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High-performance recyclable polymers enabled by stereo- and sequence-controlled polymerization

Nature Chemistry volume 17, pages 1119–1128 (2025)Cite this article

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Abstract

Monomer design strategy has become a powerful tool to access chemically recyclable polymers with desired and diverse properties. The presence of two or multiple stereogenic centres in one monomer offers a new dimension to fine-tune the polymer performance. However, it is still a formidable challenge in synthetic polymer chemistry to achieve precise stereocontrol and sequence control over the polymer microstructure. Here we report a stereo- and sequence-controlled polymerization of 5H-1,4-benzodioxepin-3(2H)-one-based monomers with two stereogenic centres (M) to furnish a series of isoenriched AB diblock polymers P(cis-M)-b-P(trans-M) and ABA triblock polymers P(trans-M)-b-P(cis-M)-b-P(trans-M). Notably, P(cis-M2)900-b-P(trans-M2)38 delivered impressive toughness and ductility, comparable to the commodity plastic isotactic polypropylene; the ABA triblock P(trans-M2)26-b-P(cis-M2)900-b-P(trans-M2)26 appeared to be softer and resembled low-density polyethylene. These various materials could fully convert to the monomer M. The establishment of stereo- and sequence-controlled polymerization not only provides an effective and robust strategy to tailor polymer properties on the molecular level, but also delivers various chemically recyclable materials that can be converted back to monomers.

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Fig. 1: Accessing chemically recyclable polymers with tunable properties via stereo- and sequence-controlled polymerization.
Fig. 2: Stereocontrolled ROP of cis-M1 and trans-M1.
Fig. 3: Stereocomplexation of P(cis-M1) and P(trans-M1).
Fig. 4: Stereo- and sequence-controlled polymerization.
Fig. 5: Application of stereo- and sequence-controlled polymerization.
Fig. 6: The chemical recycling study.

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Data availability

The authors declare that the data supporting the findings of this study are provided in the main Article and the Supplementary Information and are also available from the authors upon reasonable request. Crystallographic data for the structure of (R,R)-M1 reported in this Article have been deposited at the Cambridge Crystallographic Data Centre under deposition number CCDC 2367052. Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2021YFA1501700), the National Natural Science Foundation of China (22071163, 22301197 and 22371194), and the Fundamental Research Funds from Sichuan University (2023SCUNL103) and the State Key Laboratory of Polymer Materials Engineering (sklpme2020-3-15). We thank P.-C. Deng, D. Deng and J. Li for compound testing.

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Authors and Affiliations

  1. National Engineering Laboratory of Eco-Friendly Polymeric Materials (Sichuan), College of Chemistry, Sichuan University, Chengdu, P.R. China

    Meng-Yuan Wang, Yi-Min Tu, Qing-Qian Zeng, Kun Li, Wei Xiong, Zhongzheng Cai & Jian-Bo Zhu

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  1. Meng-Yuan Wang
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  2. Yi-Min Tu
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Contributions

J.-B.Z. conceived the project. Z.C. and J.-B.Z. directed the research. M.-Y.W. designed and conducted experiments related to polymer synthesis, polymer characterizations and catalyst synthesis. Y.-M.T. and Q.-Q.Z. conducted experiments related to polymer synthesis and characterizations. K.L. and W.X. conducted catalyst synthesis. M.-Y.W., Z.C. and J.-B.Z. wrote the initial paper and all authors contributed to the data analysis and discussions and the revised paper.

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Correspondence to Zhongzheng Cai or Jian-Bo Zhu.

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Nature Chemistry thanks Claudio De Rosa and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Figs. 1–186, discussion and Tables 1–31.

Supplementary Data 1

Crystallographic data for (R,R)-M1 (CCDC 2367052).

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Wang, MY., Tu, YM., Zeng, QQ. et al. High-performance recyclable polymers enabled by stereo- and sequence-controlled polymerization. Nat. Chem. 17, 1119–1128 (2025). https://doi.org/10.1038/s41557-025-01828-6

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