Polymerization of organotrialkoxysilanes is a convenient method for introducing organic functionality into hybrid organic-inorganic materials. However, not much is known about the effects of the organic substituent on the porosity of the resulting xerogels. In this study, we prepared a series of polysilsesquioxane xerogels from organotrialkoxysilanes, RSi(OR′)3, with different organic groups (R = H, Me, Et, dodecyl, hexadecyl, octadecyl, vinyl, chloromethyl, cyanoethyl). Polymerizations of the monomers were carried out under a variety of conditions, varying monomer concentration, type of catalyst, and alkoxide substituent. The effect of the organic substituent on the sol-gel process was often dramatic. In many cases, gels were formed only at very high monomer concentration and/or with only one type of catalyst. All of the gels were processed as xerogels and characterized by scanning electron microscopy and nitrogen sorption porosimetry to evaluate their pore structure.
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