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Nature-inspired methylated polyhydroxybutyrates from C1 and C4 feedstocks

Nature Chemistry volume 15, pages 856–861 (2023)Cite this article

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Abstract

Polyolefin plastics are widely used due to their low cost and outstanding properties, but their environmental persistence presents a major societal challenge. Polyhydroxyalkanoates (PHA) are biodegradable substitutes for polyolefins, but their high cost and thermal instability are impediments to their widespread application. Here we report a series of methylated polyhydroxybutyrates, poly(3-hydroxy-2-methylbutyrate)s, which are structurally inspired by natural PHAs. The cis homopolymers exhibit tacticity-independent crystallinity, which allows for the discovery of high-melting, thermally stable and mechanically tough copolymers, and a full range of polyolefin-like properties can be further achieved by tailoring the cis/trans ratio of the repeating units. Moreover, these materials can be synthesized from inexpensive carbon monoxide and 2-butene feedstocks, and they can be chemically recycled or upcycled at their end of life. The versatile properties, abundant feedstocks and end-of-life utility of this family of polyesters will enable a powerful platform for the discovery of sustainable alternatives to polyolefin plastics.

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Fig. 1: General design of methylated polyhydroxyalkanoates and PHMB.
Fig. 2: Polymerization of cis-DMPL by different initiators to give cis-PHMB homopolymers with varied degree of syndiotacticity.
Fig. 3: Synthesis and characterization of PHMB copolymers with different cis content.
Fig. 4: Potential chemical recycling and upcycling of PHMB.

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Data availability

The data supporting the findings of this study are available within the paper and its Supplementary Information. Crystallographic data for the structure of B-HMDS reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition no. CCDC-2135622. Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. Source data are provided with this paper.

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Acknowledgements

We thank S. N. MacMillan (Cornell University) for help with X-ray crystallography. This work was supported by the Department of Energy (no. DE-FOA-0002414) and ExxonMobil. This work made use of the Cornell Center for Materials Research and the NMR Facility at Cornell University, which are supported by the NSF under awards DMR-1719875 and CHE-1531632, respectively. The funders had no role in study design, data collection and analysis, decision to publish or preparation of the manuscript.

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Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY, USA

    Zhiyao Zhou, Anne M. LaPointe & Geoffrey W. Coates

  2. ExxonMobil Technology and Engineering Company, Annandale, NJ, USA

    Timothy D. Shaffer

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Contributions

Z.Z. and A.M.L. designed and performed all experiments. G.W.C. directed the research. All authors prepared the manuscript.

Corresponding author

Correspondence to Geoffrey W. Coates.

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Competing interests

Z.Z., A.M.L. and G.W.C. are inventors on US provisional patent application 63/220,301, submitted by Cornell University, which covers the synthesis and characterization of PHMB. T.D.S. declares no competing interests.

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Supplementary information

Supplementary Information

Supplementary materials and methods, synthetic procedures, Figs. 1–46 and Tables 1–16.

Supplementary Data 1

Crystallographic data for B-HMDS; CCDC no. 2135622.

Supplementary Data 2

Raw Excel data for the PXRD data of cis-PHMB with varied syndiotacticity.

Supplementary Data 3

Raw Excel data for the tensile measurements of all PHMB samples.

Source data

Source Data Fig. 3

Source data for the tensile measurements of PHMB copolymers and commercial polyolefins (Fig. 3c).

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Zhou, Z., LaPointe, A.M., Shaffer, T.D. et al. Nature-inspired methylated polyhydroxybutyrates from C1 and C4 feedstocks. Nat. Chem. 15, 856–861 (2023). https://doi.org/10.1038/s41557-023-01187-0

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