Sol-gel polycondensation of methyltrimethoxysilane in ethanol studied by 29Si NMR spectroscopy using a two-step acid/base procedure

Sol-gel polymerization of methyltrimethoxysilane (MTMS) in ethanol using a two-step acid/base catalyzed procedure (B2) is followed by Si-29 NMR spectroscopy. Analysis of the structural evolution of the B2 system shows that esterification of monomeric and end silicon species is rate-limited while that of linear and cyclic species is able to reach pseudoequilibrium in the second basic step. Condensation reactivity is reduced with increasing network connectivity, however, to a much less degree under B2 conditions than MTMS polymerization under acidic conditions. Steric effects as well as many other factors are attributed to this trend. The concentration of cyclic and polycyclic species of the B2 system is nearly 3 times lower compared to the acid-catalyzed system. The empirical degree of condensation at the gel point is determined to be 0.88. The effects of cyclization and phase separation on MTMS gelation are discussed for both B2 and acid-catalyzed systems. Based on these results it is believed that MTMS-based gels form for B2 and not acid-catalyzed conditions due to reduced cyclization, rapid hydrolysis and condensation, effective use of functional groups, and effective contribution of branched and polycyclic species as crosslinking points to connect polymeric chains in the B2 system.