First Nitroxide-Mediated Controlled/Living Free Radical Polymerization in an Ionic Liquid

Authors

  • Julia Ryan,

    1. Department of Chemistry, National University of Ireland, Galway, Ireland
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  • Fawaz Aldabbagh,

    Corresponding author
    1. Department of Chemistry, National University of Ireland, Galway, Ireland
    • Department of Chemistry, National University of Ireland, Galway, Ireland. Fax: 00353 91 525700
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  • Per B. Zetterlund,

    Corresponding author
    1. Department of Applied and Bioapplied Chemistry, Faculty of Engineering, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan
    2. Current address: Graduate School of Science and Technology, Kobe University, Kobe 657-8501, Japan
    • Department of Applied and Bioapplied Chemistry, Faculty of Engineering, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan.
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  • Bunichiro Yamada

    Corresponding author
    1. Department of Applied and Bioapplied Chemistry, Faculty of Engineering, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan
    • Department of Applied and Bioapplied Chemistry, Faculty of Engineering, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan.
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Abstract

Summary: The controlled/living radical polymerizations of methyl acrylate in 50% v/v of an ionic liquid initiated by the alkoxyamine generated in situ from 4-oxo-2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (4-oxo-TEMPO) and 2,2′-azoisobutyronitrile (AIBN) at 140–155 °C are reported. The number-average molecular weights increased linearly with conversion, and polydispersity indices are approximately 1.4 in the best case. The rates of polymerization were greater than in anisole, and similar to the rate of spontaneous polymerization in the ionic liquid.

original image

equation image (filled symbols) and equation image (open symbols) vs. conversion for the MA polymerization in the presence of [4-oxo-TEMPO]/[AIBN] (2.8:1) in 50% v/v anisole with 0.03 M AIBN (squares) and 50% v/v [hmim][PF6] with 0.03 M AIBN (circles), and 0.06 M AIBN (triangles).

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