【作者】 陈志彬；

【导师】 李惠萍；

【作者基本信息】 郑州大学 ， 应用化学， 2007， 硕士

【摘要】 2-甲基-1，3-丙二醇（MPO）独特的支链结构、无色低毒、性能优异。在许多方面正在逐渐取代目前广泛使用的传统直链二元醇，应用前景广阔，但有关MPO的化学合成工艺研究，国内外文献报道较少，国内也无该产品的生产。作为河南省自然科学基金资助项目（No．511021100）的子课题，以异丁烯为主要原料合成MPO未见有报道。本文在前期工作的基础上，主要研究了3-氯-2-氯甲基丙烯（CCMP，由异丁烯管式反应器连续氯化获得）的碱性水解制备中间体2-亚甲基-1，3-丙二醇（MEPO）的最佳工艺条件。根据CCMP在水中溶解度小、水解速率慢的特点，通过单因素试验筛选，最终选取DMF作为该系统的水解溶剂有效提高水解率。优化出的的最佳水解工艺条件为：溶剂DMF；V（CCMP）／V（OH^-）=1:5；碱液浓度（wt）=10％；m_DMF／mC_CCMP=0.20～0.25；温度92℃；时间6h，CCMP的水解率达95％。在此基础上探讨了70℃～90℃范围CCMP（A）宏观水解动力学，得到CCMP水解反应对CCMP表现为0.82级，对NaOH（B）表现为0.12级，其宏观动力学方程为：其表观活化能Ea=33.45kJ·mol^-1。采用Pd／Al₂O₃作为加氢催化剂，常压下在自制的塔式加氢器中合成出了目的产物2-甲基-1，3-丙二醇（MPO），采用IR、GC900气相色谱仪及GC-6890，MS-5973N型气质联用仪等技术确证了本工艺合成的目的产物MPO。证明了以异丁烯为主要原料合成MPO工艺的可行性。考察了反应液温度、时间、催化剂用量等因素对加氢反应的影响。较佳的工艺条件为：氢气流量为0.4L／min，温度90℃，反应时间7小时，催化剂用量9克，此时MPO收率可达90％以上。此外，根据需要还对所用催化剂Pd／γ-Al₂O₃进行了SEM表征，为进一步的研究提供技术支持。更多还原

【Abstract】 2-Methyl-1,3-propanediol（MPO）, an unique branched diol, which bears excellent antibacterial and biodegradation properties, is gradually substituted for those linear diols widely used now. But the reports on preparation of MPO from both domestic and overseas are rare. As the project （No.511021100） funded by Henan Natural Science Foundation, a new synthesis technology using isobutene as basic material to synthesize MPO was proved to be feasible in this paper.Based on the former work, the synthesis of 2-Methylene1,3-propanediol（MEPO） from 3-Chloro-2-chloromethyl-1-propene（CCMP, obtained by isobutene continuously chlorinating in tubular reactor） in presence of DMF was studied, which solved the problem of low solubility of CCMP in water and accelerated the rate of hydrolysis. The optimum hydrolysis conditions through both Orthogonal and single factorial tests were obtained: solvent DMF; V（CCMP）/V（OH-）=1:5; NaOH（wt）=10%; m_DMF/m_CCMP= 0.20～0.25; 92℃; 6h and the conversion of CCMP reached about 95%. Also, the hydrolysis kinetics of CCMP from 70℃to 90℃was studied. The results showed that the reaction order of CCMP （B） was 0.82 and NaOH （B） was 0.12 and the macroscopic kinetic equation was:The goal product 2-Methyl-1,3-propanediol（MPO） was synthesized in self-designed tower hydrogenating reactor in presence of Pd/γ-Al₂O₃ catalyst. The structure of prepared MPO was detected by GC-MS, IR and GC900. So, the new synthesis technology of MPO from isobutene was feasible. Influences of several variables such as temperature, time, the amount of catalyst on the yield of MPO were examined. The optimum hydrogenation conditions were hydrogen flow 0.4L/min, 90℃, 7h, catalyst 9g and the yield of MPO was over 90%。In addition, the structure and components of catalyst Pd/γ-Al₂O₃ were examined by SEM, which provides the technical support for the further research.更多还原