TiO2 containing hybrid nanocomposites with active–passive oxygen scavenging capability

Ladder-like silsesquioxanes (SSQs) and TiO2 have been functionalized with methacryloyloxypropyl chains and embedded in a polybutadiene (PB) matrix giving rise to hybrid (organic–inorganic) nanocomposites (NCs) capable of acting as oxygen scavenging materials. The joint use of infrared spectroscopy, small-angle X-ray scattering, and permittivity measurements highlighted that the presence of TiO2, regardless of its modification, does not significantly alter the structure of the NCs, but just reduces the crosslinking degree and induces a local disorganization of the ladder-like SSQ stacks. The introduction of an optimum amount (0.5 wt%) of modified TiO2 within the polymeric matrix enhanced the oxygen uptake rate of ca. 70% with respect to the sole polymeric material. Moreover, the uptake kinetics changes from the first to second order with respect to the PB amount, clearly indicating different oxidation mechanisms. NCs containing modified TiO2 showed an oxygen uptake rate ranging from 30 to 60% higher than that achievable in the presence of bare TiO2. The superior activity of the materials containing modified TiO2 has been related to mechanistic aspects. Fluorescence and electron spin resonance spectroscopies allowed to underline the role of singlet oxygen within the polymeric matrix, although the known photochemical oxidation of PB and the TiO2 induced hydroxyl radical mediated oxidation cannot be excluded. These results open the route to highly efficient flexible oxygen scavenging materials for the protection of electronic devices such as organic based light emitting diodes, solar cells, and liquid crystal displays, which require high targets of protection from oxygen and water