Pinwheel-Shaped Tetranuclear Organoboron Catalysts for Perfectly Alternating Copolymerization of CO₂ and Epichlorohydrin

The copolymerization of carbon dioxide (CO₂) and epoxides to produce aliphatic polycarbonates is a burgeoning technology for the large-scale utilization of CO₂ and degradable polymeric materials. Even with the wealth of advancements achieved over the past 50 years on this green technology, many challenges remain, including the use of metal-containing catalysts for polymerization, the removal of the chromatic metal residue after polymerization, and the limited practicable epoxides, especially for those containing electron-withdrawing groups. Herein, we provide kinds of pinwheel-shaped tetranuclear organoboron catalysts for epichlorohydrin/CO₂ copolymerization with >99% polymer selectivity and quantitative CO₂ uptake (>99% carbonate linkages) under mild conditions (25-40 °C, 25 bar of CO₂). The produced poly(chloropropylene carbonate) has the highest molecular weight of 36.5 kg/mol and glass transition temperature of 45.4 °C reported to date. The energy difference (ΔEa = 60.7 kJ/mol) between the cyclic carbonate and polycarbonate sheds light on the robust performance of our metal-free catalyst. Control experiments and density functional theory (DFT) calculations revealed a cyclically sequential copolymerization mechanism. The metal-free feature, high catalytic performance under mild conditions, and no trouble with chromaticity for the produced polymers imply that our catalysts are practical candidates to advance the CO₂-based polycarbonates.