Chapter 13. Germanium- and Tin-Catalyzed Living Radical Polymerizations of Styrene and Methacrylates

  1. Prof. Dr. Michael Buback2 and
  2. A. M. van Herk3
  1. Atsushi Goto,
  2. Hirokazu Zushi,
  3. Norihiro Hirai,
  4. Tsutomu Wakada,
  5. Yungwan Kwak and
  6. Takeshi Fukuda

Published Online: 31 MAY 2007

DOI: 10.1002/9783527610860.ch13

Radical Polymerization: Kinetics and Mechanism, Volume 248

Radical Polymerization: Kinetics and Mechanism, Volume 248

How to Cite

Goto, A., Zushi, H., Hirai, N., Wakada, T., Kwak, Y. and Fukuda, T. (2007) Germanium- and Tin-Catalyzed Living Radical Polymerizations of Styrene and Methacrylates, 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.ch13

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. Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, 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:

  • germanium;
  • iodide;
  • living radical polymerization;
  • non-transition metal;
  • tin

Summary

Ge and Sn (non-transition-metal) catalyzed living radical polymerizations were developed. Low-polydispersity (Mw/Mn∼1.1–1.3) polystyrenes, poly(methyl methacrylates), poly(glycidyl methacrylates), and poly(2-hydroxyethyl methacrylate) with predicted molecular weights were obtained with a fairly high conversion in a fairly short time. The pseudo-first-order activation rate constant kact for the styrene/ GeI4 (catalyst) system was large enough, even with a small amount of GeI4, to explain why the system provides low-polydispersity polymers from an early stage of polymerization. The retardation in the polymerization rate observed for the styrene/GeI4 system was kinetically proved to be mainly due to the cross-termination between the propagating radical with GeI3. Attractive features of the Ge and Sn catalysts include their high reactivity hence small amounts (1–5 mM) being required under a mild condition (at 60–80 °C), high solubility in organic media without ligands, insensitivity to air hence sample preparation being allowed in the air, and minor color and smell. The Ge catalysts may also be attractive for their low toxicity.