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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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).
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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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