无溶剂法双氧水环氧化环己烯制备环氧环己烷  

A Solvent-Free Method for Cyclohexene Epoxidation by Hydrogen Peroxide

作　　者：王振兴[1] 章亚东[1] 田红艳[1] 储进昌[1] 

机构地区：[1]郑州大学化工与能源学院,河南郑州450001

出　　处：《高校化学工程学报》2009年第5期895-900,共6页Journal of Chemical Engineering of Chinese Universities

基　　金：河南省自然科学基金(511020800);河南省高校科技创新人才计划(2010HASTIT037)

摘　　要：使用大孔聚苯乙烯-二乙烯苯交联树脂(PS)为载体,制备出了一系列季铵盐杂多酸催化剂,对催化剂进行了红外表征,并使用电感耦合等离子体发射光谱(ICP)测定催化剂中活性组分钨的含量。将催化剂应用于无溶剂双氧水环氧化环己烯制备环氧环己烷的反应中,并对影响反应的因素如催化剂种类、数量,盐类助催化剂的种类、数量,反应温度,摩尔比等进行了讨论。结果表明盐类特别是KCl的加入可以明显提高环氧环己烷的选择性和产率。在用35%H2O2=0.22mol的实验中,使用PS接枝N,N-二甲基十二烷基铵磷钨杂多酸(PS-12-PW4)催化剂3g,助催化剂KCl0.15g,反应温度50℃,反应时间8h,环己烯与双氧水的摩尔比1.75:1的条件下,环氧环己烷的产率可达80%。催化剂重复使用7次以后活性未明显改变。Using macroporous polystyrene divinylbenzene cross-linked resin （PS） as supporter,the PS grafted quaternary ammonium phosphor-tungstic heteropoly acid catalysts were synthesized. The structures of the synthesized catalysts were characterized by IR spectrum,and the amounts of tungsten in the catalysts were determined by inductive coupled plasma emission spectrometer （ICP）. These synthesized catalysts were used in the proposed solvent-free method for cyclohexene （CH） epoxidation with aqueous hydrogen peroxide （HP） to synthesize the cyclohexene oxide （CHO）. The effects of the factors,such as the categories and amounts of catalysts and salt co-catalysts,reaction temperature and time,molar ratio of （CH） ：（HP）,and so on,on the reaction were studied. The results show that,using salt co-catalysts,especially the KCl,can significantly increase the selectivity and yield of CHO. During the experiment with 35% H2O2=0.22 mol,the yield of CHO can reach 80% under the following conditions：using catalyst PS-12-PW4 of 3 g,co-catalyst KCl of 0.15 g,reaction temperature of 50℃,reaction time of 8 h and molar ratio n（CH） ：n（HP） = 1.75 ：1. Moreover,for catalyst PS-12-PW4,even after reuse for 7 times,its catalytic activity has no obvious decrease.

关 键 词：无溶剂 环氧环己烷 双氧水 聚苯乙烯接枝催化剂 盐 KCL 

分 类 号：TQ231.14[化学工程—有机化工] TQ316.339