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Polymer Science Series C

, 53:14 | Cite as

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. ChernikovaEmail author
  • M. L. Coote
  • C. Y. Lin
  • G. Gryn’ova
Article

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-molecular-mass reversible addition-fragmentation chain-transfer agents, equilibrium constants are calculated via the methods of computational chemistry.

Keywords

Tert Butyl Polymer Science Series Spin Trap Reversible Addition Fragmen Tation Chain Transfer Tert Butyl Radical 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Copyright information

© Pleiades Publishing, Ltd. 2011

Authors and Affiliations

  • V. B. Golubev
    • 1
  • A. N. Filippov
    • 1
  • E. V. Chernikova
    • 1
    Email author
  • M. L. Coote
    • 2
  • C. Y. Lin
    • 2
  • G. Gryn’ova
    • 2
  1. 1.Faculty of ChemistryMoscow State UniversityMoscowRussia
  2. 2.ARC Centre of Excellence for Free-Radical Chemistry and Biotechnology, Research School of ChemistryAustralian National UniversityCanberraAustralia

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