Formation of hybrid films from perylenediimide-labeled core-shell silica-polymer nanoparticles

We prepared water-dispersible core-shell nanoparticles with a perylenediimide-labeled silica core and a poly(butyl methacrylate) shell, for application in photoactive high performance coatings. Films cast from water dispersions of the core-shell nanoparticles are flexible and transparent, featuring homogeneously dispersed silica nanoparticles, and exhibiting fluorescence under appropriate excitation. We characterized the film formation process using nanoparticles where the polymer shell has been labeled with either a non-fluorescent N-benzophenone derivative (NBen) or a fluorescent phenanthrene derivative (PheBMA). We used Förster resonance energy transfer (FRET) from PheBMA to NBen to follow the interparticle interdiffusion of the polymer anchored to the silica surface that occurs after the dried dispersions are annealing above the glass transition temperature of the polymer. By calculating the evolution of the FRET quantum efficiency with annealing time, we could estimate the approximate fraction of mixing (fm) between polymer from neighbor particles, and from this, the apparent diffusion coefficients (Dapp) for this process. For long annealing times, the limiting values of fm are slightly lower than for films of pure PBMA particles at similar temperatures (go up to 80% of total possible mixing). The corresponding diffusion coefficients are also very similar to those reported for films of pure PBMA, indicating that the fact that the polymer chains are anchored to the silica particles does not significantly hinder the diffusion process during the initial part of the mixing process. From the temperature dependence of the diffusion coefficients, we found an effective activation energy for diffusion of Ea=38 kcal/mol, very similar to the value obtained for particles of the same polymer without the silica core. With these results, we show that, although the polymer is grafted to the silica surface, polymer interdiffusion during film formation is not significantly decreased by the silica core. This explains the excellent properties of the photoactive high performance coatings formed from the core-shell nanoparticles.