【作者】 王振兴；

【导师】 章亚东；

【作者基本信息】 郑州大学 ， 应用化学， 2006， 硕士

【摘要】 环氧环己烷是一种重要的精细有机化工中间体，用途十分广泛。可用于农药、医药、涂料、树脂等行业，也可用于生产环己二醇、己二酸等其它化工行业。 本文采用我省有充足原料供应的双氧水和环己烯为主要原料，开展了双氧水环氧化环己烯合成环氧环己烷的关键技术研究。 主要开展了如下几方面工作： 开发出了一种反应控制相转移催化剂制备新方案，催化剂收率（以加入的季铵盐计）为94％。催化剂制备工艺简单，能耗低。对制备催化剂进行了红外表征和元素分析；该催化剂具有高活性、高选择性，且具有反应控制相转移催化剂的特性。 使用精制环己烯(w(C₆H₁₀)≈94％)和试剂双氧水（w（H₂O₂）≈30％）为原料，初步探索了反应时间、反应温度、催化剂用量、溶剂CH₃C1用量、环己烯和双氧水摩尔配比等因素对反应的影响；在两次正交实验的基础上获得了较佳反应条件为：以0.016molH₂O₂计，环己烯和双氧水摩尔比1.75：1、反应温度40℃、反应时间180min、催化剂用量0.2g、溶剂CH₃C1用量24mL。在该反应条件下，双氧水的转化率为100％，产品中环氧环己烷的选择性高达93.40％，新鲜催化剂的回收率约为60％；红外光谱表明析出的催化剂结构发生了变化。 使用工业粗环己烯(w(C₆H₁₀)≈77％)和工业双氧水（w（H₂O₂）≈35％）为原料进行环氧环己烷制备工艺的研究。探讨了催化剂用量、反应温度、反应时间、环己烯与双氧水的摩尔比、溶剂1，2-二氯乙烷用量等主要因素对反应的影响。在单因素实验和正交实验的基础上，经优化获得的较佳合成条件为：以0.08molH₂O₂计，n(C₆H₁₀)：n（H₂O₂）=2.5：1，反应温度30℃，反应时间90min，催化剂用量0.6g，溶剂1，2-二氯乙烷70mL。该条件下H₂O₂的转化率大于99.9％，环己烯的当量转化率为95.42％，环氧环己烷选择性为96.14％，环氧环己烷的收率为91.73％。 进行了以二氯甲烷为特殊溶剂的反应条件的探索，发现以二氯甲烷为溶剂可以有效控制反应温度，提高环己烯的转化率和环氧环己烷的选择性。环己烯当量转化率可达更多还原

【Abstract】 This dissertation was financial supported by the Natural Science Funds of Henan Province （511020800）.Cyclohexene oxide （CHO） is an important fine organic intermediate materal. Its application is wide range, for example, agricultural, medication, coating, resin and other fields. And CHO can also be used to produce other chemicals, such as cyclohexenediol, adipic acid and so on.In this work, We used hydrogen peroxide （HP） and cyclohexene （CH） which were rich in Henan Province as the main raw materials to carry out the key techniques on synthesis of CHO with HP as oxidant. The main works and results as follows:A new kind of production scheme of reaction controlled phase transfer catalyst has been developed. The yield of catalyst （based on the amount of quaternary ammonium salt） was 94%. The production process of this catalyst is convenient, and materials and energy exhaustion is lower than the process of Xi Zuwei. The catalyst was characterized by FT-IR and elementary analysis. The catalyst has high activity, selectivity and the characteristic of reaction controlled phase transfer catalyst.We study the technology of synthesis of CHO by fine cyclohexene (w(C₆H₁₀)≈94%) and reagent HP （w（H₂O₂）≈30%）with the reaction-controlled phase transfer catalyst. The effects of many factors, such as reaction time, reaction temperature, amount of catalysts, the volum of solvent chloroforme, mole ratio of CH to HP on epoxidation process were studied preliminary. Using orthogonal experiment technology twice, and the proper technological conditionis detailed as follows: based on 0.016 mol of H₂O₂, n(C₆H₁₀): n（H₂O₂） = 1.75 : 1, reaction temperature 40℃, reaction time 180 min, the amount of catalyst 0.2 g, the volum of solvent chloroform 24 mL. Under the condition, the conversion of HP is nearly 100%, selectivity of CHO is 93.40%, the recovery efficiency of fresh catalyst is about 60%; FT-IR spectra proved that the structure of the used catalyst has been changed.The technology research of CHO production has been carried out with raw CH (w(C₆H₁₀) ≈77%) and industry HP （w（H₂O₂）≈30%）. The main factors influencing the epoxidation were also studied, such as amount of catalysts, reaction temperature, reaction time, mole ratio of CH to HP, the volum of solvent 1,2-dichloroethane and so on. The proper synthesis condition has been obtained with the methods of single factor and orthogonal experiment. The更多还原