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

Authors

  • Christopher Barner-Kowollik,

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    1. Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia
    • Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia
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  • Michelle L. Coote,

    1. Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia
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  • Thomas P. Davis,

    1. Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia
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  • Leo Radom,

    1. Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia
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  • Philipp Vana

    1. Institut für Physikalische Chemie, Georg-August-Universität Göttingen, Tammannstraße 6, 37077 Göttingen, Germany
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Abstract

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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