Structure‐related behavior of hybrid organic–inorganic materials prepared in different synthesis conditions from Zr‐based NBBs and 3‐methacryloxypropyl trimethoxysilane

Abstract

The copolymerization of zirconium oxo‐clusters (Zr12) with 3‐methacryloxypropyl (trimethoxy)silane (MPTMS), using a Si/Zr molar ratio of 4, was investigated. The hybrid samples were prepared both with and without organosilane prehydrolysis. Differential scanning calorimetry (DSC), multinuclear liquid, and solid state NMR analyses and Fourier transform infrared (FTIR) spectroscopy were used to characterize the hybrid materials and study the influence of synthesis conditions on condensation and polymerization. The degree of condensation (DOC) of the silsesquioxane network and the polymerization yield are generally high. However, the organosilane prehydrolysis step leads to the reduction of the extent of phase interaction, thus favoring the phase separation between silica‐zirconia‐based domains. Dynamic mechanical spectroscopy (DMS) analyses were performed on the hybrid polymers obtained by means of the two synthetic pathways. The sample prepared without the organosilane prehydrolysis step presents a higher glass transition temperature (Tg) than the one with silane prehydrolysis. By heating above the Tg, the samples retain shape and size, due to the lack of viscous flow. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Effect of the Organic Functional Group on the Grafting Ability of Trialkoxysilanes onto Graphene Oxide: A Combined NMR, XRD, and ESR Study

“…Finally in the case of the Ga-M sample, in addition to the Ga peaks, metacryloxy resonances could be distinguished at 7.1 (C-1), 16.2 (C-7), 21.1 (C-2), 135.1 and 125.4 (C-5 and C-6, sharp peaks overlapped with the aromatic band), and 166.9 ppm (C-4), respectively, whereas C-3 was hidden by the C-OH Ga resonance. The chemical shift of C-4 proved that the metacryloxy ending group was preserved [26].…”

SiO2/Ladder-Like Polysilsesquioxanes Nanocomposite Coatings: Playing with the Hybrid Interface for Tuning Thermal Properties and Wettability

“…The 13 C Cross Polarization/Magic Angle Spinning (CPMAS) spectra of h-LPMASQ and LPMASQ/silica nanocomposites after irradiation are shown in Figure 8, together with the structural scheme and C labeling used for peak assignment [67]. The LPMASQ skeleton (black curve) is characterized by the three resonances due to the methylene carbon atoms in the propyl chain (a, b, c) and the three resonances of the methacrylate tail, i.e., carbonyl (d, 165 ppm), vinyl (e and g at 135 and 124 ppm respectively) and methyl (f) C atoms [68]. The UV-induced crosslinking of the LPMASQ units is demonstrated by the appearance of both the methylene peaks in the region 40-60 ppm (e', g') and by the second downfield shifted carbonyl resonance at 175 ppm (d'), which result from the partial consumption of the methacrylate vinyl bonds (signals e and g).…”

“…(a)13 C CPMAS spectra of h-LPMASQ (black line), SiO 2 /LPMASQ (red line) and SiO 2 @TMMS/LPMASQ (blue line). The LPMASQ structure with C labeling and the polymerization scheme[68] are shown in figures (b) and (c), respectively.…”

High temperature resistant silane/zirconium‐oxocluster hybrid copolymers containing “free” thiol/ene functionalities in the polymer matrix

“…Inorganic–organic (i/o) hybrid coatings and bulk materials containing the vinylacetate‐substituted zirconium‐oxocluster [Zr 6 O 4 (OH) 4 (OOCCH 2 CHCH 2 ) 12 ( n ‐PrOH)] 2 · 4(CH 2 CHCH 2 COOH) (Zr 12 ) polymerized with monomers with ene functional groups have shown transparency, hydrophobicity, and high thermo‐mechanical and chemical stability 4–7. When the monomer is a silane, the structural chemical bonds are formed through the condensation of the silanes and the radical polymerization of the vinylacetate ligands with the ene functional groups of the silanes.…”