Abstract
Based on a delocalization model for the regional selectivity and reactivity of free radicals in addition processes, developed earlier [Teor. Éksp. Khim., 23, No. 2, pp. 135–148 (1987)] and based on the concept of polarity (“phily”) of the attacking radical, a simple principle has been proposed for the selection of free radicals that model adequately the active center for the radical polymerization of olefins. In terms of donor-acceptor properties of the free radicals, imitating the corresponding growing macroradicals in a given copolymerizing system, effective criteria have been established for the alternating and statistical types of the radical copolymerization of binary systems of monomers; simple expressions have been proposed for the evaluation of the relative activities (copolymerization constants) of the olefin monomers; the probability has been analyzed of the occurrence of different variants of combination of the structural units in the copolymer chain. The efficiency of the modeling and the validity of the proposed criteria have been illustrated on examples for the copolymerization of binary systems, including olefins with different types of substituents.
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Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 23, No. 3, pp. 267–273, May–June, 1987.
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Volovik, S.V., Dyadyusha, G.G. & Staninets, V.I. Modeling of active centers for the radical copolymerization of olefins with free radicals. Theor Exp Chem 23, 249–254 (1987). https://doi.org/10.1007/BF00531375
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DOI: https://doi.org/10.1007/BF00531375