Chemically recyclable polyesters from CO₂, H₂, and 1,3-butadiene

Chemically recyclable solid polymeric materials with commercializable properties only using CO₂ and inexpensive bulk chemicals as chemical feedstock can open a brand-new avenue to economically viable, large-scale fixation of CO₂ over a long period of time. Despite previous great advancements, development of such a kind of CO₂-based polymers remains a long-term unsolved research challenge of great significance. Herein, we reported the first methodology to polymerize six-membered lactone with two substituents vicinal to the ester group (HL), a compound previously found to be non-polymerizable. The present methodology enables the first synthesis of chemically recyclable solid polyesters (polyHL) with a high CO₂ content (28 wt %) and large molecular weights (M_n up to 613.8 kg mol⁻¹). Transparent membranes with promising pressure-sensitive adhesive (PSA) properties comparable with their commercial counterparts can be conveniently fabricated from the polyesters. Mechanistic studies indicate that rigorous removal of water impurity is the key to the successful polymerization of the relatively inert disubstituted six-membered lactone. A complete monomer recovery from polyHL was also successfully achieved under mild catalytic conditions. The synthesis of polyHL only requires CO₂ and two inexpensive bulk chemicals, H₂ and 1,3-butadiene, as the starting materials, thus providing a new strategy for potential scalable chemical utilization of CO₂ with desirable economic values and concomitant mitigation of CO₂ emissions. This work should inspire future research to make useful new solid CO₂-based polymers that can meaningfully increase the scale of chemical utilization of CO₂ and promote the contribution of chemical utilization of CO₂ to global mitigation of CO₂ emissions.