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Basic Chemistry of Polystyrene


methylstyrene. At high conversions it becomes predominantly

alpha-methylstyrene; the reluctance of alpha-methylstyrene

to homopolymerize prevents complete polymerization.

Copolymer composition curves cannot be extended to 100

per cent conversion because of incomplete polymerization,

and therefore are applicable only for mixtures containing less

than 50 per cent alpha-methylstyrene. Theoretically, how-

ever, they would resemble those for styrene and butadiene

except that they would bend downward as conversion in-

creases since styrene is more reactive than alpha-methylstyrene

but less so than butadiene.

If a methyl group is substituted in any position in the

phenyl group of styrene its behavior in polymerization and

copolymerization by a free radical mechanism is similar to

that of styrene. Copolymers with styrene have a fairly uni-

form composition, with a random arrangement of monomer

units in the chain. If methyl groups are substituted in both

ortho-positions polymerization is very slow.

Molecular Weight Distributions

When polystyrene chains are formed as the result of a

given set of polymerization conditions the chains have differ-

ent lengths; therefore it is necessary to define the average

chain length or molecular weight by either a number average

or a weight average. In calculating number average all mole-

cules are given equal consideration, irrespective of their size;

in calculating weight averages size is a factor. This can be

illustrated by simple calculations of average molecular weights

as in the following hypothetical case:

Number of Molecules Molecular Weight



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