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Reversible Chain Transfer Catalyzed Polymerization with Alkyl Iodides Generated from Alkyl Bromides by in Situ Halogen Exchange

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Abstract

Reversible chain transfer catalyzed polymerization (RTCP) is a practical and efficient process for the precise synthesis of polymers with special architecture by using simple phenols (2,4,6-trimethylphenol, TMP) or hydrocarbons (xanthene, XT) as efficient organocatalysts. Herein, alkyl iodide (R-I), which was generated from in situ bromine-iodine transformation of alkyl bromide (R-Br) with sodium iodide (NaI), was served as initiator to mediate RTCP with TMP or XT. MMA and other functional methacrylates, including GMA, DEAM, DMAEMA and BzMA, were successfully initiated by combining organocatalysts and azo initiators to yield polymers with low-polydispersity (Mw/Mn=1.1–1.5) and ideal monomer conversions (50%–90%) at moderate temperature. Moreover, 3-armstar polymers were also obtained by this method. The high chain-end fidelity of the obtained poly(methyl methacrylate) with iodine as chain-end group (PMMA-I) was confirmed by chain-extension reaction. The environmentally friendly initiators and organocatalysts exhibit powerful polymerization properties toward RTCP, providing a significant method to synthesize functional polymers.

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Acknowledgments

We gratefully acknowledge the financial support from Natural Science Foundation of Fujian Province (No.2019J05040), Key Program of Qingyuan Innovation Laboratory (No. 00221003), ‘111′ program and Talent program of Fuzhou University (No. GXRC-18041).

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Authors and Affiliations

  1. Department of Materials-Oriented Chemical Engineering, School of Chemical Engineering, Fuzhou University, Fuzhou, 350116, China

    Dan-Ni Gao, Yu-Lai Zhao, Jing-Yu Cai, Lin-Xi Hou & Long-Qiang Xiao

  2. Qingyuan Innovation Laboratory, Quanzhou, 362801, China

    Lin-Xi Hou & Long-Qiang Xiao

  3. Fujian Key Laboratory of Advanced Manufacturing Technology of Specialty Chemicals, Fuzhou University, Fuzhou, 350116, China

    Long-Qiang Xiao

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  1. Dan-Ni Gao
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  2. Yu-Lai Zhao
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  4. Lin-Xi Hou
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  5. Long-Qiang Xiao
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Correspondence to Lin-Xi Hou or Long-Qiang Xiao.

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Reversible Chain Transfer Catalyzed Polymerization with Alkyl Iodides Generated from Alkyl Bromides by in Situ Halogen Exchange

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Gao, DN., Zhao, YL., Cai, JY. et al. Reversible Chain Transfer Catalyzed Polymerization with Alkyl Iodides Generated from Alkyl Bromides by in Situ Halogen Exchange. Chin J Polym Sci 39, 1161–1168 (2021). https://doi.org/10.1007/s10118-021-2611-2

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  • DOI: https://doi.org/10.1007/s10118-021-2611-2

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