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Preparation of self-healable, reshapable, and hydrolysable flexible polymer films via crosslinking with five-membered cyclic phosphoesters

Polymer Journal (2026) Cite this article

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Abstract

Designing dynamic covalent networks (DCNs) that can spontaneously undergo bond exchange reactions without catalysts is a promising strategy for producing self-healing, recyclable polymeric materials. In this study, flexible polymer films with phosphoester-based DCNs were prepared by subjecting a solution containing poly(2-hydroxyethyl methacrylate) (poly(HEMA)) and 2-methoxy-2-oxo-1,3,2-dioxaphospholane (MP) to heat-assisted solvent evaporation. The ring-opening esterification of MP with the hydroxy groups of poly(HEMA) resulted in the formation of β-hydroxy groups, which promoted continuous esterification with neighboring groups. The esterification proceeded without any catalysts, affording crosslinked network structures. The chemical structure of the networks was characterized by 1H–31P heteronuclear multiple bond correlation (HMBC) spectroscopy, which revealed the presence of repeating units of phosphoesters and crosslinks. The Young’s modulus of the films was controlled by changing the amount of phosphoester units in the films. When the amount of phosphoester units exceeded 0.7 molar equivalents per HEMA unit, flexible films could be obtained. More interestingly, the flexible films exhibited self-healing, reshaping, and degradable properties. This design approach could be applied to various polymers containing hydroxy groups, providing access to diverse sustainable polymeric materials.

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Acknowledgements

This work was supported by the Ministry of Trade, Industry and Energy (MOTIE) of Korea (Grant No. 20018324), KAKENHI from the Japan Society for the Promotion of Science (Grant No. 23H03750), and JST SPRING, Japan (Grant No. JPMJSP2150).

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Authors and Affiliations

  1. Graduate School of Science and Engineering, Kansai University, Suita, Japan

    Kazuho Maeda

  2. Department of Chemistry and Materials Engineering, Faculty of Chemistry, Materials and Bioengineering, Kansai University, Suita, Japan

    Yota Okuno & Yasuhiko Iwasaki

  3. ORDIST, Kansai University, Suita, Japan

    Yota Okuno & Yasuhiko Iwasaki

  4. Division of Materials Science, Nara Institute of Science and Technology, Ikoma, Japan

    Kanako Okuda & Hiroharu Ajiro

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  1. Kazuho Maeda
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  2. Yota Okuno
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  5. Yasuhiko Iwasaki
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Correspondence to Yasuhiko Iwasaki.

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Maeda, K., Okuno, Y., Okuda, K. et al. Preparation of self-healable, reshapable, and hydrolysable flexible polymer films via crosslinking with five-membered cyclic phosphoesters. Polym J (2026). https://doi.org/10.1038/s41428-026-01169-2

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