Hybrid materials obtained in microemulsion from methyl methacrylate, methacryloxypropyltrimethoxysilane, tetraethoxysilane

Fourier transform Raman spectroscopy was used in order to study acid catalyzed hydrolysis and polycondensation processes from the sol via the gel until the xerogel state in binary mixtures of vinyltriethoxysilane (ViTEOS) and tetraethoxysilane (TEOS). Supplementary 29Si-, 13C-MAS-NMR, and FT-IR data were considered. Intermediate hydrolysates, oligomers, and polycondensates were detected independently of the sample's physical state. Vibrational assignments are given for pure ViTEOS and its partially hydrolyzed intermediates. The corresponding mono-, di-, and tri-hydroxylated species are found to exhibit characteristic νsym(CSiO3) vibrational modes in the 650-672 cm-1 region. Subsequent oligomerization results in a progressive shift of the νsym(CSiO3) bands towards lower wavenumbers. Condensation proceeds faster in ViTEOS-TEOS mixtures than in pure ViTEOS. Assignments for some early oligomeric species and some network connectivity are given. The Raman spectra suggest that the main building blocks of the evolving network are already present in the wet gels. Moreover, it is shown that residual ethoxy groups attached to the siloxane network are still present in xerogels, whereas no silanol groups are detected. The spectra demonstrate that the vinyl groups did not react under the applied conditions. This system has potential for the preparation of UV-curable abrasion-resistant coatings for plastic substrates.

FT-Raman Spectroscopic Study of the Structural Evolution in Binary UV-Curable Vinyltriethoxysilane/Tetraethoxysilane Mixtures from the Sol to the Xerogel State

The styrene (St), butyl acrylate (BuA), and methyl methacrylate (MMA) polymerization in microemulsion in the presence of sodium dodecylsulfate is studied. This process is conducted in the presence of some comonomers having groups that can participate in sol–gel processes: 3(trimethyloxysilyl) propyl methacrylate (MPTS), triethoxy vinylsilane (VTES), and a comonomer with a sulfate group, styrene sodium sulfonate (StSO3Na). It has been observed that stabile latexes are obtained by radical polymerization at pH = 7, followed by a sol–gel process in the presence of ammonia. Latex particles sizes and zeta potential grow with MTPS concentration and in StSO3Na presence. VTES effect depends on its reactivity in St, MMA, and BuA copolymerization. Glass transition temperature and thermal decomposing temperature are influences by functional comonomer concentration and chemical structure. The Fourier transform infrared spectrum and inorganic residue growth after organic part thermal decomposition shows the presence of silica in obtained latexes.

Polymer–silica hybrids obtained by microemulsion polymerization

This paper describes a method to prepare silica particles able to encapsulate 3 different hydrophobic dyes: Disperse Red, Solvent Red and 2-{4-[4-(Benzyl-ethyl-amino)-phenylazo]-benzenesulfonyl}-ethanol (HESA). Dye doped silica particles were prepared by the sol–gel process in aqueous medium, with a base catalyst, using various concentrations of a “home made” surfactant (named NP9-Si). The surfactant is the addition byproduct of –OH groups of polyethylene glycol nonylphenyl ether Tergitol® NP-9 with -NCO groups from (3-isocyanatopropyl) triethoxysilane and was added to increase both the stabilization of the silica particles and the compatibility of the inorganic network versus the dopant (the aromatic dye). It was shown that there is an optimum range of the amount of surfactant which should be added in the sol–gel reaction system. If a higher amount of surfactant is used, it forms probably micelles which entrap the dye and prevent its encapsulation in the formed silica particles. Because the silica particles are designed to encapsulate systems containing aromatic derivatives (aromatic dyes) we used phenyltriethoxy silane and tetraethylorthosilicate as silica precursors. As coupling agent for the silica network we used a bis (trialkoxysilane) derivative—1,2-bis (triethoxy silyl) ethane.

J.F. Cornu

Papers

Physico-Chemical Properties of an Hybrid Glass