Ultra-Productive Upcycling CO₂ into Polycarbonate Polyols via Borinane-Based Bifunctional Organocatalysts

We herein report the synthesis of commercially attractive low molar mass polycarbonate polyols obtained through the ring-opening copolymerization of CO2 and epoxides, using a series of borinane-based bifunctional organocatalysts in the presence of chain transfer agents (CTAs). These catalysts enable CO2/epoxide copolymerizations with high linear vs cyclic selectivity and outstanding productivity for both poly(cyclohexane carbonate) polyols (18.2 kg/g catalyst) and poly(ether propylene carbonate) polyols (1.1 kg/g catalyst). These copolymerizations exhibit all features of living processes; the molar mass of the resulting polycarbonates could be precisely controlled by varying the [monomer]/CTA ratio. The high performance of these catalysts implying a low loading shows a great potential for applications in large-scale preparation of CO2-based polyols.