硫代氨基甲酸酯的及副产品开发研究

【作者】 曾湘晖；

【导师】 钟宏；

【作者基本信息】 中南大学 ， 化学工艺， 2003， 硕士

【摘要】 硫代氨基甲酸酯(简称硫氨酯)是一类重要的硫化矿捕收剂。本文对硫氨酯的性能、合成方法以及应用状况进行了综述。着重研究了硫氨酯的合成工艺，认为黄药酯化氨解法是在生产实践上较易于实现的工艺。然而该工艺致命的缺点在于巯基乙酸钠副产品的产生，导致生产成本较高，所以对巯基乙酸钠溶液的合理处理将直接影响该工艺的经济效益。论文开发出巯基乙酸异辛酯副产品，广泛应用于制造聚氯乙烯塑料制品的热稳定剂。 首先研究了O-异丙基-N-乙基硫氨酯的合成工艺。实验得出最佳工艺条件为：一氯乙酸：碳酸钠：异丙基黄药：乙胺=1：0.58：1：1.05(mol比)，水用量为30 ml／0.1mol一氯乙酸，酯化温度80℃，酯化时间2小时，氨解温度70℃，氨解时间1小时。在此条件下，乙硫氨酯产率达96％以上，纯度也可达96％。 然后，对产生的巯基乙酸钠溶液的处理进行了探讨。巯基乙酸钠溶液经酸化，异辛醇三级逆流萃取后得到巯基乙酸含量为150g／L的有机相，在对甲苯磺酸催化下进行酯化反应制得巯基乙酸异辛酯，研究表明酯化反应的工艺条件为：反应温度110℃，反应时间1小时，苯用量为30ml／50ml萃取液，对甲苯磺酸与巯基乙酸的质量比为1％：1，酯化率达到93％。 原料成本效益计算结果表明，开发巯基乙酸异辛酯工艺的原料总成本占总产值的百分比较未开发工艺降低了16.1％，经济效益提高显著。更多还原

【Abstract】 Thionocarbamates are a kind of important sulphide minerals collectors. The properties, synthetic methods and application status of thionocarbamates are reviewed. Synthetic technics of thionocarbamates are emphatically studied. It is regarded the technics that xanthate esterified by organic halide and ammonolyzed by amine is very easy to be practised to produce thionocarbamates. But the by-pruduct therglycolic acid sodium is also made in the technics, which results high cost. So whether the thergiycolic acid sodium solution is treated reasonably will straightly affects the economic efficiency of the technics. By-product isooctyl mercaptoacetate was expoited, largely used to produce heat stabilization reagent of chloroethylene polymer plastic.Firstly, the synthetic technics of O-isopropyl-N-ethyl thionocarbamate was worked over. The optimal conditions determineded by experiments were as follow: chloracetic acid : sodium carbonate : isopropyl xanthate : ethylamine=l : 0.58 : 1 : 1.05(mol), water usage is 30 ml/O.lmol chloracetic acid, esterification temperature was 80癈, esterification time was 2h, ammonolysis temperature was 70 "C, ammonolysis time was Ih. In such conditions, the yield and purity of O- isopropyl-N-ethyl thionocarbamate reached above 96%.Secondly, the treatment to by-product therglycolic acid sodium solution was discussed. After acidified and third class countercurrent extracted by isooctanol, organic phase contended therglycolic acid(150g/L )was obtained. Under the catalysis of P-Toluene sulphonic acid, esterifying reaction took palce in the organic phase and isooctyl mercaptoacetate was made. The studied results showed the esterifiable conditions were that reaction temperature was 110癈, reaetion time was Ih, benzene usage was 30ml/50ml organic phase, P-Toluene sulphonic acid: therglycolic acid=l% : l(mass). Esterifiable yield got to 93%.The account results of material cost indicates that the ratio of gross material cost to production value was decreased 16.1% after exploitingisooctyl mercaptoacetate. Economic efficiency was notablely boosted.更多还原