Density functional theory study on disproportionation reaction of methylchlorosilane azeotrope byproducts catalyzed by AlCl<sub>3</sub>

TAN Jun; OUYANG Yuxia; SUN Ping; LIU Hui; CHEN Jie; WEI Xiaoyan

doi:10.11949/j.issn.0438-1157.20141522

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Density functional theory study on disproportionation reaction of methylchlorosilane azeotrope byproducts catalyzed by AlCl₃

更新时间：2025-12-10

- Density functional theory study on disproportionation reaction of methylchlorosilane azeotrope byproducts catalyzed by AlCl₃
- CIESC Journal Issue 5, Pages: 1730-1737(2015)
- 作者机构：
  
  嘉兴学院生物与化学工程学院,浙江,嘉兴,314001
- 作者简介：
- 基金信息：
- DOI：10.11949/j.issn.0438-1157.20141522
  CLC： 641O647
- Online First：05 May 2015，
  
  Published：05 May 2015
- 稿件说明：
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TAN Jun, OUYANG Yuxia, SUN Ping, et al. Density functional theory study on disproportionation reaction of methylchlorosilane azeotrope byproducts catalyzed by AlCl₃[J]. CIESC Journal, 2015, (5): 1730-1737. DOI: 10.11949/j.issn.0438-1157.20141522.
DOI：

TAN Jun, OUYANG Yuxia, SUN Ping, et al. Density functional theory study on disproportionation reaction of methylchlorosilane azeotrope byproducts catalyzed by AlCl₃[J]. CIESC Journal, 2015, (5): 1730-1737. DOI: 10.11949/j.issn.0438-1157.20141522. DOI：

摘要

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543.15～593.15 K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593.15 K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。

Abstract

The disproportionation reaction between (CH3)3SiCl and SiCl4 catalyzed by AlCl3 involves three reactions; the reaction between (CH3)3SiCl and SiCl4 to form (CH3)2SiCl2 and CH3SiCl3 (R1)

the reaction between (CH3)2SiCl2 and SiCl4 to form CH3SiCl3(R2) and the reaction between (CH3)3SiCl and CH3SiCl3 to form (CH3)2SiCl2(R3). Density functional theory was used to study these reactions. The possible catalytic mechanisms of AlCl3 were stepwise reaction pathway of forming intermediate CH3AlCl2 and co-adsorption pathway of two reactants on AlCl3. The co-adsorption mechanism was more likely for these three reactions. The energy barrier ranking of these reactions was R2 >R1 >R3. By analyzing the thermodynamics data of these reactions

the effect of temperature on the Gibbs reaction energy of R2 was almost negligible within a temperature range of 543.15 K to 593.15 K. However

the Gibbs reaction energy of R1 and R3 significantly decreased at 593.15 K. These studies indicated that through appropriate temperature regulation

the reactions of R1 and R3 could be the dominant reactions while R2 would be effectively suppressed

influencing product distribution and facilitating formation of (CH3)2SiCl2.

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Density functional theory study on disproportionation reaction of methylchlorosilane azeotrope byproducts catalyzed by AlCl3

DOI：10.11949/j.issn.0438-1157.20141522

摘要

Abstract

关键词

Keywords

references

Density functional theory study on disproportionation reaction of methylchlorosilane azeotrope byproducts catalyzed by AlCl₃