Interconvertible Living Radical and Cationic Polymerization through Reversible Activation of Dormant Species with Dual Activity

Authors

  • Dr. Hiroshi Aoshima,

    1. Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan)
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  • Mineto Uchiyama,

    1. Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan)
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  • Prof. Dr. Kotaro Satoh,

    Corresponding author
    1. Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan)
    • Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan)

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  • Prof. Dr. Masami Kamigaito

    Corresponding author
    1. Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan)
    • Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan)

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  • This work was supported in part by JSPS Research Fellowships for Young Scientists for H.A. (No. 24-10127), a Grant-in-Aid for Young Scientists (A) (No. 23685023) and Scientific Research (A) (No. 26248032) for K.S. by the Japan Society for the Promotion of Science, and Program for Leading Graduate Schools “Integrative Graduate Education and Research Program in Green Natural Sciences”.

Abstract

The polymerization of vinyl monomers generally requires the selection of an appropriate single intermediate, whereas in copolymerization, the selection of the comonomer is limited by the intermediate. Herein, we propose interconvertible dual active species that can connect comonomers through different mechanisms to produce specific comonomer sequences in a single polymer chain. More specifically, two different stimuli, that is, a radical initiator and a Lewis acid, are used to activate the common dormant C[BOND]SC(S)Z group into radical and cationic species, thereby inducing interconvertible radical and cationic copolymerization of acrylate and vinyl ether to produce a copolymer chain that consists of radically and cationically polymerized segments. The dual reversible activation provides control over molecular weights and multiblock copolymers with tunable segment lengths.

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