Types

– bulk polymerisation
– solution polymeriztion

– suspension polymerisation
– emulsion polymeriztion
Bulk polymerisation
• Monomer – liquid
• Initiator - dissolved in monomer
• Chain transfer agent – dissolved in monomer

• The reaction mass is then heated or exposed to

radiation for polymerisation.
Advantages
• The system is simple
• The polymer obtained is pure.
• Product can be used directly
• High molecular weight and broad
molecular weight distribution.
 Disadvaantages
• High viscosity
• Broad molecular weight distribution.
• ‘autoacceleration’ may occur.
• Highly exothermic.
Autoacceleration/gel effect
• a dangerous reaction behavior that can occur in free-radical
polymerization systems. It is due to the localized increases in
viscosity of the polymerizing system that slow termination
reactions.
Applications
• Used for ethylene, styrene, methyl
methacrylate to get molding powders.
• PVC sheets.
Solution polymerisation
• suitable “inert” solvent
• Monomer – dissolved in solvent
• Initiator - dissolved in solvent
• Chain transfer agent – dissolved in solvent
• Removal of polymer – evaporation or precipitation from
non-solvent.
 Advantages
• Stirring is easy because the solution is
low viscous
• Heat transfer is easy due to presence of
solvent
• The product obtained is in liquid form and
can be directly used for applications such
as adhesives
• Easy removal of polymer
 Disadvantages
• rate of polymerization is low
• Complete removal of solvent is more
difficult
• Polymer obtained is Impure
• high molecular weight polymers
cannot be formed
 Applications
• Widely used for coating and adhesives.
• Industrial production of PAN by free radical polymerization
• Polyisobutylene by cationic polymerization use this
technique
Suspension polymerization
• monomer – dispersed in water
• Intiator - dissolved in monomer
• Stabilize the dispersion with stabilizers (PVA or
methyl cellulose)
• Polymerize the monomer
• Polymer is formed as a granular bead.
• product formed being insoluble in water
• also known as Pearl polymerization / Granular
polymerization / Bead polymerization.
 Advantages
• Product isolation is easy since the product
is insoluble in water.
• Agitation & temperature control is easy.
• Viscosity increase is negligible.
• The process is comparatively cheap as it
involves only water instead of solvents.
 Disadvantages
• can be adopted only for water insoluble
monomers.
• The method cannot be used for tacky
polymers such as elastomers because of
the tendency for agglomeration of
polymer particles.
• Requires long time for very high
conversions
 Applications
• Expandable polystyrene beads.
• styrene-divinylbenzene copolymer beads used in preparation
of ion exchange resins are produced.
• PVA beads are produced by this technique using free radical
initiators.