Metal-Free Living Cationic Polymerization via Carbon-Sulfur Bonds (2)

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  • UCHIYAMA Mineto
    Department of Applied Chemistry, Graduate School of Engineering, Nagoya University
  • SATOH Kotaro
    Department of Applied Chemistry, Graduate School of Engineering, Nagoya University Precursory Research for Embryonic Science and Technology, Japan Science and Technology Agency
  • KAMIGAITO Masami
    Department of Applied Chemistry, Graduate School of Engineering, Nagoya University

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Other Title
  • 炭素－硫黄結合を介する金属触媒フリーの新しいリビングカチオン重合（2）
  • 炭素-硫黄結合を介する金属触媒フリーの新しいリビングカチオン重合(2)チオエーテルを用いたDT機構によるカチオン重合
  • タンソ-イオウ ケツゴウ オ カイスル キンゾク ショクバイ フリー ノ アタラシイ リビングカチオン ジュウゴウ(2)チオエーテル オ モチイタ DT キコウ ニ ヨル カチオン ジュウゴウ
  • チオエーテルを用いたDT機構によるカチオン重合
  • DT Mechanism Using Thioethers

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Abstract

This second review on novel metal-free cationic polymerizations is directed to living cationic polymerization that proceeds via reversible activation of carbon-sulfur bonds of thioethers via degenerative chain-transfer (DT) mechanism. In a similar way to cationic RAFT polymerization in the first review, a small amount of triflic acid generates the cationic propagating species, which interchanges with the thioether-dormant species via the sulfonium intermediate stabilized by the sulfur atom, to induce living cationic polymerization via the DT mechanism. This system can similarly control the molecular weight up to 1×105 with narrow molecular weight distributions (Mw/Mn < 1.2) and controlled chain-end groups in cationic polymerization of vinyl ethers and p-alkoxystyrene. The thioether-dormant species is highly stable and tolerant in comparison to the dormant species thus far reported in living cationic polymerization. This makes the obtained polymers applicable for subsequent post-polymerization reactions without any significant damages on the C-S bonds.

Journal

  • NIPPON GOMU KYOKAISHI

    NIPPON GOMU KYOKAISHI 88 (12), 461-465, 2015

    THE SOCIRETY OF RUBBER SCIENCE AND TECHNOLOGYY, JAPAN

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