【作者】 胡英鹏；

【导师】 李东亮； 杨琴；

【作者基本信息】 西安建筑科技大学 ， 应用化学， 2006， 硕士

【摘要】 通过单因素实验,重点考察并确定了在硫酸催化下,以尿素和乙二醛为原料合成甘脲时尿素/乙二醛的摩尔比、pH值、温度、反应时间、乙二醛的滴加速度等因素对合成甘脲的产率和纯度的影响。确定的最优制备条件为:尿素/乙二醛摩尔比为2.5,硫酸调pH值为2,反应时间2小时,反应温度70℃,乙二醛的加入速度1ml/min,此时甘脲的收率可达73%。对甘脲进行的IR分析结果表明,该条件下得到的确为甘脲且纯度较高,可直接作为合成瓜环的原料。 选取酸浓度、温度、时间、甘脲相对于酸的浓度为实验因素,通过四因素四水平正交实验,确定了混合瓜环的最佳合成条件:甘脲相对于酸的比例215mg/ml,催化剂盐酸的浓度9mol/L,反应温度100℃,反应时间3小时,其中催化剂浓度和反应温度是影响瓜环合成产率的显著影响因素。通过IR、¹H NMR波谱和¹³C NMR波谱对合成出来的瓜环进行了表征。 利用盐酸重结晶法完成了混合瓜环的逐一分离,但收率较低。在考察了碱金属、碱土金属盐溶液对各元瓜环溶解性影响的基础上,提出了利用碱金属、碱土金属盐溶液实现混合瓜环分离的两套方案,即利用碱金属、碱土金属盐溶液对各元瓜环溶解性影响的差异逐元分离混合瓜环,以及利用碱金属、碱土金属盐溶液对各元瓜环溶解性影响的差异先将混合瓜环分成CB[5、7]和CB[6、8]两组,再利用碱金属、碱土金属盐溶液将每组瓜环逐一分离。结果表明利用碱金属、碱土金属盐对各元瓜环溶解性影响的差异可以完成混合瓜环的分离,但就操作过程、产品收率、以及瓜环纯度而言,并不比盐酸重结晶法先进。在研究碱金属、碱土金属盐溶液对瓜环溶解度的影响时,首次提出其实质主要是盐析效应和盐效应,前者使瓜环溶解度减小,后者使瓜环溶解度增大,且混合瓜环的溶解度不是CB[5]、CB[6]、CB[7]、CB[8]的溶解度的简单加和。 通过实验,给出了优化的水—盐酸两步分离法:用蒸馏水将制得的混合瓜环按40g/L浓度进行选择性溶解,不溶物为CB[6、8],滤液含CB[5、7],后者经蒸更多还原

【Abstract】 With the one-factor experiement, the author mainly investigates the influences of the following factors: the molar rate of urea and glyoxal;the pH value;the temprature;the reaction time;and the titration speed of glyoxal and so on, on the purity degree and the yield of Glycoluri, when urea and glyoxal are used as compositions to produce Glycoluril with the catalyzer, vitriol. The best production condition which is determined in the paper is that the molar rate of urea and glyoxal is 2.5 the pH value 2. reaction time 2 hours, the temprature 70℃ and the titration speed of glyoxal is lml/min under which circumstance the the producation rate of Glycoluri will be 73%. Also the result of IR analysis indicates that the product is highly pure Glycoluri and it can be used directly to compound Cucurbituril.Then the concentration of hydrochloric acid temprature time and the density of Glycoluril in hydrochloric acid being choosen as the experiment factors in the orthorhombic experimentation (four factors four level) , the best conditions for compounding mixed Cucurbituril are determined. They are as follows: the density rate of Glycoluril in vitriol is 215 mg/ml and concentration of the catalyzer hydrochloric acid 9 mol/L the reaction temprature 100℃ and the reaction time is 3 hours among which the concentration of the catalyzer and the temprature are major factors. The Cucurbituril is showed in the spectrum of IR ~1H NMR and ~13C NMR.Because of the low seperating rate of mixed Cucurbituril by the way of hydrochloric acid recrystalization.at the beginning the author on the foundation of the effects of alkali metals and the solution of alkali metals on the solubility of different Cucurbituril suggests two methods to seperate the mixed Cucurbituril. Firstly accoding to the different solubility of Cucurbituril influenced by alkali metals and thesolution of alkali metals, we can divide the mixed Cucurbituril step by step. Secondly we can group the mixed Cucurbituril into two categories: CB[5> 7] and CB [6, 8];next seprate the each group one by one. However the experiement result shows although the different solubility of each kind of Cucurbituril under the influence of alkali metals and the solutionof alkali metals is helpful to part the mixed Cucurbituril, the method doesn’t have any advantage over the hydrochloric acid recrystalization on terms of operating process, the amount of production and the purity of Cucurbituril.The improved two-step water-hydrochloric acid seperating methods is given with the experiement. Dissolve the mixed Cucurbituril at the rate of 40% in distilled water;the indiscerptible is CB[6^ 8] and CB[5> 7] are melted in the solution. Then.after vaporizing and crystallizing, the latter becomes the solid of CB[5> 7];at last, each Cucurbituril group is seperated in the way of hydrochloric acid crytalization. The method has many advantages such as no metal ion introduced lower amount of hydrochloric acid quicker process of seperation higher production, and much purer Cucurbituril. The seperated Cucurbituril have been examined by the IR and’H NMR and the content of CB[5]> CB[6]> CB[7], CB[8] in mixed one are respectively as 19% , 50%, 25%, and 6%.Finally the essay studys the removal of Au+> Ag\ Cu2+ in water by different Cucurbituril. It implys that in Au solution CB[6] and CB[8] have better effect on the removal of Au than CB[6, 8];and the more Cucurbituril in the solution the higher removal rate of Au;however too much Cucurbituril will increase the removal rate but the utilization of Cucurbituril will decrease accordingly. In the mixed solution of Au+ , Ag\ Cu2+ the removal of a bit ofCu2+ and Ag+ is better than that of Au+. CB[6> 8] even can remove all the Cu when there is little in the water. We can use different types of Cucurbituril to seperate Au+, Ag+> Cu2+ For example, we can firstly use CB[6> 8] to seperate Cu2+ and then use CB[5 > 6> 7> 8] to seperate Au+ and Ag+.更多还原