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化工学报  2015 

三氯化铝催化有机硅单体副产共沸物歧化反应密度泛函理论研究

DOI: 10.11949/j.issn.0438-1157.20141522, PP. 1730-1737

Keywords: 三甲基氯硅烷,四氯化硅,三氯化铝,歧化反应,密度泛函理论

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Abstract:

AlCl3催化(CH3)3SiCl和SiCl4的歧化反应体系中可能存在(CH3)3SiCl与SiCl4生成(CH3)2SiCl2与CH3SiCl3(反应1),(CH3)2SiCl2与SiCl4生成CH3SiCl3(反应2)和(CH3)3SiCl与CH3SiCl3生成(CH3)2SiCl2(反应3)等反应。本文采用密度泛函理论对这3种反应进行了研究。结果发现在AlCl3催化剂上,可能发生CH3AlCl2中间体生成的分步反应和反应物共吸附反应,对两种情况下3种反应的反应路径均进行了计算,发现3种反应均偏向于以双分子共吸附机理进行。3种反应的能垒排序是反应2>反应1>反应3。同时,热力学数据分析发现,在543.15~593.15K之间,温度变化对反应2的摩尔Gibbs反应能变基本无影响,但在593.15K时,反应1和反应3的Gibbs自由能变显著减小。这些计算结果显示,如果适当调控反应温度,就能够在保证反应1和3进行的同时,抑制反应2的进行,从而实现歧化产物组成的调控,有利于(CH3)2SiCl2的生成。

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