Abstract
A novel kinetic treatment is proposed for the copolymerization of two monomers, M 1 and M 2, when M 2 has a low ceiling temperature. In the mechanism used, the growing copolymer with a terminal −M 2M 2· can undergo depropagation to −M 2· and M 2. If [M 1] ⪢ [M 2], as is possible experimentally when M 2 is radioactively labelled, a value of the reactivity ratio r 1 which is independent of the ceiling temperature effect can be obtained. This value is then used to obtain a value of the reactivity ratio r 2 which is also independent of the ceiling temperature effect. The derivation is valid provided that r 2 is small, which is often the case when M 2 has a low ceiling temperature. The method involves solution for r 2 by means of intersecting parabolas, each one representing a given monomer feed ratio and copolymer composition ratio.
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