【作者】 段二红；

【导师】 赵地顺；

【作者基本信息】 天津大学 ， 工业催化， 2009， 博士

【摘要】 1,4-二氮杂双环[2.2.2]辛烷是具有独特双环“笼状”结构的叔胺化合物,主要用作聚氨酯泡沫塑料的凝胶催化剂,在化学工业中用途十分广泛。本文以乙醇胺或乙二胺为原料,研究筛选合适的催化剂,催化合成1,4-二氮杂双环[2.2.2]辛烷,其与现有技术相比具有转化率高、选择性强和催化剂寿命长的优点。由于1,4-二氮杂双环[2.2.2]辛烷容易结块,因此本文拟通过研究其结晶过程,优化结晶工艺,以得到粒度均匀的1,4-二氮杂双环[2.2.2]辛烷产品,从而延缓1,4-二氮杂双环[2.2.2]辛烷的结块速率,延长其存贮时间。由于MFI型分子筛的孔径非常适合1,4-二氮杂双环[2.2.2]辛烷催化反应,本文以HZSM-5和HTS-1分子筛作为载体,分别负载碱金属、碱土金属、铜和镍等过渡金属,制备一系列催化剂,对催化剂进行表征和活性评价,分别得到了乙二胺或乙醇胺合成1,4-二氮杂双环[2.2.2]辛烷的最佳催化剂,并且分别优化了在最佳催化剂下的工艺条件。作为新型溶剂或催化剂离子液体已经广泛应用于有机合成中,探索离子液体催化合成1,4-二氮杂双环[2.2.2]辛烷,对于降低反应温度、减少污染,实现其合成路线的绿色化具有前瞻性意义。筛选合成多种离子液体,如:[Bmim]Br、[Bmim]BF₄、[Bmim]PF₆、[BPy]Br、[BPy] BF₄和[BPy] PF₆,并对其进行表征;利用合成的离子液体催化乙醇胺或乙二胺合成1,4-二氮杂双环[2.2.2]辛烷,对反应工艺参数进行了优化,对离子液体的使用次数进行了研究。结晶热力学是影响结晶工艺的关键因素。利用激光测示技术测定了在不同温度下,1,4-二氮杂双环[2.2.2]辛烷在甲醇、乙醇、异丙醇、正丁醇、丙酮、乙酸乙酯和正己烷中的溶解度;还利用激光法,测定了不同温度下其在甲醇、乙醇和异丙醇中的超溶解度,从而获得1,4-二氮杂双环[2.2.2]辛烷在上述体系中的介稳区数据。实验测定了1,4-二氮杂双环[2.2.2]辛烷在乙醇溶剂中结晶的诱导期,计算得到其固液界面张力。在上述研究的基础上,采用冷却结晶的方法对1,4-二氮杂双环[2.2.2]辛烷工艺进行了研究,研究各种结晶参数对结晶过程的影响,得到了较优的结晶工艺,解决了1,4-二氮杂双环[2.2.2]辛烷的结块问题,为进一步深入研究和工业生产提供了一定的依据。更多还原

【Abstract】 1,4-diazabicyclo（2.2.2）octane exhibits certain unusual tertiary amine properties which are due to its bicyclic or“cage”structure. It is an important intermediate and end product in the chemical industry, which is used mainly as a catalyst in the production of polyurethane foams. The preparation of 1,4-diazabicyclo（2.2.2）octane by reaction of ethylenediamine or monoethanolaimine in the presence of catalyst were studied to get the right catalyst, which have good yield and selectivity and long catalyst life. 1,4-diazabicyclo（2.2.2）octane are easy to agglomeration. To get the good particle size of the 1,4-diazabicyclo（2.2.2）octane products which could decrease the agglomeration rate and extend the storage time, the crystallization process was studied in the manuscript.The zeolite of the MFI type is used, because of right pore diameters. In a particular embodiment, the zeolites （HZSM-5 or HTS-1） were doped by applying alkali, alkaline earth or transition metals of subgroups （such as Cu or Ni compounds） IA, IIA and IVB to VIII and a series of catalysts were get. The catalysts were characterized. The catalytic activities of catalysts were studied in the fixed-bed catalytic reactor. The right catalyst of each reaction was gain. The influences of various reaction parameters were discussed respectively.Ionic liquids have been widely utilized in the area of organic chemistry as novel solvents or catalysts. It is an object of the present invention to find an economical process for the preparation of 1,4-diazabicyclo（2.2.2）octane from readily accessible starting compounds which is improved compared with the prior art. Ionic liquids based on 1-n-butyl-3-methylimidazolium [Bmim] and 1-n-butyl-pyridine [BPy] with different anions such as Br^-, BF₄^- and PF₆^- were synthesized and chanractered. The influences of various parameters of the reactions were discussed. The ionic in the studies on conversion of ethylenediamine or Monoethanolamine over ionic liquids, 1,4-diazabicyclo（2.2.2）octane was obtained in good yield. The influences of various reaction parameters were discussed. The ionic liquids were possible to recycle and reuse.Crystallization threomdymics is the key factor in design and optimization of the crystallization process. In this thesis, the solubility and metastable zone of 1,4-diazabicyclo（2.2.2）octane in several pure solvents such as methanol, ethanol, isopropanol, n-butanol, acetone, acetic ester and n-hexane different temperatures were measured by laser monitoring method. The effects of cooling speed and mole fraction of methanol, ethanol and isopropanol on metastable zone were studied. The induction period and interfacial tension of ethanol was also measured. On the basis of thermodynamics study, the cooling crystallization process was optimized experimentally. To get the scoopable product of 1,4-diazabicyclo（2.2.2）octane, the effect of process parameters （such as cooling rate and concentration of original solution） on the product quality was studied in detail. As a result, the relative better crystallization process was brought forward. The basic data for further study and for industrial production was supplied.更多还原