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A general statistical theory in direct relation to the kinetics of polymerization is developed for free radical polymerization with chain transfer. In the present paper this relationship is displayed in detail; analytical expressions are derived for the probabilities of reaction as functions of the reaction rates and the monomer conversion. The statistical treatment (cascade theory) of the polyreaction allows the calculation of the weight average degree of polymerization Pw, the z‐average mean square radius of gyration 〈S2〉z, and the particle scattering factor Pz(θ). While for linear chains the mentioned averages are determined by a single link probability, in the branched system these averages are characterized by a stochastic matrix whose elements are the various link probabilities. The theory is applied to poly(vinyl acetate). A good agreement is obtained with the experimental results of D. J. Stein for this polymer.
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Wolf et al. (1976) studied this question.
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