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Journal of Polymer Science Part B: Polymer Physics, Vol.42, No.14, 2801-2812, 2004
Heterochain model for simultaneous long-chain branching and crosslinking. III. Multicomponent polymerization
The matrix formula developed in the context of heterochain theory, M, (M) over bar (wp) + WF(I - M)S-1, was applied to describe the molecular weight development during free-radical multicomponent polymerization. All of the required probabilistic parameters are expressed in terms of the kinetic-rate constants and the various concentrations associated with them. In free-radical polymerization, the number of heterochain types, N, needs to be extrapolated to infinity, and such extrapolation is conducted with only three different N values. This matrix formula can be used as a benchmark test if other approximate approaches can give reasonable estimates of the weight-average molecular weights. The moment equations with the average pseudokinetic-rate constants for branching and crosslinking reactions may provide poor estimates when the copolymer composition drift during polymerization is very significant. (C) 2004 Wiley Periodicals, Inc.
Keywords:average molecular weight;radical polymerization;crosslinking;branched;Markovian statistics;method of moments;pseudo-kinetic-rate constants