四苯基卟啉钴配合物催化环氧环己烷与CO_2的交替共聚反应（英文）

Alternating Copolymerization of Carbon Dioxide and Cyclohexene Oxide Catalyzed by Cobalt Tetraphenylporphyrin Complexes

合成了一系列高效的四苯基卟啉配合物(4d^4e首次报道),并以二甲氨基吡啶为助催化剂催化了二氧化碳在环氧环己烷的聚合.以四苯基卟啉氯化钴配合物为例,系统考察了反应温度、时间、压力、溶剂种类、助催化剂用量及轴向阴离子等因素对催化活性的影响.结果表明:80℃,6 h,5 MPa,1当量的助催化剂为最佳条件,配合物的轴向阴离子和卟啉的取代基对催化活性有很大影响.通过IR和1H NMR表明所得到的聚合物是高选择性的交替聚碳酸酯,碳酸酯键含量超过99%.这种聚碳酸酯的平均分子量高达59600,是目前已知卟啉类催化体系中活性最好的.

A series of highly efficient cobalt tetraphenylporphyrin complexes（ 4d ~ 4e were first reported） were synthesized and tested as catalysts for chemical fixation of carbon dioxide and cyclohexene oxide using dimethylaminopyridine as cocatalyst. With chlorocobalt tetraphenylporphyrin as the typical example,various factors influencing the catalytic activity,such as reaction temperature,time,pressure,solvent type,and the ratio of co-catalyst to catalyst and axial group,were investigated. The results indicated that the optimal conditions were 80℃,6 h,5 MPa with 1 equiv of cocatalyst. The axial anion of the complex and the substituents of the porphyrin influenced the catalytic activity greatly. IR and1 H NMR confirmed that all the obtained polymers were alternating polycarbonate with high selectivity,with more than 99% content of carbonate linkage. The highest average molecular weight of the polycarbonate was up to 59600,and the catalytic activity was the highest among all reported porphyrin catalyst systems.