Abstract
Alkoxysilanes and organoalkoxysilanes are primary materials in several industries, e.g. coating, anti-corrosion treatment, fabrication of stationary phase for chromatography, and coupling agents. The hydrolytic polycondensation reactions and final product can be controlled by adjusting the hydrolysis reaction, which was investigated under a variety of conditions, such as different alkoxysilanes, solvents, and catalysts by using gas chromatography. The hydrolysis rate of alkoxysilanes shows a dependence on the alkoxysilane structure (especially the organic attachments), solvent properties, and the catalyst dissociation constant and solubility. Some of the alkoxysilanes exhibit intramolecular catalysis. Hydrogen bonding plays an important role in the enhancement of the hydrolysis reaction, as well as the dipole moment of the alkoxysilanes, especially in acetonitrile. There is a relationship between the experimentally calculated polarity by the Taft equation and the reactivity, but it shows different responses depending on the solvent. It was found that negative and positive charges are respectively accumulated in the transition state in alkaline and acidic media. The reaction mechanisms are somewhat different from those previously suggested. Finally, it was found that enthalpy–entropy compensation (EEC) effect and isokinetic relationships (IKR) are exhibited during the hydrolysis of CTES in different solvents and catalysts; therefore, the reaction has a linear free energy relationship (LFER).
Highlights
Alkoxysilanes and organoalkoxysilanes are primary materials in several industries, e.g. coating, anticorrosion treatment, fabrication of stationary phase for chromatography, and coupling agents
Åkerman et al.[1] reported that the hydrolysis rate constant is proportional to the polarity (σ) of phenoxy derivatives according to the Hammet equation (Eq 5), while Brinker et al.[19] stated that the hydrolysis rate is related to the pKa of the parent alcohol of the leaving group
The reactivity of AS toward the hydrolysis reaction depends on the AS nature and on the used solvent, and significantly on the catalyst
Summary
Alkoxysilanes and organoalkoxysilanes are primary materials in several industries, e.g. coating, anticorrosion treatment, fabrication of stationary phase for chromatography, and coupling agents. The hydrolytic polycondensation reactions and final product can be controlled by adjusting the hydrolysis reaction, which was investigated under a variety of conditions, such as different alkoxysilanes, solvents, and catalysts by using gas chromatography. The hydrolysis rate of alkoxysilanes shows a dependence on the alkoxysilane structure (especially the organic attachments), solvent properties, and the catalyst dissociation constant and solubility. It was found that enthalpy–entropy compensation (EEC) effect and isokinetic relationships (IKR) are exhibited during the hydrolysis of CTES in different solvents and catalysts; the reaction has a linear free energy relationship (LFER). Though there is a difference between the silanes, AS and OAS, these names will be used interchangeably in this paper to refer to the same compound The reactivity of these compounds is controlled by the hydrolysis reaction, represented in Eq 1. The rate constant is controlled by (ΔG‡), and any change in the free energy will lead to a change in the rate constant
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