You are on page 1of 1

48 Polystyrene

Monomers frequently used in copolymerization are acry-

lonitrile, CH2=CH-CN; butadiene, CH2=CH-CH=CH2;

alpha-methylstyrene, CH2=C—CH3; and maleic anhydride.

CH=CH.

II

cc

II \ / \

ooo

The chemical composition of copolymer chains rarely cor-

responds exactly to that of the monomers since the copolymer

chains formed at the beginning of polymerization have a

different composition from that of the monomer mixture. This

is because the double bonds of two monomers usually differ

in their reactivity; one monomer will enter the copolymer

chain faster than the other. The most reactive monomer is

used up more rapidly, thus the monomer composition changes

as the conversion increases. As the monomer composition

changes the composition of the copolymer being formed also

changes. Extensive studies of the kinetics of copolymerization

have clarified the rules governing the proportions of two

monomers which go into the chain and the manner in which

they are arranged in the chain. This is determined by the

values of constants known as monomer reactivity ratios.

In copolymerization, chains are initiated as in homopoly-

merization, while their growth is usually terminated by the


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

reaction of two polymer radicals with each other. These re-

actions are important in controlling molecular weight. It is

the propagation reaction, however, that determines the com-

position of the copolymer. There are four propagation re-

actions to consider, since there are two types of polymer

radicals which may have either of the monomers on the active

end (here called —Mi- and —M2"). Each of these polymer


Public Domain, Google-digitized / http://www.hathitrust.org/access_use#pd-google

You might also like