Basic Chemistry of Polystyrene

49

radicals may react with each of the two monomers Mx and

M2. This is shown by the following equations:

-Mx- + Mt fen -Mt-M, • k

r, =

11

-Mt- + M2 ^12 -Mt-M2- *"

—M2« + M2 ^22 —M2—M2- ^

-M2- + M1 *2i -M2-Mx- 2

21

Each of these reactions has its own specific rate constant.

Although these constants are not easy to measure, the ratios

of these constants can be measured experimentally, as first

shown by Mayo and Lewis.1 These ratios can be used to show

not only the proportions of the two monomers going into the

copolymer chain at any conversion, but also the arrangement

of the monomer units in the chain.

The two most common cases are:

(1) One ratio is greater than unity and the other is less

than unity. If rt X r2 approaches unity, the units are

arranged at random along the chain as in the copoly-

merization of styrene and butadiene, with ratios of

approximately 0.6 and 1.5. If n X r2 is considerably

less than unity there is a tendency toward alternation.

(2) Both ratios are less than unity. There is a tendency

Generated for camelia_moise@yahoo.com on 2013-04-10 16:39 GMT / http://hdl.handle.net/2027/mdp.39015016511761

for the units to alternate in the chain as in the copoly-

merization of styrene and acrylonitrile, with ratios of

0.40 and 0.03. If both ratios approach zero there is

nearly perfect alternation as in the copolymerization

of styrene and maleic anhydride, with ratios of 0.04

and 0.00.

-M1-M2-M1-M2-M1-M2-

1 Mayo and Lewis, /. Am. Chem. Soc, 66, 1954 (1944); cf. Mayo

and Walling, Chem. Revs., 46, 191 (1950) for complete listing of re-

activity ratios.
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