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Hydrolysis and condensation kinetic studies of mercaptopropyl trimethoxysilane using in-situ Raman spectroscopy
Chemical Engineering Journal ( IF 13.3 ) Pub Date : 2023-06-02 , DOI: 10.1016/j.cej.2023.143887
Chunli Han , Jian Deng , Guangsheng Luo

The hydrolysis and condensation kinetic parameters of mercaptopropyl trimethoxysilane (MPTMS, HS(CH2)3Si(OCH3)3) have rarely been quantitatively studied due to the fast reaction rate with the presence of catalysts. In this work, we employed the in-situ Raman spectroscopy to monitor the hydrolysis and condensation reactions of MPTMS in real time. First, with CH3OH as the solvent and NH4OH as the catalyst, the hydrolysis kinetics of MPTMS was investigated via the initial rate method. The reaction orders with respect to MPTMS, H2O, and NH4OH are 1.0, 1.0, and 1.0, respectively. The activation energy (Ea) and pre-exponential factor (A) of MPTMS hydrolysis reaction are (28.4 ± 1.1) kJ/mol and 938.1 (mol/L)-2·min−1, respectively. Then, an ‘acid-catalyzed hydrolysis and base-catalyzed condensation’ two-step strategy was employed to decouple the hydrolysis and condensation reactions. With the hydrolysates, trihydroxy silanols HS(CH2)3Si(OH)3, as the starting reactant, the early-stage condensation reaction kinetics was studied. The reaction orders with respect to HS(CH2)3Si(OH)3 and NH4OH are 1.4 and 2.8, respectively. The activation energy (Ea) and pre-exponential factor (A) of the condensation reaction are (52.2 ± 0.4) kJ/mol and 7.5 × 1013 (mol/L)-3.2·min−1, respectively. The kinetic parameters determined in this work could provide quantitative guidance for the design and control of MPTMS reaction process.



中文翻译:

使用原位拉曼光谱研究巯基丙基三甲氧基硅烷的水解和缩合动力学

巯基丙基三甲氧基硅烷 (MPTMS, HS(CH 2 ) 3 Si(OCH 3 ) 3 )的水解和缩合动力学参数由于在催化剂存在下的快速反应速率而很少被定量研究。在这项工作中,我们采用原位拉曼光谱实时监测 MPTMS 的水解和缩合反应。首先,以CH 3 OH为溶剂,NH 4 OH为催化剂,采用初始速率法研究了MPTMS的水解动力学。MPTMS、H 2 O和NH 4 OH的反应级数分别为1.0、1.0和1.0。活化能 ( E a)和MPTMS水解反应的指前因子( A )分别为(28.4±1.1)kJ/mol和938.1(mol/L) -2 ·min -1。然后,采用“酸催化水解和碱催化缩合”两步策略来分离水解和缩合反应。与水解产物,三羟基硅醇HS(CH2个)3个硅(OH)3个,作为起始反应物,研究了早期缩合反应动力学。反应顺序相对于HS(CH2个)3个硅(OH)3个和NH 4 OH分别为1.4和2.8。缩合反应的活化能( E a )和指前因子( A )分别为(52.2±0.4)kJ/mol和7.5×10 13 (mol/L) -3.2 ·min -1。本工作确定的动力学参数可为MPTMS反应过程的设计和控制提供定量指导。

更新日期:2023-06-02
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