Highly Efficient Synthesis of Functionalizable Polymers from a CO₂/1,3-Butadiene-Derived Lactone

Making polymers from CO₂ and olefins has been long sought and is of particular significance for chemical utilizations of CO₂. Herein, high molecular-weight polymers with 29 wt % CO₂ were obtained by polymerizing a δ-lactone (L) synthesized from a C-C coupling reaction between CO₂ and 1,3-butadiene, an economical large-volume chemical that can also be derived from top biomass platform chemicals. Although L has been known for many years, little was investigated in its polymerization. We found that L's polymerizability can be vitalized upon simply heating in the presence of O₂. The polymerization is additive/solvent-free with abundant preserved olefins and up to full monomer conversion, providing a convenient, economical, and scalable avenue to obtain CO₂-derived polymers with potentially tailorable properties via the readily modifiable olefins.