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The principles for application of heterogeneous reaction models to the description of a chain process proceeding in a noncrystalline polymer body matrix were discussed. The basic experimental material required for constructing such models was obtained with the help of the model chain reaction of macromolecule arylation by dibenzoyl peroxide (11-18). Such study of this reaction on a number of polymers, performed in their glassy-like, highly elastic, and melt state, allowed us to clarity its significant kinetic features that differ from the dibenzoyl peroxide reaction with liquid analogues of the polymers studied.