Facile Aluminum Porphyrin Complexes Enable Flexible Terminal Epoxides to Boost Properties of CO ₂ ‐Polycarbonate

Incorporation of flexible monomer is regarded as a valid way to the chemical modification of the highly brittle poly(cyclohexene carbonate) (PCHC), which derived from the copolymerization of CO2 and cyclohexene oxide (CHO). However, toxic metal catalyst such as cobalt dominates these terpolymerizations which against the green development philosophy. Here, a series of environmentally benign aluminum porphyrin catalysts with different steric and electronic effects for the terpolymerization of CO2, CHO, and terminal epoxides with various flexible pendant alkyl groups to adjust the properties of PCHC is reported. The resulting terpolymers display a random distribution of cyclohexene carbonate along the backbone with a regulated terminal epoxide insertion from 30% to 70%. Moreover, the mechanical properties can be well regulated in a wide range indicating the feasibility of the present approach. The present study provides a green way to chemical modification of rigid PCHC.