【作者】 康武魁；

【导师】 胡常伟；

【作者基本信息】 四川大学 ， 物理化学， 2003， 硕士

【摘要】 用“绿色化学品”碳酸二甲酯代替光气合成苯异氰酸酯的中间体—苯氨基甲酸甲酯，具有反应条件温和，催化剂便宜，仅有副产物甲醇生成等优点。若同时与甲醇氧化羰基化生产碳酸二甲酯反应相结合，可构成“零排放”的绿色合成工艺过程，是清洁生产的重要发展方向。苯氨基甲酸甲酯是生产异氰酸酯的重要中间体，本文对碳酸二甲酯和苯胺反应合成苯氨基甲酸甲酯的催化剂及工艺条件进行了研究。 对一系列单组分和双组分催化剂进行了评价，发现α-PbO、SnOBu₂、ZnO-Pb₃O₄等催化剂有较好的催化性能。进一步研究表明： α-PbO较适宜的反应条件为：反应回流温度170℃，反应回流时间4h，Aniline：DMC=1:5（摩尔比），催化剂用量为苯胺物 四川大学硕士学位论文质的量的7，5%，此时催化效果达到最佳，苯胺的转化率为81%; SnOBuZ较适宜的反应条件为:反应回流温度180℃，反应回流时间4h，A刀iline:DMC=l:5（摩尔比），催化剂用量为苯胺物质的量的5.5%，此时催化效果达到最佳，苯胺的转化率为77.8%: 二元复合催化剂ZnO一Pb3O;较适宜的反应条件为:金属配比Zn:Pb二3:1，反应回流温度170℃，反应回流时间4h，A刀iline:DMC月:5（摩尔比），催化剂总用量为苯胺物质的量的10%，此时催化效果最佳，苯胺的转化率可以达到75.6%;对金属氧化物作为催化剂的催化机理进行了初步探讨。 建立了一套可靠的可以对主产物和副产物同时进行分析的高效液相色谱分析方法。确立了色谱条件:色谱柱为认恤ters Sy^etryShield RP 18（3.gmmX 150tnln），流动相为甲醇:水=55:45，流速为0.6切刀n五n，紫外检测波长260lun。采用外标法对主产物进行了定量分析，在此色谱条件下，对实验结果进行了准确度和精密度实验，反应物和主副产物分离度良好，符合色谱分析的要求。 对氨基甲酸甲酷（MC）代替碳酸二甲酷与苯胺反应来制取苯氨基甲酸甲醋进行了初步探讨，发现二乙二醇二甲醚为溶剂时，反应结果比较理想，苯胺的转化率、苯氨基甲酸甲酷的产率及选择性都比较高，尤其是使用SnX时，在回流温度为180℃，回流时间为sh，催化剂用量为苯胺物质的量的10%，Ani 1 ine:MC=1:2的条件下，苯胺的转化率高达99.4%。更多还原

【Abstract】 Methyl phenyl carbamate(MPC)- the intermediate of phenyl isocyanate is synthesized from aniline and Dimethyl Carbonate(DMC), which is considered as green chemistry substance, instead of phosgene. This synthesis route has some distinct advantage, such as moderate reaction conditions, inexpensive catalyst and the only by-product methanol which could be used in the synthesis of DMC by gas-phase oxidative carbonylation of methanol, and then high atom economic process can be acquired. So it is a prospective route for further development in clean production. Methyl Phenyl Carbamate(MPC) is an important intermediate for synthesis of isocyanate, the following research work concerning the catalysts and the process of MPC synthesis from DMC and aniline has been systematically done hi this thesis.A series of catalysts were estimated. Some kinds of catalysts, such as a -PbO, SnOBua, ZnO-Pb3O4 , and so on, which have good performance were selected out for the further research.It has been found that at 170 ℃, Aniline: DMC= 1: 5 (mol ratio ), after 4h of reaction, using 7.5 mol% of aniline ,the a -PbO catalyst exhibited high activity with 81% conversion of aniline; at 180℃, Aniline: DMC=1: 5 (mol ratio ), after 4h of reaction, using 5.5 mol% of aniline ,the SnBu2O catalyst exhibited high activity with 77.8% conversion of aniline; at 170℃, Aniline: DMC=1: 5 (mol ratio ), Zn: Pb=3:1(mol ratio), after 4h of reaction, the amount of catalyst used was 10 mol% of that of aniline, the composed catalysts by two metals ZnO-Pb3O4 catalyst exhibited high activity with 75.6% conversion of aniline. Reaction mechanism of metal oxides catalysts was proposed.A set of credible HPLC analysis conditions was set up, as the following: chromatographic column: Waters Symmetry Shield RP18(3.9rnmX150mm), mobile phase: V(CH3OH):V(H2O)=55:45, flow speed: 0.6ml/min, wavelength of ultraviolet detector: 260nm.Quantitative analysis of MPC was carried out by external standard method. The accuracy and precision of recovery test were done and the results were excellent.The study of synthesis of MPC from aniline and Methyl carbamate(MC) instead of DMC was carried out. It has found that at 180#, Aniline: MC=1: 2 (mol ratio ) , after 8h of reaction, the amount of catalyst used was that of 10 mol% of aniline, the SnX catalyst exhibited high activity with 99.4% conversion of aniline whendiethylene glycol dimethyl ether as dissolvent.更多还原