TECHNIQUES OF POLYMERIZATION

Main Objective of Polymerisation techniques are

Reduce viscosity
Improve thermal control
Minimum contamination of the product
Various techniques are

Bulk or Melt Polymerization

Solution Polymerization

Suspention or Pearl Polymerization

Emulsion Polymerization
Bulk / Melt Polymerization
Raw Materials : Monomer in liquid state,
nitiator soluble in Monomer
Chain transfer agent soluble in Monomer

The process is initiated by heating the flask on a thermostat under constant

agitation. The contents are in homogeneous phase.The reaction is
exothermic. During polymerisation viscosity of the medium increases.
Two possibilities of product formation:

polymer soluble in monomer (example: polystyrene)

polymer insoluble in monomer (example: vinylidene chloride)

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If the polymer is soluble in the monomer, then some physical changes

occur with increasing molecular weight (e.g., viscosity, etc.)

Advantages
The polymer obtained has minimum contamination
Large castings may be prepared directly.
Molecular weight distribution can be easily changed with the use of a
chain transfer agent.
The product obtained has high optical clarity

Disadvantages
Heat transfer and mixing become difficult as the viscosity of reaction
mass increases.
At higher temperatures, the initiator decomposes to form radicals at a
faster rate therefore low molecular weight polymers are obtained.
Polymerization is highly exothermic.

Example: This process can be used for free radical polymerization.

PMMA, PS , PVC are prepared by bulk polymerization.
Applications
The polymers obtained by this method are used in casting
formulations.
Low molecular weight polymers obtained by this method are used as
adhesives, plasticizers and lubricant.

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Solution Polymerization
Raw Materials : Monomer
Initiator
Chain transfer agent
nert solvent or diluent ( aqueous / organic)
The whole mixture is homogeneous and kept under constant
agitation.

Heat can be removed by conducting the polymerization in an organic
solvent or water and reduces built up viscosity.

Initiator or monomer must be soluble in solvent

Solvents have acceptable chain-transfer characteristics
Polymer formations there are two possibilities:
Both the monomer and polymer are soluble in the diluent
Example: polystyrene in toluene
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 Monomer is soluble and the polymer is insoluble in the diluent

Example: acrylonitrile in chloroform

Advantages
Heat control is better than bulk polymerisation
Inert solvent controls viscosity build up
The mixture can be agitated easily
Disadvantages
The removal of solvent is difficult
Difficult to get very high molecular weight product
Examples: Polyacrylic acid, polyisobutylene and polyacrylonitrile are
prepared by this method.
Applications
As the polymer is in solution form it is used as adhesive material

Suspension / Pearl Polymerization

Raw Materials : water-insoluble monomer,
water-insoluble initiator/ initiator soluble in monomer
suspention medium (water-usually, PVA, gelatin)

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The process is used only for water insoluble polymers. This reaction is
carried out in heterogeneous medium in a reactor.. The water insoluble
monomer is suspended in water as tiny droplets and an initiator is dissolved
in it by continuous agitation. The suspension is prevented from coagulation
by using suspending agents like PVA, gelatin etc. Each droplet of the
monomer contains dissolved initiator. The whole content is taken in a flask
and heated at constant temperature with agitation.
At the end of polymerization polymer is separated out as spherical beads or
pearls. Polymer is filtered and separated out. The method is also called as
pearl polymerization.
Advantages
Efficient heat control
Low viscosity due to suspension
Stirring is easy
Separation process is easy
Products obtained are highly pure
Since water is used as solvent this method is more economical.
Disadvantages
Reactor capital costs are higher than for solution polymerization
This method is applicable only for water insoluble monomers
Examples: polymers like Poly styrene, PMMA ,PVC can be prepared by
this method.
Applications
Polystyrene beads are used as ion exchangers
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Suspension Polymerisation
Reactor

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Emulsion Polymerization

Raw Materials : water-insoluble monomer, ( Hydrophobic)

water-soluble initiator ( Hydrophillic)
dispersing medium (water)
surfactant or emulsifier such as sodium salt of a long chain
fatty acid ( soap)

Emulsion polymerization is used for water insoluble monomer and water

soluble initiator. The monomer is dispersed in a large amount of water and
then emulsified by the addition of surfactants. The whole contents are heated
at a constant temperature with vigorous agitation for 4 to 6 hours.
When the concentration of surfactant exceeds critical micelle concentration
(CMC), the molecules form aggregates called micelles. Each micelle
contains non-polar tail of emulsifier molecules inside and polar head
outwards.
The monomer molecules dissolve in the hydrocarbon center of the micelles.
The free radicals are generated in the aqueous phase. The free radicals
diffuse into the micelles centre through the aqueous phase, penetrate into the
micelle and initiate the polymerization in each micelle. The milky white
dispersion formed is called latex.

The polymer is isolated from latex by spray drying or by freezing.

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Advantages:
High molecular weight polymer is obtained
Rate of polymerization is high
Heat can be easily controlled
Viscosity is low
Disadvantages:
The process requires rapid agitation
Polymer needs purification
Surfactants and other polymerization reagents remain in the polymer
and are difficult to remove
For dry (isolated) polymers, water removal is an energy-intensive
process
Examples: preparation of Vinyl chloride, butadiene.
Applications
The polymer can be used as such for making adhesives, water-soluble
emulsion paints, adhesives etc.
Also used for manufacturing tacky polymers like butadiene and
chloroprene

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