54

Polystyrene

The number average is the total weight divided by the total

number of molecules, or (2 X 1,000,000 + 10 x 100,000 +

5 X 10,000 + 5 X 2,000) divided by (2 + 10 + 5 + 5)

which equals 139,091. The weight average is determined by

multiplying each molecular weight by the total weight of

molecules of this size, adding the values and dividing by the

total weight. Thus (1,000,000 X 2,000,000 + 100,000 X

1,000,000 + 10,000 X 50,000 + 2,000 X 10,000) divided

by (2 x 1,000,000 + 10 X 100,000 + 5 X 10,000 + 5 X

2,000) equals 686,444. It is readily seen that molecules with

a weight of 2,000 make virtually no contribution to the weight

average; if they are ignored completely the average is 688,689,

an increase of 0.33 per cent, which is too small to measure.

On the other hand if they are ignored in the calculation of the

number average, that average is changed from 139,091 to

179,412, an increase of 29 per cent.

The width of distribution is indicated by the ratio of weight

average to number average which, in this hypothetical case,

is 4.93. Commercial polystyrenes rarely have so broad a dis-

tribution; the ratio is usually between 2.0 and 3.0. The ratio

obtained is dependent on the polymerization mechanism in-

volved. Thus it ran he jhown hy kinetjc_Jreatrnents thatjnr

free radicaljjplymerization the theoretical minimum ratio is 1.5

if _polymer chains are terminated by coupling, 2.0 if they are

. terminated by a_ chain transfer reaction. Broader distribution

usually is obtained in commercial practice as a result of

changing conditions during the course of polymerization.

Anionic polymerization by the "living polymer" technique

gives a theoretical minimum ratio of 1.00, closely approached

in experimental work; with heterogeneous catalysts it prob-

ably gives a much broader distribution, although there are no

published data.

A distribution curve for polystyrene with a number average

molecular weight of 80,000 prepared by free radical poly-

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