Oligo‐Condensation Reactions of Silanediols with Conservation of Solid‐State‐Structural Features.

Abstract

Oligo‐ and polysiloxanes are usually prepared by condensation reactions in solvents without control of stereochemistry. Here we present a solventless thermal condensation of stable organosilanols which act as precursors in a thermal condensation reaction. We investigated the condensation reactions of organosilanediols with different organic substituents, having in common at least one aromatic group. The condensation kinetics of the precursors observed by NMR spectroscopy revealed a strong dependence on temperature, time, and substitution pattern at the silicon atom. SEC measurements showed that chain length increases with increasing condensation temperature and time and lower steric demand of the substituents, which also influences the glass transition temperatures (Tg). X‐ray diffraction studies of the crystalline silanediols and their condensation products revealed a structural correlation between the substituent location in the crystalline precursors and the formed polysiloxanes induced by the hydrogen bond pattern. In certain cases, it is possible to carry out topotactic polymerization in the solid‐state, which has its origin in the crystal structure.