为制备高纯度甲硅烷气体,用强碱性季铵碱阴离子交换树脂催化三甲氧基硅烷溶液进行歧化反应.采用脉冲放电氦离子化检测器测试粗甲硅烷气体,用气相色谱-质谱联用仪、感应耦合等离子体质谱仪测试精馏提纯的副产物四甲氧基硅烷.实验结果表明：在30～50℃和0.2～0.3 MPa条件下反应制备的粗甲硅烷气体中,H2、O2、Ar、N2、CH4的质量浓度分别为221.12、1.76、1.61、17.97、0.15μg/L,纯度达到99.9%;副产物四甲氧基硅烷中,金属杂质总质量浓度低于0.15μg/L,可用来制备高纯度硅溶胶;季铵碱催化三甲氧基硅烷歧化反应,反应条件温和,三甲氧基硅烷转化率96%,硅烷产率95%.催化剂易于购买,采用固定床反应器易于控制反应,易于连续加料,此工艺具有工业化生产价值.
High purity monosilane was prepared from disproportionation of trimethoxysilane catalyzed with quaternary ammonium hydroxide resin.Crude monosilane was analyzed by pulse discharge helium ionization detector.By-product tetramethoxysilane rectified was analyzed with gas chromatography-mass spectrometry and inductively coupled plasma-mass spectrometry.Experimental results show that the reaction conditions is the temperature range of 30~50 ℃ and the pressure range of 0.2~0.3 MPa.Contents of H2,O2,Ar,N2,and CH4 of crude monosilane were 221.12,1.76,1.61,17.97 and 0.15 μg/L,respectively.Content of tetramethoxysilane was 99.9wt%,and total metal impurities of tetramethoxysilane was less than 0.15 μg/L.Furthermore,the tetramethoxysiane can be material of high purity silica sol.The disproportionation reaction of trimethoxysilane catalyzed with quaternary ammonium hydroxide resin was happen at mild reaction conditions,and conversation of trimethoxysilane was 96wt%,and yield of monosilane was 95wt%.Catalyst is easy to buy,and fixed bed reactor is easy to control the reaction,and easy to continuous feeding,and then the technology has industrial production value.
参考文献
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