POLYMER REACTION ENGINEERING

Polymer reaction engineering is a specialized but important branch of chemical reaction

engineering. The odds strongly favor the involvement of chemical engineers with the
understanding of polymers at some point in their career. The kinetics of polymerization
reactions can be treated using the basic concepts covered earlier, but the chemistry and
mathematics are more complicated than in the examples covered. The number of chemical
species participating in a polymerization is potentially infinite, and the mathematical
description of a batch polymerization requires an infinite set of differential equations.
Analytical and numerical solutions are more difficult than for the small sets of equations dealt
with thus far. Polymerizations also present some interesting mechanical problems in reactor
design. Viscosity increases dramatically with molecular weight, and a polymer solution is
typically 102 to 106 times more viscous than an ordinary liquid. Molecular diffusivities in
polymer solutions are lowered by similar factors. Laminar flow is the rule, pressure drops
are high, agitation is difficult, and heat and mass transfer limitations can be very severe.
The polymer reaction engineer sometimes confronts these problems head on, but most often
seeks to avoid them through clever reactor design.

Several important differences exist between the industrial production of polymers and low-
molecular weight compounds:

1. Generally, polymers of industrial interest have high molecular weights, usually in the
range of 104 to107. Also, in contrast to simple compounds, the molecular weight of a
polymer does not have a unique value but, rather, shows a definite distribution. The
high molecular weight of polymers results in high solution or melt viscosities.
2. The formation of a large polymer molecule from small monomer results in a decrease in
entropy. It follows therefore, from elementary thermodynamic considerations that the
driving force in the conversion process is the negative enthalpy gradient. This means,
of course, that most polymerization reactions are exothermic. Consequently, heat
removal is imperative in polymerization reactions.
3. In industrial formulations, the steady-state concentration of chain carriers in chain and
ionic polymerization is usually low. These polymerization reactions are therefore, highly
sensitive to impurities that could interfere with the chain carriers. Similarly, in step-
growth polymerization, a high degree of conversion is required in order to obtain a
product of high molecular weight.
4. The quality of a product from a low-molecular-weight compound can be usually
improved by such processes as distillation, crystallization, etc. However, if the
performance of a product from a polymerization process is inadequate, it is virtually
impossible to upgrade its quality by subsequent processing.

Given these possible differences in the production processes between polymers and low-
molecular weight compounds, it is vitally important to choose the most suitable reactor and
operating conditions to obtain the required polymer properties from a polymerization reaction.
This demands a detailed knowledge of the phenomena that occur in the reactor. This, in turn,
requires an accurate model of the polymerization kinetics, the mass and heat transfer
characteristics of the polymerization process.

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Polymerization processes may be conveniently classified as homogeneous or heterogeneous. In
homogeneous polymerization, all the reactants, including monomers, initiators, and
solvents, are mutually soluble and compatible with the resulting polymer. On the other hand,
in heterogeneous systems, the catalyst, the monomer, and the polymer product are mutually
insoluble. Homogeneous polymerization comprises bulk (mass) or solution systems while
heterogeneous polymerization reactions may be categorized as bulk, solution, suspension
precipitation, emulsion, gas phase, and interfacial polymerization.

POLYMERIZATION IN HOMOGENEOUS and HETEROGENEOUS

SYSTEMS

Introduction

There are many forms of polymerization and different systems exist to categorize them. The
polymer systems are broadly divided as Homogeneous and Heterogeneous for the purpose of
their study on the basis of the phase in which the monomer and the polymer exists.

(A) The homogeneous polymerization techniques involve pure monomer or homogeneous

solutions of monomer and polymer is a solvent. There are two such systems:

1. Bulk System

Polymerization in bulk, perhaps the most obvious method of synthesis of polymers, is widely
practiced in the manufacture of condensation polymers, where the reactions are only mildly
exothermic, and most of the reaction occurs when the viscosity of the mixture is still low
enough to allow ready mixing, heat transfer, and bubble elimination. Control of such
polymerizations is relatively easy.

Bulk polymerization of vinyl monomers is more difficult, since the reactions are highly
exothermic and, with the usual thermally decomposed initiators, proceed at a rate that is
strongly dependent on temperature. This, coupled with the problem in heat transfer incurred
because viscosity increases early in the reaction, leads to difficulty in control and a tendency
to the development of localized "hot spots" and "runaways" Except in the preparation of
castings, for example, of poly(methy1 methacrylate), bulk polymerization is seldom used
commercially for the manufacture of vinyl polymers.

Some of polymers prepared using Bulk polymerization are: Polycaproamide (Nylon 6), LDPE,
PET

2. Solution System

Polymerization of vinyl monomers in solution is advantageous from the standpoint of' heat
removal (e.g., by allowing the solvent to reflux) and control, but has two potential
disadvantages. First, the solvent must be selected with care to avoid chain transfer and,
second, the polymer should preferably be utilized in solution, as in the case of poly(viny1

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acetate) to be converted to poly(viny1 alcohol) and some acrylic ester finishes, since the
complete removal of solvent from a polymer is often difficult to the point of impracticality,
and is indeed a very expensive affair commercially.

Some of polymers prepared using Solution polymerization are: HDPE, Polypropylene,

Polystyrene, poly (acrylic acid), polyacrylamide

(B) Heterogeneous polymerization techniques involve heterogeneous solutions of monomer

and polymer in a solvent. These systems can be either emulsions, dispersions, suspensions or
interfacial.

1. Polymerization from Gaseous Monomers

The polymerization of gaseous monomers can take place with the formation of a liquid phase
(polymer melt) or a solid polymer. In each case the polymerization of ethylene provides the
most important industrial example.

The high-pressure polymerization of ethylene to branched polyethylene takes place by a free-

radical mechanism in the presence of a liquid phase, at temperatures above the melting
point of the polymer. The polymerization is carried only to low conversion, with the remaining
ethylene recovered when the pressure is lowered and recycled.

The low-pressure polymerization of' ethylene to linear polyethylene takes place by coordination
polymerization using a catalyst suspended in gaseous ethylene in a fluid-bed reactor. The
ethylene polymerizes to the solid phase, with the small amount of the catalyst required remaining
in the solid polymer.

If the polymerization takes place with the formation of the solid polymer, then due to the
solid-gas interface, it becomes an example of Interfacial polymerization.

Some of the polymers that undergo this polymerization include: Polyethylene, Polypropylene

2. Emulsion Polymerization

Emulsion polymerization is a type of radical polymerization that usually starts with an emulsion
incorporating solvent (usually water), monomer, initiator, and surfactant. These latex
particles are typically 100 nm in size, and are made of many individual polymer chains.

Process

The monomer has only a very limited (but finite) solubility in the solvent (e.g. styrene in
water). Most of it is present initially in dispersed droplets (hence the term “emulsion”
polymerization); one role of the (anionic) surfactant is to help stabilise these droplets, by
adsorbing at the droplet / water interface. However, some of the monomer is present in the
water phase – this is important!

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 Schematic diagram of emulsion polymerization

 the surfactant is present at a concentration > its critical micelles concentration (c.m.c.)
(at the reaction temperature). Therefore, most of it is present as micelles, again in the
water phase.

Note: some of the monomer will be solubilized in the micelles – also important! Thus the
monomer is actually distributed in 3 locations:

droplets > aqueous solution (small amount) > micelles

 the initiator is soluble (and therefore present) in the water phase. The initial locus of
polymerization is, therefore, again in the aqueous solution (as in dispersion
polymerization), i.e. that is the first monomer to polymerize.

Advantages of emulsion polymerization include:

 High molecular weight polymers can be made at fast polymerization rates. By contrast,
in bulk and solution free radical polymerization, there is a tradeoff between molecular
weight and polymerization rate.
 The continuous water phase is an excellent conductor of heat and allows the heat to be
removed from the system, allowing many reaction methods to increase their rate.
 Since polymer molecules are contained within the particles, viscosity remains close to
that of water and is not dependent on molecular weight.
 The final product can be used as is and does not generally need to be altered or
processed.

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Disadvantages of emulsion polymerization include:

 Surfactants and other polymerization adjuvant remain in the polymer or are difficult to
remove.
 For dry (isolated) polymers, water removal is an energy-intensive process.
 Emulsion polymerizations are usually designed to operate at high conversion of
monomer to polymer. This can result in significant chain transfer to polymer.
 Usually, cannot be used for condensation, ionic or Ziegler-Natta polymerization.

Polymers produced by emulsion polymerization can be divided into three rough categories.

Synthetic rubber
 Some grades of styrene-butadiene (SBR)
 Some grades of Polybutadiene
 Polychloroprene (Neoprene)
 Nitrile rubber
 Acrylic rubber
 Fluoroelastomer (FKM)

Plastics
 Some grades of PVC
 Some grades of polystyrene
 Some grades of PMMA
 Acrylonitrile-butadiene-styrene terpolymer (ABS)
 Polyvinylidene fluoride
 Polyvinyl fluoride
 PTFE

Dispersions (i.e. polymers sold as aqueous dispersions)

 polyvinyl acetate
 polyvinyl acetate copolymers
 latex acrylic paint
 Styrene-butadiene
 VAE (vinyl acetate - ethylene copolymers)

3. Suspension Polymerization

Suspension polymerization (also known as pearl polymerization, bead polymerization and

granular polymerization) is a polymerization process that uses mechanical agitation to mix the
monomer or mixture of monomers in a liquid phase such as water, polymerizing the
monomer droplets while they are dispersed by continuous agitation. This process is used in the
production of most PVC, a widely used plastic, as well as Sodium polyacrylate, a
superabsorbent polymer used in disposable diapers.

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Suspension polymerization consists of an aqueous system with monomer as a dispersed phase
and results in polymer as a dispersed solid phase.

The Suspension Polymerization Method

A reactor fitted with a mechanical agitator is charged with a water insoluble monomer and
initiator (+ a chain-transfer agent to control molecular weight).

Droplets of monomer (containing the initiator and chain-transfer agent) are formed (50 – 200
µm). These sticky droplets are prevented by the addition of a protective colloid (PVA). Near the
end of polymerization, the particles are hardened, are then recovered by filtration, and followed
by washing step.

Advantages

• Excellent heat transfer because of the presence of the solvent.

• Solvent cost and recovery operation are cheap.

Disadvantages

• Contamination by the presence of suspension and other additives low polymer purity.
• Reactor cost may be very high.

4. Precipitation Polymerization

In the preparation of a polymer insoluble in its monomer, or in polymerization in the

presence of a non solvent for the polymer, marked deviations from the kinetics of
homogeneous radical polymerization may occur. The normal bimolecular termination
reaction is not effective, as the result of trapping or occlusion of radicals in the non-swollen,
tightly coiled precipitating polymer. The lifetime of the trapped radicals is many hours at room
temperature, and if polymer containing such radicals is heated in the presence of monomer to a
temperature where the mobility of the radicals is increased, extremely rapid polymerization
takes place.

Difference between Dispersion and Precipitation Polymerization:

A distinction should be made between precipitation and dispersion polymerization, due to the
similarities. A dispersion polymerization is actually a type of precipitation polymerization, but
the difference lies in the fact that precipitation polymerizations give larger and less regular
particles, as a result of little or no stabilizer present.

The main difference between dispersion and precipitation polymerization is the locus of
polymerization. In dispersion polymerization the particles are the main locus of
polymerization, whereas in precipitation polymerization the continuous phase is the locus of
polymerization because the medium or the monomer does not swell the precipitated polymer.

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 5. Solid Phase Polymerization

A large number of olefin and cyclic monomers can be polymerized from the crystalline solid
state. Among those that react rapidly under these conditions are styrene, acrylonitrile,
methacrylonitrile, formaldehyde, trioxane, o-propiolactone, diketene, vinyl stearate and vinyl
carbazole.

Polymerization always appears to be associated with defects in the monomer crystals, most likely
line defects; otherwise, it would be required that the monomer and the polymer be isomorphous,
that is, that they have the same crystal structure, lattice parameters, and so on. This seems
extremely unlikely and has not been observed.

EXERCISES

Example 1
Explain why bulk polymerization is generally more suited for step-growth polymerization than
for chain-growth polymerization.

Solution:
The major problems in bulk polymerization are heat removal and mixing. Both step-growth and
chain-growth polymerization are exothermic. But the enthalpy of polymerization for chain-
growth reactions is higher compared with that for step-growth polymerization. Also, chain-
growth polymerization is characterized by high viscosities even at low conversions due to the
generation of polymers early in the reaction, whereas viscosities are generally low in step-
growth polymerization until the later stages of the reaction (high conversions).

Thus the much higher exothermic nature of chain-growth polymerization, coupled with the
difficulty of mixing the reaction mixture due to high viscosities, leads to much lower heat transfer
efficiencies in chain growth polymerization than in step-growth polymerization.

Example 2
Explain the following observation. The use of internal cooling coils or an external circulating
loop and exchanger is generally not an appropriate means of providing supplemental heat
transfer area in suspension polymerization.

Solution:
Polymer fouling is generally a problem in suspension polymerization reactors. Supplemental
heat-transfer area in the form of coils is generally avoided because of the difficulty encountered
in cleaning the area between coils and the vessel wall.

Example 3
Purified styrene monomer is charged along with initiators into an aluminum prepolymerization
vessel. Polymerization is carried out at about 90°C to 30% conversion. The resulting syrup is
then poured into molds where the reaction is completed. Comment on the probable molecular
weight distribution of the product polymer.

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Solution:
This process is essentially batch polymerization of styrene. Most of the conversion takes place in
the finishing trays. Because of the relatively poor heat transfer in these trays, the polymerizing
mass may reach high temperatures at some spots. Consequently, the resulting polystyrene will
have a broad molecular weight distribution, with very high molecular weights being produced at
low temperatures and lower molecular weights produced at high temperature.

Example 4
Describe briefly the potential implications with respect to process operation and/or the resulting
product of the following problems.

a. Power or equipment failure in solution polymerization

b. Addition of excess amount of initiator in suspension polymerization

Solution:
a. The reaction must be stopped in an appropriate way depending on the nature of the reactants.
Failure to stop a highly exothermic polymerization during an extended power loss can be
potentially dangerous since agitators and compressors stop functioning and the necessary heat
transfer to the coolant is effectively terminated. The reaction may proceed to a violent stage or a
completely solidified mass depending on the reactants. A deactivator such as a ketone, an
alcohol, or water is effective with a coordination-type initiator. In some cases, e.g., the phenolic
type, the reaction is effectively terminated by lowering the temperature and adding more solvent.
For a free-radical polymerization reaction, a free-radical acceptor (“shot stop”) halts the
polymerization. These additives are charged into the reactor where necessary or, preferably,
after the batch leaves the reactor. In the case of a train of reactors, the reactor in which the rate
of polymerization is highest is dumped into an off-grade vessel and terminated there.

b. An excess of initiator should be avoided because of the undesirable effects it has on process
control and product quality. Some of these adverse effects include low-molecular-weight polymer
formation resulting from chain termination, difficult control of temperature due to enhanced
reaction rate and exothermic heat resulting in gel formation and agglomerization, and decreased
thermal stability of the product polymer due to the presence of the excess peroxide causing
degradation of the product at processing temperatures.

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