Formation of Hybrid Spherical Silica Particles Using a Novel Alkoxy-Functional Polysilsesquioxane Macromonomer as a Precursor in an Acid-Catalyzed Sol-Gel Process.

The interest in macromolecular alkoxysilyl-functionalized hybrids (self-assembling or nanostructured), which could be used as precursors in biomimetic silica precipitation and for the synthesis of hollow spherical silica particles, is growing. Nevertheless, reports on all-organosilicon systems for bioinspired silica precipitation are scarce. Therefore, a new kind of polyalkoxysilane macromonomer-linear polysilsesquioxane (LPSQ) of ladder-like backbone, functionalized in side chains with trimethoxysilyl groups (LPSQ-R-Si(OMe)), was designed following this approach. It was obtained by photoinitiated thiol-ene addition of 3-mercaptopropyltrimethoxysilane to the vinyl-functionalized polysilsesquioxane precursor, carried out in situ in tetraethoxysilane (TEOS). The mixture of LPSQ-R-Si(OMe) and TEOS (co-monomers) was used in a sol-gel process conducted under acidic conditions (0.5 M HCl/NaCl) in the presence of Pluronic F-127 triblock copolymer as a template. LPSQ-R-Si(OMe) played a key role for the formation of microparticles of a spherical shape that were formed under the applied conditions, while their size (as low as 3-4 µm) was controlled by the stirring rate. The hybrid materials were hydrophobic and showed good thermal and oxidative stability. Introduction of zinc acetate (Zn(OAc)) as an additive in the sol-gel process influenced the pH of the reaction medium, which resulted in structural reinforcement of the hybrid microparticles owing to more effective condensation of silanol groups and a relative increase of the content of SiO. The proposed method shows directions in designing the properties of hybrid materials and can be translated to other silicon-organic polymers and oligomers that could be used to produce hollow silica particles. The established role of various factors (macromonomer structure, pH, and stirring rate) allows for the modulation of particle morphology.