The reversible addition-fragmentation chain transfer process and the strength and limitations of modeling: Comment on "The magnitude of the fragmentation rate coefficient"

Christopher Barner-Kowollik, Michelle L. Coote, Thomas P. Davis, Leo Radom, Philipp Vana

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There is appreciable uncertainty concerning the magnitude of the fragmentation rate coefficient of the intermediate radical in reversible addition-fragmentation chain transfer (RAFT) polymerizations. A large proportion of the experimental and theoretical evidence suggests that it is a stable species with a lifetime longer than 0.0001 s. This is particularly the case when the intermediate macro-RAFT radical is stabilized by a phenyl group attached to the radical center or has a poor leaving group. Although the occurrence to some extent of irreversible termination reactions cannot be excluded, we argue that such reactions are more likely to be a result of slow fragmentation of the intermediate macro-RAFT radical.

Original languageEnglish
Pages (from-to)2828-2832
Number of pages5
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Issue number18
Publication statusPublished - 15 Sept 2003
Externally publishedYes


  • Kinetics (polym.)
  • Living free-radical polymerization
  • Modeling
  • Quantum chemistry
  • Reversible addition-fragmentation chain transfer (RAFT)

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