乙炔二聚反应非水相催化体系的研究

Study on Anhydrous Catalyst in Acetylene Dimerization to Monovinylacetylene

乙烯基乙炔是一种重要的精细化工中间体,广泛用于氯丁橡胶、苯和苯乙烯等各种重要化工产品的生产。传统方法是乙炔在水相Nieuwland(Cu Cl-NH4Cl-HCl-H2O)催化剂作用下发生二聚反应制得,但存在转化率较低等问题。本文研究了一种乙炔二聚非水相催化体系,结果表明:当以Cu Cl为主催化剂,DMF/1,4-dioxane(7/3,v/v)的混合溶液作为溶剂,Et NH2HCl为助溶剂时,乙炔转化率和乙烯基乙炔选择性分别可达到34.6%和75.4%。另外,在此反应体系中通过添加第2种金属盐考察了双金属协同催化乙炔二聚反应,结果显示:当加入10%mol的Cu Cl2时,乙炔转化率可达44.6%,且催化剂的稳定性明显提高。

Monovinylacetylene is an important fine chemical intermediates, which is used forthe preparation of chloroprene rubber, benzene, styrene et al. Nieuwland catalyst(Cu Cl- NH4Cl- HCl- H2O) catalyzed acetylene dimerization was the traditional method forvinyl acetylene preparation. However, low acetylene conversion was still a challenge. In this paper,we studied an anhydrous catalyst foracetylene dimerization to synthesis monovinylacetylene. The results indicated that 34.6 % of acetylene conversion and 75.4 % of vinyl acetylene selectivity were obtained, when Cu Cl as the catalyst, a mixture of DMF/1,4- dioxane(7/3, v/v) as the solvent,Et NH2·HCl as the solubilizer. Moreover, collaborative bimetallic catalysis foracetylene dimerization was also studied by adding second metal salts, and the results show that the addition of 10 % mol of Cu Cl2 can efficiently enhance the acetylene conversion, which up to 44.6 % yield, and improved the stability of the catalytic system.