Basic Chemistry of Polystyrene

45

necessary to add a chain transfer agent. Generally aliphatic

mercaptans are used for this purpose in the manufacture of

synthetic rubber from styrene and butadiene.

When polymerization is complete the polymer particles

have a diameter of 0.02 to 0.2 microns. The beads in a sus-

pension polymerization system have a diameter of 50 to 1000

microns; thus the particle and bead volumes differ consider-

ably. There may be more than one polymer radical in each

droplet or bead in suspension polymerization; there is usually

only one in each emulsion particle.

Since polymerization in each emulsion particle is inde-

pendent of that in other particles the over-all rate of poly-

merization will depend on the number of particles present.

This in turn depends on the quantity of soap used. As the

temperature is increased in a particular system the rate of

chain propagation increases and, consequently, that of poly-

merization. An increase in initiator concentration frequently

does not cause an increase in the rate of polymerization since

the number of particles remains constant and only half are

active at any time. There have been instances in which in-

creased initiator concentration has increased the rate of poly-

merization. It is believed that either the number of particles

was also increased or the free radical concentration was so

high that there was more than one free radical per particle.
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Molecular weight is decreased as the rate of free radical

formation is increased (either by an increase in temperature

or initiator concentration) since free radicals enter the par-

ticles more often and cause more frequent interruptions of

chain growth. Thus the frequency of alternation between ac-

tivity and inactivity in each particle is increased.

In emulsion polymerization it is possible to obtain a much

higSerjiter7)FpdTy^ the bulk and sus-

pension processes which produce polymers having the same

moiecula^weight. In suspension and in bulk polymerization

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