Soft nanostructured films with an ultra-low volume fraction of percolating hard phase.

In this study, aqueous emulsion polymerization of n-butyl acrylate is performed in batch conditions without surfactants using a poly(acrylic acid)-trithiocarbonate macro-RAFT agent to control the polymerization and to stabilize the emulsion. According to the polymerization-induced self-assembly (PISA) approach, well-defined amphiphilic PAA-b-PBA diblock copolymers form and self-assemble during synthesis to yield highly stable core-shell particles with an extremely thin hard PAA shell. For the first time, we report here the specific properties of films obtained from these particular latexes. After drying the aqueous dispersion, tough and transparent films are obtained. Although the films are not chemically cross-linked, they do not dissolve in good solvents for PBA. Moreover, they remain transparent even after immersion in water. Rheology shows that the films are both stiff and ductile, thanks to the nanostructured but very low volume fraction (less than 3 wt%) of PAA forming a percolating network in the soft PBA. Compared with conventional core-shell-based films, this approach affords for the first time a route to a thin percolating honeycomb nanostructure with a sharp and strong interface between the two phases. The versatility of the synthetic procedure opens perspectives for a large range of functional materials.

Synthesis and characterization of a thermoresponsive polyoxometalate-polymer hybrid.

We report the synthesis of the first organo-POM with thermoresponsive properties. Our concept will provide chemists with a new tool to design POMs whose solubility is reversibly controllable through an external stimulus. POM-polymer TBA(7)[POM]-poly(N,N-diethylacrylamide) (POM-PDEAAm), was prepared by grafting PDEAAm-NH(2) (obtained by RAFT polymerization) onto the activated Dawson acyl-POM, α(2)-[P(2)W(17)O(61)SnCH(2)CH(2)C(=O)](6-). Extensive MS analysis was used to monitor the chain-functionalization steps and to confirm the formation of the hybrid. Aqueous solutions of the (NH(4))(7)[POM-PDEAAm] exhibited a LCST of 38 °C. Thus, the solubility/aggregation of the hybrid was reversibly controlled by changing the temperature. Above 38 °C, the solution became cloudy, and cleared again upon cooling. Dynamic light scattering (DLS) revealed the formation of small aggregates in the range 100 nm. We assumed that the charged POM head units prevented the formation of the larger-scattering aggregates that are usually observed for PDEAAm, and promoted the formation of micelle-like structures. The conjugate exhibited a temperature transition, which was different from that of the polymer and depended on the counterions associated with the POM. This result demonstrates the potential for merging organic (in this case, polymer) and inorganic structures to afford materials that exhibit new properties.