Chapter 17. A Missing Reaction Step in Dithiobenzoate-Mediated RAFT Polymerization

  1. Prof. Dr. Michael Buback1 and
  2. A. M. van Herk2
  1. Prof. Dr. Michael Buback,
  2. Olaf Janssen,
  3. Rainer Oswald,
  4. Stefan Schmatz and
  5. Philipp Vana

Published Online: 31 MAY 2007

DOI: 10.1002/9783527610860.ch17

Radical Polymerization: Kinetics and Mechanism, Volume 248

Radical Polymerization: Kinetics and Mechanism, Volume 248

How to Cite

Buback, M., Janssen, O., Oswald, R., Schmatz, S. and Vana, P. (2007) A Missing Reaction Step in Dithiobenzoate-Mediated RAFT Polymerization, in Radical Polymerization: Kinetics and Mechanism, Volume 248 (eds M. Buback and A. M. van Herk), Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany. doi: 10.1002/9783527610860.ch17

Editor Information

  1. 1

    Institute of Physical Chemistry, Georg-August-University Göttingen, Tammannstrasse 6, D-37077 Göttingen, Germany

  2. 2

    Laboratory for Polymer Chemistry, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven, The Netherlands

Author Information

  1. Institute of Physical Chemistry, Georg-August-University Göttingen, Tammannstrasse 6, D-37077 Göttingen, Germany

Publication History

  1. Published Online: 31 MAY 2007
  2. Published Print: 13 APR 2007

ISBN Information

Print ISBN: 9783527320561

Online ISBN: 9783527610860

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Keywords:

  • radical polymerization;
  • kinetics;
  • mechanism;
  • dithiobenzoate-mediated RAFT polymerization;
  • living polymerization;
  • quantum chemistry;
  • reaction mechanism;
  • reversible addition fragmentation chain transfer (RAFT);
  • missing step reaction;
  • reaction enthalpies;
  • reaction free enthalpies

Summary

The debate on the mechanism of dithiobenzoate-mediated RAFT polymerization may be overcome by taking the so-called “missing step” reaction between a highly reactive propagating radical and the three-arm star-shaped product of the combination reaction of an intermediate RAFT radical and a propagating radical into account. The “missing step” reaction transforms a propagating radical and a not overly stable three-arm star species into a resonance-stabilized RAFT intermediate radical and a stable polymer molecule. The enormous driving force behind the “missing step” reaction is estimated via DFT calculations of reaction enthalpies and reaction free enthalpies.