高分子负载聚季鏻盐的制备及其催化CO_2与环氧化物环加成  

CO_2 cycloaddition with epoxides catalyzed by polymer supported poly(phosphonium ionic liquid)

作　　者：熊玉兵[1] 郭娜[1] 崔紫鹏[1] 摆峰[1] 王荣民[1] 

机构地区：[1]西北师范大学化学化工学院,生态环境相关高分子材料教育部重点实验室,甘肃兰州730070

出　　处：《西北师范大学学报（自然科学版）》2013年第5期57-62,共6页Journal of Northwest Normal University(Natural Science)

基　　金：国家自然科学基金资助项目(20804031,21164008);甘肃省自然科学基金资助项目(1208RJZA167);聚合物分子工程国家重点实验室(复旦大学)开放基金资助项目(KF12-07)

摘　　要：制备了基于季鏻盐的离子液体单体,通过表面引发原子转移自由基聚合在氯球表面接枝了聚离子液体,对所得接枝聚离子液体氯球的结构和性能进行了热重分析和红外表征,并考察了不同条件下氯球负载聚季鏻盐催化CO2与环氧化物环加成反应的活性.结果表明,最佳条件为:CO2压力5MPa,环氧氯丙烷3mL,反应时间14h,反应温度150℃,反应催化剂用量0.1g,生成环碳酸酯的产率可达96.2%,选择性高于99%.对催化剂的重复使用性考察表明,重复使用5次后,催化活性没有明显降低.对氯球负载聚季鏻盐催化CO2环加成反应的机理进行了初步探讨.In this study, first, poly（phosphonium ionic liquid）（PPIL） is prepared, then it is grafted onto the polymer via surface initiated atom transfer radical polymerization. The structure and property are measured using Fourier transform infrared （FT-IR） spectrum and thermogravimetric analysis （TGA）, respectively. In addition, polymer-supported PPIL is found to be effective catalyst for the coupling reaction of carbon dioxide with epoxides. The results indicate that cyclic carbonates with high yields （95%） and excellent selectivity（99%） can be prepared at the conditions of 5 MPa CO2, 150℃, 14 h and 0.1 g catalyst without the addition of any organic solvents or co-catalysts. The effects of various reaction conditions on the catalytic performance are investigated in detail. The catalyst is applicable to a variety of epoxides, producing the corresponding cyclic carbonates in good yields. Furthermore, the catalyst can be recovered easily and reused for five times without loss of catalytic activity obviously. A proposed mechanism for cyclic addition reaction in the presence of polymer-supported PPIL is discussed.

关 键 词：离子液体 CO2固定 非均相催化 表面引发原子转移自由基聚合 

分 类 号：O621.256.9[理学—有机化学] O643[理学—化学]