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Polystyrene

starts in tiny micelles of sodium stearate (much smaller than

the droplets) which are dispersed in the water phase. Styrene

diffuses from the monomer droplets into the micelles while

free radicals, formed in the water phase by decomposition of

the initiator, also diffuse into the soap micelles and start poly-

merization. As polymerization proceeds in the micelle more

soap is required to cover its surface so that by the time poly-

merization has reached 15 per cent conversion all the soap

micelles have disappeared. From then on the system consists

of relatively large droplets of monomer and small polymer

particles swollen by monomer and stabilized by a surface

layer of soap. These small particles were designated by the

late Professor W. Harkins as the "principal locus of reaction";

the soap micelles were called the "locus of initiation."

One chain grows in each micelle or particle until by

diffusion it receives another initiator free radical from the

aqueous phase; then the two free radicals react instantly with

each other and chain growth stops. No additonal polymeriza-

tion occurs in this particle until another initiator free radical

diffuses into it. Half the initiator free radicals initiate chain

growth and half terminate it. Thus it can be shown mathe-

matically that at any given instant only half the particles con-

tain a growing polymer radical.

A growing polymer radical in one particle cannot react


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with one in another because the two are physically isolated

by the water phase. Since a polymer radical may have a rela-

tively long time to grow (e.g. 10 to 100 seconds) 1 before an

initiator free radical can enter the particle, the molecular

weight obtained may be higher than that generally ob-

tained in bulk polymerization. Molecular weights as high as

20,000,000 have been obtained in emulsion polymerization

of styrene. In order to control molecular weight it is usually

1 Smith, J. Am. Chem. Soc, 70, 3695 (1948).


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