Abstract: 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-MoO₂(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-MoO₂(acac)were also discussed.Epoxycyclohexane synthesized by the reaction of cyclohexene and t-butyl hydroperoxide(t-BuOOH)with PS-PEG-MoO₂(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(cyclohexene)∶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.

Key words:

钼(Ⅵ)合乙酰丙酮, 环己烯, 环氧环己烷, 聚苯乙烯

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0.1mol计，环己烯与叔丁基过氧化氢摩尔比为3∶1，溶剂用量5ml，反应温度80℃，时间60min.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5次后未发现活性明显减低.

关键词:

钼(Ⅵ)合乙酰丙酮, 环己烯, 环氧环己烷, 聚苯乙烯