聚苯乙烯接枝钼(Ⅵ)络合物催化合成环氧环己烷的研究  

Study on Process of Epoxycyclohexane Synthesized with Polystyrene-supported Molybdenum Dioxobis(2,4-pentanedione) as Catalyst

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

机构地区：[1]郑州大学化工学院,河南郑州450002

出　　处：《化学反应工程与工艺》2002年第4期304-309,共6页Chemical Reaction Engineering and Technology

基　　金：河南省杰出人才创新基金项目资助 (0 12 10 0 190 0 )

摘　　要：合成了钼 ( )络合物——钼 ( )合乙酰丙酮 ,并用元素分析和红外光谱技术对其进行了表征。合成、纯化了叔丁基过氧化氢 (t- Bu OOH) ,以此为环氧化剂。合成出了大孔聚苯乙烯 -二乙烯苯树脂 ,采用相转移催化法接枝引入钼 ( )合乙酰丙酮 ,以它为催化剂 ,研究了反应物料配比 ,溶剂、催化剂用量 ,反应温度、时间等因素对合成过程的影响 ,建立了聚苯乙烯 -二乙烯苯接枝钼 (VI)合乙酰丙酮催化剂中 Mo的新分析方法和环氧环己烷气相色谱分析方法。采用正交实验技术 ,优化出了较佳合成工艺条件 ,即 ,n()∶n(t- Bu OOH) =3∶ 1,溶剂 10 m L ,催化剂 (以 Mo计 )～ 2 .0 3× 10 -2 g,反应温度～ 80℃ ,反应时间～ 6 0 min。以 t- Bu OOH计 ,环氧环己烷收率在 99.5 %以上 ,纯度约 99.9%(GC分析 )。Molybdenum(Ⅵ)complex, namely molybdenum dioxobis(2,4-pentanedione)[ MoO 2 (acac) 2] used as epoxidation catalysis species, has been synthesized. It has been characterized by element analysis and infrared spectrum technique. Polystyrene-supported molybdenum dioxobis(2,4-pentanedione)[MoO 2(acac) 2] used as a catalyst in the process of synthesizing cyclohexane oxide has been obtained by phase transfer catalysis method. t- Butyl hydroperoxide (t-BuOOH) used as epoxidation agent has also been prepared. Effects of many factors on the reaction process of synthesizing epoxycyclohexane have also be discussed. In the presence of nitrogen, processes of epoxycyclohexane synthesized by reaction of cyclohexene and t-BuOOH with polystyrene-supported MoO 2(acac) 2 as catalyst, have been investigated. Analysis method of volume of Mo in polystyrene-supported MoO 2(acac) 2 catalyst and gas chromatogram (GC) method of epoxycyclohexane has been set up. Effects of mole ratio of cyclohexene to t-BuOOH and amounts of catalyst, solvent etc. on reaction yield have also been investigated by orthogonal experiment design. The optimum reaction condition has been obtained, that is, according to n(t-BuOOH) =0.1mol,n()∶n(t-BuOOH)=3∶1, volume of solvent is about 10ml, reaction temperature ～ 80℃, reaction time ～ 60 min, and weight of molybdenum in the catalyst is ～2.03×10 -2 g. In the condition, the yield of epoxycyclohexane calculated by amounts of t-BuOOH is over 99.5%, purity of epoxycyclohexan is about 99.9% by GC analysis.

关 键 词：聚苯乙烯接枝钼(Ⅵ)络合物 催化合成 环氧环己烷 环己烯 聚苯乙烯-二乙烯苯 环氧化 催化剂 

分 类 号：O623.425[理学—有机化学] O64[理学—化学]