Unit 2 2024

METHODS OF POLYMERIZATION

polymerisation is an exothermic reaction almost all commercial process of polymerization are

liquid phase reactions. The polymerisation process may be carried out in two systems :

(1) Homogeneous system 2) Heterogeneous system

(1) Homogeneous System

In this system, following types of polymerisation is possible:

(a) Bulk Polymerisation (b) Solution Polymerisation (c) Melt Polycondensation

(a) Bulk Polymerisation:

In this type of polymerization the monomer is taken in liquid form. The initiators, chain transfer
agent are dissolved in monomer. Now the system becomes homogenous. The reaction mass is
heated for the purpose of initiating the polymerization reaction and is kept under agitation for
proper heat and mass transfer. As the polymerization proceeds the viscosity of the medium
increases and mixing becomes difficult leading to products with very broad molecular weight
distribution. The reaction is purely exothermic.

The advantages of bulk polymerisation are the use of simple equipment, direct recovery of the
polymer and minimum chances of contamination. This technique of polymerisation is widely
used in the free-radical polymerisation of methyl methacrylate or styrene to get cast sheetings
and transparent moulding powder. It is also used to get polyvinyl chloride resin from vinyl
chloride.

Fig1: Bulk polymeriztion of styrene

SOLUTION POLYMERIZATION

Monomer is dissolved in suitable solvent along with chain transfer agents and initiators (free
radical initiator). Catalyst may be ionic or co-ordination catalyst which can either dissolved or
suspended. The presence of inert solvents medium helps to control viscosity, increase and

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promote proper heat transfer. Process may be continuous/batch wise operation. The product
obtained is in liquid phase. For most cases water is taken as solvent.

The advantage of this process is that the presence of inert solvent medium helps to control
viscosity and promote a uniform heat transfer. Solution technique is used in industrial production
of polyacrylonitrile by free-radical polymerisation and also polyisobutylene by cationic
polymerisation. This technique is exclusively used in the production of block co-polymers.

Fig2: cationic polymerization of isobutylene

Melt Polycondensation

In this method, one of the monomers used is solid, which cannot decompose around its melting
point. The reaction has to be carried out in an inert atmosphere of N2 or CO2 to avoid side
reactions such as oxidation, decarboxylation, etc. Sometimes, the reaction is carried out under
reduced pressure to initiate the removal of the by product. The production of polyethylene
terephthalate from dimethyl terephthalate and ethylene glycol, and nylon 66 are prepared by
using melt polycondensation technique.

The major disadvantage of this technique is removal of the byproduct becomes extremely
difficult because there is much increase in the viscosity of the medium. The polymer formed is in
molten state at the reaction temperature and it is important to isolate it from the reactor during
hot condition, otherwise it will solidify inside the reactor and removal becomes very hard.

Fig3(a): schematic representation of melt

polycondensation (b)melt polycondensation of PTTA

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Heterogeneous System

Heterogeneous system falls under two categories;

(a) Suspension Polymerisation (b) Emulsion Polymerisation

(a) Suspension Polymerisation

In this technique only water-insoluble monomers can be polymerised. The monomer molecules
are suspended in water and mixed with surface active agents and water-soluble protective
colloids. The initiators are monomer soluble. This is an economical process because here water is
taken as heat transfer medium and polymerisation proceeds to 100% conversion. The product is
obtained as spherical beads or pearls. For this reason, this technique is known as beads or pearl
polymerisation.

Isolation of the product is quite easy because this technique involves only filtration of the beads.
The washed and dried polymer products can be used as such for moulding, coating and adhesive
purposes. By suspension polymerisation method, polyvinyl acetate beads, polystyrene beads and
styrene-divinyl copolymer beads can be produced. A fairly narrow molecular weight product can
be achieved by this technique.

(b) Emulsion Polymerisation

In this system, the monomer is dispersed in the aqueous phase as a uniform emulsion, and the
emulsion is stabilised by surfactants (i.e., surface active agents), protective colloids and by
certain buffers. persulftes or hydrogen peroxide can be used as initiators. Redox initiators are
also widely used in this system. The surfactant molecule consists of two parts a long non-polar
hydrocarbon chain, and a polar group. In emulsifier molecule, the non-polar part attached with
polar end, and form micelle. The hydrocarbon ends of all the emulsifier come close to each other
at the interior and polar end align themselves outward. Emulsification can be achieved when the
monomer is added and agitated. In the emulsion system, a monomer droplets and micelles are
dispersed uniformly.

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Fig 5: emulsion polymerization of styrene which

is used in thermocol preperation

In this process, the rate of polymerisation is very high, because the polymerisation is proceeded
at the micelles, where the surface/volume ratio is much large. Emulsion polymerisation is a most
widely used industrial technique. The monomers e.g., butadiene, chloroprene, vinyl acetate, vinyl
chloride, acrylates and methacrylates, etc., are used to polymerised by this method. A very high
molecular weight product can be achieved by this technique.

INTERFACIAL CONDENSATION POLYMERISATION

In this type of polymerisation, two different medium are taken and polymer is formed at the
point of interface between two phases. Here, one phase is an aqueous solvent and another phase
is an organic medium. The two solutions are thoroughly agitated, and thus formation of an
emulsion takes place. At the same time, the interface surface/volume ratio is increased and,
hence, both the rate and degree of polymerisation becomes too high. The formed polymer
precipitates out, isolated from the slurry and washed well.

The formation of polymer at the interface is a diffusion-controlled process, a very high molecular
weight polymer can be obtained by this technique. A typical example of interfacial condensation,
p-phenylene diamine is dissolved in water and terephtholoyl chloride is taken in chloroform or
carbon tetrachloride. When these two solutions are brought in contact with each other, the
diamine molecules diffuse into the organic phase and react with acid chloride to give polymides
at the interface which is precipitated out immediately.

Fig 6: (a) schematicrepresentation

of interface polymerization
(b) synthesis of a polymer in lab
(c) preparation of a polyamide
using interface polymeriztion

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