聚苯乙烯接枝聚乙二醇钼(Ⅵ)络合物合成、表征及对环己烯环氧化催化活性  

SYNTHESIS AND CHARACTERIZATION OF POLYSTYRENE-GRAFTED PEG MOLYBDENUM COMPLEX AND ITS CATALYTIC ACTIVITIES IN EPOXIDATION OF CYCLOHEXENE

作　　者：章亚东[1] 蒋登高[1] 高晓蕾[1] 陈霞[1] 王自健[1] 

机构地区：[1]郑州大学化学工程学院,河南郑州450002

出　　处：《化工学报》2003年第5期670-675,共6页CIESC Journal

基　　金：河南省杰出人才创新基金资助项目(No 0 12 10 0 190 0 )~~

摘　　要：合成了聚苯乙烯 二乙烯苯 (PS)接枝聚乙二醇 (PEG)钼 (Ⅵ )合乙酰丙酮 [MoO2 (acac) 2 ][简写为PS PEG MoO2 (acac) ],并对其进行了结构表征 .实验表明 ,作为催化剂用于环己烯环氧化反应比小分子络合物MoO2 (acac) 2 具有更优良的催化活性和选择性 .建立了PS PEG MoO2 (acac)催化剂中Mo分析和环氧环己烷气相色谱分析方法 ;探讨了PS PEG MoO2 (acac)催化剂合成过程诸因素的影响 ;优化出环氧环己烷合成条件 ,即 :以叔丁基过氧化氢为 0 1mol计 ,环己烯与叔丁基过氧化氢摩尔比为 3∶1,溶剂用量 5ml,反应温度 80℃ ,时间60min .该条件下 ,环氧环己烷收率 (以t BuOOH计 )在 99 5 %以上 ,质量分数约 99 5 % (GC检测 ) .PS接枝PEG MoO2 (acac)催化剂使用Polyethylene glycol-400(PEG-400)grafted in polystyrene-divinyl benzene(PS) supporter as macromolecule ligand was synthesized.The effects of such factors as temperature,time and solvent etc are also studied, and the structure of the ligand was characterized by IR spectrum.Polystyrene-supported PEG-400 molybdenum(Ⅵ) dioxo(2,4-pentanedione)[PS-PEG-MoO 2(acac)] used as epoxidation catalysis species,was for the first time synthesized by the phase transfer catalysis method,and was characterized by infrared spectrum technique.The affecting factors on the synthesis process of PS-PEG-MoO 2(acac)were also discussed.Epoxycyclohexane synthesized by the reaction of cyclohexene and t-butyl hydroperoxide(t-BuOOH)with PS-PEG-MoO 2(acac) as catalyst was investigated in the presence of nitrogen.The analysis method of Mo in the catalyst and the gas chromatogram (GC) method of epoxycyclohexane analysis were set up.The optimum reaction condition was obtained by orthogonal experiment design, that is,according to n(t-BuOOH)=0.1 mol,n()∶n(t-BuOOH)=3∶1, volume of solvent is about 5 ml, reaction temperature～80 ℃,time～60 min,and mass of molybdenum in the catalyst is～0.0198 g.Under this condition, the yield of epoxycyclohexane calculated by the amount of t-BuOOH is more than 99.5%,the purity of epoxycyclohexan is about 99.5% by GC analysis.

关 键 词：钼(Ⅵ)合乙酰丙酮 环己烯 环氧环己烷 聚苯乙烯 

分 类 号：TQ231.1[化学工程—有机化工]