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Thermoresponsive behavior of dual hydrophilic diblock copolymers prepared via organotellurium-mediated living radical polymerization

Polymer Journal volume 56, pages 1129–1141 (2024)Cite this article

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Abstract

This study prepared dual thermoresponsive diblock copolymers (E95Nn; n = 93 and 291) comprising poly(ethylene glycol) ethyl ether acrylate (PeDEGA; E) and poly(N-isopropylacrylamide) (PNIPAM; N) blocks with different lower critical solution temperatures (LCSTs). E95Nn was prepared via organotellurium-mediated living radical polymerization through a one-pot synthesis method. Energy-dispersive X-ray spectroscopy revealed that tellurium residue at the polymer chain end was removed during purification via dialysis. The LCST of the PeDEGA was lower than that of PNIPAM. At temperatures below the LCST of PeDEGA, E95Nn dissolved as a single polymer chain (the unimer state). When an aqueous solution of E95Nn was heated, polymer micelles with a PeDEGA core and PNIPAM shells formed above the LCST of the PeDEGA. In pure water, 7–10 polymer micelles formed intermicellar aggregates. The polymer micelles encapsulated hydrophobic guest molecules into the hydrophobic core formed from the PeDEGA chains. Large intermicellar aggregates formed above the LCST of PNIPAM owing to hydrophobic interactions between the PNIPAM shells. It is expected that E95Nn polymer micelles can be applied as drug carriers for thermoresponsive controlled drug release.

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Acknowledgements

This research was partially supported by KAKENHI grants (21H02005, 23H04088, 21H05027) from the Japan Society for the Promotion of Science (JSPS), JSPS Bilateral Joint Research Projects (JPJSBP12022359, JPJSBP120203510), the Cooperative Research Program of the Network Joint Research Center for Materials and Devices (20,234,041), and the MEXT Promotion of Distinctive Joint Research Center Program (JPMXP 0621467946). The SAXS experiments were carried out at Spring-8 under the approval of JASRI. We would like to thank KJ Chemical for the gift of NIPAM. We would also like to thank Otsuka Chemical for the gift of BTEE.

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Authors and Affiliations

  1. Department of Applied Chemistry, University of Hyogo, Shosha, 2167, Himeji, Hyogo, Japan

    Misato Hayashi, Thi Ngan Vu & Shin-ichi Yusa

  2. Department of Energy Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8603, Aichi, Japan

    Rintaro Takahashi

  3. School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa, 923-1211, Japan

    Kazuaki Matsumura

  4. Institute for Chemical Research, Kyoto University, Uji, Kyoto, 611-0011, Japan

    Shigeru Yamago

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  1. Misato Hayashi
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Correspondence to Shin-ichi Yusa.

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Hayashi, M., Takahashi, R., Vu, T.N. et al. Thermoresponsive behavior of dual hydrophilic diblock copolymers prepared via organotellurium-mediated living radical polymerization. Polym J 56, 1129–1141 (2024). https://doi.org/10.1038/s41428-024-00952-3

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