CAJ | 학술논문

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。
AlCl3최화(CH3)3SiCl 화 SiCl4적기화반응체계중가능존재(CH3)3SiCl 여 SiCl4생성(CH3)2SiCl2여 CH3SiCl3（반응1），(CH3)2SiCl2여SiCl4생성CH3SiCl3（반응2）화(CH3)3SiCl여CH3SiCl3생성(CH3)2SiCl2（반응3）등반응。본문채용밀도범함이론대저3충반응진행료연구。결과발현재AlCl3최화제상，가능발생CH3AlCl2중간체생성적분보반응화반응물공흡부반응，대량충정황하3충반응적반응로경균진행료계산，발현3충반응균편향우이쌍분자공흡부궤리진행。3충반응적능루배서시반응2＞반응1＞반응3。동시，열역학수거분석발현，재543.15～593.15 K지간，온도변화대반응2적마이Gibbs반응능변기본무영향，단재593.15 K시，반응1화반응3적Gibbs자유능변현저감소。저사계산결과현시，여과괄당조공반응온도，취능구재보증반응1화3진행적동시，억제반응2적진행，종이실현기화산물조성적조공，유리우(CH3)2SiCl2적생성。
The disproportionation reaction between (CH3)3SiCl and SiCl4 catalyzed by AlCl3 involves three reactions; the reaction between (CH3)3SiCl and SiCl4 to form (CH3)2SiCl2and CH3SiCl3(R1), the reaction between (CH3)2SiCl2and SiCl4to 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.