The use of spin traps for the kinetic investigation of elementary events of pseudoliving radical reversible addition-fragmentation chain-transfer polymerization

V. B. Golubev, A. N. Filippov, E. V. Chernikova, M. L. Coote, C. Y. Lin, G. Gryn'ova

Research output: Contribution to journalArticlepeer-review

7 Citations (Scopus)

Abstract

The spin-trapping technique is used for the first time to study the kinetics and mechanism of addition and fragmentation elementary events in reversible addition-fragmentation chain-transfer pseudoliving radical polymerization. As shown by the example of the spin-trap-reversible addition-fragmentation chaintransfer agent model system, the constants of addition (substitution) of the model tert-butyl radical to polymeric reversible addition-fragmentation chain-transfer agents (poly(styrene dithiobenzoate), poly(n-butyl acrylate) dithiobenzoate, etc.) are one to two orders of magnitude higher than the constants of addition reactions involving low-molecular-mass reversible addition-fragmentation chain-transfer agents (tert-butyl dithiobenzoate, benzyl dithiobenzoate, di-tert-butyl trithiocarbonate, and dibenzyl trithiocarbonate). This circumstance makes it possible to significantly widen the synthetic possibilities of reversible addition-fragmentation chain-transfer polymerization. Rate constants of the fragmentation reaction for a number of intermediates are estimated, and the relationship between their structure and stability is ascertained. For the model reaction of the interaction (addition and fragmentation) of the tert-butyl radical with low-molecularmass reversible addition-fragmentation chain-transfer agents, equilibrium constants are calculated via the methods of computational chemistry.

Original languageEnglish
Article number14
Pages (from-to)14-26
Number of pages13
JournalPolymer Science - Series C
Volume53
Issue number1
DOIs
Publication statusPublished - 6 Sep 2011
Externally publishedYes

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