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Sulfanion-initiated open-vessel anionic ring-opening polymerization (AROP) of N-sulfonyl aziridines

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Abstract

Anionic ring-opening polymerization (AROP) of N-sulfonyl aziridines is an important synthetic route to linear polyethyleneimine (PEI) and its derivatives. In most cases, inert atmosphere and dry solvent were needed because of the oxygen- and water-sensitive initiators/catalysts used. Therefore, the AROP of N-sulfonyl aziridines that can be entirely operated in air atmosphere is still a challenging task. Herein, we report a series of sulfanions, including xanthates, dithiocarbamates, dithiobenzoates, thioacetates, and thiolates, as the initiators for the AROP of N-sulfonyl aziridines. Due to their good stability, open-vessel polymerization was achieved with high livingness, affording a range of well-defined α-, ω-telechelic poly(N-sulfonyl aziridine) homopolymers and block copolymers with narrow dispersities and tunable molecular weights. The α-end group of these polyaziridines was readily converted to thiol group, which enabled further post-polymerization functionalization with benzyl acrylate and poly(ethylene glycol) via thiol-ene click chemistry. The establishment of open-vessel sulfanion-initiated AROP of N-sulfonyl aziridines thus lays a solid foundation for the bulk preparation and application of poly(N-sulfonyl aziridine)s and PEI derivatives.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21905171, 21774077) and Shanghai Municipal Government (18JC1410800).

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Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Key Laboratory of Electrical Insulation and Thermal Aging, Shanghai Jiao Tong University, Shanghai, 200240, China

    Meng Huo, Yawen Bian, Chunyang Yu, Gangsheng Tong & Xinyuan Zhu

  2. Key Laboratory of Surface & Interface Science of Polymer Materials of Zhejiang Province, Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou, 310018, China

    Meng Huo

  3. Shanghai Aerospace Equipments Manufacturer Co., Ltd., Shanghai Engineering Research Center of Specialized Polymer Materials for Aerospace, Shanghai, 200245, China

    Chongyin Zhang

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  1. Meng Huo
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  2. Yawen Bian
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  3. Chunyang Yu
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  4. Gangsheng Tong
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  5. Chongyin Zhang
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  6. Xinyuan Zhu
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Correspondence to Chunyang Yu, Chongyin Zhang or Xinyuan Zhu.

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Huo, M., Bian, Y., Yu, C. et al. Sulfanion-initiated open-vessel anionic ring-opening polymerization (AROP) of N-sulfonyl aziridines. Sci. China Chem. 64, 1778–1785 (2021). https://doi.org/10.1007/s11426-021-1053-y

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  • DOI: https://doi.org/10.1007/s11426-021-1053-y

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