【作者】 周彩荣；

【导师】 蒋登高；

【作者基本信息】 郑州大学 ， 化学工艺， 2003， 博士

【摘要】 “由环己烯制备1，2-环己二醇的研究”是河南省杰出人才创新基金资助项目内容之一。本文针对国民经济发展的需求，结合我国精细化工行业的实际，进行了以环己烯为主要原料，合成1，2-环己二醇的研究。 1，2-环己二醇是制备邻苯二酚的一个重要的有机中间体。而邻苯二酚是一个重要的精细化工产品，在医药、农药、香料、精细有机合成等众多领域有着广泛的应用。有关1，2—环己二醇的合成工艺，国内外文献报道很少，以环己烯、有机酸、过氧化氢为主要原料合成1，2-环己二醇的文献报道就更少。为此本文对以环己烯、有机酸、过氧化氢为基本原料，采用原位法直接制备反式-1，2-环己二醇的新工艺进行了较为系统的研究。 本文根据环己烯分子结构特点及有关单元合成反应的基础理论，首先制定出1，2-环己二醇合成的初步实验方案，并对得到的结果进行比较，确定了影响该复杂反应体系的关键因素：温度、静置时间、有机酸用量、过氧化氢用量、有机酸浓度。进而重点探讨了温度、有机酸用量、过氧化氢用量等因素对合成反应的影响。利用熔点测试、DSC、FTIR等分析方法，证实本工艺合成的产物是反式-1，2-环己二醇。 采用本文优化出的最佳工艺条件来合成反式-1，2-环己二醇，用乙酸作载氧剂环己烯的转化率为77.9％，1，2-环己二醇的单程收率可达74％，用甲酸作载氧剂环己烯的转化率为99.5％，1，2-环己二醇的单程收率可达90％，而且未反应的环己烯和催化剂以及萃取剂等均可以循环利用，该工艺堪称为绿色环保工艺。 本研究还由DSC测试技术，实验测定了顺式-1，2-环己二醇和反式-1，2-环己二醇的熔点、熔化焓和定压热容，建立了两种不同几何结构(顺式-，反式-1，2-环己二醇)的混合物的熔化温度与组成之间的关系，以及熔化焓与组成之间的关系，同时还建立起了定压热容与温度之间的关系；由绝热氧弹测定仪，实验测定了1，2-环己二醇的标准摩尔燃烧焓，根据热力学原理计算出了1，2-环己二醇的标准摩尔生成焓以及本文研究氧化反应的标准反应焓。 另外，还建立了一套带激光监视系统，可以控制升温速率的溶解度测定实验装置，测定了反式-1，2-环己二醇在水、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酰乙酸乙酯、丙烯酸甲酯、丙烯酸乙酯和甲基丙基酮等9个二元体系中的溶解度。郑州大学博士学位论文摘要所测物系的溶解度数据均未见有相关文献报导。 利用UNIFAC模型对1，2一环己二醇在极性溶剂中的溶解度进行了估算，定义了C6H12O:和CHZ=CHC00等新基团，并对基团体积参数、表面积参数和基团交互作用参数进行优化，建立了本文的NUIFAC模型。模型对实验溶解度的预测获得了良好结果，其溶解度总的平均相对误差为7.48%。另外本文模型与简单方程、兄h方程相比，其预测结果与简单方程、兄h方程的精度基本相当。采用本文建立的UNIFAC模型，对水+1，2一环己二醇十乙酸乙醋和水+1，2一环己二醇+乙酸丁酷三元物系的平衡数据进行估算，总的平均相对误差分别为10.77%和9.80%，进而验证了本文模型的适用性。 本文以实验溶解度数据为基础，对溶剂萃取1，2一环己二醇的热力学行为进行了讨论，建立了萃取热力学模型，考察了盐析作用对萃取过程的影响。更多还原

【Abstract】 "The study of New Technology study of Synthesizing 1,2-cyclohexanediol " is one of subjects funded by Henan Outstanding Person Foundation. Aiming at demand of national economy and linking the actual condition of domestic refinery chemical , a routine with cyclohexene as main raw material was developed in the thesis.To prepare O-dihydroxybenzene with cyclohexene, trans-1.2- cyclohexanediol is a very important organic intermediate. As a kind of important fine chemical product, O-dihydroxybenzene has a prosperous future in the field of medicine, pesticide, spice and fine organic synthesis. Firstly, there is quite a few reports on the synthetic technology of trans-1,2-cyclohexanediol in the country and the reports are even less about cyclohexene abroad. So thie thesis developed and obtained the new technology routine which adopts the original position method to synthesize 1,2-cyclohexanediol directly.At first, on the base of the formula structure of cyclohexene and correlative organic synthesis theory, we draw up the experimental scheme of the synthesis of trans-1.2-cyclohexanediol. Then with the orthogonal design method and single-factor-experiment, the key factors affecting this complicate reaction were determined,. Furthurmore we refocused the influence of temperature, acetic acid, hydrogen peroxide, the ratio of acetic acid and acetic anbydride. The ideal synthetic process conditions are acquired.In this better condition, the yield is 74 % for acetic acid and is 90% for formic acid, but the unused cyclohexene and catalyst as well as ethyl acetate can be recycled for the reaction. In addition, the most pivotal is the selectivity, and not the percentage yield. The selectivity in the reaction is up to 95 percent calculated with unitary method. The technology can be regard as a environmental protection process because the excessive organic acid and uncreative cyclohexylene, and as well as solvent can be cycled used for Synthesis of 1,2-cyclohexanediol, and the organic salt is by-product.On basis of the work in this paper, we have gotten melting point, melting heat and heat capacities for 1,2-cyclohexanediol by DSC, standard combustion enthalpy have obtained by calorimeter, standard formation enthalpy, standard reaction enthalpy of1,2-cyclo-hexanediol have been calculated according to thermodynamic principle. Then, we have studied the relationship on melting temperature and component of trans-1,2-cyclohexanediol , melting heat and component of trans-1,2-cyclohexanediol in the mixture of cis- and trans-1,2-cyclohexanediol, as well as heat capacities of 1,2-cyclohexanediol as a function of temperature.A set of laser monitoring observation system to be used for measure the solubility with a high speed, which is programmed heating apparatus , have designed. The solubility of 1,2-cyclohexanediol were measured in water, methyl acetate, acetic ester, propyl acetate, butyl acetate, methyl acrylate, ethyl acrylate, acetoacetic ester at different temperature. There are 114 data points which are reported first time.A modified UNIFAC model is set up by defining new functional groups which are CHD and CH2=CHCOO. And, group volume parameters, group surface-aera parameters and group interaction parameters are optimized by means of computer program. This new modified UNIFAC model can perfectly predict the solubility on the above systems .The total mean relative error is 7.48% for solubility, The total mean relative errors are respectively 0.37% and 3.18% for the solubility of ideal equation and h equation. The result of ideal equation, h equation and the new model are similar. These show that the new model is successful. By means of new modified UNIFAC model can perfectly predict solid-liquid equilibriums on the above systems. The total mean relative errors are respectively 10.77% and 9.80% for ternary system solid-liquid equilibrium data of water+l,2-cyclohaxanediol + acetic ester and water+l,2-cyclohaxanediol+ butyl acetate between the experimental results and the values predicted by the更多还原