Synthesis of organic-inorganic hybrids via a high-pressure-ramp process: the effect of inorganic nanoparticle loading on structural and photochromic properties.

Organic polymerization remains a limiting step in the preparation of organic-inorganic hybrid materials with a strong concentration of the inorganic component. In this work, a high-pressure-ramp process was applied to achieve pHEMA-TiO2 nanoparticulate solids with an unprecedentedly high concentration (12 mol l-1) of the inorganic component, which is four times higher than that obtained after radical polymerization induced thermally or by photons. The inorganic nanoparticles underwent morphological and structural changes with an increase of Ti concentration above 1.5 mol l-1: they slightly coarsen and crystallize into an anatase polymorph. The material possesses a strong photochromic response related to the electron-hole separation at the organic-inorganic interface and can store 1e- per 5 Ti atoms. The electron storage capacity of the titania nanoparticles decreases upon crystallization.

A New Route for High-Purity Organic Materials: High-Pressure-Ramp-Induced Ultrafast Polymerization of 2-(Hydroxyethyl)Methacrylate.

The synthesis of highly biocompatible polymers is important for modern biotechnologies and medicine. Here, we report a unique process based on a two-step high-pressure ramp (HPR) for the ultrafast and efficient bulk polymerization of 2-(hydroxyethyl)methacrylate (HEMA) at room temperature without photo- and thermal activation or addition of initiator. The HEMA monomers are first activated during the compression step but their reactivity is hindered by the dense glass-like environment. The rapid polymerization occurs in only the second step upon decompression to the liquid state. The conversion yield was found to exceed 90% in the recovered samples. The gel permeation chromatography evidences the overriding role of HEMA2(••) biradicals in the polymerization mechanism. The HPR process extends the application field of HP-induced polymerization, beyond the family of crystallized monomers considered up today. It is also an appealing alternative to typical photo- or thermal activation, allowing the efficient synthesis of highly pure organic materials.

Laser-assisted high-pressure-induced polymerization of 2-(hydroxyethyl)methacrylate.

We report on a successful room-temperature polymerization of 2-(hydroxyethyl)methacrylate (HEMA) under high pressure. The polymerization is observed in a limited range of pressures 0.1 to 1.6 GPa without the use of any initiator. When the compressed sample is irradiated at 488 or 355 nm by a laser, the polymerization reaction rate is increased by a factor of 10 or 30, respectively. Moreover, the shift of the laser wavelength to the UV improves the polymerization yield of the recovered sample to 84%. The catalysis of the polymerization process by light results from a one-photon-assisted electron transfer to π* antibonding states of the monomer molecule. The observed polymerization is irreversible and almost complete, which makes this synthesis process suitable for applications.