Chapter 15. NMR Spectroscopy in the Optimization and Evaluation of RAFT Agents

  1. Prof. Dr. Michael Buback3 and
  2. A. M. van Herk4
  1. Bert Klumperman1,2,
  2. James B. McLeary2,
  3. Eric T.A. van den Dungen2 and
  4. Gwenaelle Pound2

Published Online: 31 MAY 2007

DOI: 10.1002/9783527610860.ch15

Radical Polymerization: Kinetics and Mechanism, Volume 248

Radical Polymerization: Kinetics and Mechanism, Volume 248

How to Cite

Klumperman, B., McLeary, J. B., van den Dungen, E. T.A. and Pound, G. (2007) NMR Spectroscopy in the Optimization and Evaluation of RAFT Agents, 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.ch15

Editor Information

  1. 3

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

  2. 4

    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. 1

    Eindhoven University of Technology, Lab of Polymer Chemistry, P.O. Box 513, 5600MB Eindhoven, The Netherlands

  2. 2

    University of Stellenbosch, Dept. of Chemistry and Polymer Science, Private Bag X1, 7602 Matieland, South Africa

Publication History

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

ISBN Information

Print ISBN: 9783527320561

Online ISBN: 9783527610860



  • radical polymerization;
  • kinetics;
  • mechanism;
  • dithiobenzoates;
  • Dithioesters;
  • initialisation;
  • NMR spectroscopy;
  • RAFT-mediated polymerization;
  • xanthates


The selection of a suitable mediating agent in Reversible Addition-Fragmentation Chain Transfer (RAFT) mediated polymerization is crucial to the degree of control that can be achieved. An overview of work from the Stellenbosch group is presented in which the use of NMR spectroscopy as a tool for evaluating RAFT-agents is highlighted. The occurrence of selective initialization, i.e. the selective conversion of a RAFT-agent into its single monomer adduct is discussed for various classes of monomers, as well as for copolymerization. One of the general rules for living polymerization is that chains should start growing early in the polymerization reaction. Selective initialization is claimed to be the extreme case where all chains have begun growing after the conversion of only one monomer equivalent per RAFT-agent.