52

Polystyrene

of the monomers gives the same copolymer composition at

any conversion as shown by the straight line in Figure 3.7.

If the mixture contains 70 per cent styrene, however, the

copolymer chains formed at low conversions contain more

than 70 per cent styrene. The proportion of styrene in the

copolymer being formed decreases slowly as conversion in-

creases until the styrene is nearly consumed; then it drops

sharply and approaches zero. As polymerization approaches

100 per cent conversion the polymer chains being formed are

essentially pure polyacrylonitrile. A similar situation exists

when the monomer mixture contains 56 per cent or 33 per

cent styrene, the initial copolymer containing more styrene

than the monomer mixture. After the styrene is consumed,

however, polyacrylonitrile is formed. Some mixtures of the

copolymer and polyacrylonitrile may be opaque since the

different polymers present are not soluble in each other.

If the monomer mixture contains more than 76 per cent

styrene (e.g. 88 per cent) the copolymer chains formed at

low conversion will contain less than 88 per cent styrene. The

proportion of styrene increases as the conversion increases.

As 100 per cent conversion is approached copolymer chains

are formed which consist principally of styrene as contrasted

with the former case in which the proportion of acrylonitrile

increased with conversion.

Alpha-methylstyrene does not polymerize by a free radical

mechanism under the conditions used for styrene because

steric interference of the alpha-methyl groups and phenyl

groups causes excessively tight packing along the chain. A

mixture of styrene and alpha-methylstyrene (less than 50 per

cent) will copolymerize, however, though both rate and

molecular weight will be less in comparison with styrene

polymerization. Styrene, more reactive than alpha-methyl-

styrene, is consumed more rapidly; as conversion increases

the unreacted monomer mixture becomes richer in alpha-

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