Kinetics of hydrolysis and self condensation reactions of silanes by NMR spectroscopy

Abstract

The hydrolysis of four alkoxy-silane coupling agents, 3-methacryloxypropyl trimethoxy silane (MPMS), 3-mercaptopropyl trimethoxy silane (MRPMS), octyl triethoxy silane (OES) and 3-aminopropyl triethoxy silane (APES) was carried out in an ethanol/water 80/20 (w/w) solution under acidic, alkaline and neutral conditions and followed by 1H, 13C and 29Si NMR spectroscopy. It was found that the kinetic rate of the hydrolysis of the silanes under neutral conditions was very low, except for APES, which displayed the fastest reaction speed. The addition of TEA catalyzed both silane hydrolysis and self condensation reactions. Acidic conditions enhanced the hydrolysis and the ensuing silanol entities were quite stable. In fact, these conditions slowed down the rate of the self condensation reactions, as deduced from in situ 1H and 13C NMR. Thanks to in situ 29Si NMR spectroscopy, the nature of the intermediary species versus reaction time was established.