40

Polystyrene

radicals, no free radicals are destroyed; the active center is

transferred from one chain to the beginning of another.

■ + H—SR' k,r RH -SR'

or > or + or

CI—CC13 RC1 -CC13

R'S-

or +

CI3O

Hydrocarbons such as toluene and ethylbenzene, as well as

styrene monomer, are weak transfer agents. Tf styrfpp jg

polymerized by heating in the absence of an initiator, poly-

mer chains are terminated principany_bychain transfer with

styrene. Since a radical may undergo several chain transfer"

reactions, several molecules of polystyrene may form before

it reacts with another free radical and is destroyed.

The above equations for the various rates contain a quan-

tity (R-), the concentration of free radicals, which cannot

readily be measured. From these equations it is possible to

derive simple relationships which contain only constants and

initiator concentration (I). Thus it can be shown that the rate

of polymerization is proportional to the square root of the

initiator concentration. Figure 3.4 shows the typical results

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obtained when styrene is polymerized at 100°C. The rate is

not zero at zero concentration because of thermal initiation.

If chain transfer is unimportant the reciprocal of the de-

gree of polymerization, ^, also is proportional to the square

root of the initiator concentration (see Figure 3.4). The value

of does not extrapolate to zero at zero concentration be-

cause of chain transfer with the monomer.

It can be shown that at any temperature the reciprocal of

degree of polymerization is proportional to the polymerization

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