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Tunable and recyclable polyesters from CO2 and butadiene

Nature Chemistry volume 14, pages 877–883 (2022)Cite this article

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Abstract

Carbon dioxide is inexpensive and abundant, and its prevalence as waste makes it attractive as a sustainable chemical feedstock. Although there are examples of copolymerizations of CO2 with high-energy monomers, the direct copolymerization of CO2 with olefins has not been reported. Here an alternative route to functionalizable, recyclable polyesters derived from CO2, butadiene and hydrogen via an intermediary lactone, 3-ethyl-6-vinyltetrahydro-2H-pyran-2-one, is described. Catalytic ring-opening polymerization of the lactone by 1,5,7-triazabicyclo[4.4.0]dec-5-ene yields polyesters with molar masses up to 13.6 kg mol−1 and pendent vinyl side chains that can undergo post-polymerization functionalization. The polymer has a low ceiling temperature of 138 °C, allowing for facile chemical recycling, and is inherently biodegradable under aerobic aqueous conditions (OECD-301B protocol). These results show that a well-defined polyester can be derived from CO2, olefins and hydrogen, expanding access to new polymer feedstocks that were once considered unfeasible.

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Fig. 1: EVP is a promising platform chemical derived from the telomerization of CO2 and butadiene that is underutilized in polymer synthesis.
Fig. 2: Synthesis and thermodynamic comparisons.
Fig. 3: Molecular weight studies of EtVP polymerization.
Fig. 4: The cis–trans interconversion of EtVP via α-epimerization.
Fig. 5: Recycling and degradation of poly(EtVP).
Fig. 6: Post-polymerization modification of poly(EtVP).

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Data availability

All primary data files63 are available free of charge from the Data Repository for the University of Minnesota at https://doi.org/10.13020/sy3d-cf59.

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Acknowledgements

The funding for this work was provided by the NSF Center for Sustainable Polymers (no. CHE-1901635 to I.A.T.) at the University of Minnesota. Instrumentation for the University of Minnesota Chemistry NMR facility was supported by a grant through the National Institutes of Health (no. S10OD011952).

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  1. Department of Chemistry, University of Minnesota – Twin Cities, Minneapolis, MN, USA

    Rachel M. Rapagnani, Rachel J. Dunscomb & Ian A. Tonks

  2. Department of Chemistry, Purdue University, West Lafayette, IN, USA

    Alexandra A. Fresh

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R.M.R., R.J.D. and A.A.F. designed and performed all experiments and carried out data analysis. I.A.T. directed the research. R.M.R. and I.A.T. prepared the manuscript.

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Correspondence to Ian A. Tonks.

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Competing interests

I.A.T. and R.M.R. are co-inventors on a provisional US patent covering the methods of polymerization and composition of matter presented in this work, filed through the University of Minnesota (application no. 63/156,135). R.J.D. and A.A.F. declare no competing interests.

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Materials and Methods, Supplementary text, Figs. 1 to 35, Tables 1 to 5, references, OECD-301B report from Situ Biosciences

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Rapagnani, R.M., Dunscomb, R.J., Fresh, A.A. et al. Tunable and recyclable polyesters from CO2 and butadiene. Nat. Chem. 14, 877–883 (2022). https://doi.org/10.1038/s41557-022-00969-2

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