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Basic Chemistry of Polystyrene


(3) Rate of free radical formation is constant. Both the

rate and molecular weight increase as the tempera-

ture increases, though the rate of free radical forma-

tion is held constant either by changing initiator type

and concentration or using a constant source of


The above discussion on the polymerization of styrene

applies to styrene in bulk in the absence of a solvent. If a

solvent is present the same general principles are qualitatively

correct except that the molecular weight usually is reduced.

Styrene can be suspended in water in the form of droplets

and polymerized with or without a peroxide initiator. The

droplets normally have diameters of 0.1 to 1.0 mm or 100 to

1000 microns. The same general principles of polymeriza-

tion apply to suspension as to bulk polymerization. Thus

each droplet of styrene acts as an individual reaction vessel

in which free radicals are formed; polymer chains grow until

they are terminated by reaction of the radicals with each

other. A typical suspension system described by GrimJ^con.-

sists of equal quantities of water and styrene. a peroxide

initiator, 0.5 per cent tricalcium phosphate of very small

particle size and 0.01 per cent of an anionic surface agent

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Emulsion polymerization, employed extensively in the

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preparation of styrene-butadiene copolymer latices used in

water-base paints and synthetic rubber, is governed by

principles markedly different from those of bulk and suspen-

sion polymerization. A mixture of styrene, water, emulsifier

(e.g. sodium stearate) and a water-soluble catalyst (e.g:

potassium persulfate) is used. A suspension of relatively large

styrene droplets (up to 1 mm in diameter) is formed. Poly-

merization does not occur in these droplets, however, but

1 U. S. Patent, 2,673,194 (March 23, 1954).

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