Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
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Solubility and Thermoresponsiveness of PMMA in Alcohol-Water Solvent Mixtures

Richard Hoogenboom A B F , C. Remzi Becer A C D , Carlos Guerrero-Sanchez A D E , Stephanie Hoeppener A C D and Ulrich S. Schubert A C D F
+ Author Affiliations
- Author Affiliations

A Laboratory of Macromolecular Chemistry and Nanoscience, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven, The Netherlands.

B Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135, 6525AJ Nijmegen, The Netherlands.

C Laboratory of Organic and Macromolecular Chemistry, Friedrich-Schiller-University Jena, Humboldtstrasse 10, 07743 Jena, Germany.

D Dutch Polymer Institute (DPI), PO Box 902, 5600 AX Eindhoven, The Netherlands.

E Current address: CSIRO, Molecular and Health Technologies Division, Bag 10, Clayton South MDC, 3169 Victoria, Australia.

F Corresponding authors. Email: r.hoogenboom@tue.nl; ulrich.schubert@uni-jena.de

Australian Journal of Chemistry 63(8) 1173-1178 https://doi.org/10.1071/CH10083
Submitted: 13 February 2010  Accepted: 10 March 2010   Published: 10 August 2010

Abstract

To reduce the environmental burden of polymer processing, the use of non-toxic solvents is desirable. In this regard, the improved solubility of poly(methyl methacrylate) (PMMA) in ethanol/water solvent mixtures is very appealing. In this contribution, detailed investigations on the solubility of PMMA in alcohol/water solvent mixtures are reported based on turbidimetry measurements. PMMA revealed upper critical solution temperature transitions in pure ethanol and ethanol/water mixtures. However, around 80 wt-% ethanol content a solubility maximum was observed for PMMA as indicated by a decrease in the transition temperature. Moreover, the transition temperatures increased with increasing PMMA molar mass as well as increasing polymer concentration. Careful analysis of both heating and cooling turbidity curves revealed a peculiar hysteresis behaviour with a higher precipitation temperature compared with dissolution with less than 60 wt-% or more than 90 wt-% ethanol in water and a reverse hysteresis behaviour at intermediate ethanol fractions. Finally, the transfer of poly(styrene)-block-poly(methyl methacrylate) block copolymer micelles from the optimal solvent, i.e. aqueous 80 wt-% ethanol, to almost pure water and ethanol is demonstrated.


Acknowledgement

The authors would like to thank the Dutch Polymer Institute and the Netherlands Scientific Organization (Veni-grant of RH and Vici-award of USS) for their financial support. This work has been carried out with support of the Soft Matter cryo-TEM Research Unit, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology.


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