有机铜催化剂催化合成三乙氧基硅烷

张磊, 郝素娥, 李季, 冀鸽, 杨春晖

哈尔滨工业大学化工学院



摘要:

传统的直接法合成三乙氧基硅烷多以卤化铜为催化剂,存在产品卤素含量高,反应过程中产物易水解的问题.本文以乙酸铜和自制双二乙基磷酸铜为催化剂,对硅粉与催化剂的混合体(触体)进行微波活化处理,研究了活性触体和乙醇进行反应合成三乙氧基硅烷的工艺影响因素,主要考察了微波功率、微波处理时间、反应温度、促进剂及搅拌速度等因素对三乙氧基硅烷的选择性和硅粉转化率的影响.通过对两种有机铜催化剂的对比研究发现,双二乙基磷酸铜的催化效果较好.微波处理触体[m(Si):m(双二乙基磷酸铜)=10∶1],以氟化铵和噻吩为双重促进剂,得到三乙氧基硅烷的选择性达到99.3%,硅粉转化率为41%.

关键词:  三乙氧基硅烷  乙酸铜  双二乙基磷酸铜  微波  促进剂

DOI：10.11951/j.issn.1005-0299.20110216

分类号:TQ264.1

基金项目:国家科技支撑计划资助项目(2006BAE01B09)



The synthesis of triethoxysilane using organocopper salts as catalyst

ZHANG Lei, HAO Su-e, LI Ji, JI Ge, YANG Chun-hui

School of Chemical Engineering and Technology,Harbin Institute of Technology,Harbin 150001,China

Abstract:

To solve the problem of higher content of halogen in the direct synthesis of triethoxysilane,the catalyst of copper halide was replaced by organic copper in this paper.Using copper acetate and copper(Ⅱ)bis(diethyl phosphate) as catalyst,the catalyst and silicon was heated by the microwave.Triethoxysilane was synthesized by the reaction between contact mass and ethanol.The influencing factors,such as microwave power,microwave time,reaction temperature,promoters and the rate of stirring have been investigated to ascertain the selectivity of triethoxysilane and the conversion of silicon.When using the copper(Ⅱ)bis(diethyl phosphate) as catalyst which has been pretreated by microwave with silicon,and adding double promoters,the result shows that the selectivity of triethoxysilane reaches 99.32% and conversion of silicon reaches 41%.

Key words:  triethoxysilane  copper acetate  copper(Ⅱ)bis(diethyl phosphate)  microwave  promoter