环己烯液相环氧化合成环氧环己烷

Synthesis of Epocyclohexane by Cyclohexene Epoxidation in Liquid Phase

合成了钼(Ⅵ)络合物——钼(Ⅵ)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。以过氧化羟基异丙苯为环氧化剂,以钼(Ⅵ)合乙酰丙酮为催化剂,研究了反应物料配比,溶剂用量,催化剂用量,反应温度,时间等因素对环氧化合成过程的影响,阐述了钼(Ⅵ)合乙酰丙酮催化环己烯和过氧化羟基异丙苯(CHP)合成环氧环己烷反应的机理。通过对影响反应过程的诸因素考察和分析,优化出了较佳合成工艺条件,即:( CHP )∶n( )n=3∶1。以n(CHP)=0.04mol计,溶剂10mL,钼(Ⅵ)合乙酰丙酮0.1g,反应温度80℃,反应时间60min。以过氧化羟基异丙苯计,环氧环己烷收率在99%以上,纯度约99.9%(GC分析)。

Molybdenum(VI) complex-molybdenum dioxobis (2,4-pentanedione)[MoO2(acac)2] used as epoxidation catalyst, was synthesized. It was characterized by element analysis and infrared spectrum technique. Cumene hydroperoxide (CHP) used as epoxidation agent was also synthesized. In the presence of nitrogen, process of synthesis epocyclohexane by reaction of cyclohexene (CHX) and cumene hydroperoxide using MoO2(acac)2 as catalyst, was investigated. Effects of many factors on reaction process of synthesis epoxycyclohexane was discussed. The possible mechanism of epoxidation reaction between cyclohexene and cumene hydroperoxide catalyzed by MoO2(acac)2 was described. Effects of mole ratio of cyclohexene to CHP and amounts of catalyst, solvent etc. on reaction yield were also studied by orthogonal experiment design. The optimum reaction condition has been obtained, that is, according to n(CHP) = 0.04 mol, n(CHX):n(CHP) =3:1, volume of solvent is about l0 mL, reaction temperature is about 80°C, reaction time is about 60 min. Under above conditions, the yield of epoxycyclohexane calculated by amounts of cumene hydroperoxide is over 99%, purity of epoxycyclohexan is about 99.9% by GC analysis.