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Polymer Reaction Engineering!

! Polymers a brief market overview! ! Introduction to polymerization processes! ! Coordination polymerization! ! Free radical polymerization! ! Suspension polymerization! ! Emulsion polymerization! ! Step-growth polymerization! ! Control of polymerization reactors!

Suspension Polymerization!
! The suspension polymerization process is typically carried out in wellstirred batch reactors! ! ! The volume of the reaction vessel can be up to 150 m3! The monomer(s) is (are) initially dispersed in the continuous phase (commonly water) by the combined action of surface active agents (inorganic or/and water-soluble polymers) and agitation! ! All the reactants (monomer(s), initiator(s), etc.) reside in the organic or oil phase!

Suspension Polymerization Reactor!

Suspension Polymerization!
! The polymerization occurs in the monomer droplets that are progressively transformed into sticky, viscoelastic monomerpolymer droplets and nally into rigid, spherical polymer particles in the size range of 50500 m! ! The polymer solids content in the fully converted suspension is typically 3050% w/w! ! In the inverse suspension polymerization, the hydrophilic monomer(s) (e.g., acrylamide, acrylic acid) and initiator are dispersed in the hydrophobic continuous organic phase (e.g., hexane, parafn oil)!

Suspension Polymerization!

Bead and Powder! suspension polymerization!

Bead suspension polymerization:! ! The polymer is soluble in its monomer and smooth spherical particles are produced! ! The most important thermoplastic produced by the bead suspension polymerization process is PS! ! In the presence of volatile hydrocarbons (C4C6), foamable beads, the so-called EPS, are produced!

Bead and Powder! suspension polymerization!

Powder suspension polymerization:! ! The polymer is insoluble in its monomer and, thus, precipitates out leading to the formation of irregular grains or particles! ! PVC is an example of the powder type suspension polymerization!

Advantage of suspension polymerization!

The main advantages of suspension polymerization compared to the bulk process are! ! Easier control of the reaction temperature due to the presence of the dispersion medium (e.g., water)! ! ! Milder reaction conditions! Product homogeneity, especially for monomers having a very low solubility in the continuous phase! ! Higher purity than those produced by emulsion polymerization!

Disadvantage of suspension polymerization!

! Low reactor productivity due to the presence of the dispersion medium (e.g., 50% v/v)! ! The required post-treatment of the dispersion medium for removing all the undesired impurities (e.g., suspending agents, etc.)! ! Difculty in the production of homogeneous copolymers, especially when the monomers have different reactivities and solubilities in the continuous phase!

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Control of PSD!
! In general, the initial monomer droplet size distribution (DSD) as well as the polymer PSD depends on the type and concentration of the surface active agent, the quality of agitation (e.g., reactor geometry, impeller type, power input, etc.) and the physical properties (e.g., densities, viscosities, interfacial tension) of the continuous and dispersed phases! ! The dynamic evolution of the droplet/PSD is controlled by the rates of two physical processes, namely, the drop/particle breakage and coalescence!

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Control of PSD!

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Control of PSD!
Droplet breakage:! ! Mainly occurs in regions of high shear stress (i.e., near the agitator blades) or as a result of turbulent velocity and pressure uctuations along the drops surface! Drop/particle coalescence! ! ! Can be increased / decreased by the turbulent ow eld! At sufciently high concentrations of surface active agents, it can be assumed to be negligible for very dilute dispersions!

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Control of PSD!
The suspension polymerization process can be divided into three stages! ! At low monomer conversions (i.e., low viscosity of the monomerpolymer phase, stage one), drop breakage is the dominant mechanism! ! During the second sticky-stage of polymerization, the drop breakage rate progressively decreases while drop/particle coalescence becomes the dominant mechanism! ! At higher monomer conversions, the particles are sufciently hard so the collisions between them are elastic and, thus, the particle coalescence ceases (identication point)! ! After this point, the PSD has been established!

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Surface active agents!

! ! Play a very important role in the stabilization of liquidliquid dispersions! They can be water-soluble copolymers (e.g., poly(vinyl alcohol) (PVA) and cellulose ethers) or colloidal inorganic powders (Pickering dispersants, e.g., tricalcium phosphate, barium sulfate, calcium carbonate, etc.)! ! ! These stabilizers reduce the drop/particle coalescence! Water-soluble substituted celluloses are mainly used in the manufacture of PVC!

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Droplet size!

Dependence of the steady-state Sauter mean diameter on the agitation speed for (a) various PVA grades and (b) concentrations!
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Bead suspension polymerization!

! The polymer is soluble in its monomer and, thus, the monomerpolymer mixture is homogeneous! ! ! Polystyrene for injection molding! Poly(methyl methacrylate) and its copolymers containing small amounts of acrylate esters! ! Styreneacrylonitrile copolymers azeotropic monomer/comonomer composition to minimize copolymer compositional drift!

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EPS!
! Suspension polymerization in the presence of a blowing agent (e.g., pentane)! ! It is also possible to introduce the blowing agent to the polymer after polymerization and allowing it to diffuse into the beads!

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EPS!
! Once the beads are hard, the reaction mixture is heated to a temperature above the glass transition temperature of the PS, 100C! ! During heating, the reactor is pressurized with a blowing agent (usually npentane) at 58% w/w! ! Subsequently, the reactor is pressurized with nitrogen at 79 bars and the so-called impregnation stage starts! ! ! n-pentane diffuses into the beads! The system is cooled down to 2030C, so that no bead expansion can take place during the discharge! ! In the next stage, the excess of stabilizer is chemically removed!

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EPS!
! In the nal processing, the EPS beads are warmed up to 80110C, generally with steam that causes the beads to expand by foaming and their volume to increase by a factor of 3050!

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Powder suspension polymerization!

! The powder suspension polymerization is the most important polymerization process for manufacturing PVC! ! The main advantage of this process is that large (e.g., 300500 m), porous polymer particles can be produced! ! ! ! Fast residual monomer removal rate! Large plasticizer uptake capacity! The production of polymer particles with desired PSD and porosity can be achieved by changing the quantities and types of stabilizers as well as the agitator speed!

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Powder suspension polymerization!

! The polymerization is commonly carried out isothermally! ! Temperatures in the range of 4570C (depending on MW)!

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PVC suspension polymerization!

! The main difference between the bulk and the suspension process is that agitation is used to control not only the aggregation of the primary particles but also the size distribution of the nal grains!

Above a critical monomer conversion (i.e., xc 30%) the volume contraction of the polymerizing particles stops, which partially explains the appearance of internal particle porosity!

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PVC suspension polymerization!

In the VCM suspension polymerization, two types of stabilizers, primary and secondary are used! ! The main function of the primary surface active agents is to control the grain size (grain porosity)! ! Secondary stabilizers are surface active agents with a higher lipophilic content (e.g., PVA stabilizers with low degree of hydrolysis and cellulose ethers with high degree of substitution of the hydroxyl-groups)! ! Decrease of the primary particles aggregation rate!

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Suspension Polymerization Reactor!

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Scale-up of suspension polymerization!

! The scale-up of suspension polymerization reactors (i.e., from lab to pilot and then to industrial scale) is not straightforward! ! The most signicant problem in scale-up occurs when different physical processes become limiting at different scales!

Commercial-scale suspension reactors have to perform several functions simultaneously! Dispersion, reaction and heat transfer (do not scale-up in the same manner)!

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Scale-up of suspension polymerization!

! Heat removal can become a limiting factor for reactor performance at large scales while it is rarely a problem for lab-scale reactors! ! In suspension polymerization, scale-up of an agitated tank reactor should keep unchanged the particle morphology (e.g., PSD, porosity, bulk density) ! ! ! The reactor design can guarantee the heat removal! Thus, the problem reduces to the scale-up of a liquidliquid dispersion in an agitated vessel! (criteria: constant power input per unit volume, the impeller tip speed, the Weber number, the Reynolds number)!

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Evolution of PSD!

Dynamic evolution of the PSD with respect to polymerization time for VCM suspension polymerization! TP: 56.5C! Impeller speed: 330 rpm! Dispersed phase volume fraction: 40%!

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Evolution of PSD!

Dynamic evolution of the Sauter mean diameter of PVC particles with respect to polymerization time!

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