Molecular orbital theory of reactivity in radical polymerization. Part II

Abstract

Abstract Several problems in the process of radical polymerization, e.g. , the relation between the chemical structure of vinyl monomer and its chemical reactivity, the prevalence of head‐to‐tail configuration, the reactivity of initiator radicals, the alternation tendency in heteropolymerization, and the relative ease of coupling in several cases of homopolymerization, are treated by the theory previously proposed by the present authors, in which reactivity is represented by the magnitude of stabilization energy due to π conjugation between a monomer and a radical in the transition state. In addition, a brief discussion on the existing theories of reactivity and some applications of Hush's method to the problem of termination are presented. The agreement between results of calculation and experiment is shown to be almost statisfactory.