Marvin Geyer, Felix Leven, Johannes Limberg, Corina Andronescu, Rainer Ostermann

• Abstract In this study, we report highly crosslinked hybrid aerogels with an organic backbone based on vinylmethyldimethoxysilane (VMDMS) with tuneable properties. For an improved and highly reproducible synthesis, a prepolymer based on 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (D4V4) and VMDMS as monomers was prepared and purified. Di-tert-butylperoxide (DTBP) concentrations of 1 mol% initiate the radical polymerization of the mentioned monomers to achieve high yields of polymers. After purification, the obtained viscous polyorganosilane precursor could be reproducibly crosslinked with dimethyldimethoxysilane (DMDMS) or methyltrimethoxysilane (MTMS) to form gels in benzylic alcohol (BzOH), water (H2O) and tetramethylammonium hydroxide (TMAOH). Whereas freeze-drying these silica-based hybrid aerogels led to high thermal conductivity (>20 mW m−1K−1) and very fragile materials, useful aerogels were obtained via solvent exchange and supercritical drying with CO2. The DMDMS-based aerogels exhibit enhanced compressibility (31% at 7 kPa) and low thermal conductivity (16.5 mW m−1K−1) with densities around (0.111 g cm−3). The use of MTMS results in aerogels with lower compressibility (21% at 7 kPa) and higher density (0.124 g cm−3) but excellent insulating properties (14.8 mW m−1K−1).