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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 finally
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, paraffin 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.)

Difficulty 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 fluctuations along
the drops surface

Drop/particle coalescence

Can be increased / decreased by the turbulent flow field

At sufficiently 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 sufficiently hard so the

collisions between them are elastic and, thus, the particle coalescence
ceases (identification 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 final 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 final 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 significant 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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