Chapter 9. Scope for Accessing the Chain Length Dependence of the Termination Rate Coefficient for Disparate Length Radicals in Acrylate Free Radical Polymerization

  1. Prof. Dr. Michael Buback2 and
  2. A. M. van Herk3
  1. Tara M. Lovestead,
  2. Thomas P. Davis,
  3. Martina H. Stenzel and
  4. Christopher Barner-Kowollik

Published Online: 31 MAY 2007

DOI: 10.1002/9783527610860.ch9

Radical Polymerization: Kinetics and Mechanism, Volume 248

Radical Polymerization: Kinetics and Mechanism, Volume 248

How to Cite

Lovestead, T. M., Davis, T. P., Stenzel, M. H. and Barner-Kowollik, C. (2007) Scope for Accessing the Chain Length Dependence of the Termination Rate Coefficient for Disparate Length Radicals in Acrylate Free 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.ch9

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. Centre for Advanced Macromolecular Design, School of Chemical Sciences and Engineering, The University of New South Wales, Sydney, New South Wales 2052, Australia

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:

  • backbiting;
  • chain length dependent termination (CLDT);
  • kinetics;
  • reversible addition fragmentation chain transfer (RAFT);
  • simulations

Summary

A method that utilizes reversible addition fragmentation chain transfer (RAFT) chemistry is evaluated on a theoretical basis to deduce the termination rate coefficient for disparate length radicals ks;lt in acrylate free radical polymerization, where s and l represent the arbitrary yet disparate chain lengths from either a “short” or “long” RAFT distribution. The method is based on a previously developed method for elucidation of ks;lt for the model monomer system styrene. The method was expanded to account for intramolecular chain transfer (i.e., the formation of mid-chain radicals via backbiting) and the free radical polymerization kinetic parameters of methyl acrylate. Simulations show that the method's predictive capability is sensitive to the polymerization rate's dependence on monomer concentration, i.e., the virtual monomer reaction order, which varies with the termination rate coefficient's value and chain length dependence. However, attaining the virtual monomer reaction order is a facile process and once known the method developed here that accounts for mid-chain radicals and virtual monomer reaction orders other than one seems robust enough to elucidate the chain length dependence of ks;lt for the more complex acrylate free radical polymerization.