Chapter 3. Propagation Kinetics of Free-Radical Methacrylic Acid Polymerization in Aqueous Solution. The Effect of Concentration and Degree of Ionization

  1. Prof. Dr. Michael Buback3 and
  2. A. M. van Herk4
  1. Sabine Beuermann1,3,
  2. Prof. Dr. Michael Buback3,
  3. Pascal Hesse3,
  4. Silvia Kukučková2,3 and
  5. Igor Lacík2

Published Online: 31 MAY 2007

DOI: 10.1002/9783527610860.ch3

Radical Polymerization: Kinetics and Mechanism, Volume 248

Radical Polymerization: Kinetics and Mechanism, Volume 248

How to Cite

Beuermann, S., Buback, M., Hesse, P., Kukučková, S. and Lacík, I. (2007) Propagation Kinetics of Free-Radical Methacrylic Acid Polymerization in Aqueous Solution. The Effect of Concentration and Degree of Ionization, 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.ch3

Editor Information

  1. 3

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

  2. 4

    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. 1

    University of Potsdam, Institute of Chemistry, Polymer Chemistry, Karl-Liebknecht-Str. 24-25, D-14476 Golm/Potsdam, Germany

  2. 2

    Polymer Institute of the Slovak Academy of Sciences, Dúbravská cesta 9, 842 36 Bratislava, Slovakia

  3. 3

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

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:

  • aqueous-phase polymerization;
  • free-radical polymerization;
  • methacrylic acid;
  • PLP-SEC;
  • propagation rate coefficients;
  • pulsed-laser initiation;
  • water-soluble monomers

Summary

Propagation rate coefficients, kp, of free-radical methacrylic acid (MAA) polymerization in aqueous solution are presented and discussed. The data has been obtained via the pulsed laser polymerization – size-exclusion chromatography (PLP-SEC) technique within extended ranges of both monomer concentration, from dilute solution up to bulk MAA polymerization, and of degree of ionic dissociation, from non-ionized to fully ionized MAA. A significant decrease of kp, by about one order of magnitude, has been observed upon increasing monomer concentration in the polymerization of non-ionized MAA. Approximately the same decrease of kp occurs upon varying the degree of MAA ionization, α, at low MAA concentration from α=0 to α=1. With partially ionized MAA, the decrease of kp upon increasing MAA concentration is distinctly weaker. For fully ionized MAA, the propagation rate coefficient even increases toward higher MAA concentration. The changes of kp measured as a function of monomer concentration and degree of ionization may be consistently interpreted via transition state theory. The effects on kp are essentially changes of the Arrhenius pre-exponential factor, which reflects internal rotational mobility of the transition state (TS) structure for propagation. Friction of internal rotation of the TS structure is induced by ionic and/or hydrogen-bonded intermolecular interaction of the activated state with the molecular environment.