Precise Synthesis of New Triblock Co- and Terpolymers by a Methodology Combining Living Anionic Polymers with a Specially Designed Linking Reaction

Authors

  • Yuri Matsuo,

    1. Polymeric and Organic Materials Department, Graduate School of Science and Engineering, Tokyo Institute of Technology, S1-6, 2-12-1, Ohokayama, Meguro-ku, Tokyo, 152-8552, Japan
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  • Toshiyuki Oie,

    1. Polymeric and Organic Materials Department, Graduate School of Science and Engineering, Tokyo Institute of Technology, S1-6, 2-12-1, Ohokayama, Meguro-ku, Tokyo, 152-8552, Japan
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  • Raita Goseki,

    1. Polymeric and Organic Materials Department, Graduate School of Science and Engineering, Tokyo Institute of Technology, S1-6, 2-12-1, Ohokayama, Meguro-ku, Tokyo, 152-8552, Japan
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  • Takashi Ishizone,

    1. Polymeric and Organic Materials Department, Graduate School of Science and Engineering, Tokyo Institute of Technology, S1-6, 2-12-1, Ohokayama, Meguro-ku, Tokyo, 152-8552, Japan
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  • Kenji Sugiyama,

    1. Chemical Science and Engineering Department, Faculty of Bioscience and Applied Chemistry, Hosei University, 3-7-2, Kajino-cho, Koganei, Tokyo, 184-8584, Japan
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  • Akira Hirao

    Corresponding author
    1. Polymeric and Organic Materials Department, Graduate School of Science and Engineering, Tokyo Institute of Technology, S1-6, 2-12-1, Ohokayama, Meguro-ku, Tokyo, 152-8552, Japan
    • Fax: (+81)5734 2887
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Abstract

Five A-B-A′, A-C-A′, B-A-B′, C-A-C′, and C-B-C′ triblock terpolymers with block orders difficult to synthesize by sequential polymerization have been successfully synthesized by a new methodology combining living anionic polymers with a specially designed linking reaction using α-phenylacrylate as the reaction site. Here, A(A′), B(B′), and C(C′) represent groups of polymers (having chain-end anions with different nucleophilicities), which are only polymerizable from A(A′) to B(B′) to C(C′) via sequential polymerization. The corresponding polymers are polystyrene (A) and poly(α-methylstyrene) (A′), poly(2-vinylpyridine) (B) and poly(4-vinylpyridine) (B′) and polymers from methacrylate type monomers like poly(methyl methacrylate) (C), poly(tert-butyl methacrylate) (C′), poly(2-hydroxyethyl methacrylate) (C′), poly(2,3-dihydroxypropyl methacrylate) (C′), and poly(ferrocenylmethyl methacrylate) (C′). Furthermore, three synthetically difficult B-A-B, C-A-C, and C-B-C triblock copolymers with molecular asymmetry in both side blocks have also been synthesized by the developed methodology. All of the polymers thus synthesized are quite new triblock terpolymers and copolymers with well-defined structures, i.e., precisely controlled molecular weights, compositions and narrow molecular weight distributions (Mw/Mn ≤ 1.05).

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