Polymerization techniques

Bulk polymerization
Solution polymerization
Suspension polymerization
Emulsion polymerization

Introduction
The processes for manufacturing macromolecules
can be divided into three different categories as
shown in the scheme below.
Process for manufacturing
macromolecular compounds
Process in solution:
-Aqueous solutions
-Organic solutions

Process in
dispersion:
-Suspension
-Emulsion

polymerization technique

Process in bulk:
-Liquid state
-Solid state
-Gas phase
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 The method of synthesis and the manufacturing

process has a large influence on size and structure
of the molecules and the physical properties of
polymers.
Changes in the reaction conditions will change
properties of the products of the same
manufacturing process.
For example, PVC produced by radical
polymerization in suspension differs in MWD
from PVC obtained by radical polymerization in
bulk.
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Bulk polymerization
The simplest and gives the highest purity polymer.

Polymerizations are carried out without solvents or

diluents.
It uses monomer, a monomer soluble initiator and chain
transfer agent to control molecular weight.
This method is economical and eco-friendly due to
recycling and purification of solvents or dispersants, as
well as the disposal of liquid waste are not necessary (as in
the case of aqueous suspension or emulsion
polymerizations).
On the other hand, an increase in temperature will
increase the polymerization rate, thus generating
additional heat to be dissipated.
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 Heat removal becomes particularly difficult near the end

of the polymerization when viscosity is high.
This is because high viscosity limits the diffusion of longchain radicals as required for termination i.e. radical
concentration will increase, thus increasing the rate of
polymerization (Rp > Rt)
By comparison, the diffusion of small monomer
molecules to the propagation sites is less restricted, thus
Rt decreases more rapidly than Rp.
R0 will increase, accompanying additional heat
production and is called autoaccelaration process.
In practice, heat dissipation during bulk polymerization
can be improved by providing special baffles for improve
heat transfer or by performing in separate steps of low to
moderate conversion.
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polymerization technique

Autoaccelaration
Radical chain polymerizations are characterized by the
presence of an autoacceleration in the polymerization
rate as the reaction proceeds .
Normally, a reaction rate falls with time (i.e. the extent
of conversion), since the monomer and initiator
concentrations decrease with time.
However, an opposite behavior is observed in many
polymerizations, where the reaction rate increases with
conversion.
A typical example is shown in Fig. 1 for the
polymerization of MMA in benzene solution.
The plot for the 10% MMA solution shows the expected
behavior of conversion vs time.
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Figure 1: Autoaccelaration in benzoyl peroxide-initiated polymerization of

MMA in benzene at 500C. The different plots represent various
concentrations of monomer in solvent.
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 The plot for 100% monomer (pure) shows a dramatic

autoacceleration in the polymerization rate. Such
behavior is referred to as the gel effect or Trommsdorff
effect and NorrishSmith effect.
Similar behavior has been observed for a variety of
monomers including styrene and vinyl acetate.
It turns out that the gel effect is the normal behavior
for most polymerizations and is observed under
isothermal reaction conditions.

polymerization technique

polymerization technique

Homogenous bulk polymerization

In homogeneous bulk polymerization, the polymer
remains dissolved in the monomer. In some cases, this can
only be achieved by carrying out the reaction above the
softening temperature+ of the polymer.
The number of chain polymerizations that can be
performed in a homogeneous phase is very limited, only a
few monomers are able to dissolve their own polymers
(e.g. styrene and methyl methacrylate).
However, temperatures above the softening point often
cannot be used for kinetic and thermodynamic reasons
(e.g. ceiling temperature*, low molecular weights, increase
of side reactions).
+ For

a substance which does not have a definite melting point, the temperature at which viscous flow changes to plastic flow.
*The temperature at which the propagation and de-propagation rates are equal, that is, the net rate of polymer formation is
zero. Above the ceiling temperature, de-polymerization (i.e. an unzipping reaction to reform monomer) occurs.
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 In contrast, the stepwise polymerizations in the

homogeneous phase are the most frequently performed
processes on an industrial scale.
This is due to the resulting polymers usually have high
softening points (above 250 C are necessary) and high
molecular weight, thus the melt viscosity increases with
progressing reaction.
However, the removal of the highly volatile reaction
products (e.g. water, alcohol) to obtain high molecular
masses, is difficult.
This can be minimized by evacuation and intensive
mixing, which create larger surfaces and short diffusion
paths.
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 High thermal stabilities of the starting materials and the

polymers produced are necessary for long reaction time
and high temperatures.
Many high-melting polyamides (2100C 2650C) are not
accessible by this process and must be prepared in
solution or by interfacial condensation polymerization

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Heterogeneous bulk polymerization

In heterogeneous polymerizations in bulk, the formed
polymer is insoluble in its monomer and the reaction is
performed below the softening point of the polymer.
On an industrial scale, this type of process is especially
utilized for chain polymerizations e.g. radical
polymerization of liquid vinyl chloride or coordination
polymerization of liquid propylene with ZN or
metallocene catalysts.
Besides in the liquid phase, some reactions are also
performed in the solid state, for example, the
polymerization of acrylamide

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 A third possible heterogeneous bulk polymerization is in

the gaseous phase i.e. the reaction is performed with
gaseous monomers.
The gaseous monomer is adsorbed on the solid catalyst
particles and be polymerized.
With proceeding polymerization, the catalyst particles are
encapsulated by the solid polymer layer. The monomer
must diffuse from the gaseous phase through the polymer
layer to the catalytically active centers.
The reaction medium is now a gas/solid dispersion of a
solid polymer in its gaseous monomer.

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Advantages:
High yield per reactor volume
Easy polymer recovery (pure polymer)
Option to casting the polymerization
mixture into final product form i.e. cast
polymerization.
Disadvantages:
Difficulty of removing the last traces of
monomer.
Poor heat dissipation exothermic reaction

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