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POLYMER SCIENCE AND TECHNOLOGY

Table 10.6 Characteristics, Advantages and Disadvantages of Various Polymerization Types

Polymerization
Process

Characteristics

Advantages

Bulk

Reaction mixture consists

essentially of monomer;
and initiator in the case
of chain reaction
polymerization
Monomer acts as solvent
for polymers

Products relatively pure due to

minimum contamination
Enhanced yield per reactor volume

Solution

Solvent miscible with

monomer, dissolves
polymer

Heat transfer efficiency greatly

enhanced resulting in better process
control
Resulting polymer solution may be
directly usable

Suspension

Monomer and polymer

insoluble in water,
initiator soluble in
monomer

Heat removal and temperature control

relatively easier
Polymer obtained in a form that is
convenient and easily handled
Resulting polymer suspension or
granules may be directly usable

Emulsion

Monomer and polymer

insoluble in water,
initiator soluble in water
Emulsifier needed for
stabilization of system
component particularly
at initial stages of
polymerization
Polymer insoluble in
monomer or monomer
miscible with precipitant
for polymer

Physical state of the system enhances

heat transfer efficiency
Possible to obtain high rates of
polymerization and high average
chain lengths
Narrow molecular weight distribution
Latex (emulsion) often directly usable

Polymerization occurs at
interface of two
immiscible solvents,
usually water and an
organic solvent

Polymerization is rapid and occurs at

low temperatures
High conversions are not necessarily
required to obtain high molecular
weight
Unnecessary to start with
stoichiometric quantifiers of
reactants

Precipitation

Interfacial

Physical state of system permits easy

agitation
Relatively low temperatures
employed

Disadvantages
Exothermic nature of polymerization
reactions (particularly chain reaction
polymerizations) makes temperature
control of system difficult
Product has broad molecular weight
distribution
Removals of tracers of unreacted
monomer difficult
Necessary to select an inert solvent to
avoid possible transfer to solvent
Lower yield per rector volume
Reduction of reaction rate and average
chain length
Not particularly suitable for production
of dry or relatively pure polymer due
to difficulty of complete solvent
removal
Need to maintain stability of droplets
requires continuous and a minimum
level of agitation
Possibility of polymer contamination
by absorption of stabilizer on particle
surface
Continuous operation of system
difficult
Difficult to get pure polymer due to
contamination from other
components of polymerization
system
Difficult and expensive if solid
polymer product is required
Presence of water lowers yield per
reactor volume
Separation of product difficult and
expensive
Catalyst systems are special and need
careful preparation
Molecular weight distribution depends
on type of catalyst
Limited to highly reactive systems
Need appropriate choice of solvent to
dissolve reactants

affects the conversion of the monomer to the polymer. The reactor also effectively establishes the ultimate
properties of the polymer such as polymer structure, molecular weight, molecular weight distribution,
and copolymer composition. To perform its functions satisfactorily, the reactor must remove the heat of
polymerization, provide the necessary residence time, provide good temperature control and reactant
homogeneity, control the degree of back-mixing in a continuous polymerization, and provide surface
exposure. In addition, the reactor must be applicable to mass production and economical to operate.

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