Zhou Yanchuan, Duan Ranlong, Li Xiang, Pang Xuan, Wang Xianhong, Chen Xuesi
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, P. R. China.
University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
Chem Asian J. 2017 Dec 14;12(24):3135-3140. doi: 10.1002/asia.201701048. Epub 2017 Nov 22.
A dinuclear Salph-Al complex/bis(triphenylphosphine)iminium chloride catalyst system was synthesized and employed for cyclohexene oxide (CHO) and CO copolymerization. The catalyst system had an excellent selectivity of 99 % for carbonate linkages and the resultant poly(cyclohexene carbonate) (PCHC) had a high glass transition temperature (T ) of 123.8 °C and a thermal decomposition temperature (5 % weight loss; T ) of 265 °C. Furthermore, this catalyst system was active in the polymerization of phthalic anhydride (PA) and epoxides. Poly(CHO-alt-PA) was completely alternating, and had improved thermal properties (T =142.7 and T =295 °C) compared with PCHC. The T values of the polyesters could be adjusted by addition of PO to the CHO/PA reaction system. For the CHO/PO/PA terpolymerization, CHO and PO participated concurrently and proportionally in the chain growth and the obtained terpolyesters had tunable T values from 62.8 to 142.7 °C depending on the CHO/PO feed ratio.
合成了一种双核Salph-Al配合物/双（三苯基膦）亚胺氯化物催化剂体系，并将其用于环氧环己烷（CHO）与CO的共聚反应。该催化剂体系对碳酸酯键的选择性高达99%，所得聚（环己烯碳酸酯）（PCHC）具有123.8℃的高玻璃化转变温度（T）和265℃的热分解温度（失重5%；T）。此外，该催化剂体系对邻苯二甲酸酐（PA）与环氧化物的聚合反应具有活性。聚（CHO-alt-PA）完全交替排列，与PCHC相比，其热性能有所改善（T = 142.7，T = 295℃）。通过向CHO/PA反应体系中加入PO，可以调节聚酯的T值。对于CHO/PO/PA三元共聚反应，CHO和PO同时且按比例参与链增长，所得三元聚酯的T值可根据CHO/PO进料比在62.8至142.7℃之间调节。
