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A versatile approach for the synthesis of degradable polymers via controlled ring-opening metathesis copolymerization

Nature Chemistry volume 14, pages 53–58 (2022)Cite this article

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Abstract

Norbornene derivatives (NBEs) are common monomers for living ring-opening metathesis polymerization and yield polymers with low dispersities and diverse functionalities. However, the all-carbon backbone of poly-NBEs is non-degradable. Here we report a method to synthesize degradable polymers by copolymerizing 2,3-dihydrofuran with NBEs. 2,3-Dihydrofuran rapidly reacts with Grubbs catalyst to form a thermodynamically stable Ru Fischer carbene—the only detectable active Ru species during copolymerization—and the addition of NBEs becomes rate determining. This reactivity attenuates the NBE homoaddition and allows uniform incorporation of acid-degradable enol ether linkages throughout the copolymers, which enables complete polymer degradation while maintaining the favourable characteristics of living ring-opening metathesis polymerization. Copolymerization of 2,3-dihydrofuran with NBEs gives low dispersity polymers with tunable solubility, glass transition temperature and mechanical properties. These polymers can be fully degraded into small molecule or oligomeric species under mildly acidic conditions. This method can be readily adapted to traditional ring-opening metathesis polymerization of widely used NBEs to synthesize easily degradable polymers with tunable properties for various applications and for environmental sustainability.

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Fig. 1: Different strategies and compound types for producing ROMP-based materials.
Fig. 2: DHF–NBE copolymers and copolymer degradation products.
Fig. 3: 13C NMR spectroscopic analysis of dyads in P1a.
Fig. 4: Tensile properties of NBE–DHF copolymers.

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All data supporting the findings of this study are available within the Article and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

We thank the National Science Foundation for financial support (CHE-2106511). Y.X. thanks the Alfred Sloan Foundation for the Sloan fellowship.

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Authors and Affiliations

  1. Department of Chemistry, Stanford University, Stanford, CA, USA

    John D. Feist, Daniel C. Lee & Yan Xia

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  1. John D. Feist
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Contributions

J.D.F. and Y.X. conceived this project. J.D.F. performed the majority of the experiments and D.C.L. synthesized and characterized the water-soluble copolymers. J.D.F. and Y.X. wrote the manuscript with input from D.C.L.

Corresponding author

Correspondence to Yan Xia.

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Competing interests

J.D.F. and Y.X. are named inventors on a patent application (US Provisional Application 63/169,588) filed by Stanford University on the copolymerization method described in this work.

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Peer review information Nature Chemistry thanks the anonymous reviewers for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–33, Discussion and Tables 1 and 2.

Supplementary Video 1

Video showing degradation of crosslinked polymer P7bx upon addition of 1 drop of 1M HCl.

Source data

Source Data Fig. 2

Numerical data or dRI from GPC traces shown in Fig. 2.

Source Data Fig. 4

Numerical stress–strain data presented in Fig. 4.

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Feist, J.D., Lee, D.C. & Xia, Y. A versatile approach for the synthesis of degradable polymers via controlled ring-opening metathesis copolymerization. Nat. Chem. 14, 53–58 (2022). https://doi.org/10.1038/s41557-021-00810-2

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