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Postpolymerization modification of poly(2-alkoxyethoxycarbonylmethylene)s: Efficient formation and reactivity of the ketene silyl acetal repeating units in the polymer main chain

Polymer Journal (2024)Cite this article

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Abstract

Postpolymerization modifications of poly(2-methoxyethoxycarbonylmethylene) (pMEDA’) and poly(2-phenoxyethoxycarbonylmethylene) (pPEDA’) are described. The reactions of these polymers with mixtures of chlorotrimethylsilane (Me3SiCl) and lithium diisopropylamide (LDA) efficiently transformed the alkoxycarbonylmethylene repeating units to ketene silyl acetals to yield a product with up to 93 mol% composition of the latter unit. The ketene silyl acetal composition of the product was controlled by changing the feed ratio of Me3SiCl/LDA with respect to the alkoxycarbonylmethylene unit. Tetrabutylammonium fluoride (TBAF)-mediated benzylation of the highly silylated polymer with benzyl bromide yielded a polymer containing side chain O (major)- and main chain C (minor)-benzylated units along with the unreacted ketene silyl acetal unit.

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Acknowledgements

This work was supported by JSPS KAKENHI (Grant Numbers JP18H02021, JP19K05586, JP19K22219, JP21H01988, and JP22K05219). The authors thank the Advanced Research Support Center (ADRES) at Ehime University for its assistance in NMR measurements and elemental analyses.

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  1. Department of Applied Chemistry, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama, 790-8577, Japan

    Hiroaki Shimomoto, Shota Inouchi, Tomomichi Itoh & Eiji Ihara

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  1. Hiroaki Shimomoto
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Shimomoto, H., Inouchi, S., Itoh, T. et al. Postpolymerization modification of poly(2-alkoxyethoxycarbonylmethylene)s: Efficient formation and reactivity of the ketene silyl acetal repeating units in the polymer main chain. Polym J (2024). https://doi.org/10.1038/s41428-024-00891-z

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