Ring-opening copolymerization of CO_(2) and epoxides is a promising way to manufacture high value-added materials.Despite a variety of catalyst systems have been reported,the reaction is still limited by low activity ...Ring-opening copolymerization of CO_(2) and epoxides is a promising way to manufacture high value-added materials.Despite a variety of catalyst systems have been reported,the reaction is still limited by low activity and polymer selectivity.Herein,a strategy of polymerization-enhanced Lewis acidity is reported to construct a series of highly efficient polymeric aluminum porphyrin catalysts(PAPCs).The characterization of the coordination equilibrium constant(K_(eq))showed significantly enhanced Lewis acidity of PAPC(K_(eg)=18.2 L/mol)compared to the monomeric counterpart(K_(eq)=6.4 L/mol),accompanied with increased turnover frequency(TOF)from 136 h^(-1) to 5500 h^(-1).Through detailed regulation of Lewis acidity,the highly Lewis acidic PAPC-OTs displayed a record high TOF of 30,200 h^(-1) with polymer selectivity of up to 99%.展开更多
基金supported by National Natural Science Foundation of China(Nos.51988102,22271275,22201280,22101277)Special Project of High-tech Industrialization of Cooperation between Jilin Province and Chinese Academy of Sciences(No.2022SYHz0004)Changchun Science and Technology Development Plan Funding Project(No.21ZY10).
文摘Ring-opening copolymerization of CO_(2) and epoxides is a promising way to manufacture high value-added materials.Despite a variety of catalyst systems have been reported,the reaction is still limited by low activity and polymer selectivity.Herein,a strategy of polymerization-enhanced Lewis acidity is reported to construct a series of highly efficient polymeric aluminum porphyrin catalysts(PAPCs).The characterization of the coordination equilibrium constant(K_(eq))showed significantly enhanced Lewis acidity of PAPC(K_(eg)=18.2 L/mol)compared to the monomeric counterpart(K_(eq)=6.4 L/mol),accompanied with increased turnover frequency(TOF)from 136 h^(-1) to 5500 h^(-1).Through detailed regulation of Lewis acidity,the highly Lewis acidic PAPC-OTs displayed a record high TOF of 30,200 h^(-1) with polymer selectivity of up to 99%.
