Chapter 17. A Missing Reaction Step in Dithiobenzoate-Mediated RAFT Polymerization
- Prof. Dr. Michael Buback1,
- A. M. van Herk2
Published Online: 31 MAY 2007
DOI: 10.1002/9783527610860.ch17
Copyright © 2007 Wiley-VCH Verlag GmbH & Co. KGaA
Book Title
Radical Polymerization: Kinetics and Mechanism, Volume 248
Additional Information
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
Institute of Physical Chemistry, Georg-August-University Göttingen, Tammannstrasse 6, D-37077 Göttingen, Germany
- 2
Laboratory for Polymer Chemistry, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven, The Netherlands
Publication History
- Published Online: 31 MAY 2007
- Published Print: 13 APR 2007
Book Series:
ISBN Information
Print ISBN: 9783527320561
Online ISBN: 9783527610860
- Summary
- Chapter
- References
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.