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Stereocontrolled acyclic diene metathesis polymerization

Nature Chemistry volume 15, pages 14–20 (2023)Cite this article

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Abstract

The cis/trans geometry of olefins is known to dramatically influence the thermal and mechanical properties of polyalkenamers. Yet, polymerization methods that efficiently control this parameter are scarce. Here we report the development of a stereoretentive acyclic diene metathesis polymerization that uses the reactivity of dithiolate Ru carbenes combined with cis monomers. These Ru catalysts exhibit exquisite retention of the cis geometry and tolerate many polar functional groups, enabling the synthesis of all-cis polyesters, polycarbonates, polyethers and polysulfites. The stereoretentive acyclic diene metathesis polymerization is also characterized by low catalyst loadings and tolerance towards trans impurities in the monomer batch, which should facilitate large-scale implementation. Modulation of the reaction temperature and time leads to an erosion of stereoretention, permitting a stereocontrolled synthesis of polyalkenamers with predictable cis:trans ratios. The impact of the stereochemistry of the repeating alkenes on the thermal properties is clearly demonstrated through differential scanning calorimetry and thermogravimetric analysis.

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Fig. 1: Design of stereocontrolled ADMET.
Fig. 2: Monomers and Ru catalysts.
Fig. 3: Polymer scope of stereocontrolled ADMET.
Fig. 4: Selectivity in stereocontrolled ADMET.
Fig. 5: Relationship between polymer stereochemistry and thermal properties.

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All data are available in the main text or the Supplementary Information.

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Acknowledgements

This article is dedicated to the memory of Robert H. Grubbs. This work was supported by Texas A&M University. The NMR facility in the Department of Chemistry and the Soft Matter Facility (RRID:SCR_022482) were utilized. We thank Umicore for the generous donation of metathesis catalysts, A. Johns for helpful discussions, J. Pribyl for insightful discussions on ADMET polymerization and P. Wei for his help with TGA/DSC analysis. We acknowledge the financial support of the National Institute of General Medical Sciences at the National Institutes of Health under Award Number R35GM138079, the Petroleum Research Fund managed by the American Chemical Society under Grant Number 60540-DNI7 and the Welch Foundation under Grant Number A-2004-20190330.

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Author notes

  1. These authors contributed equally: Ting-Wei Hsu, Samuel J. Kempel.

Authors and Affiliations

  1. Department of Chemistry, Texas A&M University, College Station, TX, USA

    Ting-Wei Hsu, Samuel J. Kempel, Alyssa P. Felix Thayne & Quentin Michaudel

  2. Department of Materials Science and Engineering, Texas A&M University, College Station, TX, USA

    Quentin Michaudel

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Contributions

T.-W.H., S.J.K. and A.P.F.T. performed the research. All authors designed the research and analysed the data. Q.M., S.J.K. and T.-W.H. wrote the paper and Supplementary Information.

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Correspondence to Quentin Michaudel.

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Hsu, TW., Kempel, S.J., Felix Thayne, A.P. et al. Stereocontrolled acyclic diene metathesis polymerization. Nat. Chem. 15, 14–20 (2023). https://doi.org/10.1038/s41557-022-01060-6

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