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. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2828–2832, 2003
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