【作者】 盛卫坚；

【导师】 王煜华； 高建荣；

【作者基本信息】 浙江工业大学 ， 农药化学， 2003， 硕士

【摘要】 烯烃环氧化反应在有机合成中占有重要地位，有机环氧化合物由于其活泼环氧基的存在，使其能与多种物质反应生成具高附加值的精细有机合成产品和中间体。 论文在查阅国内外有关文献基础上，对烯烃环氧化反应的合成工艺及研究进展作了概述，对本论文的代表产品环氧环己烷的合成路线及工业化应用作了综合评述。论文避开了工艺复杂、污染严重的传统环氧化法，探索开发了一条适合工业化生产的环氧环己烷绿色催化合成新工艺路线。 论文采用酸催化脱水法，对环己醇在磷钨酸、硅钨酸、多聚磷酸-硫酸催化下脱水反应及工艺过程进行了实验研究，合成了较高纯度的环己烯。对杂多酸的特性及催化脱水机理进行了探讨。 论文研究了次氯酸法在环己烯环氧化反应中的应用，次氯酸法是传统的烯烃环氧化法，低选择性、污染严重等缺点在较大程度上限制了次氯酸法的工业化应用。 论文重点研究了以环己烯为原料，杂多离子／PTC／H₂O₂复合体系绿色催化环氧化合成环氧环己烷的新工艺。由杂多酸分解及钨酸与磷酸缩合合成了具环氧化催化活性的杂多离子结构，经筛选确定了合适的相转移催化剂。对反应合成、相转移催化机理和合成工艺进行了研究和实验探索，经条件优化实验确定了较佳的合成工艺参数。 浙江工业大学2003硕士学位论文 论文研究了钦硅分子筛的特性及合成工艺，探讨了分子筛的合成机理及反应条件对钦硅分子筛结构的影响。应用水热合成法合成了中孔的含钦分子筛Ti一MCM一41，分别以过氧化氢与叔丁基过氧化氢为氧源，对Ti一MCM一41在环己烯环氧化反应中的应用进行了实验探索。 论文研究和探讨了由环己醇经硅钨酸催化脱水合成环己烯，由环己烯经杂多离子/PTC/HZO:复合体系绿色催化合成环氧环己烷的工程化开发原理和流程组织原则等。完成了中试工艺流程设计，确定了操作规程。中试放大试验结果验证了新合成工艺的工业化可行性。确定了可行的_}二业化应用_<sub>I二艺放大原则。为绿色催化合成环氧环己烷系化合物的工业化合成新工艺开发提供了理论依据和可行的工艺参数组合。更多还原

【Abstract】 Epoxide reaction is one of the important reactions in organic synthesis. Because of their active oxido existence, organic expoxy compounds can react with many organic compounds getting lots of high additional evaluation substances.Based on evaluation of the literatures from all kinds of channels, the applications and the processes for preparation of expoxycyclohexane were reviewed while expoxycyclohexane was the delegate product in this dissertation. To avoid the traditional methods which are much complex and make the pollution of enviaronment, the novel environment benign process for preparation of expoxycyclohexane by catalyst was studied.Effects of different catalysts’ systems on the yield of cyclohexene were deserved, using cyclohexanol as raw material through dehydration by catalysts. The optimum process parameters were determined about the dehydration of cyclohexanol. The chatacteristic of the process and the mechanism of dehydration catalyzed by heterpoly acids were studied.Hypochloride’s application in the preparation of expoxycyclohexane was studied. The method by hypochloride is a traditional way for alkene oxidition. The application in producing alkene oxide was limited for its lower selectivity.Using cyclohexanol as material, heterpoly ion /PTC/H2O2 system was discussed in emphases. Heterpoly ion which has catalyzed activity was synthesized from heterpoly acids’ decompose or by the combination H2WO4 with H3PO4. The phase transfer catalyst was selected by experiments. The mechanism of the reaction and that of phase transfer catalysis were studied. The process parameters were selected by optimum experiment.The characteristic and process of preparation of titanium-containing molecular sieve(zolite) were studied. The mechanism of reaction and the effectsof different reaction conductions on structure of molecular sieve were discussed. Titanium-containing molecular sieve Ti-MCM-41 was synthesized by hydrothermal method. Using H2O2 and TBHP as oxidation agent the characteristic of titanium-containing molecular sieve catalyst in the process for preparation of expoxy cyclohexane was reviewed by experiments.The novel process parameters were selected by optimium experimental. The industrial process was designed and the novel process for preparation of cyclohxene and expoxy cyclohexane starting from cyclohexanol by heterpoly acid catalyst and with the system of heterpoly ion/PTC/H2O2. was tested in the industrial-model process. It provides the theoretical basis and the feasible process parameters for the industrialization of expoxy cyclohexane compounds.更多还原