Simulation of gradient copolymers synthesis via conformation-dependent graft copolymerization near a uniform adsorbing surfaceстатья
Статья опубликована в высокорейтинговом журнале
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Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.
Аннотация:A statistical model is developed for radical graft copolymerization in a solution of monomers A and B in the vicinity of a surface selectively absorbing the monomers of type A and corresponding copolymer sections. The influence of the monomer concentrations and the short-range monomer A-surface attraction on the copolymer sequence is investigated. It is shown that under certain conditions, the adsorption copolymerization can yield gradient copolymers. We find three copolymerization regimes corresponding to different values of dimensionless adsorption energy u. When the growing macroradical is weakly or nonadsorbed, u < u(c) (u(c) is the critical adsorption energy), the statistical properties of graft copolymers approach asymptotically, in the long-chain limit, to those of a random copolymer. If u greater than or similar to u(c), the statistics of designed and random copolymers is very different. In the vicinity of uc, the adsorption copolymerization leads to copolymers with the largest compositional nonuniformity and well-pronounced gradient that extends along the entire chain. In the strong adsorption regime, u >> u(c), the statistical properties of the graft copolymers do not depend on u and are determined mainly by the concentration of the monomer A in the adsorption layer.