Insights into the Distinct Behaviors between Bifunctional and Binary Organoborane Catalysts through Terpolymerization of Epoxide, CO₂, and Anhydride

Alkyl borane compounds-mediated polymerizations have expanded to Lewis pair polymerization, free radical polymerization, ionic ring-opening polymerization, and polyhomologation. The bifunctional organoborane catalysts that contain the Lewis acid and ammonium or phosphonium salt in one molecule have demonstrated superior catalytic performance for ring-opening polymerization of epoxides and ring-opening copolymerization of epoxides and CO₂ than their two-component analogues, i.e., the blend of organoborane and ammonium or phosphonium salt. To explore the origin of the differences of the one-component and two-component organoborane catalysts, here we conducted a systematic investigation on the catalytic performances of these two kinds of organoborane catalysts via terpolymerization of epoxide, carbon dioxide and anhydride. The resultant terpolymers produced independently by bifunctional and binary organoborane catalyst exhibited distinct microstructures, where a series of gradient polyester-polycarbonate terpolymers with varying polyester content were afforded using the bifunctional catalyst, while tapering diblock terpolymers were obtained using the binary system. The bifunctional catalyst enhances the competitiveness of CO₂ insertion than anhydride, which leads to the premature incorporation of CO₂ into the polymer chains and ultimately results in the formation of gradient terpolymers. DFT calculations revealed the role of electrostatic interaction and charge distribution caused by intramolecular synergistic effect for bifunctional organoborane catalyst.