Well-controlled Organocatalytic Ring-opening Polymerization of Seven-membered Cyclic Carbonates with Cyclohexyl Fusion

Developing green and well-controlled polymerization methods is of great significance for the preparation of biomedical polymer materials. In this contribution, an efficient organocatalytic ring-opening polymerization (ROP) of a class of seven-membered cyclic carbonates (T6DO, T6HDO, C6DO, C6HDO) containing cis- or trans-cyclohexane structure was established. Organic catalyst 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) promoted living polymerization of these cyclic carbonates to deliver polycarbonate and block copolymer products with predictable molecular weights and narrow dispersity. The robust TBD-mediated ROP at 90 °C showcased turnover frequency (TOF) up to 10³ h⁻¹. The resulting amorphous polycarbonates displayed good thermal stability.