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Non-hydrolytic formation of silica and polysilsesquioxane particles from alkoxysilane monomers with formic acid in toluene/tetrahydrofuran solutions

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Abstract

Silica and polysilsesquioxane particles are used as fillers in composites, catalyst supports, chromatographic separations media, and even as additives to cosmetics. The particles are generally prepared by hydrolysis and condensation of tetraalkoxysilanes and/or organotrialkoxysilanes, respectively, in aqueous alcohol solutions. In this study, we have discovered a new, non-aqueous approach to prepare silica and polysilsesquioxane particles. Spherical, nearly monodisperse, silica particles (600–6,000 nm) were prepared from the reaction of tetramethoxysilane with formic acid (4–8 equivalents) in toluene or toluene/tetrahydrofuran solutions. Polymerization of organotrialkoxysilanes with formic acid failed to afford particles, but bridged polysilsesquioxane particles were obtained from monomers with two trialkoxysilyl group attached to an organic-bridging group. The mild acidic conditions allowed particles to be prepared from monomers, such as bis(3-triethoxysilylpropyl)tetrasulfide, which are unstable to Stöber or base-catalyzed emulsion polymerization conditions. The bridged polysilsesquioxane particles were generally less spherical and more polydisperse than silica particles. Both silica and bridged polysilsesquioxane nanoparticles could be prepared in good yields at monomer concentrations considerably higher than used in Stöber or emulsion approaches.

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Authors and Affiliations

  1. Systems and Technology Group, Materials Engineering Department, International Business Machines, Tucson, AZ, 85744, USA

    Dylan J. Boday & Jason T. Wertz

  2. Departments of Materials Science and Engineering & Chemistry and Biochemistry, The University of Arizona, Tucson, AZ, 85721-0012, USA

    Stephanie Tolbert, Zhe Li, Beatrice Muriithi & Douglas A. Loy

  3. Department of Mechanical Engineering, The University of Tulsa, Tulsa, OK, 74104, USA

    Michael W. Keller

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  1. Dylan J. Boday
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  2. Stephanie Tolbert
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  4. Zhe Li
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Correspondence to Douglas A. Loy.

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Boday, D.J., Tolbert, S., Keller, M.W. et al. Non-hydrolytic formation of silica and polysilsesquioxane particles from alkoxysilane monomers with formic acid in toluene/tetrahydrofuran solutions. J Nanopart Res 16, 2313 (2014). https://doi.org/10.1007/s11051-014-2313-6

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