【作者】 田华荣；

【导师】 倪沛红；

【作者基本信息】 苏州大学 ， 工程， 2005， 硕士

【摘要】 丁二酰丁二酸二甲酯(简称:DMSS)是合成喹吖啶酮类颜料、1, 4-环己二酮和光敏聚合物的重要中间体。本论文利用石油的低级产物——丁二酸为原料,通过大分子树脂催化酯化反应、狄克曼缩合反应、酸碱中和反应及一系列的物理分离等方法,获得了一条对环境友好、生产成本低的工艺路线;得到与欧洲大公司(如荷兰DSM公司等)相媲美的高质量的丁二酰丁二酸二甲酯,为我公司获得了又一新的自主知识产权。首先,将丁二酸与过量的甲醇在大分子树脂催化剂的催化下发生酯化反应,经精馏获得纯度99.8 %以上的中间产物丁二酸二甲酯(简称:DMS),一次反应收率达92 %,循环反应收率达98 %以上;而且大分子树脂催化剂可以无限次的循环使用;过量的甲醇及精馏的残余物丁二酸甲酯(简称:单酯)循环到下一批酯化反应中。没有废渣等产生,对环境无污染。接着,采用过量的DMS与甲醇钠发生狄克曼反应,得到丁二酰丁二酸二甲酯钠盐(简称:DMSS钠盐)与DMS的混合物,采用高压力的膜压滤分离装置将二者分离,DMS循环回用,DMSS钠盐再用稀硫酸中和、分离即得到目标产物DMSS;纯度达99.5 %以上(注:是液相色谱含量),外观奶黄～白色;DMSS产品的主原料丁二酸消耗为1.8 t/t(理论消耗为1.034 t/t,一般的文献提供的消耗在2.4 t/t以上);不使用二甲苯、二甲亚砜等对环境有害的溶剂,整个工艺是绿色环保的。更多还原

【Abstract】 Dimethyl 1,4-cyclohexanedione-2,5-dicarboxylate (DMSS) is an important intermediate for Quinairdone pigment, 1,4-cyclohexdianone and photosensitive polymer. In the present dissertation, a series of high-quality DMSS have been synthesized using succinic acid from the low level outcome of petroleum as an initial material and macromolecule resin as catalyst. The processes included esterification, Dieckmann reaction, neutralization and physical separating methods. The obtained products exhibit the same quality lever as European top manufacturer (e.g. DSM Corporation in Holland).The esterification reaction was performed with succinic acid and excess methanol in the present of macromolecule resin, yielded dimethyl succinate (DMS) with a purity over 99.8 %. Significantlly, the macromolecule resin catalyzer could be recycle endlessly. The excess methanol and the remaining methyl succinate ( Monoester ) could be circulated in next esterifying reaction. There are not waste residue in this route. It won’t cause pollution.Dieckmann reaction was carried out between excess DMS and sodium methylate. A mixture of dimethyl 1,4-cyclohexanedione-2,5-dicarboxylate sodium salt (sodium salt of DMSS) and DMS were obtained. Subsequently, a high-pressure thin-film separator was used to separate above mixture. DMS could be circulated in the process. The salt of DMSS was neutralized by sulfuric acid, separated by centrifugal machine, and then a purified DMSS solid was obtained with purity over 99.5%. The appearance of DMSS shows milk-yellow to white color. The consume amount of main material was 1.8 tons of succinic acid per ton of DMSS. The theoretic consume is 1.034 t/t, and normal literature reported was over 2.4 t/t. In this modified process, harmful organic solvents such as xylene, dimethyl sulfoxide were not employed, indicated that the novel route is of friendly-environment.更多还原