第 46 卷第 5 期Vol. 46 No. 5
2016 年 10 月Oct 2016
所属栏目：功能材料

Zn-EDTA-2Na配合物催化环氧丙烷与CO2反应合成碳酸丙烯酯的研究
陈 盛2，唐灵生2，兰东辉1* （1. 湖南大学 化学化工学院，湖南 长沙 410082；2. 雅礼中学，湖南 长沙 410007）
摘　要：以水为溶剂，利用无毒、稳定、廉价易得且具有强配位能力的乙二胺四乙酸钠盐（EDTA-nNa）与金属卤化物配位，构建了多种配合物MX2-EDTA-nNa（M=Zn、Fe、Co、Ni；X=Cl、Br、I、NO3；n=0、2、4）。配合物催化环氧丙烷与CO2反应合成碳酸丙烯酯研究表明，配合物中金属中心Lewis酸性和阴离子离去能力越强，其催化活性越高；其中ZnBr2-EDTA-2Na表现出最优异的催化性能，碳酸丙烯酯的收率和选择性分别为96.9%和99.3%，TOF达96.9 h-1。通过复合氧化石墨烯，可以进一步提高ZnBr2-EDTA-2Na的耐水性。另外，结合Redlich-Kwong方程和实验结果探讨了溶于反应液中CO2的量，在25℃和1.25 MPa下溶于反应液中的CO2量超过9.3 mmol，将有利于CO2转化为碳酸丙烯酯。
关键词：Zn-EDTA-2Na配合物；催化；二氧化碳；碳酸丙烯酯；环加成反应
中图分类号：O621.3　　文献标识码：A　　文章编号：1009-9212（2016）05-0056-07
Synthesis of Propylene Carbonate from CO2 and Propylene Oxide Using Zn-EDTA-2Na Complexes as Catalysts
CHEN Sheng2, TANG Ling-sheng2, LAN Dong-hui1* (1. College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China; 2. Yali Middle School, Changsha 410007, China)
Abstract：A series of novel MX2-EDTA-nNa(M=Zn, Fe, Co, Ni; X=Cl, Br, I, NO3; n=0, 2, 4) complexes were prepared through the coordination of metal halides with ethylenediaminetetraacetic acid sodium salts (EDTA-nNa) in aqueous solution. These prepared complexes were non-toxic, cheap, and stable. Based on the activities of MX2-EDTA-nNa, it was deduced that a strong acidity of metal and a strong leaving ability of anion were favorable for the cycloaddition reaction of CO2 with propylene oxide. In the case of using ZnBr2-EDTA-2Na as the catalyst, propylene carbonate(PC) selectivity and yield are 99.3% and 96.9%, respectively, showing a turnover frequency of 96.9 h-1. The stability of ZnBr2-EDTA-2Na could be improved by graphene oxide. Furthermore, the mount of CO2 dissolved in the liquid phase was calculated using the Redlich-Kwong equations on the basis of PC yield. It was found that the amount of CO2 dissolved in the reaction solution was higher than 9.3 mmol at a temperature of 25℃ and a pressure of 1.25 MPa. The good solubility of CO2 in the reaction liquid was favorable for CO2 conversion.
Key words：Zn-EDTA-2Na complex; catalyst; carbon dioxide; propylene carbonate; cycloaddition
作者简介：陈 盛（1999-），男，湖南长沙人，主要从事功能材料研究。
联 系 人： 兰东辉，讲师，博士，研究方向：二氧化碳资源化利用、功能材料研究。
收稿日期：2016-09-1