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Ring-opening alternating copolymerization of cyclic anhydrides and isobutylene oxide using organobase catalysts

Polymer Journal (2025)Cite this article

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Abstract

Ring-opening alternating copolymerization (ROAC) of cyclic anhydrides and epoxides is a promising approach for the well-controlled synthesis of polyesters with versatile structures. ROAC typically yields amorphous polyesters owing to challenges in controlling the main-chain stereochemistry, whereas most applied polyesters are crystalline. Isobutylene oxide (IBO), a highly symmetric epoxide, can overcome this issue, thus facilitating the synthesis of crystalline polyesters via ROAC. However, low reactivity and potential side reactions remain major obstacles to achieving an IBO-based ROAC in a controlled manner. In this study, we successfully developed a well-controlled ROAC of cyclic anhydrides and IBO using environmentally benign organobase catalysts. Using t-BuP2 as a catalyst, the ROAC of phthalic anhydride (PA) and IBO proceeds smoothly, yielding crystalline P(PA-alt-IBO) with narrow molecular weight distribution (Đ ≤ 1.1). This method was extended to other cyclic anhydrides and initiators, enabling the synthesis of polyesters with diverse structures. Additionally, this ROAC system was applied to the synthesis of copolymers, including statistical copolymer of P(PA-alt-IBO) and P(PA-alt-butylene oxide), as well as block copolymer comprising P(PA-alt-IBO) and poly(trimethylene carbonate). This study not only expands the scope of epoxides in ROAC but also provides a straightforward and precise strategy for synthesizing crystalline polyesters and further macromolecular designs.

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Acknowledgements

This work was financially supported by the Japan Society for the Promotion of Science (JSPS) Grant-in-Aid for Scientific Research(A) (24H00766), Grant-in-Aid for Early-Career Scientists (24K17719), Grant-in-Aid for JSPS Research Fellows, the Frontier Chemistry Center (Hokkaido University), the Photo-Excitonic Project (Hokkaido University), the List Sustainable Digital Transformation Catalyst Collaboration Research Platform (List-PF, Hokkaido University), the Project of Junior Scientist Promotion (Hokkaido University), and ENEOS TONENGENERAL Research/Development Encouragement & Scholarship Foundation. R.S. and T.G. gratefully acknowledges the JSPS Fellowship for Young Scientists. We would like to express our gratitude to Dr. Pingyu Jiang from the Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University for his help to the DFT calculation.

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Authors and Affiliations

  1. Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, Japan

    Moeno Sugiyama & Hiroto Ayakawa

  2. Division of Applied Chemistry, Faculty of Engineering, Hokkaido University, Sapporo, Japan

    Ryota Suzuki, Tianle Gao, Feng Li, Takuya Yamamoto, Takuya Isono & Toshifumi Satoh

  3. List Sustainable Digital Transformation Catalyst Collaboration Research Platform, Institute for Chemical Reaction Design and Discovery, Hokkaido University, Sapporo, Japan

    Toshifumi Satoh

  4. Department of Chemical & Materials Engineering, National Central University, Taoyuan, Taiwan

    Toshifumi Satoh

Authors
  1. Moeno Sugiyama
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  2. Ryota Suzuki
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  3. Hiroto Ayakawa
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  5. Feng Li
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Contributions

Moeno Sugiyama: Writing original draft, Methodology, Visualization, Data curation, Ryota Suzuki: Methodology, Data curation, Funding acquisition, Hiroto Ayakawa: Methodology, Tianle Gao: Data curation, Writing – review & editing, Funding acquisition, Feng Li: Supervision, Conceptualization, Methodology, Writing original draft, Writing – review & editing, Funding acquisition. Takuya Yamamoto: Supervision. Takuya Isono: Supervision, Writing – review & editing. Toshifumi Satoh: Supervision, Conceptualization, Writing – review & editing, Funding acquisition.

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Correspondence to Feng Li or Toshifumi Satoh.

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Sugiyama, M., Suzuki, R., Ayakawa, H. et al. Ring-opening alternating copolymerization of cyclic anhydrides and isobutylene oxide using organobase catalysts. Polym J (2025). https://doi.org/10.1038/s41428-025-01087-9

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  • DOI: https://doi.org/10.1038/s41428-025-01087-9

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