Tunable and recyclable polyesters from CO₂ and butadiene

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. [Figure not available: see fulltext.].