CHE417 O. R.

OBANLA

DEPARTMENT OF CHEMICAL ENGINEERING,

COVENANT UNIVERSITY, OGUN STATE
CHE417: POLYMER PROCESS ENGINEERING
Lecture 8

POLYMERIZATION METHODS

The polymerization process requires combining monomers with suitable initiator/catalyst in

a reactor, to convert the monomers into polymer molecules consisting several thousands of
monomers linked together. The processes can be classified to terms of the reacting medium
as bulk, solution, suspension, slurry and emulsion. These processes of manufacturing polymer
can be grouped into two:

(1) Polymerization in homogeneous systems. (2) Polymerization in heterogeneous systems.

Polymerization in Homogeneous Systems:

The homogeneous polymerization techniques involve pure monomer or homogeneous

solutions of monomer and polymer in a solvent. These techniques can be divided into two
methods: (i) the bulk and (ii) the solution polymerizations.

Bulk polymerization

Bulk polymerization is the simplest technique and produces the highest-purity polymers. It is
sometimes called mass polymerization. The polymerization is carried without any solvent or
dispersant. It is therefore the simplest in terms of formulation. Only monomer and a
monomer-soluble initiator are used. This method helps easy polymer recovery and minimum
contamination of product, because only the monomer, polymer and initiator are present in
the reaction medium. The polymerization is very rapid and strongly exothermic which can
lead to hazardous temperature build up and run-away reactions. The viscosity of the mixture
is low initially to allow ready mixing, heat transfer, and bubble elimination, this method is
used for the preparation of polyethylene, polystyrene, etc. Bulk polymerization is more often
used for step-growth polymers such as polyurethanes, polycaprolactam (Nylon 6),
polycarbonates and polyester (PET).

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Advantages: Mass polymerization offers several advantages over other polymerization

techniques; since there is no solvent or diluent present, it provides polymers of high clarity
and higher molecular weight. It is also a very environmental friendly polymerization method
since no purification is required and the final product is a 100% solid resin. It produces the
greatest yield of polymer per unit volume.

Disadvantages: Reaction medium becomes increasingly viscous as reaction goes to higher

conversion, making stirring, heat removal and processing more difficult, leading to uneven
polymerization and loss of monomer.

Free-radical polymerizations are typically highly exothermic, an increase in temperature will

increase the polymerization rate; generate heat dissipation and a tendency to develop
localized “hot spots”. Towards the end of the polymerization, the viscosity is very high and it
becomes difficult to control the rate as the heat is “trapped” inside. This leads to auto
acceleration process in which the propagation rate is very higher than that of termination
rate, this method is seldom used in commercial manufacture.

Solution polymerization:

Solution polymerization is a method of industrial polymerization. In this procedure, a

monomer is dissolved in a non-reactive (inert) solvent that contains a catalyst or initiator.
The reaction results in a polymer which is also soluble in the chosen solvent. This method is
used to solve the problems associated with the bulk polymerization because the solvent is
employed to lower the viscosity of the reaction, thus help in the heat transfer and reduce
auto acceleration. The solvent should be carefully selected to avoid chain transfer reactions
that may limit the growth of the polymer.
Both the initiator and monomer should be soluble in each other and in the solvent, which
should be of suitable boiling points, in order to ease the solvent-removal steps. The process
involved dissolving the Monomer along with initiator in the solvent, the formed polymer
also remains dissolved in the solvent. The mixture is kept at polymerization temperature
and constantly agitated. Depending on concentration of monomer the viscosity of solution
does not increase.

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After the reaction is over, the polymer is used as such in the form of polymer solution or the
polymer is isolated by evaporating the solvent. Polymer so formed can be used for surface
coating.
This method is used for the preparation of polyvinyl acetate, poly (acrylic acid), and
polyacrylamide. It is often used to produce copolymers.

Advantages: (i) Solvent has low viscosity, reaction mixture can be stirred (ii) Solvent acts as a
diluent and aids in removal of heat of polymerization (iii) Solvent reduces viscosity, making
processing easier (iv)Thermal control is easier than in the bulk and (v) “Cheap” materials for
the reactors (stainless steel or glass lined)

Disadvantages: (i) Reduce monomer concentration which results in decreasing the rate of the
reaction and the degree of polymerization (ii) Mobility is reduced and this can affect
termination events, so the rate of reaction is increased (iii) Solvent may terminate the growing
polymer chain, leading to low molecular weight polymers (iv) Difficult to remove solvent from
final form, causing degradation of bulk properties (v) Clean up the product with a non-solvent
or evaporation of solvent (vi) Small production per reactor volume (vii) Not suitable for dry
polymers.

Figure 1: schematic representation of solution polymerization process

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Polymerization in Heterogeneous Systems:

Polymerization occurs in disperse phase as large particles in water or occasionally in another

non-solvent (suspension polymerization), or dispersed as fine particles (emulsion
polymerization).

Suspension (Bead or Pearl) polymerization

Suspension polymerization is a heterogeneous radical polymerization process that uses

mechanical agitation to mix a monomer or mixture of monomers in a liquid phase, such as
water, while the monomers polymerize, forming spheres of polymer. Monomer, initiator
(soluble in monomer) and polymer must be insoluble in the suspension media such as water
i.e., the reaction mixture is suspended as droplets in an inert medium.

Suspension polymerization consists of an aqueous system with monomer as a dispersed

phase and results in polymer as a dispersed solid phase. The polymerization begins by radical
initiators in monomer droplets, in a reactor fitted with a mechanical agitator.

Droplets of monomer (containing the initiator) are formed, as the polymerization proceeds,
the viscosity of dispersed phase increases and they become sticky. Protective colloid, e.g.,
water-soluble colloid such as gum acacia, are added to prevent coagulation of the particles.
This acts as dispersing agent. The water absorbs the heat of reaction. Sometimes, cooling
jackets are used to facilitate heat removal. Towards the end of the polymerization, the
particles are hardened and bead or pearl shaped polymers formed. They are recovered by
filtration, and followed by several washing steps.

This method is used for the preparation of polystyrene, polyvinyl chloride, polyvinyl acetate,
etc.

Advantages: (i) Polymerization to high conversion (ii) Low viscosity due to the suspension (iii)
Easy heat removal due to the high heat capacity of water (iv) Excellent heat transfer because
of the presence of the solvent (v) Solvent cost and recovery operation are cheap (vi)
Polymerization yields finely divided, stable latexes and dispersions to be used directly in
coatings, paints, and adhesives

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Disadvantages (i) Contamination by the presence of suspension and other additives give low
polymer purity (ii) There is need to separate and purify the polymer, or accept contaminated
product (iii) Reactor cost may be higher than the solution cost.

Emulsion polymerization

Emulsion polymerization is like suspension polymerization in which monomer is dispersed in

water, but in smaller droplets created with the use of emulsifiers, such as, soaps. It is the most
widely used method of polymerization. It overcomes the difficulty of heat control and low
degree of polymerization. It consists of water (solvent or as the heat-transfer agent),
monomer, initiator (which is soluble in water and insoluble in the monomer), and a surfactant
or emulsifier (such as sodium salt of long-chain fatty acid). In the presence of soapy water,
the monomer droplets and subsequently formed polymer molecules are kept apart and
dispersed.

When a small amount of soap is added to water, the soap ionizes and the ions move around
freely, the soap anion consists of a long oil-soluble portion (R) terminated at one end by the
water-soluble portion, so emulsifier molecules arrange themselves into colloidal particles
called micelles. In water containing an insoluble monomer molecule, the soap anion
molecules orient themselves at the water–monomer interfaces with the hydrophilic ends
facing the water, while the hydrophobic ends face the monomer phase.

When the process begins, the temperature increases leading to generation of free radicals
that monomers are attracted to and come out of the droplets, start adding on to the free
radical sites in a micelle, the active micelles grow in size with polymer formation, and finally
finish producing the polymer molecules cocooned in the micelle. To preserve their stability;
these growing polymer particles absorb the soap of the parent micelles. This process takes
place simultaneously in different micelles, resulting into many polymer particles. Emulsion
polymerization takes place almost exclusively in the micelles. In the reaction medium are
polymer particles, monomers, initiators, surfactants and coagulants residues. These are hard
to remove on completion of the polymerization thus, contribute to high impurity levels of the
product.

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This method is used for the preparation of polyvinyl acetate, polychloroprene, polymethyl
methacrylate, butadiene/styrene/acrylonitrile copolymers, etc.

Figure 2: schematic representation of emulsion polymerization process

Gas-phase polymerization

In addition to the above four methods, there is gas-phase polymerization process. The
monomer is usually in gaseous state and heterogeneous coordination catalyst is used. The
catalyst is supported on suitable substance, such as, SiO2. The polymer is formed on the active
sites of the catalyst and gradually expand into polymer-catalyst particle. Fresh gaseous
monomer diffuses through the polymer-catalyst particle to reach the active site for addition.
This method is used mainly for production of polyolefin such as HDPE.

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Table 1. Summary of the different polymerization methods with examples