液-液相转移反应萃取法高选择性合成二烯丙基胺

A Liquid-Liquid Phase Transfer Reactive Extraction Process for Highly Selective Synthesis of Diallylamine

为提高氯丙烯催化氨解合成二烯丙基胺(DAA)的选择性,研究提出了液-液相转移反应萃取新工艺。通过萃取剂和相转移促进剂的筛选,建立了一高效的液-液相转移反应萃取体系。通过物料配比、反应时间和温度等因素的考察,确定了适宜的反应条件。分别用气相色谱(GC)、气相色谱-质谱联用(GC-MS)、核磁氢谱(1H-NMR)和红外光谱(FT-IR)等方法对产物DAA进行定性与定量分析。结果表明:氯苯是合适的反应萃取剂,苄基三乙基氯化铵(BTEC)是合适的相转移促进剂,氯化亚铜是合适的氨解催化剂;在较合适的原料配比(质量比m(氨水(25%)):m(氯丙烯):m(氯化亚铜):m(氯苯):m(BTEC)=255:58.5:1.5:120:1.0)下,35℃反应3 h,氯丙烯转化率达95.9%,DAA的选择性达91.9%(收率为88.1%)。含催化剂、过量的氨及中间产物单烯丙基胺(MAA)等的水相可方便地循环利用,而且在循环过程中将副产物氯化铵以固体形式分出,从而避免废液排放,降低生产成本。

A liquid-liquid phase transfer reactive extraction process was developed for highly selective synthesis of diallylamine（DAA） via catalytic ammonolysis of allyl chloride. An efficient extraction system was established by screening different extractants and phase transfer promoters. Reaction conditions were optimized by studying feed ratio, reaction time and temperature. DAA was qualitatively analyzed by FT-IR, GC-MS and 1 H-NMR and quantitatively analyzed by GC. The results show that chlorobenzene is a suitable extractant, benzyl triethyl ammonium chloride（BTEC） is a suitable phase transfer promotor and Cu Cl is a suitable ammonolysis catalyst. High DAA selectivity（91.9%）（yield 88.1%） at 95.9% conversion of allyl chloride is achieved when studied under feed ratio of ammonia solution（25%） ： allyl chloride ： Cu Cl ： chlorobenzene ： BTEC = 255 ： 58.5 ： 1.5 ： 120 ： 1（wt） at 35℃ for 3 h. The water phase containing catalyst, ammonia and intermediate product – monoallylamine（MAA） can be easily recycled, and the by-product ammonium chloride can be separated in solid form during the cyclic process to avoid waste and reduce production cost.