Synthesis of Diverse Polycarbonates by Organocatalytic Copolymerization of CO₂ and Epoxides: From High Pressure and Temperature to Ambient Conditions

Abstract

Organophosphazenes combined with triethylborane (TEB) were selected as binary organocatalyts for the copolymerization of CO₂ and epoxides. Both the activity and selectivity were highly dependent on the nature of phosphazenes. 2,4,6-Tris[tri(1-pyrrolidinyl)-iminophosphorane]-1,3,5-triazine (C₃ N₃ -Py-P₃ ) with a relatively low basicity (pK_a =26.5 in CD₃ CN) and a bulky molecular size (φ=1.3 nm) exhibited an unprecedented efficiency (TON up to 12240) and selectivity (>99 % polymer selectivity and >99 % carbonate linkages) toward copolymerization of CO₂ and cyclohexene oxide (CHO), and produced CO₂ -based polycarbonates (CO₂ -PCs) with high molar masses (M_n up to 275.5 kDa) at 1 MPa of CO₂ and 80 °C. Surprisingly, this binary catalytic system achieved efficient CO₂ /CHO copolymerization with TOF up to 95 h^-1 at 1 atm pressure and room temperature.