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Modeling of free-radical polymerization with crosslinking: monoradical assumption and stationary-state hypothesis

The validity of the monoradical assumption and the stationary-state hypothesis in modeling of free-radical polymerization with branching and/or cross-linking was evaluated using the method of moments. The polymerization system involved the reactions of chain transfer to polymer and radical recombination. Therefore, the system was capable of gelation. The gelation behavior was controlled by the three groups of parameters: K fp M 0 /K t R, K tc /K t , and K p /K r . It can be shown that polyradical chains accumulate only in the vicinity of the gel point and beyond. The presence of polyradical chains gives higher chain growth rates and thus promotes gelation