Polymerization

Muhammad Furqan
Roll No : 16103123-006
How can we define polymerization
A chemical reaction in which two or more
small molecules combine to form larger
molecules that contain repeating structural
units of the original molecules.
 Techniques Of Polymerization
 Monomers may be polymerized by the
following methods:
 (1) Polymerization in homogeneous systems
 (2) Polymerization in heterogeneous systems
Polymerization in Homogeneous system
 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) Bulk polymerization
 (ii) Solution polymerization
 Bulk Polymerization
 Bulk polymerization is the simplest technique and
produces the highest-purity polymers.
 This method helps easy polymer recovery and

minimum contamination of product.

 The viscosity of the mixture is low initially to allow

readily mixing, heat transfer, and bubble elimination,

this method is used for the preparation of polyethene,
polystyrene, etc.
 Disadvantage
 Reaction medium becomes increasingly viscous as
reaction goes to higher conversion, making stirring,
heat removal and processing more difficult.
 Loss of monomer
 Near the end of polymerization, the viscosity is very

high and difficult to control the rate as the heat is

“trapped” inside.
 It leads to the 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
 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.
 It requires the correct selection of the solvent. Both

the initiator and monomer be soluble in each other

and that the solvent are suitable for boiling points.
 It is often used to produce copolymers, this method is
used for the preparation of:
 polyvinyl acetate (C H O )
4 6 2 n
 poly (acrylic acid) (C H O )
3 4 2 n
 Polyacrylamide (C H NO)
3 5 n
 Advantages
 Solvent has low viscosity, reaction mixture can be
stirred.
 Thermal control is easier than in the bulk.
 Aids in removal of heat of polymerization.
 Disadvantage
 Reduce monomer concentration which results in
decreasing the rate of the reaction and the degree of
polymerization.
 Difficult to remove solvent from final form, causing

degradation of bulk properties.

 Small production per reactor volume.
 Not suitable for dry polymers.
Polymerization in heterogeneous system
 Heterogeneous polymerization is a process that
begins initially as a homogeneous system in the
continuous phase, where the monomer and initiator
are completely soluble, but upon initiation the formed
polymer is insoluble and thus precipitates.
 Suspension polymerization
 Suspension polymerization consists of an aqueous
system with monomer as a dispersed phase and
results in polymer as a dispersed solid phase
 Monomer, initiator (must soluble in monomer) and

polymer must be insoluble in the suspension media.

 This method is used for the preparation of

polystyrene, polyvinyl chloride, polyvinyl acetate,

etc.
 Emulsion polymerization
 An emulsion polymerization consists of
(a) Water (solvent or as the heat-transfer agent)
(b) Monomer
(c) Initiator (is soluble in water and insoluble in the
monomer)
(d) An emulsifier : It is a compound or substance that
acts as a stabilizer for emulsions preventing the
liquids from separating(such as sodium salt of
long-chain fatty acid).
 This method is used for the preparation of

polyvinyl acetate, butadiene/styrene/acrylonitrile

(C8H8·C4H6·C3H3N)n , polychloroprene copolymers
etc