Chapter 1. The Cutthroat Competition Between Termination and Transfer to Shape the Kinetics of Radical Polymerization

  1. Prof. Dr. Michael Buback2 and
  2. A. M. van Herk3
  1. Gregory B. Smith and
  2. Gregory T. Russell

Published Online: 31 MAY 2007

DOI: 10.1002/9783527610860.ch1

Radical Polymerization: Kinetics and Mechanism, Volume 248

Radical Polymerization: Kinetics and Mechanism, Volume 248

How to Cite

Smith, G. B. and Russell, G. T. (2007) The Cutthroat Competition Between Termination and Transfer to Shape the Kinetics of Radical 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.ch1

Editor Information

  1. 2

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

  2. 3

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

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:

  • chain transfer;
  • radical polymerisation;
  • termination;
  • kinetics (polym.)

Summary

There is a fascinating interplay between termination and transfer that shapes the kinetics of radical polymerization (RP). In one limit all dead-chain formation is by termination, in the other by transfer. Because of chainlength-dependent termination (CLDT), the rate law for RP takes a different form in each limit. However, common behaviour is observed if one instead considers how the average termination rate coefficient varies with average degree of polymerization. Examples are given of using these principles to understand trends in actual RP data, and it is also demonstrated how to extract quantitative information on CLDT from simple steady-state experiments.