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Metal-free synthesis of responsive polymers: Cloud point tuning by controlled “click” reaction

Authors

  • C. Remzi Becer,

    1. Laboratory of Organic and Macromolecular Chemistry, Friedrich-Schiller-University Jena, Humboldtstrasse 10, 07743 Jena, Germany
    2. Laboratory of Macromolecular Chemistry and Nanoscience, Eindhoven University of Technology, Den Dolech 2, 5612 AZ Eindhoven, The Netherlands
    3. Dutch Polymer Institute (DPI), John F. Kennedylaan 2, 5612 AB Eindhoven, The Netherlands
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  • Kenta Kokado,

    1. Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan
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  • Christine Weber,

    1. Laboratory of Organic and Macromolecular Chemistry, Friedrich-Schiller-University Jena, Humboldtstrasse 10, 07743 Jena, Germany
    2. Dutch Polymer Institute (DPI), John F. Kennedylaan 2, 5612 AB Eindhoven, The Netherlands
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  • Aydin Can,

    1. Laboratory of Organic and Macromolecular Chemistry, Friedrich-Schiller-University Jena, Humboldtstrasse 10, 07743 Jena, Germany
    2. Laboratory of Macromolecular Chemistry and Nanoscience, Eindhoven University of Technology, Den Dolech 2, 5612 AZ Eindhoven, The Netherlands
    3. Dutch Polymer Institute (DPI), John F. Kennedylaan 2, 5612 AB Eindhoven, The Netherlands
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  • Yoshiki Chujo,

    1. Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan
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  • Ulrich S. Schubert

    Corresponding author
    1. Laboratory of Organic and Macromolecular Chemistry, Friedrich-Schiller-University Jena, Humboldtstrasse 10, 07743 Jena, Germany
    2. Laboratory of Macromolecular Chemistry and Nanoscience, Eindhoven University of Technology, Den Dolech 2, 5612 AZ Eindhoven, The Netherlands
    3. Dutch Polymer Institute (DPI), John F. Kennedylaan 2, 5612 AB Eindhoven, The Netherlands
    • Laboratory of Organic and Macromolecular Chemistry, Friedrich-Schiller-University Jena, Humboldtstrasse 10, 07743 Jena, Germany
    Search for more papers by this author

Abstract

Nitroxide-mediated radical polymerization has been used for the preparation of pentafluorostyrene (PFS) homopolymers and random copolymers of PFS and oligo(ethyleneglycol) methacrylate (OEGMA8.5). The poly(pentafluorostyrene) homopolymers were reacted with thiophenol at different ratios at room temperature in the presence of triethylamine. The “clicked” polymers were characterized by 1H and 19F NMR spectroscopy and size exclusion chromatography. Moreover, the copolymerization kinetics of the PFS and OEGMA8.5 copolymers was followed, and the phase transition behavior of random copolymers with different compositions was discussed. Furthermore, copolymers of PFS and 2-(dimethylamino) ethyl methacrylate (DMAEMA) were prepared at various mole ratios, and the copolymer with a 10:90 ratio, respectively, was soluble in water at room temperature. Turbidimetry measurements were performed for PFS and OEGMA8.5 or DMAEMA copolymers to determine their cloud points. Finally, the PFS and OEGMA8.5 copolymer with a mole ratio of 60:40 was reacted further with thiophenol to increase the hydrophobic part in the copolymer. The cloud points of the obtained copolymers could be tuned from 87 to 33 °C by using not only the controlled radical polymerization but also the “click” reaction in a controlled fashion. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1278–1286, 2010

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