Abstract

In addition to the structural determination for the polymer main chain, such as tacticity and comonomer sequence as discussed in previous chapters (Chaps. 3, 4), analysis of end groups or abnormal linkages in polymer chains, which are very small in their weight fractions within the polymers, is a powerful technique for studies of the mechanism of polymerization [1, 2]. In the study of radical polymerization of vinyl monomers, 14C-labeled initiators were used to investigate the number of initiator fragments attached to the polymer chain ends [3, 4]. The number reflects the extent of two possible termination reactions, combination and disproportionation, as far as chain-transfer reactions are negligible. When a polymer molecule is formed through combination, the chain contains two initiator fragments on both ends, while that formed through disproportionation contains one fragment (Structure 5.1).

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