Chapter 19. Reaction Calorimetry for the Development of Ultrasound-Induced Polymerization Processes in CO2-Expanded Fluids

  1. Prof. Dr. Michael Buback3 and
  2. A. M. van Herk4
  1. Maartje F. Kemmere,
  2. Martijn W.A. Kuijpers and
  3. Jos T.F. Keurentjes

Published Online: 31 MAY 2007

DOI: 10.1002/9783527610860.ch19

Radical Polymerization: Kinetics and Mechanism, Volume 248

Radical Polymerization: Kinetics and Mechanism, Volume 248

How to Cite

Kemmere, M. F., Kuijpers, M. W.A. and Keurentjes, J. T.F. (2007) Reaction Calorimetry for the Development of Ultrasound-Induced Polymerization Processes in CO2-Expanded Fluids, 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.ch19

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. Process Development Group, Department of Chemical Engineering & Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB, The Netherlands

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:

  • radical polymerization;
  • kinetics;
  • mechanism;
  • polymer reaction engineering;
  • polymer materials;
  • reaction calorimetry;
  • ultrasound-induced polymerization;
  • processes in CO2-expanded fluids;
  • cavitation;
  • molecular weight distribution;
  • pressurized carbon dioxide;
  • radical polymerization;
  • ultrasound

Summary

A strong viscosity increase upon polymerization hinders radical formation during an ultrasound-induced bulk polymerization. Since CO2 acts as a strong anti-solvent for most polymers, it can be used to reduce the viscosity of the reaction mixture. In this work, a process for the ultrasound-induced polymerization in CO2-expanded fluids has been developed. Temperature oscillation calorimetry has been applied to study the influence of CO2 on the viscosity during the ultrasound-induced polymerization. In contrast to polymerizations in bulk, the results show that a low viscosity is maintained during polymerization reactions in CO2-expanded methyl methacrylate (MMA). As a consequence, a constant or even increasing polymerization rate is observed when pressurized CO2 is applied. Moreover, the ultrasound-induced polymer scission in CO2-expanded MMA is demonstrated, which appears to be a highly controlled process. Finally, a preliminary sustainable process design is presented for the production of 10 kg/hour pure PMMA (specialty product) in CO2-expanded MMA by ultrasound-induced initiation.