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Synthesis of block copolymers through umpolung or treatment of propagating end of living cationic polytetrahydrofuran

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Abstract

Block copolymers containing polytetrahydrofuran segments were synthesized by umpolung or propagating end of the cationic living polymer and successive anionic polymerization of methacrylates (RMAs) or radical polymerization of RMAs, acrylonitrile (AN), and styrene (St). Living polytetrahydrofuran (poly-THF) was prepared by cationic polymerization of tetrahydrofuran (THF), whose propagation end was reduced by samarium(II) iodide (SmI2). Anionic polymerizations of RMAs were conducted by addition of the monomers to the reduced poly-THF to obtain poly(THF-b-RMAs). On the other hand, the 2-bromoisobutyrate group, which can act as an initiator of radical polymerization, was introduced to the cationic propagating end of poly-THF by adding sodium 2-bromoisobutyrate. Block copolymers were synthesized by living radical polymerization of RMAs, St, or AN using the 2-bromoisobutyrate-capped poly-THF as a macroinitiator and copper(I) bromide (CuBr) as a catalyst.

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Notes

  1. See supporting information.

  2. Broad absorptions are observed at 557 and 618 nm for the divalent samarium derivatives [37, 38] and 363 nm for the trivalent ones.

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Acknowledgements

This work was financially supported by JSR Corporation Inc.

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Authors and Affiliations

  1. Molecular Engineering Institute, Kindai University, 11-6 Kayanomori, Iizuka, Fukuoka Prefecture, 820-8555, Japan

    Ryota Seto, Shuhei Yamada, Kozo Matsumoto & Takeshi Endo

  2. Department of Biological and Environmental Chemistry, Kindai University, 11-6 Kayanomori, Iizuka, Fukuoka Prefecture, 820-8555, Japan

    Kozo Matsumoto

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  1. Ryota Seto
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  2. Shuhei Yamada
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Correspondence to Takeshi Endo.

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Seto, R., Yamada, S., Matsumoto, K. et al. Synthesis of block copolymers through umpolung or treatment of propagating end of living cationic polytetrahydrofuran. Polym. Bull. 76, 3355–3370 (2019). https://doi.org/10.1007/s00289-018-2527-3

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