Polymeric Catalyst with Discrete Distributed Active Centers for Regulating Backbone Structure of Poly(propylene carbonate)†

Comprehensive Summary Converting CO 2 into valuable chemicals is an effective means to alleviate environmental pressure and the depletion of oil resources. Among them, polymers derived from the copolymerization of PO and CO 2 have been widely studied because of their excellent properties. To meet the expansion of the application range of CO 2 ‐based polymers, regulation of the CU in the polymer is imperative. Based on the understanding of the relationship between catalyst synergy and structure, we designed a new generation of polyester‐based polymeric catalysts APEPC‐R and RPEPC‐N with discretely distributed active centers to achieve the synthesis of CO 2 ‐based polymers with regulated CU (from 50% to 90%). The discrete arrangement of catalyst active centers was demonstrated by 1 H NMR and UV‐vis characterization. Benefiting from multi‐site synergy, high molecular weight ( M n > 100 kg/mol) CO 2 ‐based copolymers with CU among 50%—90% were successfully synthesized and their properties were firstly investigated. This work not only contributes to enriching the scope of the application of CO 2 ‐based copolymers but also provides a new platform for the development of a new generation of catalysts.