摘要
本文研究了由甲基氨基甲酰氯(MCC)制备甲基异氰酸酯(MIC)后,再由MIC制备甲萘威的非四氯化碳过程。文中主要选用了甲苯、氯仿、四氯乙烯三种溶剂来替代四氯化碳。同时在MCC制备MIC的工段引入了有机碱作为除去HCl的缚酸剂;文中主要介绍了三乙胺、N-甲基咪唑(MIM)、N-丁基咪唑(BIM)三种缚酸剂。实验中首先研究了缚酸剂与HCl反应生成的有机碱盐酸盐与MIC溶液的分离,实验证明甲苯、四氯乙烯作为反应溶剂时,采用压滤的分离方法;氯仿作为反应溶剂时采用蒸馏的分离方法。
分离方法确定后,研究了影响甲萘威产率的各个影响因素;对于MCC分解为MIC的反应,主要研究了有机碱的滴加速度、有机碱的用量、MCC的分解温度、溶剂的用量、有机碱的种类等因素对甲萘威产率的影响;对于MIC溶液与1-萘酚的反应,主要研究了该反应的最佳反应时间,反应中1-萘酚的用量对甲萘威产率的影响。通过对以上影响因素的研究确定了甲萘威的最佳反应条件:甲苯为溶剂时,MCC:甲苯=1:6(m/m),有机碱:甲苯=1:1(m/m),1-萘酚:MCC:有机碱=1:1:0.98(mol/mol/mol),有机碱的滴加速度在6滴/分钟,MCC分解温度为50℃,MIC的甲苯溶液与1-萘酚的反应温度为108℃,反应时间为2小时;氯仿为溶剂时,MCC:氯仿=1:5(m/m),有机碱:氯仿=1:1(m/m),1-萘酚:MCC:有机碱=1:1:0.98(mol/mol/mol),控制有机碱的滴加速度在6滴/分钟,MCC分解温度为50℃,MIC的氯仿溶液与1-萘酚的反应温度为58℃,反应时间为4小时。在上述最优反应条件下,不论溶剂为甲苯或者氯仿,三乙胺和BIM作为缚酸剂时,甲萘威收率相近,都明显的高于MIM为缚酸剂;在缚酸剂一定时,氯仿为溶剂时甲萘威收率要明显的比甲苯为溶剂时高。
文章最后研究了以BIM为缚酸剂时,对BASIL工艺的应用,并且还考察了BIM的回收再利用。以NaOH回收BIM时,BIM溶液中水含量升高导致甲萘威的收率降低,可以采用热分解的方法回收BIM。
This thesis is focused on the preparation of methyl isocyanate (MIC) by methyl carbamyl chloride (MCC) and the preparation of Carbaryl by MIC. During these two processes carbon tetrachloride was not used as solvent. Fistly, three solvents including toluene, chloroform, and tetrachloroethylene were selected to substitute carbon tetrachloride. Meanwhile three kinds of organic alkalies including triethylamine, N- methyl imidazole, N- butyl imidazole were selected to react with hydrochloric acid, which is produced during the process of decomposing MCC to prepare MIC.
When the organic alkali reacted with hydrochloric acid, it will be neutralized to muriate. The method of separing MIC from the muriate was studied fistly. For the solvents of toluene and tetrachloroethylene, pressurized filtration method of separation was used, while for chloroform solvent, the distillation method of separation was used.
After the separation method was determined, influence factors of preparing carbaryl by MCC were investigated experimentally. These influencing factos included the droping speed of organic alkali, the amount of organic alkali, the temperature of the decomposition of MCC, the amount of solvent, the sort of organic alkali and so on.
Through the study on the influencing factors, the optimum condition had been determined. When toluene is used as solvent, the optimum condition was as follows:
MCC:toluene=1:6(mass ratio, m/m); organic alkali:toluene =1:1(m/m); 1-naphthol:MCC:organic alkali=1:1:0.98(mol/mol/mol); The decomposition temperature of MCC was set to 50℃; The synthesis temperature of carbaryl with MIC and 1- naphthol was 108℃and the reaction time was 2 hours.
When chloroform is used as solvent, the optimum condition was as follows:
MCC:toluene =1:5(m/m); organic alkali:toluene =1:1(m/m); 1- naphthol: MCC:organic alkali =1:1:0.98(mol/mol/mol); The decomposing temperature of MCC was set to 50℃; The synthesis temperature of carbaryl with MIC and 1- naphthol was 58℃and the reaction time was 4 hours.
Under the optimum condition, no matter the solvent was toluene or chloroform, the yield of carbaryl was the highest when the organic alkali was N- butyl imidazole. The yield of carbaryl was the lowest when the organic alkali was N- methyl imidazole. When the organic alkali was triethylamine, the yield of carbaryl was close to N- butyl imidazole. For a specified alkali, the yield of carbaryl in chloroform solvent was obviously higher than that in toluene solvent.
When the organic alkali was N- butyl imidazole, the BASIL process could be applied in the reaction of decomposing MCC to prepare MIC. The used N- butyl imidazole can be reclaimed using sodium hydroxide, however, the water content in the recycled N-butyl imidazole is relatively high, which may reduce the yield of carbaryl. Pyrolytic process could be used to recover N- butyl imidazole from its hydrochloric salt via decomposing at high temjperature.
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