Chapter 6. Studying the Fundamentals of Radical Polymerization Using ESR in Combination with Controlled Radical Polymerization Methods

  1. Prof. Dr. Michael Buback2 and
  2. A. M. van Herk3
  1. Atsushi Kajiwara

Published Online: 31 MAY 2007

DOI: 10.1002/9783527610860.ch6

Radical Polymerization: Kinetics and Mechanism, Volume 248

Radical Polymerization: Kinetics and Mechanism, Volume 248

How to Cite

Kajiwara, A. (2007) Studying the Fundamentals of Radical Polymerization Using ESR in Combination with Controlled Radical Polymerization Methods, 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.ch6

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. Nara University of Education, Takabatake-cho, Nara 630-8528, Japan

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:

  • atom transfer radical polymerization (ATRP);
  • ESR/EPR;
  • kinetics (polym.);
  • radical polymerization

Summary

Electron spin resonance (ESR) spectroscopy can contribute to understanding both the kinetics and mechanism of radical polymerizations. A series of oligo/poly(meth)acrylates were prepared by atom transfer radical polymerization (ATRP) and purified to provide well defined radical precursors. Model radicals, with given chain lengths, were generated by reaction of the terminal halogens with an organotin compound and the radicals were observed by ESR spectroscopy. This combination of ESR with ATRPs ability to prepare well defined radical precursors provided significant new information on the properties of radicals in radical polymerizations. ESR spectra of the model radicals generated from tert-butyl methacrylate precursors, with various chain lengths, showed clear chain length dependent changes and a possibility of differentiating between the chain lengths of observed propagating radicals by ESR. The ESR spectrum of each dimeric, trimeric, tetrameric, and pentameric tert-butyl acrylate model radicals, observed at various temperatures, provided clear experimental evidence of a 1,5-hydrogen shift.