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Nitroxide-mediated radical polymerization of carbon dioxide-expanded methyl methacrylate

  1. Da Wei Pu,
  2. Frank P. Lucien*,
  3. Per B. Zetterlund*

Article first published online: 13 OCT 2010

DOI: 10.1002/pola.24343

Issue

Journal of Polymer Science Part A: Polymer Chemistry

Journal of Polymer Science Part A: Polymer Chemistry

Volume 48, Issue 23, pages 5636–5641, 1 December 2010

Additional Information

How to Cite

Pu, D. W., Lucien, F. P. and Zetterlund, P. B. (2010), Nitroxide-mediated radical polymerization of carbon dioxide-expanded methyl methacrylate. J. Polym. Sci. A Polym. Chem., 48: 5636–5641. doi: 10.1002/pola.24343

Author Information

  1. Centre for Advanced Macromolecular Design (CAMD), School of Chemical Engineering, The University of New South Wales, UNSW Sydney, NSW 2052, Australia

*Centre for Advanced Macromolecular Design (CAMD), School of Chemical Engineering, The University of New South Wales, Sydney, NSW 2052, Australia

Publication History

  1. Issue published online: 28 OCT 2010
  2. Article first published online: 13 OCT 2010
  3. Manuscript Accepted: 23 AUG 2010
  4. Manuscript Received: 16 JUL 2010

Funded by

  • Australian Research Council for a Discovery. Grant Number: DP1093343

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Keywords:

  • carbon dioxide;
  • kinetics (polym.);
  • living radical polymerization (LRP);
  • nitroxide-mediated polymerization;
  • radical polymerization
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Nitroxide-mediated radical polymerization based on TEMPO has been performed for methyl methacrylate under conditions of CO2-expanded monomer at 7 MPa and 90°C. The fraction of propagating radicals lost due to disproportionation with nitroxide, a well-known problem in NMP of methacrylates, decreased in the presence of CO2. This is consistent with deactivation between propagating radical and nitroxide proceeding more rapidly in the lower viscosity induced by CO2. However, the polymerization ceased at relatively low conversions of approximately 19% both with and without CO2, indicating that disproportionation between propagating radical and nitroxide is a major problem also in CO2-expanded MMA.

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