-NO= corrno
Used to select a correlation number. If a correlation number greater than the number of built-in
correlations (currently 2) is specified then the user should supply a Fortran subroutine containing the user
gel effect correlation.
MAX-PARAMS= maxparams
Used to enter the maximum number of gel effect parameters for the correlation selected.
GE-PARAMS= paramlist
Used to enter a list of parameters for the correlation selected.
SUBROUTINE User subroutines sentence.
GEL-EFFECT=
subname
Used to specify the name of the subroutine containing user gel effect correlations. The user gel-effect
subroutine argument list was shown in the Gel Effect section in Chapter 3. A Fortran template called
USRGEL.F is available for your use.
ABS-MIC Used to specify rate of radical absorption by micelles.
ampre-exp Preexponential factor
amact-energy Activation energy
ABS-PART Used to specify rate of radical absorption by particles.
appre-exp Preexponential factor
apact-energy Activation energy
DES-PART Identifier for radical desorption.
dppre-exp Preexponential factor
dpact-energy Activation energy
EMUL-PARAMS Used to specify emulsion parameters for micellar
nucleation.
emulid Emulsifier ID
cmc-conc Critical micelle concentration
area Surface coverage or area per unit mole
of emulsifier
Input Language Example for Emulsion Polymerization
REACTIONS EMLRXN EMULSION
DESCRIPTION "EXAMPLE EMULSION INPUT" PARAM KBASIS=MONOMER SPECIES
INITIATOR=APS MONOMER=STY NBA EMULSIFIER=EMUL &
DISPERSANT=H2O POLYMER=POLYMER INIT-DEC DISPERSANT APS 1.0000E+16
1.4020E+08 &
0.0 EFFIC=.80 NRADS=2 PROPAGATION POLYMER STY STY 2341450.0 2.6000E+07
PROPAGATION POLYMER STY NBA 3265600.0 2.6000E+07 PROPAGATION POLYMER NBA NBA
1909530.0 2.2400E+07 PROPAGATION POLYMER NBA STY 1.4918E+07 2.2400E+07 CHAT-
MON POLYMER STY STY 3310000.0 5.3020E+07 CHAT-MON POLYMER STY NBA 3310000.0
5.3020E+07 CHAT-MON POLYMER NBA NBA 438.90 2.7600E+07 CHAT-MON POLYMER NBA
STY 438.90 2.7600E+07 TERM-COMB POLYMER STY STY 1.6125E+09 7000000.0 TERM-
COMB POLYMER STY NBA 7.3204E+09 1.4600E+07 TERM-COMB POLYMER NBA NBA
3.3217E+10 2.2200E+07 TERM-COMB POLYMER NBA STY 7.3204E+09 1.4600E+07 ABS-MIC
1.0000E-07 0.0 ABS-PART 1.0000E-07 0.0 DES-PART 0.0 0.0 EMUL-PARAMS EMUL 0.0
5.0000E+08 SPLIT-PM STY .40 SPLIT-PM NBA .40
Specifying Ziegler-Natta Polymerization

Kinetics
Following is the input language for the part of the polymerization REACTIONS paragraph specific to
Ziegler-Natta kinetics. Ziegler-Natta inputs may be used to define the reaction kinetics for a wide variety
of homo- and co-polymers produced by catalyzed polymerization, including HDPE. A subset of the built-in
kinetics can be defined for a simulation by including the reaction keywords for the desired reactions and
specifying the rate coefficient parameters for these reactions. The reaction keywords and rate coefficient
parameters for Ziegler- Natta polymerization are also provided. Currently for two phase systems the
polymerization reactions are applied to the liquid phase in the reactor. For gas phase polymerization
systems the solid polymer, or the amorphous part of the polymer, is modeled as a liquid.
Input Language for Ziegler-Natta Polymerization
REACTIONS reacid ZIEGLER-NAT
SPECIES PRECAT=cid CATALYST=cid COCATALYST=cid MONOMER=cid CHAINTAG=cid & SOLVENT=cid
POISON=cid BYPRODUCT=cid HYDROGEN=cid POLYMER=cid & ELECDONOR=cid TDBSEGMENT=cid ACT-
SPON site-id cid1 aspre-exp asact-energy asorder ref-temp ACT-COCAT site-id cid1 cid2
acpre-exp acact-energy acorder ref-temp ACT-EDONOR site-id cid1 cid2 aepre-exp aeact-
energy aeorder ref-temp ACT-H2 site-id cid1 cid2 ahpre-exp ahact-energy ahorder ref-
temp ACT-MON site-id cid1 cid2 ampre-exp amact-energy amorder ref-temp CHAIN-INI site-
id cid1 cipre-exp ciact-energy ciorder ref-temp
PROPAGATION site-id cid1 cid2 prpre-exp pract-energy prorder ref-temp CHAT-MON site-id
cid1 cid2 cmpre-exp cmact-energy cmorder cmtdb-frac ref-temp CHAT-AGENT site-id cid1
cid2 capre-exp caact-energy caorder catdb-frac ref-temp CHAT-SOL site-id cid1 cid2
cspre-exp csact-energy csorder cstdb-frac ref-temp CHAT-COCAT site-id cid1 cid2 ccpre-
exp ccact-energy ccorder cctdb-frac ref-temp CHAT-H2 site-id cid1 cid2 chpre-exp
chact-energy chorder chtdb-frac ref-temp CHAT-EDONOR site-id cid1 cid2 cepre-exp
ceact-energy ceorder cetdb-frac ref-temp CHAT-SPON site-id cid1 cid2 cnpre-exp cnact-
energy cnorder cntdb-frac ref-temp DEACT-POISON site-id cid1 dppre-exp dpact-energy
dporder ref-temp DEACT-COCAT site-id cid1 dcpre-exp dcact-energy dcorder ref-temp
DEACT-MON site-id cid1 dmpre-exp dmact-energy dmorder ref-temp DEACT-EDONOR site-id
cid1 depre-exp deact-energy deorder ref-temp DEACT-H2 site-id cid1 dhpre-exp dhact-
energy dhorder ref-temp DEACT-SPON site-id dspre-exp dsact-energy dsorder ref-temp
COCAT-POISON cid1 cid2 copre-exp coact-energy coorder ref-temp FSINH-H2 site-id cid1
fhpre-exp fhact-energy fhorder ref-temp RSINH-H2 site-id cid1 rhpre-exp rhact-energy
rhorder ref-temp FSINH-POISON site-id cid1 fppre-exp fpact-energy fporder ref-temp
RSINH-POISON site-id cid1 rppre-exp rpact-energy rporder ref-temp TDB-POLY site-id
cid1 cid2 tdpre-exp tdact-energy tdorder ref-temp ATACT-PROP site-id cid1 cid2 atpre-
exp atact-energy atorder ref-temp CAT-ACTIVATE cid1 cid2 avpre-exp avact-energy
avorder ref-temp OPTIONS REAC-PHASE=phaseid SUPPRESS-WARN=yes/no USE-BULK=yes/no
Input Language Description for Ziegler-Natta Polymerization
reacid Reaction paragraph ID.

associate components in the simulation with the reactive species in the built-in kinetic scheme. The
following species keywords are currently valid
PRECAT CATALYST COCATALYST MONOMER CHAINTAG SOLVENT POISON BYPRODUCT
HYDROGEN POLYMER ELECDONOR TDBSEGMENT
MON-RSEG Specifies the pairing between monomers and their
corresponding repeat segments in a polymer.
monomer Monomer ID
r-seg Corresponding repeat segment ID
ACT-SPON Reaction identifier for spontaneous site activation of a catalyst potential site to a vacant
active site of type k.
site-id Site type identifier for active site formed
(k = 1, 2, ... , NSITE)
cid1 Component ID of catalyst
aspre-exp Preexponential factor (default is 0.0)
asact-energy Activation energy (default is 0.0)
asorder Reaction order for potential site
concentration (default is 0.0)
ACT-COCAT Reaction identifier for site activation by cocatalyst of a catalyst potential site to a vacant
site-id Site type identifier for active site
(k = 1, 2, ... , NSITE)
cid2 Component ID of cocatalyst
acpre-exp Preexponential factor (default is 0.0)
acact-energy Activation energy (default is 0.0)
acorder Reaction order for cocatalyst concentration
(default is 0.0)
ACT-EDONOR Reaction identifier for site activation by electron donor of a
catalyst potential site to a vacant active site of type k.
(k = 1, 2, ... , NSITE)
cid2 Component ID of electron donor
aepre-exp Preexponential factor (default is 0.0)
aeact-energy Activation energy (default is 0.0)
aeorder Reaction order for electron donor
ACT-H2 Reaction identifier for site activation by hydrogen of a
catalyst potential site to a vacant active site of type k.
(k = 1, 2, ... , NSITE)
cid2 Component ID of hydrogen
ahpre-exp Preexponential factor (default is 0.0)
ahact-energy Activation energy (default is 0.0)
ahorder Reaction order for hydrogen concentration
(default is 0.0)
ACT-MON Reaction identifier for site activation by monomer of a catalyst potential site to a vacant active
site of type k.
(k = 1, 2, ... , NSITE)
cid2 Component ID of monomer
ampre-exp Preexponential factor (default is 0.0)
amact-energy Activation energy (default is 0.0)
amorder Reaction order for monomer concentration
(default is 0.0)
CHAIN-INI Reaction identifier for polymer chain initiation on a vacant
active site of type k. The vacant site becomes a propagation site of type k.
site-id Site type identifier (k = 1, 2, ... , NSITE)
cipre-exp Preexponential factor (default is 0.0)
ciact-energy Activation energy (default is 0.0)
ciorder Reaction order for monomer concentration
(default is 0.0)
PROPAGATION Reaction identifier for polymer chain propagation on an
cid1 Component ID of active segment (specified
in terms of the corresponding monomer ID)
prpre-exp Preexponential factor (default is 0.0)
pract-energy Activation energy (default is 0.0)
prorder Reaction order for monomer concentration
(default is 0.0)
CHAT-MON Reaction identifier for chain transfer to monomer on active
site of type k.
cmpre-exp Preexponential factor (default is 0.0)
cmact- energy
Activation energy (default is 0.0)
cmorder Reaction order for monomer concentration
(default is 0.0)
cmtdb-frac Fraction of generated dead polymer chains with terminal double bonds (default is 0.0)
CHAT-AGENT Reaction identifier for chain transfer to agent on active site
of type k.
cid2 Component ID of chain transfer agent
capre-exp Preexponential factor (default is 0.0)
caact-energy Activation energy (default is 0.0)
caorder Reaction order for agent concentration
(default is 0.0)
catdb-frac Fraction of generated dead polymer chains with terminal double bonds (default is 0.0)
CHAT-SOL Reaction identifier for chain transfer to solvent on active
site of type k.
cid2 Component ID of solvent
cspre-exp Preexponential factor (default is 0.0)
csact-energy Activation energy (default is 0.0)
csorder Reaction order for solvent concentration
(default is 0.0)
cstdb-frac Fraction of generated dead polymer chains with terminal double bonds (default is 0.0)
CHAT-COCAT Reaction identifier for chain transfer to cocatalyst on active
site of type k.
ccpre-exp Preexponential factor (default is 0.0)
ccact-energy Activation energy (default is 0.0)
ccorder Reaction order for cocatalyst concentration
(default is 0.0)
cctdb-frac Fraction of generated dead polymer chains with terminal double bonds (default is 0.0)
CHAT-H2 Reaction identifier for chain transfer to hydrogen on active
site of type k.
chpre-exp Preexponential factor (default is 0.0)
chact-energy Activation energy (default is 0.0)
chorder Reaction order for hydrogen concentration
(default is 0.0)
chtdb-frac Fraction of generated dead polymer chains with terminal double bonds (default is 0.0)
CHAT-EDONOR Reaction identifier for chain transfer to electron donor on
cepre-exp Preexponential factor (default is 0.0)
ceact-energy Activation energy (default is 0.0)
ceorder Reaction order for electron donor
cetdb-frac Fraction of generated dead polymer chains with terminal double bonds (default is 0.0)
CHAT-SPON Reaction identifier for spontaneous chain transfer on active
site of type k.
cnpre-exp Preexponential factor (default is 0.0)
cnact-energy Activation energy (default is 0.0)
cnorder Reaction order (not used)
cntdb-frac Fraction of generated dead polymer chains with terminal double bonds (default is 0.0)
DEACT-POISON Reaction identifier for site deactivation by poison of a
catalyst active site of type k to a dead site.
cid1 Component ID of poison
dppre-exp Preexponential factor (default is 0.0)
dpact-energy Activation energy (default is 0.0)
dporder Reaction order for poison concentration
(default is 0.0)
DEACT-COCAT Reaction identifier for site deactivation by cocatalyst of a
dcpre-exp Preexponential factor (default is 0.0)
dcact-energy Activation energy (default is 0.0)
dcorder Reaction order for cocatalyst concentration
(default is 0.0)
DEACT-MON Reaction identifier for site deactivation by monomer of a
dmpre-exp Preexponential factor (default is 0.0)
dmact-energy Activation energy (default is 0.0)
dmorder Reaction order for monomer concentration
(default is 0.0)
DEACT- EDONOR Reaction identifier for site deactivation by electron donor of
a catalyst active site of type k to a dead site.
depre-exp Preexponential factor (default is 0.0)
deact-energy Activation energy (default is 0.0)
deorder Reaction order for electron donor
DEACT-H2 Reaction identifier for site deactivation by hydrogen of a
dhpre-exp Preexponential factor (default is 0.0)
dhact-energy Activation energy (default is 0.0)
dhorder Reaction order for hydrogen concentration
(default is 0.0)
DEACT-SPON Reaction identifier for spontaneous site deactivation of a
dspre-exp Preexponential factor (default is 0.0)
dsact-energy Activation energy (default is 0.0)
dsorder Reaction order (not used)
COCAT- POISON
Reaction identifier for cocatalyst poisoning reaction.
copre-exp Preexponential factor (default is 0.0)
coact-energy Activation energy (default is 0.0)
coorder Reaction order (not used)
FSINH-H2 Reaction identifier for site inhibition by hydrogen-forward
reaction.
fhpre-exp Preexponential factor (default is 0.0)
fhact-energy Activation energy (default is 0.0)
fhorder Reaction order for hydrogen concentration
(default is 0.0)
RSINH-H2 Reaction identifier for site inhibition by hydrogen-reverse
reaction.
rhpre-exp Preexponential factor (default is 0.0)
rhact-energy Activation energy (default is 0.0)
rhorder Reaction order for inhibited site
FSINH-POISON Reaction identifier for site inhibition by poison-forward
reaction.
fppre-exp Preexponential factor (default is 0.0)
fpact-energy Activation energy (default is 0.0)
fporder Reaction order for poison concentration
(default is 0.0)
RSINH-POISON Reaction identifier for site inhibition by poison-reverse
reaction.
rppre-exp Preexponential factor (default is 0.0)
rpact-energy Activation energy (default is 0.0)
rporder Reaction order for inhibited site
TDB-POLY Reaction identifier for terminal double bond propagation
reaction.
in terms of the corresponding monomer)
cid2 Component ID of TDB segment
tdpre-exp Preexponential factor (default is 0.0)
tdact-energy Activation energy (default is 0.0)
tdorder Reaction order (not used)
ATACT-PROP Reaction identifier for atactic propagation reaction.
in terms of the corresponding monomer)
atpre-exp Preexponential factor (default is 0.0)
atact-energy Activation energy (default is 0.0)
atorder Reaction order for monomer concentration
(default is 0.0)
CAT-ACTIVATE Reaction identifier for catalyst activation reaction.
cid1 Component ID for pre-catalyst
avpre-exp Preexponential factor (default is 0.0)
avact-energy Activation energy (default is 0.0)
avorder Reaction order for catalyst
REAC-PHASE= phaseID
SUPRESS- WARN= yes/no
USE-BULK= yes/no
Input Language Example for Zielger-Natta Polymerization
REACTIONS ZN-R2 ZIEGLER-NAT
DESCRIPTION "ZIEGLER-NATTA KINETIC SCHEME" SPECIES CATALYST=CAT
COCATALYST=CCAT MONOMER=E2 &
SOLVENT=HEXANE HYDROGEN=H2 POLYMER=HDPE ACT-SPON 1 CAT .080 0.0 1.0
ACT-SPON 2 CAT .080 0.0 1.0 ACT-SPON 3 CAT .080 0.0 1.0 ACT-SPON 4 CAT .080
0.0 1.0
ACT-COCAT 1 CAT CCAT .150 0.0 1.0 ACT-COCAT 2 CAT CCAT .150 0.0 1.0 ACT-COCAT
3 CAT CCAT .150 0.0 1.0 ACT-COCAT 4 CAT CCAT .150 0.0 1.0 CHAIN-INI 1 E2
255.0 0.0 1.0 CHAIN-INI 2 E2 90.0 0.0 1.0 CHAIN-INI 3 E2 255.0 0.0 1.0 CHAIN-
INI 4 E2 90.0 0.0 1.0 PROPAGATION 1 E2 E2 255.0 0.0 1.0 PROPAGATION 2 E2 E2
90.0 0.0 1.0 PROPAGATION 3 E2 E2 255.0 0.0 1.0 PROPAGATION 4 E2 E2 90.0 0.0
1.0 CHAT-MON 1 E2 E2 .090 0.0 1.0 CHAT-MON 2 E2 E2 .240 0.0 1.0 CHAT-MON 3 E2
E2 .090 0.0 1.0 CHAT-MON 4 E2 E2 .240 0.0 1.0 CHAT-H2 1 E2 H2 5.550 0.0 1.0
CHAT-H2 2 E2 H2 18.50 0.0 1.0 CHAT-H2 3 E2 H2 5.550 0.0 1.0 CHAT-H2 4 E2 H2
18.50 0.0 1.0 CHAT-SPON 1 E2 .0040 0.0 1.0 CHAT-SPON 2 E2 .0120 0.0 1.0 CHAT-
SPON 3 E2 .0040 0.0 1.0 CHAT-SPON 4 E2 .0120 0.0 1.0 DEACT-SPON 1 .00010 0.0
1.0 DEACT-SPON 2 .00060 0.0 1.0 DEACT-SPON 3 .00010 0.0 1.0 DEACT-SPON 4
.00060 0.0 1.0 OPTIONS REAC-PHASE=L
Specifying Ionic Polymerization Kinetics

Following is the input language for the IONIC REACTIONS paragraph.
Input Language for Ionic Polymerization
REACTIONS reacid IONIC
SPECIES ASSO-INI=cid INIT=cid CATALYST=cid & EX-AGENT=cid CT-AGENT=cid TM-AGENT=cid &
POLYMERS MON-RSEG cid segid / cid segid / ... INIT-DISSOC cid1 cid2 idpre-exp-f idact-
ener-f idpre-exp-r idact-ener-r idasso-no &
idref-temp ACT-CATALYST site-id cid1 cid2 acpre-exp-f acact-ener-f acpre-
exp-r acact-ener-r &
accoefb accoefd acref-temp CHAIN-INI-1 site-id cid i1pre-exp-f i1act-ener-
f i1ref-temp CHAIN-INI-2 site-id cid1 cid2 i2pre-exp-f i2act-ener-f i2coefd CHAIN-INI-
T site-id cid itpre-exp-f itact-ener-f itref-temp PROPAGATION site-id cid1 cid2 prpre-
exp-f pract-ener-f prref-temp ASSOCIATION site-id cid aspre-exp-f asact-ener-f aspre-
exp-r asact-ener-r EXCH-GENERAL rxn id site-id1 cid1 site-id2 cid2 egpre-exp-f egact-
ener-f egref-temp EXCH-AGENT rxn id site-id1 cid1 site-id2 cid2 eapre-exp-f eaact-
ener-f &
eapre-expr eaact-ener-r eacoefd earef-temp EQUILIB-CION site-id1 cid1 site-id2 eqpre-
exp-f eqact-ener-f eqpre-exp-r &
eqexp-ener-r eqcoefd eqref-temp CHAT-SPON site-id cid cspre-exp-f csact-
ener-f csref-temp CHAT-MONOMER site-id cid1 cid2 cmpre-exp-f cmact-ener-f cmref-temp
CHAT-DORM-P rxn id site-id1 cid1 site-id2 cid2 cdpre-exp-f cdact-ener-f cdref-temp
CHAT-AGENT site-id cid1 cid2 capre-exp-f caact-ener-f caorder caref-temp TERM-C-ION
site-id cid tcpre-exp tcact-energy tccoefb tcref-temp TERM-AGENT site-id cid1 cid2
tapre-exp-f taact-ener-f taorder taref-temp COUPLING site-id1 site-id2 site-id3 copre-
exp-f coact-ener-f copre-exp-r &
coact-eng-r coref-temp OPTIONS REAC-PHASE=phaseid SUPPRESS-WARN=yes/no USE-BULK=yes/no
Input Language Description for Ionic Polymerization
reacid Reaction paragraph ID.

associate components in the simulation with the reactive species in the built-in kinetic scheme. The
following species keywords are currently valid:
ASSOC-INIT INITIATOR CATALYST EXCH-AGENT CHAT-AGENT TERM-AGENT POLYMER
MON-RSEG Identifying the reacting monomer and the corresponding
repeat segment associated with it.
cid2 Component ID of corresponding repeat
segment
INIT-DISSOC Reaction identifier for initiator dissociation reaction.
Associated initiator of type m dissociates into type p initiator.
cid1 Component ID of associated initiator
idpre-exp-f Preexponential factor for forward reaction
idact-ener-f Activation energy for forward reaction
idpre-exp-r Preexponential factor for reverse reaction
idact-ener-r Activation energy for reverse reaction
idasso-no Initiator Association number
idref-temp Reference temperature
ACT-CATALYST Reaction identifier for active species activation by catalyst
of type n of an initiator of type m to form active species and/or counter-ion of type i.
site-id Site type identifier for active species formed
(i = 1, 2, ..., NSITE)
cid1 Component ID of initiator
acpre-exp-f Preexponential factor for forward reaction
acact-ener-f Activation energy for forward reaction
acpre-exp-r Preexponential factor for reverse reaction
acact-ener-r Activation energy for reverse reaction
accoefb 0 if cid2 does not participate in the reaction.
1 if cid2 participates in the reaction
accoefd 0 if counter-ion is absent. 1 if counter-ion is
present
acref-temp Reference temperature
CHAIN-INI-1 Reaction identifier for chain initiation of active species of
type i by monomer of type j.
(i = 1, 2, ..., NSITE)
cid Component ID of monomer
i1pre-exp-f Preexponential factor
i1act-ener-f Activation energy
i1ref-temp Reference temperature
CHAIN-INI-2 Reaction identifier for chain initiation of active species of
type i by monomer of type j reacting with initiator of type m.
(i = 1, 2, ..., NSITE)
cid1 Component ID of initiator
i2pre-exp-f Preexponential factor
i2act-ener-f Activation energy
i2coefd 1 if counter-ion is formed. 0 otherwise
tref Reference temperature
CHAIN-INI-T Reaction identifier for chain initiation of transfer active
species of type i by monomer of type j.
(i = 1, 2, ..., NSITE)
cid Component ID of monomer
itpre-exp-f Preexponential factor
itact-ener-f Activation energy
itref-temp Reference temperature
PROPAGATION Reaction identifier for polymer chain propagation on an
active species of type i.
(i = 1, 2, ..., NSITE)
cid1 Component ID of active segment
prpre-exp-f Preexponential factor
pract-ener-f Activation energy
prref-temp Reference temperature
ASSOCIATION Reaction identifier for polymer association with active
species of type i.
(i = 1, 2, ..., NSITE)
cid Component ID of active segment
aspre-exp-f Preexponential factor for forward reaction
(forming aggregate polymer)
asact-ener-f Activation energy for forward reaction
aspre-exp-r Preexponential factor for reverse reaction
asact-ener-r Activation energy for reverse reaction
asasso-no Polymer association
asref-temp Reference temperature
EXCH-GENERAL Reaction identifier for general exchange reaction between
two growing polymer chains with unique active species and end segments attached to them.
rxn id Reaction ID for a unique rate constant
site-id1 Site type identifier for first active species
(i = 1, 2, ... , NSITE)
cid1 Component ID of active segment on siteid1
site-id2 Site type identifier for second active species
(i = 1, 2, ... , NSITE)
egpre-exp-f Preexponential factor
egact-ener-f Activation energy
egref-temp Reference temperature
EXCH-AGENT Reaction identifier for exchange between growing i polymer
species with k segment attached to it and an exchange- agent of type m.
(i = 1, 2, ... , NSITE)
(i = 1, 2, ... , NSITE) formed
cid2 Component ID of exchange agent
eapre-exp-f Preexponential factor for forward reaction
eaact-ener-f Activation energy for forward reaction
eapre-exp-r Preexponential factor for reverse reaction
eaact-ener-r Activation energy for reverse reaction
eacoefd 0 if Po is absent. 1 if Po is present
earef-temp Reference temperature
EQUILIB-CION Reaction identifier for equilibrium with counter-ion between
i and j active species with kth segment attached to it.
(i = 1, 2, ... , NSITE)
(j = 1, 2, ... , NSITE)
eqpre-exp-f Preexponential factor for forward reaction
eqact-ener-f Activation energy for forward reaction
eqpre-exp-r Preexponential factor for reverse reaction
eqact-ener-r Activation energy for reverse reaction
eqcoefd 0 if counter-ion is absent. 1 if counter-ion is
present
eqref-temp Reference temperature
CHAT-SPON Reaction identifier for spontaneous chain transfer on active
species of type i.
site-id Site type identifier for active species
(i=1, 2, ... , NSITE)
cspre-exp-f Preexponential factor
csact-ener-f Activation energy
csref-temp Reference temperature
CHAT-MONOMER Reaction identifier for chain transfer to monomer of type j
on active species of type i.
(i=1, 2, ... , NSITE)
cmpre-exp-f Preexponential factor
cmact-ener-f Activation energy
cmref-temp Reference temperature
CHAT-DORM-P Reaction identifier for chain transfer on active species of
type i to form dormant polymer of type j.
site-id1 Site type identifier for growing active species
(i = 1, 2, ... , NSITE)
site-id2 Site type identifier for product active species
(j = 1, 2, ... , NSITE) formed
cdpre-exp-f Preexponential factor
cdact-ener-f Activation energy
cdref-temp Reference temperature
CHAT-AGENT Reaction identifier for chain transfer to chain transfer agent
on active species of type i.
(i=1, 2, ... , NSITE)
cid2 Component ID of chain transfer agent
capre-exp-f Preexponential factor
caact-ener-f Activation energy
caorder Reaction order for chain transfer agent
concentration
caref-temp Reference temperature
TERM-C-ION Reaction identifier for chain termination with counter-ion.
(i=1, 2, ... , NSITE)
tcoefb 0 if counter-ion does not participate in the
reaction. 1 if it does
tcref-temp Reference temperature
TERM-AGENT Reaction identifier for termination with terminating agent.
site-id Site type identifier (i = 1, 2, ... , NSITE)
cid1 Component ID of active agent
cid2 Component ID of terminating agent
tapre-exp-f Preexponential factor
taact-ener-f Activation energy
taorder Reaction order for terminating agent
concentration
taref-temp Reference temperature
COUPLING Reaction identifier for coupling reaction between active
species of type i and type j to form active species of type k.
site-id1 Site identifier for active species of type i
participating in the reaction
site-id2 Site identifier for active species of type j
participating in the reaction
site-id3 Site identifier for active species of type k
formed by coupling reaction
copre-exp-f Preexponential factor
coact-ener-f Activation energy
copre-exp-r Preexponential factor
coact-ener-r Activation energy
coref-temp Reference temperature
OPTIONS Specify reaction model options.
REAC-PHASE= phaseid
USE-BULK= yes/no
Input Language Example for Ionic Polymerization
REACTIONS rxnid SEGMENT-BAS DESCRIPTION '...' PARAM TREF=value PHASE=V/L/L1/L2 SOLVE-
ZMOM=YES/NO &
[SUPRESS-WARN=yes/no] [USE-BULK=yes/no] CBASIS=basis & [REAC-SITE=siteno S-
BASIS=basis]
SPECIES POLYMER=polymerid STOIC reactionno compid coef / ... RATE-CON reactionno pre-
exp act-energy [t-exp] [TREF=ref-temp] &
[CATALYST=cid CAT-ORDER=value] [USER-RC=userid] / ... POWLAW-EXP reactionno
compid exponent / [ASSIGN reactionno [ACTIVITY=value] RC-SETS=setno-list]
SUBROUTINE RATECON=rcname MASSTRANS=mtname USER-VECS NINTRC=nintrc NREALRC=nrealc
NINTMT=nintmt NREALMT=nrealmt &
NIWORKRC=niwork NWORKRC=nwork NIWORKMT=niwork NWORKMT=nwork & NURC=nurc INTRC value-
list REALRC value-list INTMT value-list REALMT value-list
Specifying Segment-Based Polymer

Modification Reactions
The input language for the SEGMENT-BAS REACTIONS paragraph is described here.
Input Language for Segment-Based Polymer Modification Reactions
REACTIONS rxnid SEGMENT-BAS
DESCRIPTION '...' PARAM T-REFERENCE=value PHASE=V/L/L1/L2 CBASIS=basis &
SOLVE-ZMOM=YES/NO SPECIES POLYMER=polymerid STOIC reactionno compid
coef / ... RATE-CON reactionno pre-exp act-energy [t-exp] / ... POWLAW-EXP
reactionno compid exponent /
The keywords for specifying rate constant parameters, reaction stoichiometry, and reacting polymer are
described here.
Input Language Description for Segment-Based Polymer Modification Reactions
reacid Unique paragraph ID.

DESCRIPTION Up to 64 characters between double quotes.
PARAM Used to enter reaction specifications.
T-REF= value
Reference temperature. If no reference temperature is given, the term 1/Tref is dropped from the rate
expression:
rate ( j C j )
k oi
e
ij
-
Ea R T 1 -
T
1
For more information, see the Segment- Based Reaction Model section in Chapter 3.
PHASE=V/L/L1 /L2
=
ref
Reacting phase
CBASIS Basis for power law rate expression. Choices
are:
MOLARITY MOLALITY MOLEFRAC MASSFRAC MASSCONC
USE-BULK= yes/no
SOLVE- ZMOM=
Option to explicitly solve for zeroth moment based on segment types (default=no)
YES/NO
REAC- SITE=siteno
Site number associated with all reactions in this model
S- BASIS=basis
For multi-site kinetics there are two options for calculating the segment concentrations used by the
reactor model:
COMPOSITE: use the composite segment concentrations (from SFLOW)
SITE: use the site-based segment concentrations (from SSFLOW)
SPECIES Used to specify reacting polymer.
POLYMER= polymerid
Polymer component ID (for reacting polymer)
STOIC Used to specify stoichiometry for user reactions.
compid Component ID
coef Stoichiometric coefficient (negative for
reactants and positive for products)
POWLAW-EXP Used to specify power-law exponents.
compid Component ID
exponent Power law exponent
ASSIGN Used to assign rate constant(s) to user reactions.
ACTIVITY= value
Multiplying factor used to calculate net rate constant
RC-SETS = setno-list
List of rate constants (from RATE-CON) which apply to this user reaction
RATE-CON Used to specify rate constant parameters.
SetNo Rate constant set number
pre-exp Pre-exponential factor in inverse time units
act-energy Activation energy in mole enthalpy units
t-exp Temperature exponent
T-ref Reference temperature (default is global
reference temperature in PARAM sentence)
USER- RC=number
Used to specify an element number in the user rate constant array (default=do not apply user rate
constant)
CATALYST= Optional catalyst ID
compid
CAT- ORDER=value
Optional reaction order for catalyst (default=1)
SUBROUTINE Used to provide the names of user-supplied Fortran
subroutines. The subroutine argument lists are documented in the User Subroutines section of Chapter 3.
RATECON= rcname
User rate constant subroutine name
BASIS= mtname User concentration basis / mass-
transfer subroutine name
USER-VECS Used to specify the size of vectors for user subroutines.
NINTRC=nintrc Length of integer array rate constant
routine
NREALRC= nrealrc
Length of real array for rate constant routine
NINTMT=nintmt Length of integer array for basis subroutine
NREALMT= nrealmt
Length of real array for basis subroutine
NIWORKRC= niwork
Length of integer workspace for rate constant subroutine
NWORKRC=nwork Length of real workspace for rate
constant subroutine
NIWORKMT= niwork
Length of integer workspace for basis routine
NWORKRC=nwork Total length of real workspace for
basis subroutine
NURC Number of rate constants returned by
user rate constant routine
INTRC Used to enter integer parameters for user rate constant
subroutine
REALRC Used to enter real parameters for user rate constant
subroutine
INTMT Used to enter integer parameters for user basis subroutine
REALMT Used to enter real parameters for user basis subroutine
Input Language Example for Segment-Based Polymer Modification Reactions
REACTIONS R-1 SEGMENT-BAS
SPECIES POLYMER=PU STOIC 1 DEG -1. / MDI -1. / DEG-E 1. / MDI-E 1. / &
URETHANE 1.
STOIC 2 DEG -1. / MDI-E -1. / DEG-E 1. / MDI-R 1. / &
URETHANE 1. STOIC 3 DEG-E -1. / MDI -1. / DEG-R 1. / MDI-E 1. / &
URETHANE 1. STOIC 4 DEG-E -1. / MDI-E -1. / DEG-R 1. / MDI-R 1. / &
URETHANE 1. STOIC 5 MDI-E -1. / H2O -1. / MDA-E 1. / CO2 1. STOIC 6 MDA-E
-1. / MDI -1. / MDI-R 1. / MDI-E 1. / &
UREA-R 1. STOIC 7 MDA-E -1. / MDI-E -1. / MDI-R 2. / UREA-R 1. STOIC 8
MDI -1. / URETHANE -1. / MDI-E 1. / ALLOPHAN 1. STOIC 9 MDI-E -1. / URETHANE
-1. / MDI-R 1. / ALLOPHAN 1. STOIC 10 MDI -1. / UREA-R -1. / MDI-E 1. /
BIURET 1. STOIC 11 MDI-E -1. / UREA-R -1. / MDI-R 1. / BIURET 1 RATE-CON 1
2500. <1/sec> 10. RATE-CON 2 1000. <1/sec> 10. RATE-CON 3 5000. <1/sec> 10.
RATE-CON 4 10. <1/sec> 10. RATE-CON 5 100. <1/sec> 10. ASSIGN-URC 1
ACTIVITY=4. RC-SETS=1 ASSIGN-URC 2 ACTIVITY=2. RC-SETS=1 ASSIGN-URC 3
ACTIVITY=2. RC-SETS=1 ASSIGN-URC 4 RC-SETS=1 ASSIGN-URC 5 RC-SETS=2 ASSIGN-
URC 6 ACTIVITY=2. RC-SETS=3 ASSIGN-URC 7 RC-SETS=3 ASSIGN-URC 8 ACTIVITY=2.
RC-SETS=4 ASSIGN-URC 9 RC-SETS=4 ASSIGN-URC 10 ACTIVITY=2. RC-SETS=5 ASSIGN-
URC 11 RC-SETS=5 POWLAW-EXP 1 DEG 1. / MDI 1. POWLAW-EXP 2 DEG 1. / MDI-E 1.
POWLAW-EXP 3 DEG-E 1. / MDI 1. POWLAW-EXP 4 DEG-E 1. / MDI-E 1. POWLAW-EXP 5
MDI-E 1. / H2O 1. POWLAW-EXP 6 MDA-E 1. / MDI 1. POWLAW-EXP 7 MDA-E 1. / MDI-
E 1. POWLAW-EXP 8 MDI 1. / URETHANE 1. POWLAW-EXP 9 MDI-E 1. / URETHANE 1.
POWLAW-EXP 10 MDI 1. / UREA-R 1. POWLAW-EXP 11 MDI-E 1. / UREA-R 1.
References
Aspen Physical Property System Physical Property Data. Burlington, MA: Aspen Technology, Inc.
Index
A
Absorption 213 Acrylic acid 199 Activated initiation 211 Activation energy
fitting 356 Active species formation 254 Adding
emulsion reactions 221 free-radical reactions 194 gel-effect 196, 222 ionic reactions 261 segment-based
reactions 287 user basis subroutine 161, 289 user kinetic subroutine 161 user rate constant subroutine
161, 289 user step-growth reactions 159 Ziegler-Natta reactions 246 Addition polymerization
about 81 ionic process differences 250 step-growth processes 266 Addition polymers 57 Addition
reactions 103 Aggregate polymer 34, 35 Aggregation reactions 256 Aliphatic polycarbonates 89
Amorphous polymers 16 Analysis tools
available 11, 37580 calculation procedure 376 optimization 377 sensitivity 377 Application tools 294
Applications
data fitting 339
example uses 375 tools 37580 Architecture
Aspen Polymers 381 Aromatic polycarbonates 89 Aspen Plus
distillation models 296, 301 Dupl 29698 equilibrium reactor models 304 Flash2 298 Flash3 298
fractionation models 296 FSplit 299 Heater 299 kinetic reactor models 30435 mass-balance reactor
models
3024 Mixer 299 Mult 299 Pipe 300 Pump 300 RadFrac 301 RBatch 32735 RCSTR 30417 reaction
models 86 reactor models 296, 302 REquil 304 RGibbs 304 RPlug 31727 RStoic 302 RYield 303 Sep
301 Sep2 301 stream manipulators 295 unit operation models 35965 Aspen Polymers
application tools 294, 37580 architecture 381 built-in models 85
Index 507
component attribute treatment in
unit operations 33537 component databanks 387429 configuring 38182 data fitting 294, 33940
decomposition rate parameters
43133 emulsion model 199223 end-use properties 75 features 5, 913 files 382 flowsheets 293
fortran utilities 445 free-radical polymerization
model 16398 input language 447504 installation 382 ionic model 24963 key parameters 342
kinetic rate constant parameters
43144 model definition 12 polyester technology package 95 property approach 58 reaction models
85 segment approach 27 segment-based reaction model
26590 steady-state features 294 steady-state modeling 29194 step-growth polymerization
model 89162 templates 382 troubleshooting 38386 unit operation models 295338 unit operations
294 user models 86, 35973 user subroutines 14055, 274
84 Ziegler-Natta model 22547 Aspen PolyQuest 96 AspenTech support 3 AspenTech Support
Center 3 Association reactions 256 Attributes See also Component
attributes aggregate polymers 40, 48 bulk polymers 47 calculation methods 47 catalyst 45
handling in unit operations 336 initialization scheme 4750 initializing in streams 451 input language 451
53 live polymers 39, 48 polymers 3637 required 44, 47 scale factors 50 scaling 453 site-based
aggregate polymers
43, 50 site-based bulk polymers 49 site-based live polymers 42, 49 site-based polymers 40 specifying
conventional
component 451 user 45, 46 variables for data regression 346 Ziegler-Natta 44 Average properties 58
59
B
Backbone modifications 269 Batch reactors 330 Beta-scission 183 Bifunctional initiator decomposition
171 Bifunctional initiators 174, 175 Bimodal distributions 56 Bivariate distributions 55 Block length 35
Branch formation 270 Branching
degree of 33 free-radical polymerization 192 frequency 35 number of chains 35 reactions 240 Broyden
solver 311 Bulk
free-radical polymerization 163
98 polymer chain 169 polymer chain length moment
equation 187 polymerization 164 Bulk polymerization 85 Butadiene 199 Butyl acrylate 199
508 Index
Butyl methacrylate 199
C
Calculator block 376 Catalyst sites
inhibited 231 propagation 231 types 231 vacant 231 Catalysts
poisoning 240 preactivation 237 site activation 237 types 22629 Ziegler-Natta 24, 226 Ziegler-Natta
reactions 230 Catalyzed initiation reaction 173 Categorizing polymers 19 Chain
initiation for ionic 255 initiation for Ziegler-Natta 237 scission 269 termination 257 Chain length
average properties 59 distribution 20, 35, 5961, 65 first moment 47 instantaneous weight distribution
63 instanteous number-average 63 weight-average 63 zeroth moment 47 Chain size 55 Chain transfer
dormant polymer formation 257 ionic reactions 257 spontaneous 239, 257 to agent 239, 257 to
cocatalysts 239 to electron donor 239 to hydrogen 239 to monomer 179, 239, 257 to polymer 181 to small
molecules 178, 239 to solvent 178, 239 to transfer agent 178 Chain-growth polymerization
bulk 85 commercial polymers 84 comparison to step-growth 82 emulsion 85 overview 83
precipitation 85 solution 85 suspension 85 Characterizing approach 19 components 10, 12, 27
Chlorinated polyethylene 265 Chloroprene 199 Class 0 component attributes 34,
45, 335 Class 1 component attributes 34 Class 2 component attributes 34,
4546, 313, 335 CMC See Critical micelle
concentration Cocatalysts
poisoning 240 Combination reactions 104, 270 Component attributes
about 20 aggregate polymer 34 available 3644 calculation methods 47 categories 35 class 0 34, 45
class 0 treatment in unit
operations 335 class 1 34 class 2 34, 4546, 313 class 2 treatment in unit
operations 335 classes 34 composite 35 copolymer composition 33 degree of branching 33 degree of
cross-linking 33 degree of polymerization 23, 33 emulsion polymerization 218 for aggregate polymers 40,
48 for blocks 52 for bulk polymers 47 for catalysts 34, 44, 45 for composite aggregate
polymers 36 for composite live polymers 35 for composite polymers 35 for ionic initiators 33, 45 for live
polymers 39, 48 for polymer properties 33 for polymers 3536, 3637 for site-based aggregate
polymers 36, 43, 50 for site-based bulk polymers 49
Index 509
for site-based live polymers 36,
42, 49 for site-based polymers 36, 40
43 for site-based species 44 for streams 52 for structural properties 33 for Ziegler-Natta catalysts 33
free-radical polymerization 191 initialization 46, 52 initialization scheme 47 input language 45153 ionic
polymerization 260 live polymer 34 molecular architecture 33 molecular weight 33 required 44, 47 scale
factors 50 segment composition 33 segment-based reaction model
273 sequence length 33 specifying 5153 specifying conventional 52 specifying conventional
attributes 451 specifying scale factors 53 specifying scaling factors 453 step-growth polymerization
124 structural properties tracked 23 types 35 unit operation model treatment
33537 user-specified 45 Ziegler-Natta 44 Ziegler-Natta polymerization 244 Component databanks
about 25 for initiators 26 for PC-SAFT 26 for polymers 11, 27 for POLYPCSF 26 for pure components 25
for segments 11, 26 selecting 28 Components
adding reacting 154 catalysts 24 categories 2125 characterizing 12
conventional 22 databanks 387429 defining 12 defining types 29 fortran utilities 360 input language
44751 ionic initiators 24 naming 29, 447 oligomers 23 POLYMER databank 38791,
38891 polymers 22 pure component databank 387 segment approach 27 SEGMENT databank 392
429 segments 24 site-based 24 specifying 28 specifying catalysts 44851 specifying oligomers 44851
specifying polymers 44851 specifying step-growth 156 Composition 8 Condensation polymerization 81,
126 Condensation reactions 103 Configuring
Aspen Polymers 38182 Consumption of radicals 6162 Continuous polymerization 92 Conventional
components 22 Conventional species 268 Convergence
for RCSTR 308 improving 51 initialization options (RCSTR)
314 parameter tuning 354 RBatch troubleshooting 33135 RCSTR troubleshooting 31517 RPlug
troubleshooting 32327 scaling factors (RBatch) 332 scaling factors (RCSTR) 313 scaling factors (RPlug)
323 solver method (RBatch) 334 solver method (RPlug) 325 step size (RBatch) 334 step size (RPlug)
325 troubleshooting data regression
35355
510 Index
Conversion
energy balance 311 Copolymer
density 78 Copolymerization 64
free-radical 16398 ionic 24963 ionic propagation 256 user input for ionic model 254 user input for
Ziegler-Natta
model 236 Ziegler-Natta 22547 Copolymers 16 Coupling reactions 258 CPE See Chlorinated
polyethylene Critical micelle concentration 201 Cross linking 270 Cross-link formation 184 Cross-linking
33, 35 Crystalline polymers 16 Crystallinity 8 Custom
prop-sets 76 Custom models See User models,
See User models customer support 3 Cycle time 331 Cyclodepolymerization reactions
104
D
DAMP-FAC 311 Damping factor 311 Data
collection 341 defining regression cases 351 fitting 33940 interpreting regression results
352 literature search 340, 341 point 345 profile 345 regression 33940 review 340 sequencing
regression cases 352 trend analysis 341, 343 verification 341 Data fitting See also Data
regression applications 339 data collection 341 data review 340
data verification 341 features 294 literature search 340, 341 model development 340, 343 model
refinement 341, 344 parameters 34243 preliminary fit 340, 34243 procedure 34044 trend analysis
341, 343 Data regression See also Data
fitting activation energy 356 base-case model 345 choosing parameters 355 convergence problems
35355 data sets 345 defining cases 345, 351 entering data 345 entering operating conditions
345 flowsheet variables 37880 fortran blocks 347 interpreting results 35253 manipulating variables
347 point data 349 procedure 34044, 34558,
34558 profile data 350 Prop-Sets 347 scaling fitted parameters 356 sensitivity studies 355
sequencing cases 352 standard deviation 351 troubleshooting 35355 tuning 354 Databanks
component 25, 387429 functional group 11 INITIATOR 26 PC-SAFT 26 polymer 11 POLYMER 27, 387
91 POLYPCSF 26 pure component 25, 387 segment 11 SEGMENT 26, 391429 selecting 28 Dead
polymer 35 Dead polymer chain 169 Dead sites 45 Dead zones 308, 321 Defining
additional simulation options 13
Index 511
components 12 feed streams 13 flowsheet options 12 global simulation options 12 polymerization kinetics
13 property models 13 regression cases 351 UOS model operating conditions
13 Degree of
branching 33, 55 cross-linking 33 polymerization 33, 57 Density
as polymer property 8 function 5859 of copolymer 78 Depolymerization 269 Design-spec block 377
Desorption 213 Developing
models 12 Direct esterification 90 Displaying
distribution data for reactors 70 distribution data for streams 70 distribution data tables 70
Disproportionation 180 Distillation models
about 301 available 296 RadFrac 301 Distribution
average properties and moments
5859 calcuations 454 chain length 65 copolymerization 64 displaying data table 70 displaying for
reactors 70 displaying for streams 70 functions 56, 58 GPC 67, 68 in process models 58 kinetic reactors
65 method of instantaneous
properties 6064 moment equation 187 moments 5859 particle size 21618
plotting data 70 plug flow reactors 66 polymer 65 procedure 67 specifying calculations 6971 specifying
characteristics 69 streams 67 structural property 5572 tracking 65 verification 68 Distribution calculations
specifying input language 454 Dupl
about 29698 attribute handling 336 Duty
in RBatch 327 in RCSTR 305 in RPlug 318 Dyads 35
free-radical rate equation 187 Dynamic models 10, 13
E
EB-LOOP 311 e-bulletins 3 Editing
emulsion reactions 221 free-radical reactions 195 ionic reactions 261 segment-based reactions 287 user
step-growth reactions 159 Ziegler-Natta reactions 246 Elastomers 16 Electrophilic reactions 101
Emulsion polymerization
absorption 213 accessing model 219 activated initiation 211 adding reactions 221 applications 199
aqueous phase 208 assigning rate constants 221 attributes 218 built-in reaction listing 220 chain growth
85 desorption 213 editing reactions 221 homogeneous nucleation 2046
512 Index
industrial processes 200 input language 47784 kinetics 200215, 211 kinetics scheme (figure) 204 latex
202 latex reactions 207 micellar nucleation 2014 model 199223 model assumptions 215 model
features 21518 monomer partitioning 21516 nomenclature 208 nucleation time 203 particle growth 201,
206 particle number 203 particle phase 210 particle size distribution 21618 population balance equation
217 products produced 200 properties calculated 218 radical balance 20711 rate constant 214 rate of
particle formation 206 reactions 204 redox initiation 212 seed process 206 Smith-Ewart theory 211
specifying calculation options
222 specifying gel-effect 222 specifying model 219 specifying particle growth
parameters 223 specifying phase partitioning 222 specifying reacting species 220 stage I (seed) 202
stage II (growth) 202, 206 stage III (finishing) 202 user profiles 218 End group reformation reactions
104 End-use properties
about 7379 adding a Prop-Set 79 calculating 76, 79 density of copolymer 78 input language 45456
intrinsic viscosity 77 melt index 78 melt index ratio 79 relationship to structure 75 selecting 79 zero-shear
viscosity 77
Energy balance conversion 311 Entering
point data 349 profile data 350 standard deviations 351 Equilibrium
for ionic polymerization 258 for Ziegler-Natta polymerization
243 phase 188 reactions with counter-ion 256 reactor models 304 Equilibrium models
RGibbs 304 RYield 304 Esterification
batch process 94 direct 90 operating conditions 93 results 91 secondary 91 Estimating
property parameters 459 Ethylene
process types 227 Ethylene-propylene 226, 229 Exchange reactions 256
F
Features 5, 913 Feed streams defining 13 with polymers 23, 46 Files
startup 382 Fitting
activation energy 356 choosing parameters 355 Flash2
about 298 attribute handling 336 input variables 347 results variables 347 Flash3
about 298 attribute handling 336 input variables 347 results variables 347 Flowsheeting options 11
Flowsheets
basic unit operation models 295 calculation procedure 376
Index 513
calculator block 376 design-spec block 377 distillation models 296, 301 Dupl block 29698 equilibrium
reactor models 304 Flash2 block 298 Flash3 block 298 fractionation models 296 FSplit block 299 Heater
block 299 incorporating spreadsheets 376 kinetic reactor models 30435 mass-balance reactor models
3024 Mixer block 299 model configuration tools 376
78 Mult block 299 optimization 377 Pipe block 300 polymer process 293 process studies 37678
Pump block 300 RadFrac block 301 RBatch block 32735 RCSTR block 30417 reactor models 296, 302
REquil block 304 RGibbs block 304 RPlug block 31727 RStoic block 302 RYield block 303 sensitivity
study 377 Sep block 301 Sep2 block 301 setting fixed variables 377 steady-state 29194 stream
manipulators 295 unit operation models 295338 variables 37880 variables for data regression
37880 Fortran
arguments 445 linking 383 monitors 360 templates 383 utilities 360, 445 Fortran blocks
in data regression 347
to enforce assumptions 347 to manipulate process variables
348 to scale paramters 357 Fortran utilities
component handling 360 stream handling 360 Fractionation models 296 Free-radical iniators
decomposition rate parameters
43133 Free-radical polymerization
accessing model 193 adding reactions 194 applications 163 beta-scission reactions 183 bifunctonal
initiator
decomposition reaction 174, 175 branching 192 built-in reaction listing 194 bulk 164 bulk polymer chain
length
moment equation 187 calculation method 185 catalyzed initiation reaction 173 chain transfer reactions
178 dyads 187 editing reactions 195 gel effect 170 gel effect 18889 induced initiation reaction 173
industrial processes 164 initiation reactions 171 initiator decomposition reaction
172 input language 46777 kinetics 16583 kinetics nomenclature 166 kinetics scheme (figure) 165
live polymer chain length moment equation 186 model 16398 model assumptions 18590 model
features 18590 modifying the rate expression
170 moment-property relationship
equation 191 parameters 19093
514 Index
pendent double bond
polymerization 184 phase equilibrium 188 propagation reactions 176 properties calculated 19093
quasi-steady-state
approximation 188 rate constant 170 reactions 165 solution 164 specifying calculation options
196 specifying gel-effect 196 specifying model 193 specifying reacting species 194 specifying
reactions 195 specifying user profiles 197 structural properties 192 termination reactions 17879 user
profile properties 192 Frequency function 5859 FSplit
about 299 attribute handling 336 Functional group databank 11
G
Gas-phase process 227 Gear integrator 323, 332 Gel effect
built-in correlations 189 free-radical 170 free-radical polymerization 188
89 specifying 196, 222 user specified correlations 189 user subroutine arguments 189 Gel effect
subroutine free-radical 170 Gel permeation chromatography 67 Generation of radicals 61 Glycol recovery
91 GPC 67
H
HDPE See High density
polyethylene Heat exchangers 307 Heater
about 299 attribute handling 337
help desk 3 Heterogeneous catalysts 226 High density polyethylene
about 225 processes 227 High impact polypropylene 229 HIPP See High impact polypropylene Hold-up
in RCSTR 305 Homogeneous catalysts 226 Homogeneous nucleation
particle formation 201 process 2046 rate of particle formation 206 Homopolymers 15
I
INCL-COMPS 154 Induced initiation reaction 173 Industrial applications
polymer production steps 291
93 polymer production steps
(figure) 291 Industrial processes
emulsion polymerization 200 free-radical polymerization 164 ionic polymerization 250 model uses 375
segment-based reaction model
266 step-growth polymerization 90 Ziegler-Natta polymerization 226 Inhibited sites 231 Inhibition
catalyst sites 45, 240 Initators
for ionic polymerization 254 Initialization
hybrid option 315 integration option 314 options for RCSTR 314 solver option 314 Initiation
activated 211 catalyzed 171 decomposition rate 171 free-radical 172, 174, 175 free-radical polymerization
171 induced 171 ionic 45, 251
Index 515
reaction for catalyzed 173 reaction for decomposition 172 reaction for induced 173 redox 212 INITIATOR
databank
about 26 Initiators
databank 26 free-radical 43133 ionic 24 Injection ports 322 Input language
attribute scaling factors 453 catalysts 44851 component attributes 45153 components 44751
conventional component
attributes 451 distribution calculations 454 emulsion 47784 end-use properties 45456 for Aspen
Polymers 447504 free-radical 46777 ionic 494501 oligomers 44851 physical properties 45660
polymers 44851 property data 458 property methods 456 property parameter estimation
459 prop-set 45456 segment-based reactions 5015 step-growth 46067 streams 451 Ziegler-Natta
48493 Input variables Flash2 347 Flash3 347 MultiFrac 347 RadFrac 347 RBatch 346 RCSTR 346
RPlug 347 standard deviations 351 Installing
Aspen Polymers 382 Instantaneous
number-average 63 properties 58, 6064, 65
weight chain length 6364 Interfacial processes 84 Intermolecular reactions 103 Intramolecular
reactions 103 Intrinsic viscosity 77 Ionic initiator 24 Ionic initiators
component attributes 33 properties tracked 45 Ionic polymerization
accessing model 260 active species formation 254 adding reactions 261 aggregation 256 applications
249 assigning rate constants 262 association 256 built-in reaction listing 261 chain initiation 255 chain
termination 257 chain transfer 257 comparison to other addition
processes 250 copolymerization steps 254, 256 coupling 258 editing reactions 261 equilibrium with
counter-ion 256 exchange 256 industrial processes 250 initiator attributes 251 initiator types 254 input
language 494501 kinetics scheme 25058 kinetics scheme (figure) 252 model 24963 model
assumptions 25859 model features 25859 nomenclature 253 phase equilibria 258 polymers tracked
251 propagation 255 properties calculated 25960 rate calculations 258 rate constants 254 reactions 252
specifying model 260 specifying reacting species 260
516 Index
K
Kinetic models
RBatch 32735 RCSTR 30417 RPlug 31727 Kinetics
data fitting 33940 decomposition rate parameters
43133 defining polymerization 13 emulsion (input language) 477
84 emulsion polymerization 200
215, 211 free-radical (input language)
46777 free-radical polymerization 165
83 ionic (input language) 494501 ionic polymerization 25058 mechanisms 10 melt polycarbonate
12224 multi-site 65, 66 nylon reactions 11122 parameter influence on 342 polyester reactions 10511
polymerization 81 rate constant parameters 431
44 reactor models 30435 segment-based reaction model
270 single-site 65, 66 specifying emulsion 21923 specifying free-radical 19397 specifying ionic 260
62 specifying step-growth 5153 specifying step-growth (input
language) 46067 specifying Ziegler-Natta 24447 step-growth polymerization 101
24 user fortran arguments 445 user models 36569 user subroutine (example) 366 user subroutines
149 Ziegler-Natta (input language)
48493 Ziegler-Natta polymerization
23042
L
Latex
definition 202 number of particles per liter 203 reactions 207 Linear condensation polymers 57 Linear low
density polyethylene
about 225 processes 227, 228 Linking
fortran 383 Liquid enthalpy
user subroutine (example) 371 Liquid process 228 Live
polymer chain 169 polymer chain length moment
equation 186 Live polymer 34, 35 LLDPE See Linear low density
polyethylene Local work arrays 155, 284 Low density polyethylene 164 Low molecular weight
polymer 57
M
Mass balance 311 Mass-balance models
RStoic 302 RYield 303 Material streams 46 MB-LOOP 311 Melt index 8, 78 Melt index ratio 79 Melt
polycarbonate
rate constants 123 reaction components 122 reaction kinetics 12224 step-growth reactions 123 Melt-
phase
nylon-6,6 processes 122 polymerization 100 processes 84 Metallocene catalysts 226 Method of
instantaneous properties
58, 6064, 65 Method of moments 58, 185 Methylmethacrylate 199 Micellar nucleation 2014
MIXED
substream variables 380 Mixer
Index 517
about 299 attribute handling 337 Mixing
non-ideal in RCSTR 306 non-ideal in RPlug 320 Modeling
applications 89, 163, 199, 225,
249, 265 data fitting 294, 33940 enforcing assumptions 347 features 294 nylon 96100 nylon-6,6 116
polycarbonates 100101 polyesters 9096 polymer phase change 303 polymer processes 293 steady-
state 29194 tools 294 unit operations 294, 295338 Models
accessing variables 37880 analysis tools 37678 application tools 37580 base case 345 calculations
for user models
36065 defining 12 developing 340, 343 parameter fitting 34243 possible uses 375 process studies
37678 refining 341, 344 structure for user models 359 trend analysis 341, 343 unit operation 11 user
35973 USER2 routine 362 Molecular structure
SEGMENT databank 392429 Molecular weight
as component attribute 33 distribution 8, 58 number-average 78 weight-average 35, 78 Moment
equations
bulk polymer 187 general 186 live polymer 186 relationship to properties 191
Moments of chain length
distribution first 39, 47 Monomers
corresponding segment formulas
127 definition 15 functional groups 129 partitioning 21516 purification 292 synthesis 29293, 292
Most-probable distribution 57, 114,
120, 131 Mult
about 299 attribute handling 336 MultiFrac
attribute handling 337 input variables 347 results variables 347 Multimodal distributions 56
N
Newton solver 311 Nomenclature
for emulsion model 208 for free-radical model 166 for ionic model 253 for segment-based reaction
model 271 for step-growth model 103 for Ziegler-Natta model 234 POLYMER databank 38891
SEGMENT databank 391 Nucleation
homogeneous 201, 2046 micellar 2014 period 202 time 202 time (equation) 203 Nucleophilic reactions
about 101 nomenclature 103 Number average
chain length distribution 63 degree of polymerization 57 Number-average
degree of polymerization 35 Nylon
518 Index
aqueous salt solutions 98 melt-phase polymerization 100 production process 96100 salt preparation 98
Nylon-6
production process 96 rate constants 113 reaction components 112 reaction kinetics 111 step-growth
reactions 112 user-specified reactions 113 Nylon-6,6
melt-phase polymerization 122 modeling approaches 116 production process 98 rate constants 118, 119
reaction components 116 reaction kinetics 115 step-growth reactions 117 user-specified reactions 119
O
Occupied sites 45 Oligomers
as components 23 definition 15 fractionation 131 segments 24 specifying 30 Optimization 377 Orienticity
35
P
Packed vectors 155, 284 Parameters
data fitting 33940 decomposition rate 43133 estimating property 459 fitting 340, 34243 for free-radical
polymerization
19093 influence of kinetics 342 integer 154, 284 kinetic rate constant 43144 POLYMER property
387 real 154, 284 scaling 356 SEGMENT property 391 to manipulate process variables
348 tuning for data regression 354
Particle growth
in emulsion polymerization 206 specifying parameters 223 PBT See Polybutylene terephthalate PC-SAFT
databank 26 PC-SAFT databank
about 26 PEN See Polyethylene naphthalate Pendent double bond
polymerization 184 PET See Polyethylene terephthalate Phase equilibria
ionic polymerization 258 step-growth polymerization 126 Ziegler-Natta polymerization 243 Phase
equilibrium
free-radical polymerization 188 Phase partitioning specifying 222 Physical properties
calculations in user models 364 fitting parameters 34243 input language 45660 user models 37073
user subroutine (example) 371 Pipe 300 Plant data fitting 33940 Plot
distribution data 70 PMMA See Polymethyl methacrylate Point data
about 345 entering 349 Polyamides 90 Polybutadiene 249 Polybutene 249 Polybutylene terephthalate 95
Polycarbonates aliphatic 89 aromatic 89 production process 100101 reaction kinetics 12224
Polydispersity
index 63 Polyesters
assigning rate constants 109 polyester technology package 95 production process 9096 reaction
components 106 reaction kinetics 10511
Index 519
side reactions 109 step-growth reactions 108 user-specified reactions 110 Polyethylene
chlorinated 265 low density 164 Polyethylene naphthalate 95 Polyethylene terephthalate batch processes
9395 continuous step-growth
polymerization 9093 solid-state models 96 Polyisobutylene 249, 265 Polymer chain
bulk 169 dead 169 definition 169 live 169 POLYMER databank
about 11, 27, 387 components 38891 nomenclature 38891 Polymerization
addition 81 bulk 85 chain-growth 82, 83 condensation 81 condensation polymerization 126 continuous 92
degree of 33 emulsion 85, 199223 free-radical 16398 interfacial 84 ionic 24963 kinetics 10, 13, 81
manufacturing step 293 melt phase 84 precipitation 85 process overview 67 process types 84 reaction
types 81 reactions 81 solid-state 84 solution 84, 85 step-growth 82, 83, 89162 suspension 85 Ziegler-
Natta 22547 Polymers
acrylic acid 199 addition 57
aggregate 34, 35 aliphatic polycarbonates 89 amorphous 16 aromatic polycarbonates 89 as components
23 average properties and moments
5859 branched 16 bulk polymer chain length
moment equation 187 butadiene 199 butyl acrylate 199 butyl methacrylate 199 by chemical structure
18 by physical structure 16 by property 18 chain-growth 84 characterizing 19 chlorinated polyethylene
265 chloroprene 199 component attribute sets 3536 component attributes 33, 35 component
characterization 10 crystalline 16 data fitting procedure 34044 data regression procedure 345
58 dead 35 definition 6 elastomers 16 emulsion properties calculated
218 end-use properties 7379 ethylene-propylene 226 free-radical properties calculated
19093 high density polyethylene 225 high-impact polystyrene 163 ionic properties calculated 259
60 ladder 16 linear 16 linear condensation 57 linear low density polyethylene
225 live 34, 35 live polymer chain length moment equation 186 low density polyethylene 164 low
molecular weight 57
520 Index
mass 124, 273 method of instantaneous
properties 58, 60, 65 method of moments 58 methylmethacrylate 199 mole fraction 272 monomer
purification 292 monomer synthesis 29293, 292 network 16 nomenclature 38891 phase change 303
polyamides 90 polybutadiene 249 polybutene 249 polyesters 90 polyisobutylene 249, 265 polymerization
step 293 polymethyl methacrylate 164,
265 polyoxides 249 polypropylene 226 polystyrene 163, 164, 249 polyurethanes 90 polyvinyl acetate
163 polyvinyl alcohol 164, 265 polyvinyl chloride 163 processing 67 processing step 293 production rate
63 production steps 29193 properties 19 properties tracked 35 property distributions 5572 property
parameters 387 prop-sets 74 purification 29293 reacting 266 recovery 9, 293 segment-based properties
calculated 273 segments 24, 391 separation 9, 293 specifying 29 star 16 step-growth 83 structural
properties 23 structure 15 structure of 1519 styrene 199 synthesis 293 tetrafluroethylene 199
thermoplastics 16 thermosets 16
tracking structural properties 33 vinyl chloride 199 vinylacetate 199 Ziegler-Natta properties
calculated 243 Polymethyl methacrylate 164, 265 Polyoxides 249 POLYPCSF
databank 26 POLYPCSF databank
about 26 Polypropylene about 226 process types 228 Polypropylene terephthalate 95 Polystyrene 163,
164, 249 Polyurethanes 90 Polyvinyl acetate 163 Polyvinyl alcohol 164, 265 Polyvinyl chloride 163
Population balance
equation for emulsion polymerization 217 equation for free-radical polymerization 185 Potential sites 44
Power-law reaction model See
Segment-based reaction model:about PPT See Polyproylene terephthalate Precipitation polymerization
85 Pressure
drop 305, 319 in RBatch 328 in RCSTR 305 in RPlug 319 Process modeling data fitting 294 dynamic 10,
13 features 294 flowsheets for polymer processes
293 issues for polymers 79 steady-state 10, 13, 29194 tools 294 unit operations 294 Processing
polymers 293 Profile data
about 345 data sets 350 entering 350 RBatch 350
Index 521
RPlug 350 Propagation
depolymerization 269 free-radical polymerization 176 ionic polymerization 255 segment-based reaction
model
270 sites 231 Ziegler-Natta polymerization 238 Properties
average polymer 5859 branching 23 chain size 55 composition 8 copolymer composition 23, 55
copolymerization 64 crystallinity/density 8 degree of branching 55 degree of polymerization 23 density of
copolymer 78 end-use 7379 estimating parameters 459 for polymers 58 input language 45660 intrinsic
viscosity 77 melt index 8, 78 melt index ratio 79 method of instantaneous 60 molecular structure 23
molecular weight 23 molecular weight 8 moments of molecular weight
distribution 23 particle size 55 polymer structural 33, 55 prop-set 73 segment composition 23
specifying data 458 viscosity 8 zero-shear viscosity 77 Property distributions
bimodal 56 bivariate 55 most-probable 57 multimodal 56 Schulz-Flory 56 Stockmayer bivariate 58
structural 5572 types 55 unimodal 56
Property methods
input language 456 Property parameter databanks 11 Property set See also Prop-Sets Prop-Sets
adding 79 custom 76 defining 74 for data regression 347 for polymers 74 properties 73 uses 73
Propylene
processes 228, 229 Pseudocondensation reactions 103 Pump 300 Pure components
databank 25, 387 Purification
monomer 292 process step 29293 PVA See Polyvinyl alcohol
Q
QSSA See Quasi-steady-state
approximation Quasi-steady-state approximation
188
R
RadFrac
about 301 attribute handling 337 input variables 347 results variables 347 Radiation initiation reaction 173
Radicals
absorption 210 balance 20711 consumption of 6162 depletion 208 desorption 210 generation 208
generation of 61 rate of production 208 termination 210 Random scission 104 Rate constant parameters
data-fitting 294
522 Index
Rate constants
assigning to emulsion reactions
221 assigning to ionic reactions 262 assigning to step-growth reactions 158, 159 assigning to Ziegler-
Natta
reactions 246 data fitting 339 emulsion 214 for melt polycarbonate 123 for model generated reactions
135 for nylon-6 113 for nylon-6,6 118, 119 for polyesters 109 for user-specified reactions 139,
288 free-radical 170 ionic 254 kinetic parameters 43144 segment-based 270 specifying for segment-
based
power-law reactions 288 specifying for step-growth user
reactions 159 step-growth 153 user subroutines 144, 279 Ziegler-Natta 236 Rate expression
step-growth 133, 138 RBatch
about 32735 attribute handling 337 batch reactors 330 common problems 335 cycle time 331 duty 327
dynamic scaling 332 hybrid scaling options 333 input variables 346 pressure 328 profile data 350
residence time 329 results variables 346 scaling options 332 semi-batch reactors 330 solver method 334
specifying user profiles 197 static scaling options 332 step size 334 streams 330 temperature 327
troubleshooting convergence
33135 volume 329 RCSTR
about 30417 algorithm 308 attribute handling 337 calculation loops 309 calculation table 309 common
problems 316 component scaling 313 condensed phases 305 convergence 308 duty 305 effective hold-
up 305 external heat exchanger 307 horizontal partition 306 hybrid initialization 315 initialization options
314 input variables 346 integration initialization 314 multiphase 305 non-ideal mixing 306 pressure 305
residence time 305 results variables 346 scaling options 313 single-phases 305 solver initialization 314
substream scaling 313 temperature 305 troubleshooting convergence
31517 vertical partition 307 with dead zone 308 Reacting phase
specifying for segment-based
power-law model 286 specifying for step-growth 160 Reacting polymers 266 Reaction models
Aspen Plus 86, 35965 available 35965 basic unit operation 295 built-in 85 custom 86 distillation 296,
301 Dupl 29698 equilibrium 304 Flash2 298 Flash3 298 fractionation 296 FSplit 299
Index 523
generic 86 Heater 299 kinetic 30435 mass-balance 3024 Mixer 299 Mult 299 Pipe 300 Pump 300
RadFrac 301 RBatch 32735 RCSTR 30417 reactor 296, 302 REquil 304 RGibbs 304 RPlug 31727
RStoic 302 RYield 303 Sep 301 Sep2 301 stream manipulators 295 treatment of component attributes
33537 Reactions
active species 254 adding emulsion 221 adding free-radical 194 adding ionic 261 adding segment-based
287 adding user 159 adding Ziegler-Natta 246 addition 103 aggregation 256 assigning emulsion rate
constants 221 assigning ionic rate constants
262 assigning step-growth rate
constants 158 assigning user rate constants
159 assigning Ziegler-Natta rate
constants 246 association 256 backbone 269 beta-scission 183 bifunctional initiator
decomposition 174, 175 branching (segment-based) 270 branching (Ziegler-Natta) 240 catalyst
preactivation 237
catalyst site activation 237 catalyzed initiation 171, 173 chain initiation (free-radical 171 chain initiation
(ionic) 255 chain initiation (Ziegler-Natta)
237 chain scission 269 chain termination (free-radical)
17879 chain termination (ionic) 257 chain transfer (free-radical) 178 chain transfer (ionic) 257 chain
transfer (Ziegler-Natta)
239 chain-growth 83 classifying 81 cocatalyst poisoning 240 combination 104, 270 condensation 103
conventional species 268 coupling 258 cross linking 270 cyclodepolymerization 104 depolymerization 269
editing emulsion 221 editing free-radical 195 editing ionic 261 editing segment-based 287 editing user
159 editing Ziegler-Natta 246 electrophilic 101 emulsion polymerization 204 end group reformation 104
equilibrium with counter-ion 256 exchange 256 for step-growth polymerization
126 free-radical polymerization 165 homogeneous nucleation 204 including user 158 induced initiation
171, 173 Inhibition 181 initiator decomposition 171, 172 intermolecular 103 intramolecular 103 ionic
polymerization 252 latex 207 melt polycarbonate kinetics 122
24 micellar nucleation 201
524 Index
micellar nucleation (figure) 202 modification See Segment-based
reaction model nucleophilic 101 nylon-6 kinetics 111 nylon-6,6 kinetics 115 particle growth 206
polyester kinetics 10511 polymerization 81 propagation (free-radical) 176 propagation (ionic) 255
propagation (segment-based)
270 propagation (Ziegler-Natta) 238 pseudocondensation 103 radiation initiation 173 radical balance
207 rearrangement 104 reverse condensation 103 ring addition 104 ring closing 104 ring opening 104
side group 269 site deactivation 239 site inhibition 240 specifying segment-based 285
89 specifying user rate constants
159 spontaneous initiation 173 step-growth 83 step-growth functional groups
128 step-growth polymerization 104 step-growth rate constants 157
58 supplied by emulsion model 215
18 supplied by free-radical model
18590 supplied by ionic model 258 supplied by segment-based
model 273 supplied by step-growth model
13337 supplied by Ziegler-Natta model
243 terminal double bond 240 termination (free-radical) 178
79 termination (ionic) 257 thermal initiation 173
types affecting catalyst states
230 user-specified step-growth 138
40 viewing emulsion 220 viewing free-radical 194 viewing ionic 261 viewing segment-based 287
viewing step-growth 157 viewing Ziegler-Natta 245 Ziegler-Natta polymerization 232 Reactor models
about 302 available 296 data sets 350 equilibrium 304 input variables 346 kinetic 30435 mass-balance
3024 results variables 346 Reactors
condensed phase RCSTR 305 convergence problems for
RBatch 33135 convergence problems for RCSTR
31517 convergence problems for RPlug
32327 displaying distribution data 70 distribution 65 horizontal partition 306 multiphase RCSTR 305
multiphase RPlug 320 RCSTR algorithm 308 single-phase RCSTR 305 vertical partition 307 with dead
zones 308, 321 with external heat exchanger
307 with injection ports 322 Rearrangement reactions 104 Recovery/separation 9, 293 Redox initiation
212 Regression See Data regression Reports
for user models 365 step-growth options 160 REquil
about 304 attribute handling 337 Residence time RBatch 329 RCSTR 305
Index 525
RPlug 319 Results variables
Flash2 347 Flash3 347 MultiFrac 347 RadFrac 347 RBatch 346 RCSTR 346 RPlug 347 standard
deviations 351 Reverse condensation reactions
103 Rgibbs
about 304 RGibbs
attribute handling 337 Ring addition reactions 104 Ring closing reactions 104 Ring opening reactions
104 Routines
USER2 362 RPlug
about 31727 attribute handling 337 common problems 326 duty 318 dynamic scaling 323 hybrid scaling
325 input variables 347 multiphase 320 non-ideal mixing 320 pressure 319 profile data 350 residence
time 319 results variables 347 scaling options 323 solver method 325 specifying user profiles 197 static
scaling options 323 step size 325 temperature 318 troubleshooting convergence
32327 with dead zone 321 with injection ports 322 Rstoic
about 302 RStoic
attribute handling 337 Ryield
about 303 RYield
attribute handling 337
S
Salt
aqueous solutions 98 preparation 98 Scale factors about 50 specifying 53 Scaling
factors 453 Scaling factors
component (RCSTR) 313 dynamic (RBatch) 332 dynamic (RPlug) 323 hybrid (RBatch) 333 hybrid
(RPlug) 325 RBatch 332 RCSTR 313 RPlug 323 static (RBatch) 332 static (RPlug) 323 substream
(RCSTR) 313 Schulz-Flory distribution 56 Scission 104, 269 Secondary esterification 91 Seed process
206 Segment approach 27 SEGMENT databank
about 11, 26, 391 components 392429 nomenclature 391 Segment flow 35 Segment fraction 35
Segment-based model
assigning rate constants 288 including user rate constant
subroutine 289 Segment-based power-law model specifying reacting phase 286 user subroutines
27484 Segment-based reaction model
about 26590 accessing 285 adding reaction schemes 287 adding reactions 287 applications 265
526 Index
assumptions 272 backbone modifications 269 branch formation 270 chain scission 269 combination 270
conventional species 268 cross linking 270 depolymerization 269 editing reactions 287 features 272
including user basis subroutine
289 industrial processes 266 input language 5015 kinetics 270 mole fraction conversion 272
nomenclature 271 propagation 270 properties calculated 273 rate calculations 273 rate constants 270
reaction categories 26772 reactions allowed 26772 side group modifications 269 specifying model 285
specifying pre-exponential units
288 specifying rate constants 288 specifying reaction settings 285 Segments
composition 15, 33 copolymers 16 definition 24 homopolymers 15 methodology in Aspen Polymers
27 mole fraction 272 molecular structure 392429 nomenclature 391 property parameters 391
sequence 15 specifying 29 structure 15 types 24 Semi-batch reactors 330 Semi-crystalline copolymer
density
78 Sensitivity blocks 377 Sep
about 301 attribute handling 336 Sep2
about 301
attribute handling 336 Separation/recovery 9, 293 Side group modifications 269 Simulations
dynamic 10 templates 382 Site activation 237 Site deactivation 239 Site inhibition 240 Site-based
components
about 24 attributes 44 specifying 30 Slurry process 227, 228 Smith-Ewart theory 211 Solid-state models
96 Solid-state processes 84 Solution polymerization 85, 164 Solution process 227 Solution processes 84
Solver methods RBatch 334 RPlug 325 Specifying
additional simulation options 13 Aspen Polymers options 38182 attribute scaling factors (input
language) 453 catalysts 44851 component attributes 5153 component attributes (input
language) 45153 component attributes in blocks
52 component attributes in streams
52 component names 447 components 12, 28 components (input language)
44751 conventional component attributes 52, 451 data fit 34044 data regression 34558 databanks
28 distribution calculations 6971 distribution calculations (input
language) 454 distribution characteristics 69 emulsion calculation options 222 emulsion kinetics 219
23 emulsion kinetics (input language) 47784
Index 527
emulsion model 219 emulsion rate constants 221 emulsion reacting species 220 end-use properties 79
end-use properties (input
language) 45456 feed streams 13 fixed process variables 377 flowsheet options 12 free-radical
calculation options
196 free-radical kinetics 19397 free-radical kinetics (input
language) 46777 free-radical model 193 free-radical reacting species 194 gel-effect 196, 222 global
simulation options 12 ionic kinetics 26062 ionic kinetics (input language)
494501 ionic model 260 ionic rate constants 262 ionic reacting species 260 oligomers 30, 44851
particle growth parameters 223 phase partitioning 222 physical properties (input
language) 45660 point data 349 polymerization kinetics 13 polymers 29, 44851 pre-exponential
units 160, 288 profile data 350 property data 458 property models 13 reacting phase 286 regression
cases 351 scale factors 53 segment-based reaction model
285 segment-based reaction rate
constants 288 segment-based reaction scheme
287 segment-based reaction settings
285 segment-based reactions 28589 segment-based reactions (input
language) 5015
segments 29 site-based components 30 standard deviations 351 step-growth components 156 step-
growth kinetics 5153 step-growth kinetics (input
language) 46067 step-growth model 156 step-growth rate constants 157
58, 158, 159 step-growth reacting phase 160 step-growth report options 160 stream attributes 451
UOS model operating conditions
13 user models 35973 user profiles 197 user step-growth reactions 158 Ziegler-Natta kinetics 244
47 Ziegler-Natta kinetics (input
language) 48493 Ziegler-Natta model 244 Ziegler-Natta rate constants 246 Ziegler-Natta reacting
species
245 Spontaneous initiation reaction 173 Spreadsheets
incorporating in flowsheets 376 SSplit
attribute handling 336 Standard deviations 351 Starting
Aspen Polymers 38182 Startup files 382 Steady-state models
data fitting 294 features 294 flowsheeting 29194 tools 294 unit operation 295338 unit operations 294
Step-growth polymerization
accessing model 155 adding user reactions 159 addition processes 266 applications 89 Aspen PolyQuest
96 assigning rate constants 135,
139, 158, 159 batch PET 9395
528 Index
built-in reaction listing 157 commercial polymers 83 comparison to chain-growth 82 continuous PET 90
93 editing user reactions 159 electrophilic reactions 101 functional groups 128, 129 including user basis
subroutine
161 including user kinetic subroutine
161 including user rate constant
subroutine 161 including user reactions 158 industrial processes 90 input language 46067 interfacial
84 kinetics 10124 melt phase 84 melt polycarbonate reaction
kinetics 12224 model 89162 model features 12427 model predictions 124 model structure 12755
model-generated reactions 133
37 nomenclature 103 nucleophilic reactions 101 nylon 96100 nylon-6 reaction kinetics 111 nylon-6,6
reaction kinetics 115 oligomer fractionation 131 overview 83 PBT 95 PEN 95 phase equilibria 126
polycarbonates 100101 polyester reaction kinetics 105
11 polyester technology package 95 polyesters 9096 PPT 95 rate constants 122, 133, 153 rate
constants example 153 rate expression 133, 138 reacting groups 127 reacting species 127, 130 reaction
mechanism 126 reaction stoichiometry 132 reactions 104 solid-state 84 solid-state models 96
solution 84 specifying components 156 specifying model 156 specifying pre-exponential units
160 specifying rate constants 157
58, 159 specifying reacting phase 160 specifying report options 160 specifying subroutines 161 user
reactions 138 user subroutines 14055 Stockmayer bivariate distribution
58 Stoichiometry
step-growth 132 Streams
continuous batch charge 330 defining feed 13 displaying distribution data 70 distributions 67 initializing
attributes 451 manipulating 295 MIXED variables 380 processing in user models 361 RBatch 330 time-
averaged continuous reactor product 331 time-averaged continuous vent
product 331 time-varying continuous feed
330 variables for data regression 346 Structure
of components 22 of monomers 15 of oligomers 15, 23 of polymers 1519, 19, 23 of segments 15, 24
propertyend-use relationship 75 Styrene 199 Subroutines
fortran arguments 445 including user basis 161, 289 including user kinetic 161 including user rate
constant 161,
289 local work arrays 155, 284 updating component list 154 user 14055, 27484 user basis 140,
272, 275 user forms 156 user gel effect 189
Index 529
user kinetic (example) 366 user kinetics 149 user property (example) 371 user rate constant 144, 279
support, technical 3 Suspension polymerization 85 Synthesis
monomer 292 polymer 293
T
tacticity 35 TDB See Terminal double bond technical support 3 Temperature
in RBatch 327 in RCSTR 305 in RPlug 318 Templates
custom 382 fortran 383 simulation 382 Terminal double bond reactions
240 terminal double bonds 35 Terminal models
free-radical 169 Ziegler-Natta 236 Terminal monomer loss 104 Termination
between chain radicals 181 bimolecular 181 by combination 180 disproportionation 180 free-radical
polymerization 178
79 inhibition 181 Tetrafluroethylene 199 Thermal initiation reaction 173 Thermoplastics 16 Thermosets
16 Tips
configuration 382 data regression 35355 Transesterification 92 Trommsdorff effect 188 Troubleshooting
Aspen Polymers 38386 convergence (RBatch) 33135
convergence (RCSTR) 31517 convergence (RPlug) 32327 data regression convergence
35355 diagnostic messages 365 RBatch common problems 335 RCSTR common problems 316
RPlug common problems 326 simulation engine 385 user interface 383
U
Unimodal distributions 56 Unit operation models 11 Unit operations
Aspen Plus models 35965 available models 35965 basic models 295 calculations 364 diagnostics 365
distillation models 296, 301 Dupl 29698 equilibrium reactor models 304 features 294 Flash2 298 Flash3
298 fractionation models 296 FSplit 299 Heater 299 input variables 346 kinetic reactor models 30435
mass-balance reactor models
3024 Mixer 299 Mult 299 Pipe 300 property calculations 364 Pump 300 RadFrac 301 RBatch 32735
RCSTR 30417 reactor models 296, 302 reports 365 REquil 304 results variables 346 RGibbs 304 RPlug
31727 RStoic 302 RYield 303
530 Index
Sep 301 Sep2 301 steady-state models 295338 stream processing 361 treatment of component
attributes 33537 user model calculations 36065 user model structure 359 user models 35965
variables for data regression 346 USER 359, 365 User attributes
properties tracked 45 User fortran
arguments 445 linking 383 templates 383 User models
about 35973 calculations 36065 component list 154 diagnostics calculations 365 integer parameters
154, 284 kinetic 36569 packed vectors 155, 284 physical property 37073 property calculations 364 real
parameters 154, 284 reports 365 stream processing 361 structure 359 unit operation 35965 unit
operation calculations 364 USER block 359 USER2 block 359 User profiles
for emulsion polymerization 218 specifying 197 User prop-sets 76 User reactions
adding step-growth 159 assigning rate constants for
step-growth 159 editing step-growth 159 for polyesters 110 nylon-6 113 nylon-6,6 119 specifying rate
constants for
step-growth 159 specifying step-growth 158 step-growth polymerization 138
40 User routines
fortran linking 383 User subroutines
segment-based power-law model
27484 step-growth polymerization 140
55 USER2
about 359 model routine 362
V
Vacant sites 44, 231 Variables
accessing flowsheet 37880 indirect manipulation 347 input 346, 349, 350 results 346, 349, 350 standard
deviations 351 Vectors
packed 155, 284 Viewing
emulsion reactions 220 flowsheet variables 37880 free-radical reactions 194 ionic reactions 261
segment-based reactions 287 step-growth reactions 157 Ziegler-Natta reactions 245 Vinyl chloride 199
Vinylacetate 199 Viscosity
as polymer property 8 intrinsic 77 zero-shear 77 Volume
in RBatch 329
W
web site, technical support 3 Weight average
chain length 63 degree of polymerization 57
Z
Z-average
degree of polymerization 57 Z-average degree of
polymerization 35 Zero-shear viscosity 77 Ziegler-Natta
component attributes 44
Index 531
Ziegler-Natta catalysts
about 24 attributes 44 component attributes 33 dead sites 45 inhibited sites 45 occupied sites 45 potential
sites 44 properties tracked 44 specifying 24 vacant sites 44 Ziegler-Natta polymerization
accessing model 244 adding reactions 246 applications 225 assigning rate constants 246 built-in reaction
listing 245 catalyst preactivation 237 catalyst reactions 230 catalyst site activation 237 catalyst states 230
catalyst types 226 chain initiation 237 chain transfer to small molecules
239 cocatalyst poisoning 240 copolymerization steps 236 editing reactions 246 ethylene processes
227 gas-phase process 227, 228 industrial processes 226 input language 48493 kinetics scheme 230
42 kinetics scheme (figure) 232 liquid process 228 model 22547 model assumptions 243 model features
243 nomenclature 234 phase equilibria 243 polyethylene processes 227 polypropylene process types 228
propagation 238 properties calculated 243 propylene processes 228, 229 rate calculations 243 rate
constants 236 rate expressions 236 reactions 232 site deactivation 239
site inhibition 240 site types 231 slurry process 227, 228 solution process 227 specifying model 244
specifying reacting species 245 steps 235 terminal double bond 240
532 Index

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Aspen Polymers

Unit Operations and Reaction Models

About This Documentation Set

Aspen Polymers Guides

Aspen Plus Guides

Aspen Dynamics Guides

About Aspen Polymers

Polymer Molecular Bonds

Polymer Manufacturing Process Steps

Monomer Synthesis and Purification

Aspen Polymers Tools

Polymer Physical Properties

Defining a Model in Aspen Polymers

Polymer Types by Physical Structure

Polymer Structural Properties

Pure Component Databank

Defining Component Names and Types

Specifying Site-Based Components

Structural Properties as Component

Component Attribute Classes

Polymer Component Attributes

( )i 0 1 Mole flow SMOM

1 - ---- 2 1 Mole flow SCB SCB Number of short chain

Flow rate of diene

38 4 Polymer Structural Properties

( )i 0 1 Mole flow AFMOM

1 (, i j ) ( ) Segment mole fraction in

1 (, i j ) ( )j Second moment of chain

Site-Based Species Attributes

Zielger-Natta Catalyst attributes

Ionic Initiator Attributes

Component Attribute Initialization

Component Attribute Scale Factors

Specifying Component Attributes

Specifying Polymer Component Attributes

Specifying Site-Based Component Attributes

Initializing Component Attributes in Streams or Blocks

Property Distribution Types

Schulz-Flory Most Probable Distribution

Distributions in Process Models

Average Properties and Moments

when the property is a discrete variable, and by a

for the frequency function

. Weight or Volume average is the ratio of

. Z-average is the ratio of third to second

= Number of moles of polymer of length n

Method of Instantaneous Properties

Radical Generation and Consumption Rates [ R

Instantaneous Distribution Parameters

Where: 1 1/( + ) = Probability of growth for a polymer radical

Chain Length distribution equation

The instantaneous number-average chain length distribution is given by:

Plug Flow & Batch Reactors

Distributions in Kinetic Reactors

Calculating Distribution Increments

Where i varies between one and the specified number of points N

, and upper is the user-

For multi-site kinetics:

for multi-site kinetics.

Calculating Cumulative Distributions

Distributions in Process Streams

= Y-axis value of distribution element i

= X-axis value of distribution element i