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Vinyl polymers with fully degradable carbon backbones enabled by aromatization-driven C–C bond cleavage

Nature Chemistry volume 17, pages 746–755 (2025)Cite this article

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Abstract

Degradation of carbon-backbone polymers, which make up most plastics, remains a formidable challenge owing to strong and inert main-chain C–C bonds. While incorporation of comonomers that generate backbone radicals under certain conditions can induce degradation of the polymer chain, such strategies yield complex oligomer mixtures. Here we report aromatization-driven C–C bond cleavage as a viable and powerful strategy to endow the degradability into carbon backbones using acrylic polymers as a model example. The key to this new strategy is the efficient, living, alternating addition copolymerization of acrylates with simple, commercially available and biorenewable coumarin using a frustrated Lewis pair cooperative catalyst. The resulting acrylic copolymers are strong, transparent thermoplastics with key thermal, optical, mechanical properties comparable or superior to poly(methyl methacrylate). Under strong base, alternating copolymers can completely degrade at room temperature through efficient cleavage of main-chain C–C bonds utilizing aromatization as a thermodynamic driving force, to generate pure, pharmaceutically valuable molecules, thus affording durable, robust yet fully degradable carbon-backbone acrylic polymers.

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Fig. 1: Different strategies for producing degradable vinyl polymers.
Fig. 2: Living copolymerization of BA and CM.
Fig. 3: Energy profile of initial three conjugate-addition steps during the copolymerization of MA and CM at RT.
Fig. 4: Physical properties of acrylate/CM copolymers.
Fig. 5: Degradation behaviour of acrylate/CM copolymers.

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Data availability

All data that support the findings of this study are available within the article and its Supplementary Information, and/or from the corresponding authors on reasonable request.

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Acknowledgements

This work was supported by the National Key R&D Program of China (grant number 2021YFA1501700), the National Natural Science Foundation of China (grant numbers 22471286 and 52203020), the Science and Technology Commission of Shanghai Municipality (grant numbers 22ZR1481900, 23XD1424600 and 22YF1458100), the Strategic Priority Research Program of the Chinese Academy of Sciences (grant number XDB0610000) and the CAS Project for Young Scientists in Basic Research (YSBR-094). Y.S. is thankful for the financial support from the Youth Innovation Promotion Association CAS (2022253). The funders had no role in study design, data collection and analysis, decision to publish or preparation of the paper. We thank F. Xu at the Institute of Process Engineering, Chinese Academy of Sciences, for the assistance with the measurement of optical property.

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Author notes

  1. These authors contributed equally: Zhen-Hua Zhang, Yangyang Sun.

Authors and Affiliations

  1. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China

    Zhen-Hua Zhang, Yangyang Sun & Miao Hong

  2. Tianjin Key Lab of Composite and Functional Materials, School of Materials Science and Engineering, Tianjin University, Tianjin, China

    Zhen-Hua Zhang & Yuesheng Li

  3. LPCNO, Département de Génie Physique, INSA, Université Paul Sabatier—Toulouse III, Toulouse, France

    Thayalan Rajeshkumar & Laurent Maron

  4. School of Chemistry and Material Sciences, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou, China

    Miao Hong

Authors
  1. Zhen-Hua Zhang
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  4. Yuesheng Li
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Contributions

Z.-H.Z., Y.S. and M.H. conceived the idea and designed the experiments. Z.-H.Z. performed the polymerization experiments. Y.S. performed the degradation experiments. Z.-H.Z. and Y.L. conducted the physical property measurements. T.R. and L.M. performed the theoretical calculations. All authors participated in the data analyses and discussions. M.H. directed the project and wrote the paper.

Corresponding authors

Correspondence to Laurent Maron or Miao Hong.

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Competing interests

M.H., Z.-H.Z. and Y.S. are inventors on a Chinese patent application (number 2024104783860) submitted by the Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, that covers the synthesis of acrylate/CM random and alternating copolymers by Lewis pair catalyst and their degradations enabled by ACBC.

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Extended data

Extended Data Fig. 1 Overlay of 13C NMR spectra (CDCl3, RT) of polyacrylates and copolymers with different CM incorporations.

Long A-A and short A-A: long and short continuous acrylate sequences, respectively; A-CM: acrylate-CM alternating sequence.

Extended Data Fig. 2 Illustrative scheme of synthesis and full degradation of poly(MA-alt-CM)-based thermoset.

[BDA]0:[MA]0:[CM]0:[B(2,4-F2Ph)3]0:[PtBu3]0 = 5:200:525:2:1. In contrast to uncrosslinked analogue (Tg = 158.0 °C, Td = 274 °C), thermoset exhibited comparable Tg value (157.2 °C) and slightly lower thermal stability (Td = 251 °C).

Supplementary information

Supplementary Information

Full descriptions of the methods, computational details and optimized geometries, and Supplementary Tables 1–6 and Figs. 1–68.

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Zhang, ZH., Sun, Y., Rajeshkumar, T. et al. Vinyl polymers with fully degradable carbon backbones enabled by aromatization-driven C–C bond cleavage. Nat. Chem. 17, 746–755 (2025). https://doi.org/10.1038/s41557-025-01751-w

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