--

POLnlER REACTOR DESIG~~OPTI:llIZATIO:" A:"P CO:"'!'ROL

(:" LATEX PRODUCTIO:" TECH:"OLOGY

by

ALEXA:"DER PE:"LIDIS. DlPL. OIDI. E"G

A Thesis

Submitted to the School of Graduate Studies

in Partial Fulfilment of the Requirements for the DeRree

Doclor of Philosophy.

@ Sc?tember, 1986
 ..
LATEX PRODliCTIO:" TECH:"OLOGY - REACTOR DESIG:" CO:"SIDERATIO:"S

..,.-

....
~

"Research cun represent the revoltof man a~ain$'fthc

conditions of life, against creation itself At the same

time, it is an aspiration, toward clarity even,

paradoxically, toward order and unity !,f thought

thought that rcc?gni=es limits",

An effort by the author to paraphrase Albert Camus

~tOus YOVl:1S llOU KOI

atT] }.lV~}.l~ Eu8u}.llOU

llanaOonou.\ou

,
DOCTOR OF PHILOSOPHY ~c:'o1ASTER U:"IVERSITY

(Chemical Engineering) . Hamilton, Ontario

TITLE Polym~r RellctorDesign, Optimi:ation and Control in Latc.x

Production Technology,

".-
'. .,

ACTHOR: Alexander Penlidis, Pip!. Chem. Eng. (Aristotle University oC

Thessaloniki: Greece)
- "

SUPERVISORS: ProCessorJ.F. :'olacGregor; ProCessor A,E. Hamielec

~UMBER OF PAGES: xxvi,438

,"

II
 --

ABSTRACT

During continuous emulsion polymerization of many monomers (e.g. vinylacetlite.

vinyl chloride). sustained oscillations (limit cycles! OCcur in conversion and all the late" and

pol~'mer properties. This creates severe problems with the commercial application of

continuous reactors. As shown by Pollock (1984) advanced control theory is inadequate for

controlling these reactors. However, it was shown that the limit cycle behaviour could be

eliminated through redesign of the reactor train configuration. The redesigned production

trIli.'1 was shown via simulation to be free of oscillations and to oITer greatly increased

flexibility in controlling particle si:e and monomer conversion.

In this thesis the mathematical model of Kiparissides 1I97S) and Pollock 1I9S~1.

based on a particle age distribution analysis and incorporating detailed chemistry and

physics of the polymeri:ation phenomena involved, is modified and is used to simulate the

dynamic behaviour of these reactol';'1bf different modes of process operation tbatch, semi-

batch and continuous train) and monomer systems (PVAc, PV d.

Experimental studies which demonstrate. the improved dynamic performance of

the redesigned reactor system are carried out in a pilot plant stainless steel reactor train with

onli..'1e monitoring of monomer conversion with a set of on- line densitometers. Control of the
-- .
final1atex pa.~icle si;:e and conversion is achieved through manipulation of the initiator feed

rate to the first particle nucleating reactor, and the split of the monomer'and water fiow rates

between t..~e fU"St two reactors of the train.

The effect of monomer "rid water soluble impurities on the emulsion

.polymerization of Case I monomers is further investigated both theoretically and

experimentally. E:cper:.rnental iden:ificatior~ a..~ci "'erification of the ::lain source of stochastic

tll
 .----..

. .

ACKNOWLEDGEMENTS

I wish to thank Drs. J.F. MacGregor and A.E. Ha'l'ielec for their guidance,
'"'Patience, confidence
. and encouragement throughout this work. Thanks are also due to

Dr. G.A. Irons for his service in the dissertation committee, and to the staff of the Engineering
_
.. -

Word Processing Centre for t~lling this manuscript. :\1y gratitude is extended to Drs. O.

.Chiantore, H.A. ~1eyer and N.T. Ali for their lively dis<:ussions during the numerous aspects

of this research. I particularly ....i sh to thank the :\1d1aster Institute for Polymer Production- "
Tec~ology(~lIPPT) for pro~-iding facilities for this project. To Pavlos and Vina Kanaroglou I

wish to e:q>ress m~' appreciation for their help and friendship through many years. To the

Department of Chemical Engineering, McMaster university, I wish to express my gratitude

for pro,-iding finll.llcia! support. Finally my everlasti.'1g love goes to my parents and sister, for

their support throughout my many years of study.

..
. .
\
 TABLE OF CO"TE),'TS

Page

DESCRIPTIVE "OTE ii
ABSTRACT III
ACK"OWLEDGE~IE:\"TS l\'
TABLE OF CO"TE)'"TS v
LIST OF FIGURES
LIST OF TABLES "
:'(\"1
"OME"CLATURE ::tVll

CHAPTER 1: I:\"TRODCCTI01\ .-\;.'D OBJECTIVES 1

CHAPTER 2: ~1ATHD1ATICAL ~IODELLI"G OF E~It:LSIO" 5

HOMOPOLDIERIZ.",TIO" REACTORS

2.1 Introduction 5
2.2
2.2.1
~lodels for Emulsion PolymeriUltion
t:ses oDlodels
....,,I .9
6

2.3 ~lodel Development I 10

I
J
2.3.1 General 10
.... ....
""" .,) ~laterial Balances 11
2.33 Population Balance Approach .11
') .....
.... .,)."'t
I
Particle Size Development . 12
2.3.5 . ~lolecular Weight Development 12
2.3.6 Vinyl Acetate ~lathematical~lodel 12
2.4 ~lodel Parameter Estimation 16
2.5 Particle Size Distribution Determination 16
2.5.1 General 16
2.5.2 Population Balance Approach PSD 16
2.6- . Conclusions 21

CHAPTER 3: L.-\TEX AXD POLD1ER PROPER'l'Y CHAR.-\CTERIZATIO"

A"D ~IEASCRE~IE"T~IETHODS
23 .-
3.1 Introduction 23
3.2 Dete:m.ination of Conversion 25
3.2.1 Off-lL"le Cra...imetry 25
3.2.2 On-lL"1e Der-.sitorneti:- 2S
3.2.3 Comments on Conversion Determinatil.'n 29
3.3 Particle Size Detenni..'12.tion: Turbidity Spectra 30
3.3.1 Experime"tcl 32
304 Pa..~c!e Size Determi.'12.tion: HydrodynaI':'lic a.,,,d 33
Size Exclusion Chromatography of Particle Sus-pensions
3.4.1 General 33
3.4.2 Introduction 33

v.
 ..

Page

3.4.3 Review of Experimental Investigations 34

3.4.'l SummaryofMuin Observations -----42"
3.4.5 Detection of Colloidal Particles . 44
3.4.6 Theoretic:al Analysis ofPellk-Sepm-ation 48
3.4.7 Calculation of Particle Si:e Distributions 54
3.4.8 Experimental 6S
3.5 Monitoring of Emulsion Polymeri:ation Reactors by 69
Turbidity Spectra and Si=e Exclusion Chromatography
3.5.1 Latex Particle Si=e Determination by Turbidity Spectra 70
3.5.::l Discussion ofTurbidity Results 70
3.5.3 Latex Par'".icle Si:e Determination by SEC i3
3.5.4 Discussion orSECResults 73
3.5.5 Concluding Remarks on Turbidity Spectra and SEC 75

"
.-
'3.6
S.6.1
3.7 -I
. Particle Si:e Determination: Electron :'1icroscopy
. Experimental --
75
I Particle S::e DetermiI1lltion: Other :'leasurement :'lethods. 78
,,
.J
3.8 :'101ar :'lass :'leasurements 78
3.8.1 Light Scattering 79
3.5.2 Low Angle Laser Light Scattering lL.-\LLSPl 83
3.8.3 On-line SEC-LALLSP 84
3.9 Conclusions 85

CHAPTER 4: BATCH REACTOR STUDIES - PVAc 86

Introduction 86
...~
4.1
~ Batch Reactor :'lodel 87
4.2.i Xumerical Values of:'lodel Parameters and 88
Rate Coefficient Expressions

..."
.~~
"t ...... :'lodel Parameters and Parameter Estimation 89
, Application oOladel Equations 94
. 4.3.1 Comparison oOlodel Predictions with Literature Data 94
Comparison oOladel Predictions with Experimental 96

.
.....
4.5
Results :'leasured Herein
Discussion of Experimental Run'
ConClusions
98
1::l5
\',.",
CHAPTERS: SE:'lI-BATCH C~l'ROL POLICIES FOR THE PARTICLE SIZE 1::l6
.DlSTRlBLl'IOX

5.1 Introduction 1::l6

5.2 .~., Interesti.."lg Control Proble:n 1::l6
5.3 A Possible Approac..':l to Controlli:lg the PSD 1::l9
5.~ Extension of Stage 1 133
5.5 Emulsifier Feed Rate Policy 137
5.6 Conclusions 141

vi
 Page

CHAPTER 6: COl'OTROL OF POLniERlZATlON REACTORS 142

6.1 Introduction 142

6.2 General Trends 142
6.3 Polymeri:ation Models loU-
6.3.1 Homogeneous Polymeri:ation (Bulk and Solution) 145
6.3.2 Heterogeneous Polymeri:ation (Emulsion. 146
Precipitation:Solid Cataly::ed Ionic)
6.4 :'.1casurements 147
6.4.1 :'.1easuremcnts for Reactor Operation 14S
6.4.2 Polymer and Late>: Property :'.leasurements 1~9
6.5 Batch and Semi-Batch Reai:tor Control 151
6.5.1 :'.1olecular Weight Distribution Control 151
6.5.2
6.5.3
6.5.4
Conversion :md Composition Control
Long Chain Branching Control
Particle Si::e Distribution Control
" 153
155
156
6.5.5 Temperature Control 157
6.6 Continuous Reactor Control 1~
6.6... Steady State Optimi::ation ISS
6.6.2 Dynamic Optimi::ation 159
6.6.3 Reacto'r Design Optimi::ation 161
6.6.4 On-line State Estimation .161
6.6.5 On-li:1e Control 163
6.7 Conclusions 165

CHAPTER 7: CONTL,UOT;S REACTORS: DESIGN AND CONTROL 166

CONSIDER.-\TIONS FOR CSTR TR.-\INS

7.1 Introduction 166

Oscillations in Conventional CSTR's 167
7.~.1 An E:tplanation of the Phenomeon 167
7.2.2 Possible Solutions to the Oscillation Proble::! 1-'
"
7.3 A Split-feed Seeding Reactor Design 176

.-- 7.3.1
-,
".&f

i.5
7.6
The Effect of Process Control Variables
S>:perimental Set-up
Discussion oi"the E:cperi:nental Results
Conclusions
lSI
IS3
IS6
201

 Page

CHAPTERS: EXTENSIO!"S OF THE MODEL TO THE PRODUCTION OF 204

POLYMER A.lI;D COPOLYMER LATEXES OF VINYL
CHLORIDE ~

S.l Introduction , 204

S.2 Emulsion Polymerization of Vinyl Chloride 205
S.3 PVC Latex Reactor ~fodel Development- 207
Dynamic CSTR
8.3.1
8.3.2
Homopolymeri:ation Case
Copolymeri;ation (VC:\WAc) C~
207
208
804 Model Applications and Discussion 208
804.1 Batch Reactors . 209
804.2 .Semi-batch Reactors ,216
SA.3 Continuous Reactors 21S
8.5 Conclusions '. 230

CHAPTER 9: IMPL"RlTY EFFECTS IN CASE I DfULSION POLnmRIZATIO:s' 232

9.1 Introduction 232

9.2 Impurity Effects in Emulsion Polymeri"ation: 233
Literature Re\'i~w .
9.3 Impurity Effects in Case II Systems.
9.4 Case I Systems: :\fodelling Impurities
9.4.1 ~fodelimpurity Pa..ooameter Values 238
9.5 Case I Systems: Simulations "'ith Impurities 238
9.6 Discussion of the Experimental Plan 244
9.7 Discussion of Experimental Results 246
9.7.1 Impurity Runs: Conversion 249
Q-~
_. j ..... Impurity Runs: Pa..-ticle Si"e 256
9.8 General Prescriptions fOl"Case I and II Systems: 261
Impurity Effects

CHAPTER 10:
9.9 Conclusions
t
FINAL CONSIDERATIONS CONCER:s'ING THE ON-LINE
CONTROL OF Dll;'LSION POL Y~lERIZATION REACTORS,
262

GENERAL RECmmENDATIONS AND CONCLCDL,G

RE~Lo.RKS .

10.1 lnt..~uc:tion
10.2 Part 1: On-line Control ofE:nulsion Processes 265
10.2.1 Gene:-al 265
10.2.:! Kaloa.'"'l Fnte:-s for E:=t:.lsio:1 Polyme~~tion Syste::1s 266
10.2.3 Application of Ka1:::1a."'l FUters to the Two Reactor. 2'71
Syste=.
10.2.4 The ?o::.ential for On-1L'"'le ?;l~cle Sl::e:'1easu:"e~ent 2'75
10.2.5 Fi..."'l:ll Ste?~, E=ulsion Rea~o!." Con::-ol ~77
10.3 ?:l:"'t 2: <Y:..he:- Genc:"2.1 Ft:.tu:-e Recc:=':::1enc.a::ons 279
:0.4 p~ 3: CO:'lduc..:..~g Rc-"1"ks 282

\~.,
 \

Page

" " REFERENCES 284

APPENDIX I: Model Derivation" 302

APPENDIX II: ~ne~al Compute~ Flowchut 346
APPENDLX III: Population Balance Nume~ical Calculation orPMticle Size " 347
Distributions
APPENDIX IV: Othe~ PSD Measu~ement Methods 351
APPEoNDIX V: P~ocedure fo~ Molecula~ Weight Dete~mination by LALLS 354
APPENDIX VI: " :\lodel Pa~amete~ Values 363
APPENDIX VII: Operating P~ocedu~e fo~ :\HPPT Batch Reacto~s 384
APPENDIX VIII, Batch PVAc Results ".. 389
APPENDIX IX: Redox Initiation System 393
APPENDIX X: Continuous Runs Experimental Information 400
i'-o\PPENDIX XI: Safety Considerations .412
.o\PPENDIX XII: "Continuous PVAc Runs Data Recoro 418
APPENDIX XIII: -" VCMIVAi Emulsion Copolyme~i:ation 424-
APPENDIX XIV: :\lodel :\lodification to Include Impurities 432
.o\PPENDIX XV, Data of Batch VAc Impurity Runs 436

/
/

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:.x
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.' .
LIST OF FIGURES

Figure Page

(2-1) Schematic'Representation of Relationship (2.33) 20

(31) Applicable Range of the Most Common. Particle Size 26

Analytical Techniques

(3-2) Dependence of Rr on Latex Particle (D) and Packing Diameter criJ 37

(3-3) Effect oflonic Strength of the Eluant on the Rr OfPolyst)Tene 38

Latexes (Eluant Concentrations in gmoles ofNaCI per liter:
A. 1.76:<10- 1;B. 9.x10- 2 ; C. 2.96x10- 2; D, 4.6x10- 3;
E, 1.'x10- 3; F, 4.25x10- 4 )

(3-4) HDC Separation of a Biomodal ~1i.<ture oiBS nm and 1,6 nm Polystyrene 46

Latexes (A, Response at 200 nm; B, Response at 254 nm)

(3-5) Flow-through-bank Model of a SEC Column 52

(3-6) Estimation of the Spreading Function from Experimental . 60

Chromatogram (55 nm Sample)

(3-,) Estimation of the Spreading Function from Experimental 61

Chromatogram (109 nm Sample)

(3-5) Estimation of the Spreading Function from E:qJerimental 62

Chromatogram (l,6 nm Sample)

(3-9) Variance 0 2 I."ersus Particle Diameter, Equation (3.36) 63

(3-10) Coefficient A3 I."ersus Particle Diameter. Equation (3.36) 64

(3-11) Specific Turbidity Beha\"iourfor Runs BR" BRIO and BRll ,1

(3-12) Specific Turbidity I."ersus Conl."ersion for Runs BR, and BR5 72

(3-13) Diameters Corresponding t,;peak Retention Volumes for -.

I~

Runs BRIO and BRII

(3-1~) A Typical Light Scattering Experiment 82

 Figure Page
~
(4-1) Batch VAc Emulsion Polymerization Model Predictions for 95
(a) Particle Diameter (b) Surfll,.ce Area and (c) .Particle Volume

(4-2) (a) Average Particle Diameter and (b) Conversion versus Reaction 99
time for a Soap-free Case

(4-3) Batch Emulsion VAc: Conversion vs. Time for Two Different
101
Emulsifier Concentrations

(';"41 Blitch Emulsion VAc: Conversion vs. Time for Two Different 102
Initiator Concentrations

(';"5) Batch Emulsion VAc: (a) Conversion vs. Time 103

(b) ;:-';umber of Particles vs. Conversion

(';"61. . Batch Emulsion VAc: Diameter vs. Conversion for Two Different 107
Emulsifier Concentrations

t';" 7) Batch Emulsion 'lAc: ;:-';umber and Weight Average :Molecular 108
Weights vs. Conversion

(';"S) Schematic Representation of the Experimental Set-up for the Batch Runs 109

(';"9) (a) Run BR2 and (b) Run BR3: On-line Densitometer Conversion
\s. Time
112-113.
. .. ,

(';"10) On-line Densitometry: (a) Run BR4 (b) Runs BR2, BR4 and BR5. 115
. Induction Time Effects

(';"11) Conversion-Time Histories for the Runs ofTable 4-3 116-118

(';"12) Particle Size vs. Conversion Histories for Runs BR7, BRS, BRIO and BR11 120

.- (';"13) Weight Average :\lo1ecular Weight vs, Conversion'Histories for Runs 122
BR6. BRIO. BR11, BR1-'., BR21 and BR22

(';"1-'.) Effect of Agitation Rate on Conversion for the Batch Emulsion 123
Polymerization ofVAc

(5-1) '"'umber of Particles vs. Reaction Time for a Typical Batch 130
Emulsion 'lAc Run

(5-2) ,",umber of Particles vs. Reaction Time for a'Typical Batch Homogeneol:s . 132
Emulsion 'lAc Run (IF = 0.005 gmoleSl1it water)

xi

-

Figure . Page

(5-3) Variation of Am(t) in order to Obtain Successive Particle Generations. 135

(IF = 0.005 gmolesllit water) ,

(5-4) Number of Particles vs. Time Corresponding to the Am(t) Variation 136
of Figure 5-3

(5-5) Comparison ofNp(t) Between the Usual arid the Extended Case 138
(IF = 0.005 gmolesllit water: SF = 0.0437 gmolesllit water for the
Usual Case) . ,

(5-6) Total Polymer Particle Surface Area Corresponding to the Figure 5-3 139
Variations .

(5-7) Total Emulsifier Level in the Reactor Corresponding to Figue 5-,3 140

(7-1) Free Micellar Soap and Number.of Polymer Particles Variations for 169
a T)"pi~1 Continuous Emulsion Polymerization Case in a Single CSTR

(7-2) Conversion and Number of Particles versus Number of Residence Times' . 171
for a Single CSTR. Conditions: 8:; IS00 sec, 1= 0.01 gmoleJJit, .
S=O.OI gmolellit.

(7-3) Average Number of Branch Points per Polymer Molecule and Average 172
Particle Diameter versus Number of Residence Times for a Single CSTR.
Same Conditions as in Figure 7-2.

(7-4) Conversion and Number of Particles versus Number of Residence times 179
for the New Configuration. Conditions: 8 = IS00 sec, 1=.0.01 gmoleJJit,
S= 0.01 gmoleJJit. VI =75 ml, split= 0.4

(7-5) Average :"umber of Branch Points per Polymer ~Iolecule and Average 'lS0
Particle Diameter versus :"umber of Residence Times for the :"ew , '
Configuration. Same Conditions as in Figure 7-5

(7-61 :"ew Latex Reactor Train Configuration Experimental Layout' IS5

Experimental Conversion versus Dimensionless Time for a Typical ISS

Continuous Run with the Conventional Train

(7-8) Run CRl, Parts A and B: R2 Conversion versus Dimensionless Time IS9

(7-9) Run CRl, Part B: R2 Conversion versus (tJ62) , 190

(7-10) .' Run CR1, Parts A, B and C: R2 Conversion "ersus (tJ82) 192

o
 - .'

.
,
Figure Page

(7-111 Run CRl: On-line Surface Tension versus (tlS2) 195

(7-12) Run CRl, Part B: Average Particle Diameter versus-ft/~) 197

(7-13) Run CR2, Parts A and B: Conversion versus Dimensionless Time 199

(7-14) Run CR2, Parts A and B: On-line Conversion versus (tl62) 200

. (7-15)' Run CR2, Parts A and B: Average Particle Diameter versus 202
Dimensionless Time

Batch PVC Emulsion Polymerization: Conversion-Time Histories 211

Log (Number of Polymer Particles) vs. Log (Emulsifier concentration) 212

.!II Batch PVC Emulsion Polymerization .

Conversion-Time Histories in Batch P\I-c Emulsion Polymerization 214

. for Different Initiator and Emulsifier Concentrations

Averagll Number of Radicals per Particle During the Course of a 215

Typical'Batch VCM Emulsion Run

Semi-batch VCM Emulsion Polymerization: Number of Particles vs. 217

Ratio of(VCMlwater)
.....
'

Conversion vs. Dimensionless Time: Unseeded 'S. Seeded PVC CSTR 219

Number of Particles vs. Dimensionless Time: U nseeded vs. Seeded 220

PVCCSTR

Number Average Diameter vs. Dimensionless Time: Cnseeded vs. Seeded 221
PVCCSTR

Measured PSD's During the Continuous Production of Emulsion PVC 224

Seeded Overflow CSTR Starting Full of Recipe for the Production of

Emulsion PVC <See Table 8-2): Conversion vs. Dimensionless Time

..c. Se.eded
Overflow CSTR. Conversion vs. Dimensionless Time: Effect 228
of Process Variables (See also Table 8-2)

Conversion. Number of Par'ticles and Average Diameters vs. (tiS): 229

Split Feed Reactor System

Predictions of the New Train Configuration Behaviour: Production 231

of Emulsion PVC

xiii
 .~ ...

Figure Page

(9-1) Simulation Results: Contln\lous Latex Train Conversion vs. 240

for. Several Impurity Levels
. (tie)

(92) Simulation Results: Batch Reactor Operation 241

(9'3) Simulation Results: Batch Reactor Operation, MSI Level of 100 ppm. 243
Effect of'KMI

(94) Run IM1: Conversion vs. Time Data and Model Predictions 250

(9-5) Conversion vs. Time Data from Runs IM1 and 1M2 252

(96) Conversion vs. Time Data from Runs IM1 and IM3 253

(9i) Conversion-Time Histocies for Runs IM3,11\14', IM5 and IM6 255

(98) Average Particle Diameter "(so

, Time: Data and Model Predictions 257

(9-9) Evolution of Particle Size with Time for Runs [M1 and [:\12 258

(910) Runs [M1, [:\13 and IM6: Diameter vs. Time 259
(
(9-11) Average Particle Size vs. Batch Time for Runs [M6-[M6-IM4 260

(101) :\lodel Prediction and Filtered Estimate for Conversion and Average 274
Size from the Kalman Filter Analysis
.. :. ,
(102) Computer Control of Continuous Latex Reactors 280
, ..
(VI) Schematic Diagram of the KM..,{6 LALLSP 35i ,.
(V2) Mw-Re Relationship 358

(VI-l) Effect of the Ratio ("'m/a.p) on Conversion and Number ofParticles 3i6

(VI2) S versus Conversion 3i8

,;,

xiv
 Figure Page

(X.l) Run CRl, Parts A and B: R2 and Rl Conversioll versus (tl82) 406

(X2) Run CR2, Complete Experimental Picture: Conversion 408

(X-3) Run CR2, Cmplete Experimental Picture: Particle Diameter 409

(X-4) Run CR2, Parts A and, B: Rl Conversion versus (tl82) 411

(XIII-I) VCMNAc Emulsion Copolymerization: Cal Conversion vs, Time 431

in a Batch Reactor for Extreme Cases (b) Instantaneous Copolymer'
Composition (c) Start-up Procedures in an Unseeded CSTR

.'

xv
(

LIST OF TABLES

Table Page

2-1 Recent Work on the -Modelling of Emulsion Polymerization Reactors 8

..; 2-2 Recent Work on the Modelling ofPSD's in Emulsion Polymerization 19

Reactors

3-1 Peak Broadening Data for PolystYrene Latexes Measured by 40

Hamielec and Singh (1978) .

3-2 Comparison of the Analytical Methods for Solving thdllntegral 58

Equation

3-3 Classification of Batch.Runs 70

4-1 Kinetic Rate Constants 90

4-2 Numerical Values of Model Constants 91

4-3 Summary of Batch Runs 111

71 Comparison of Polymer Latex Properties from Reactor 2 when L sing 183

. Different Bypass Percentages as Control Variable .

8-1 Kinetic Parameters and Other Physical Constants Used in the PVC 210
- Computer Program
-'.

8-2 Summary of Seeded CSTR Recipes (Berens (1974)) 226

,
9-1 :\lonomer Soluble Impurity Effect on );umber of Particles 245

9-2 Summary of Batch VAc Impurity Runs 247

XI-I
.
Physical Property and Hazard Data for :\lajor Experim!lntal Chemicals 413-414
L~' .
, . .
XI-2 :\lortality Data for :'lajor Chemi~ls L sed 414

-. .-.
. .'

XVI
 --
--
NOMENCLATURE

a thermal expansion coefficient,litf'K. in equation (1-106)

ap(t.t) initial particle surface area at birth. dm2

ato,t particle area correspondlngto vvo.<- dm2

A constant in the free volume expressions. equation (1-112)

A..!(t) area of monomer droplets. dm211-latex

A",(t) total surface area of micelles. dm 211-latex

A p Ap(t) total polymer particle surface area. dm 211-latex "

"

B constant in the free volume expressions. equation (1-113)

Bs(t) average number oflg,ng-chain branch points per polymer molecule. 111-
latex _ "

c constant defined in equation (2.17)

Cfx ratio ofkfx to k p

CI concentration of initiator in the'initiator feed stream. gmolellit of

stream

Cm ratio ofkfm to k p

Cp ratio of kfp to k p
"
Cw concentration ofradica:ls in the water phase. gmolel1latex

d~l density of pure monomer.g/lit

dp density ofpu're polymer. gr/lit

dp(t.tl initial poly~er particle diameter. equal to the final diameter of

mice lies. dm

dp(tr,ti) particle diameter of a particle born at time ti. now being at time tr. dm
Da.ve some average particle diameter. dm

D:-; number average pol)-mer particle diameter. dm or A

xvii
J'
~Dp diffusion coefficient ofnomomeric radicals in polymer particles, dm2fsec

total (cumullitivel polymer particle diameter, dmll-latex

polymer particle diameter based on a monomer fr~ basis, dIIi

maximum degree of polymerization

weight average polymer particle diameter, dm or'A

diffusion coefficient of monomeric radicals in the water phase, dm2fsec

E(t) exit age distribution (residence time distribution) function for an ideal
CSTR,sec- 1

f efficiency factor for initiator decomposition

mole fraction of unreacted monomer I in the reactor (copolymer case)

'.
fit) net particle generation rate, 1f(1-latex)-sec

number frequency ~fthe PSD

"'mole fraction of monomer I in the copolymer' chain (instantaneous

copolymer composition) '-

FI volumetric flow rate of initiator stream, lit of s'treamlsec (mUmin in

Chapter 7)

FTOT total volumetric flow rate (mUmin) to reactor 2 (Chapter 7)

I denotes initiator

[(RI) initiator volumetric flow rate to Rl (mUmin). Chapter 7

initiator concentration in the feed, gmolefl-Iatex

I w,
.'
initiator concentration in the reactor at time t= (}, gmOlefl-latex\

Iw(tl initiator concentration in the water phase, gmolefl-latex

radical capture (absorption) rate constant, dmlsec
,
radical capture rate constant (homogeneous nucleation), dm3 /sec

rate coefficient of initiator decomposition, sec- 1

\
J
XUI