Alkylene-bridged polysilsesquioxane aerogels: highly porous hybrid organic-inorganic materials

Abstract

Alkylene-bridged polysilsesquioxane gels were prepared by sol-gel polymerizations of α, ω-bis(triethoxysilyl)alkanes 1–5. The gels were extracted with supercritical carbon dioxide to afford a novel class of hybrid organic-inorganic aerogels. The effect of the length of the alkylene bridging group and catalyst (HCl and NaOH) on the structure was examined. The molecular structure was characterized by solid-state 13C and 29Si cross polarization magic angle spinning nuclear magnetic resonance spectroscopy. The alkylene bridging groups survived sol-gel polymerization to give materials with average degrees of condensation of 79 and 90% for the acid- and base-catalyzed aerogels, respectively. Scanning electron microscopy was used to examine the macroscopic structure of the gels and nitrogen sorption porosimetry was used to measure their surface areas and pore structures. Most of the alkylene-bridged aerogels were mesoporous, high-surface-area materials. As with alkylene-bridged polysilsesquioxane xerogels, the surface area decreased with increasing alkylene bridging group length. Only the base-catalyzed tetradecylene-bridged aerogel was found to be non-porous.