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Critically Evaluated Termination Rate Coefficients for Free-Radical Polymerization, 1. The Current Situation

  1. Michael Buback1,
  2. Mark Egorov1,2,
  3. Robert G. Gilbert3,
  4. Vladimir Kaminsky2,
  5. Oskar F. Olaj4,
  6. Gregory T. Russell5,*,
  7. Philipp Vana4,6,
  8. Gerhard Zifferer4

Article first published online: 6 FEB 2003

DOI: 10.1002/macp.200290041

Issue

Macromolecular Chemistry and Physics

Macromolecular Chemistry and Physics

Volume 203, Issue 18, pages 2570–2582, December 2002

Additional Information

How to Cite

Buback, M., Egorov, M., Gilbert, R. G., Kaminsky, V., Olaj, O. F., Russell, G. T., Vana, P. and Zifferer, G. (2002), Critically Evaluated Termination Rate Coefficients for Free-Radical Polymerization, 1. The Current Situation. Macromolecular Chemistry and Physics, 203: 2570–2582. doi: 10.1002/macp.200290041

Author Information

  1. 1

    Institut für Physikalische Chemie, Universität Göttingen, Tammannstraße 6, D-37077 Göttingen, Germany

  2. 2

    Karpov Institute of Physical Chemistry, Ul. Vorontsovo pole 10, Moscow 103064, Russia

  3. 3

    Key Centre for Polymer Colloids, School of Chemistry, University of Sydney, NSW 2006, Australia

  4. 4

    Institut für Physikalische Chemie, Universität Wien, Währinger Straße 42, A-1090 Wien, Austria

  5. 5

    Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch, New Zealand

  6. 6

    Centre for Advanced Macromolecular Design, School of Chemical Engineering & Industrial Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia

*Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch, New Zealand. Fax: +64-3-364 2110

Publication History

  1. Issue published online: 6 FEB 2003
  2. Article first published online: 6 FEB 2003
  3. Manuscript Accepted: 15 AUG 2002
  4. Manuscript Revised: 31 JUL 2002
  5. Manuscript Received: 4 APR 2002

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Keywords:

  • chain-length dependence;
  • conversion dependence;
  • diffusion;
  • kinetics (polym.);
  • radical polymerization;
  • termination rate coefficient

Abstract

This is the first publication of an IUPAC-sponsored Task Group on “Critically evaluated termination rate coefficients for free-radical polymerization.” The paper summarizes the current situation with regard to the reliability of values of termination rate coefficients kt. It begins by illustrating the stark reality that there is large and unacceptable scatter in literature values of kt, and it is pointed out that some reasons for this are relatively easily remedied. However, the major reason for this situation is the inherent complexity of the phenomenon of termination in free-radical polymerization. It is our impression that this complexity is only incompletely grasped by many workers in the field, and a consequence of this tendency to oversimplify is that misunderstanding of and disagreement about termination are rampant. Therefore this paper presents a full discussion of the intricacies of kt: sections deal with diffusion control, conversion dependence, chain-length dependence, steady state and non-steady state measurements, activation energies and activation volumes, combination and disproportionation, and theories. All the presented concepts are developed from first principles, and only rigorous, fully-documented experimental results and theoretical investigations are cited as evidence. For this reason it can be said that this paper summarizes all that we, as a cross-section of workers in the field, agree on about termination in free-radical polymerization. Our discussion naturally leads to a series of recommendations regarding measurement of kt and reaching a more satisfactory understanding of this very important rate coefficient.

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