S. E. Rankin, C. W. Macosko, and A. V. McCormick, AIChE J. 1998, 44, 1141-1156.
abstract
Quantitative kinetic modeling of the condensation of methylethoxysilanes {(CH3)4-fSi(OC2H5)f} of varying functionality (f) is needed to engineer inorganic polymers, resins, and ceramics. To that end, a kinetic model that accounts for hydrolysis pseudoequilibrium, nearest-neighbor substitution effects, and unimolecular cyclization reactions in homogeneous ethoxysilane polycondensation is presented. Condensation rate parameters are determined by fitting to 29Si NMR transients. Several important features become evident: (1) the success of the hydrolysis pseudoequilibrium approximation; (2) strong negative substitution effects with unusual dependence on connectivity; (3) a strong kinetic tendency for ring formation; (4) acceleration of condensation upon methyl substitution; and (5) destabilization of three-silicon rings by methyl substitution. The first three observations are consistent with previous findings for ethylethoxysilanes, but the last two are strikingly different.