铝卟啉配合物催化二氧化碳与环氧丙烷共聚反应  

Copolymerization of Carbon Dioxide and Propylene Oxide under Aluminum Porphyrin Catalyst

作　　者：郭洪辰 秦玉升[1] 王献红[1,2] 王佛松 GUO Hongchen;QIN Yusheng;WANG Xianhong;WANG Fosong(Key Laboratory of Polymer Ecomaterials,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China;University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]中国科学院长春应用化学研究所,生态环境高分子材料重点实验室,长春130022 [2]中国科学院大学,北京100049

出　　处：《应用化学》2019年第10期1118-1127,共10页Chinese Journal of Applied Chemistry

基　　金：中国科学院前沿科学重点研究项目(QYZDJ-SSW-JSC017)的支持~~

摘　　要：铝卟啉是一类土壤环境友好的金属卟啉,尽管早在1978年Inoue就已经发现它可以催化CO 2和环氧丙烷的共聚反应,但是该催化体系一直面临催化活性低、聚合物相对分子质量低等难题。本文通过改变铝卟啉催化剂配体中苯环上取代基的种类和位置,制备出中心金属电子环境差异化的铝卟啉,并以双三苯基膦氯化铵(PPNCl)为助催化剂,探讨其对CO 2与环氧丙烷的共聚反应的催化行为。结果表明,当铝卟啉中苯环上2,4位同时被Cl-取代后,在90℃和3 MPa压力下,转化频率(TOF)达到2672 h^-1。当利用离去能力较强的对甲苯磺酸基团(OTs-)作为铝卟啉的轴向配体,可以合成出数均相对分子质量达1.84×10^5的脂肪族聚碳酸酯。Aluminum porphyrin is a soil-tolerant metal porphyrin complex.Although its catalytic activity on the copolymerization of CO 2 and propylene oxide has been disclosed by Inoue in 1978,the catalytic activity is still very low,and the synthesized poly(propylene carbonate)has low relative molecular mass.It is a big challenge to make progress on the catalytic performance of aluminum porphyrin.In this work,the electronic[JP2]environment of central aluminum was adjusted by delicate design of porphyrin ligand using meso-tetrasubstituted[JP]porphyrin derivatives that were employed to catalyze the copolymerization of CO 2 and propylene oxide with bis-(triphenyl phosphine)iminium chloride(PPNCl)as the co-catalyst.It was found that the electronic environment of the central aluminum ion had great effect on the catalytic performance of aluminum porphyrin catalysts,the turnover frequency(TOF)value of Cl substituted aluminum porphyrin catalyst[STHZ]6a[STBZ]reached 2672 h-1 at 90℃and 3 MPa,while poly(propylene carbonate)with relative molecular mass of 1.84×10 4 was afforded using catalyst[STHZ]4b[STBZ]bearing toluene sulfonic group(OTs-)as axial group of good leaving ability.Our work indicates that delicate designed aluminum porphyrin can become a possible candidate as high performance catalyst in the copolymerization of CO 2 and propylene oxide,under optimized copolymerization conditions.

关 键 词：铝卟啉 二氧化碳 环氧丙烷 聚碳酸酯 

分 类 号：O631[理学—高分子化学]