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Cyclic–acyclic monomers metathesis polymerization for the synthesis of degradable thermosets, thermoplastics and elastomers

Nature Synthesis volume 1, pages 956–966 (2022)Cite this article

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Abstract

Commercially available synthetic polymers have a variety of properties that range from ultrarigid thermosets to high-performance elastomers and include thermoplastic materials in between. However, their superior properties, such as durability and strength, are also responsible for their environmental persistence. The development of degradable and recyclable polymers is an attractive strategy to tackle this accumulation. Here we report cyclic–acyclic monomers metathesis polymerization to produce degradable thermoset, thermoplastic and elastomeric polymers. Specifically, metathesis-based copolymerization of dicyclopentadiene with a series of commercially available or easily accessible diene comonomers that bear degradable moieties can afford degradable polydicyclopentadiene thermosets. The use of triene comonomers can increase the cross-linking density and improve material properties. Copolymerization of these diene comonomers with cyclooctene or norbornene can afford degradable linear thermoplastic polymers. The introduction of a branched third comonomer leads to the formation of degradable elastomers. The material properties and degradability through different routes (including fluoride, acid and base treatment) of these polymers are investigated.

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Fig. 1: Known metathesis routes and the CAMMP approach for the synthesis of degradable polymers.
Fig. 2: ROMP approaches based on cyclic silyl ether monomers versus CAMMP approaches based on dienes to access degradable thermoset and linear polymers.
Fig. 3: Mechanical properties of the degradable thermoset materials.
Fig. 4: Degradation and recycling of the thermoset materials.
Fig. 5: Properties and recycling of the degradable thermoplastics and elastomers.

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Data availability

Source data are provided with this paper. All the data necessary to support the conclusions of this paper are available in the Supplementary Information, which includes materials, detailed experimental procedures and characterization, as well as the properties of the degradable materials (Supplementary Figs. 1–17), NMR spectroscopy of the monomers (Supplementary Figs. 18–28), NMR spectroscopy, SEC and DSC of the linear polymers (Supplementary Figs. 29–82) and NMR spectroscopy, SEC, DSC and FTIR of the degradation products (Supplementary Figs. 83–106).

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Acknowledgements

This work was supported by National Key R&D Program of China (no. 2021YFA1501700), National Natural Science Foundation of China (no. 52025031, U19B6001 and U1904212) and the K. C. Wong Education Foundation.

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Authors and Affiliations

  1. CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, China

    Guifu Si & Changle Chen

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  1. Guifu Si
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Contributions

C.C. conceived the project. G.S. performed the experiments regarding the synthesis and characterization. Both authors contributed to the data analysis and paper writing.

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Correspondence to Changle Chen.

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Nature Synthesis thanks the anonymous reviewers for their contribution to the peer review of this work. Primary Handling Editor: Alison Stoddart, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Experimental procedures, characterization, and properties of the degradable materials (Supplementary Figs. 1–17), NMR spectroscopy of monomers (Supplementary Figs. 18–28), NMR spectroscopy, SEC, DSC of linear polymers (Supplementary Figs. 29–82), and NMR spectroscopy, SEC, DSC, FTIR of degradation products (Supplementary Figs. 83–106).

Source data

Source Data Fig. 3

Stress–strain curves and DMA curves.

Source Data Fig. 4

1H NMR spectrum of the degraded product for M4 derived polydicyclopentadiene and stress–strain curves for samples of new and recycled polydicyclopentadiene.

Source Data Fig. 5

Stress–strain curves of polymer samples and hysteresis experiment of ten cycles at a strain of 300% for terpolymer of COE, COE-hex and M2.

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Si, G., Chen, C. Cyclic–acyclic monomers metathesis polymerization for the synthesis of degradable thermosets, thermoplastics and elastomers. Nat. Synth 1, 956–966 (2022). https://doi.org/10.1038/s44160-022-00163-9

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