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Chemoselective and Living/Controlled Polymerization of Alkenyl Methacrylates by the Phosphonium Ylide/Organoaluminum Lewis Pairs

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Abstract

Chemoselective, living/controlled polymerizations of allyl methacrylate (AMA) and vinyl methacrylate (VMA) with/without methyl methacrylate (MMA) by using the phosphonium ylide/organoaluminum based Lewis pairs (LPs) have been realized. The P-ylide-2/AlMe(BHT)2 (P-ylide-2 = Ph3P=CHMe and BHT = 2,6-iBu2-4-MeC6H2O) was demonstrated to be superior by which homopolymers PAMAs (Mn=27.6–111.5 kg/mol and Đ=1.14–1.25) and PVMAs (Mn=28.4–78.4 kg/mol and Đ=1.12–1.18) and block copolymers PMMA-b-PAMA, PAMA-b-PVMA, PAMA-b-PMMA, PMMA-b-PAMA-b-PMMA, PAMA-b-PMMA-b-PAMA, and PAMA-b-PVMA-b-PAMA were synthesized. In the polymerizations, all of the monomers were reacted by the conjugated ester vinyl groups leaving intactly the nonconjugated acryloxy groups. The pendant acryloxy groups attached to the main chain enable further to post-functionalization by the AIBN-induced radical “thiol-ene” reaction using PhCH2SH. The thiolether side group-containing polymers PAMA-SCH2Ph and PAMA-SCH2Ph-b-PMMA-b-PAMA-SCH2Ph were thus prepared.

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (Nos. 21972112 and 22225104) and China Postdoctoral Science Foundation (Nos. 2022TQ0115 and 2022M711297).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China

    Zhi-Kang Chen, Yi-Ling Zhao, Cong-Lei Liu, Liu-Yin Jiang & Hong-Ping Zhu

  2. State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, 130012, China

    Wu-Chao Zhao & Yue-Tao Zhang

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  1. Zhi-Kang Chen
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Chemoselective and Living/Controlled Polymerization of Alkenyl Methacrylates by the Phosphonium Ylide/Organoaluminum-Based Lewis Pairs

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Chen, ZK., Zhao, WC., Zhao, YL. et al. Chemoselective and Living/Controlled Polymerization of Alkenyl Methacrylates by the Phosphonium Ylide/Organoaluminum Lewis Pairs. Chin J Polym Sci 42, 159–167 (2024). https://doi.org/10.1007/s10118-023-3039-7

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