硫钨杂多酸阴离子功能化的离子液体催化烯烃环氧化.docVIP

  硫钨杂多酸阴离子功能化的离子液体催化 烯烃环氧化# 华丽，乔云香，陈吉忠，朱闻闻，郭立，张然，侯震山** 5 10 15 20 25 30 35 40 （结构可控先进功能材料及其制备教育部重点实验室，上海，200237） 摘要：本文将高活性的硫钨杂多阴离子[SO4W2O10]2-（记 SW2）分别与四丁基铵阳离子，十 二烷基甲基咪唑阳离子及质子化十二烷基咪唑阳离子组合构筑了有效的烯烃环氧化催化剂 （分别表示为: [TBA]2SW2，[DMIM]2SW2，[HDIM]2SW2），针对环辛烯的环氧化反应，比 较了三种催化剂的催化性能。研究发现：在反应过程中，阳离子对催化剂活性中心的结构变 化有显著的影响。当 n(环辛烯)：n(双氧水)=1:1，乙酸乙酯作为反应介质时，[DMIM]2SW2， [HDIM]2SW2 催化剂在反应完成后，催化剂可以实现自分离、回收和循环使用。另外，由咪 唑阳离子形成的催化剂在循环一次后的活性反而要高于新鲜催化剂的活性，这可能是由于双 氧水的作用，催化剂在反应一次以后，形成了高活性和高稳定性的催化中心。综合考虑三种 催化剂对烯烃环氧化的活性，选择性和循环性能，重点研究了[HDIM]2SW2 催化剂在乙酸乙 酯介质中的反应性能以及催化循环效果，并表征了此催化剂在反应过程中的状态变化。 关键词：环氧化，硫钨多酸阴离子，离子液体 中图分类号：O643 Olefin epoxidation catalyzed by oxoperoxosulfatometalate -based ionic liquids-type catalysts HUA Li, QIAO Yunxiang, CHEN Jizhong, ZHU Wenwen, GUO Li, ZHANG Ran, HOU Zhenshan (Key laboratory for advanced materials,Shanghai,200237) Abstract: The ionic liquid-type compounds consisted of the highly active oxoperoxosulfatometalate anions [SO4W2O10]2- (denoted as SW2) and three different cations, such as tetrabutylammonium, 1-dodecyl-3-methylimidazolium and N-dodecylimidazolium cations (denoted as [TBA]2SW2，[DMIM]2SW2，[HDIM]2SW2, respectively) have been constructed and utilized for the epoxidation of cis-cyclooctene. It was indicated that the cations of the ionic liquid have a significant effect on the catalytic performance. The catalysts ([DMIM]2SW2，[HDIM]2SW2) can be easily separated and recycled in ethyl acetate media, in comparison with [TBA]2SW2 catalyst at the molar ratio of the cis-cyclooctene to H2O2 = 1. It is interesting to note that the catalytic activity was increased in the second run with [DMIM]2SW2 or [HDIM]2SW2 catalyts, which resulted from catalyst activation with H2O2 in the first run. Finally, [HDIM]2SW2 has been chosen as a typical catalyst to investigate the effect of reaction solvent, catalyst separation and recyclability in ethyl acetate. Key words: Epoxidation, polyoxometalate, ionic liquid 0 引言 环氧化物是一类重要的有机中间体，被广泛应用于石油化工、精细化工和聚合物领域， 用以合成环氧树脂、涂料、表面活性剂、杀虫剂、增塑剂、