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Ring-expansion cationic cyclopolymerization of divinyl ethers: synthesis of macrocyclic cyclopolymers with 8- and 13-membered rings

Polymer Journal volume 58, pages 207–220 (2026) Cite this article

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Abstract

Herein, a ring-expansion cationic cyclopolymerization leading to the formation of macrocyclic cyclopolymers is reported. 4,4-Bis(vinyloxymethyl)cyclohexene (1), 5,5-bis(vinyloxymethyl)-2-bicyclo[2,2,1]heptane (2), 1,2-bis(vinyloxyethoxy)benzene (3) and 1,2-bis(2-vinyloxyethoxy)-3,5-di-tert-butylbenzene (4) were polymerized in toluene at 0 °C. A hemiacetal ester-incorporated cyclic initiator was used in conjunction with SnBr4 as a Lewis acid activator in the presence of 2,6-di-tert-butylpyridine (DTBP) and 1,4-dioxane was used to suppress uncontrolled initiation by adventitious proton impurities. All synthesized cyclopolymers (Cyclic-Poly(1), Cyclic-Poly(2), Cyclic-Poly(3) and Cyclic-Poly(4)) were ring-shaped, with number-average molecular weights of 5000–13,000 and respective degrees of cyclization of 98.2%, 98.9%, 96.0% and 98.0%. Except for Cyclic-Poly(3), all the macrocyclic cyclopolymers had a high degree of cyclization exceeding 98%. Cyclic-Poly(1), Cyclic-Poly(2) and Cyclic-Poly(4) were soluble in solvents up to 100% monomer conversion, whereas Cyclic-Poly(3) was partially insoluble in the later stages of polymerization (>65% monomer conversion). The glass transition temperature (Tg) was 127, 178, 98 and 136 °C for Cyclic-Poly(1), Cyclic-Poly(2), Cyclic-Poly(3) and Cyclic-Poly(4), respectively. The Tgs of the cyclic cyclopolymers were higher than those of the corresponding linear cyclopolymers.

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Acknowledgements

We are grateful to Nippon Carbide Industries (Tokyo, Japan) for providing the divinyl ethers 1 and 2.

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Authors and Affiliations

  1. School of Earth, Energy and Environmental Engineering, Faculty of Engineering, Kitami Institute of Technology, Kitami, Hokkaido, Japan

    Takeshi Namikoshi

  2. Department of Materials Science and Engineering, Graduate School of Engineering, University of Fukui, Bunkyo, Fukui, Japan

    Takafumi Yamamoto, Tamotsu Hashimoto, Michio Urushisaki & Toshikazu Sakaguchi

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  1. Takeshi Namikoshi
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  2. Takafumi Yamamoto
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  3. Tamotsu Hashimoto
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  4. Michio Urushisaki
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  5. Toshikazu Sakaguchi
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Correspondence to Takeshi Namikoshi or Tamotsu Hashimoto.

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Namikoshi, T., Yamamoto, T., Hashimoto, T. et al. Ring-expansion cationic cyclopolymerization of divinyl ethers: synthesis of macrocyclic cyclopolymers with 8- and 13-membered rings. Polym J 58, 207–220 (2026). https://doi.org/10.1038/s41428-025-01122-9

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