Stereospecific radical polymerization of N-tert-butoxycarbonylacrylamide in the presence of fluorinated alcohols

Authors

  • Tomohiro Hirano,

    Corresponding author
    1. Department of Chemical Science and Technology, Institute of Technology and Science, The University of Tokushima, Minamijosanjima 2-1, Tokushima 770-8506, Japan
    • Department of Chemical Science and Technology, Institute of Technology and Science, The University of Tokushima, Minamijosanjima 2-1, Tokushima 770-8506, Japan
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  • Ryosuke Yamaoka,

    1. Department of Chemical Science and Technology, Institute of Technology and Science, The University of Tokushima, Minamijosanjima 2-1, Tokushima 770-8506, Japan
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  • Takamasa Miyazaki,

    1. Department of Chemical Science and Technology, Institute of Technology and Science, The University of Tokushima, Minamijosanjima 2-1, Tokushima 770-8506, Japan
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  • Koichi Ute

    1. Department of Chemical Science and Technology, Institute of Technology and Science, The University of Tokushima, Minamijosanjima 2-1, Tokushima 770-8506, Japan
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Abstract

Radical polymerization of N-tert-butoxycarbonylacrylamide (NBocAAm) in toluene at low temperatures in the presence of the fluorinated alcohols, 2,2,2-trifluoroethanol, 1,1,1,3,3,3-hexafluoro-2-propanol, and nonafluoro-tert-butanol, afforded atactic, heterotactic, and syndiotactic polymers, respectively. NMR analysis revealed that the fluorinated alcohols formed hydrogen bonding-assisted complexes with NBocAAm, with different structures. The difference in the structures of the complexes was responsible for the differences in the induced stereospecificities. Based on the structures of the complexes between NBocAAm and the fluorinated alcohols, mechanisms for the three kinds of stereospecific radical polymerizations are proposed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010

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