Osmotic Pressure as Driving Force for Reducing the Size of Nanoparticles in Emulsions

We describe here a method to decrease particle size of nanoparticles synthesized by miniemulsion polymerization. Small nanoparticles or nanocapsules were obtained by generating an osmotic pressure to induce the diffusion of monomer molecules from the dispersed phase of a miniemulsion before polymerization to an upper oil layer. The size reduction is dependent on the difference in concentration of monomer in the dispersed phase and in the upper oil layer and on the solubility of the monomer in water. By labeling the emulsion droplets with a copolymer of stearyl methacrylate and a polymerizable dye, we demonstrated that the migration of the monomer to the upper hexadecane layer relied on molecular diffusion rather than diffusion of monomer droplets to the oil layer. Moreover, surface tension measurements confirmed that the emulsions were still in the miniemulsion regime and not in the microemulsion regime. The particle size can be tuned by controlling the duration during which the miniemulsion stayed in contact with the hexadecane layer, the interfacial area between the miniemulsion and the hexadecane layer and by the concentration of surfactant. Our method was applied to reduce the size of polystyrene and poly(methyl methacrylate) nanoparticles, nanocapsules of a copolymer of styrene and methyl methacrylic acid, and silica nanocapsules. This work demonstrated that a successful reduction of nanoparticle size in the miniemulsion process can be achieved without using excess amounts of surfactant. The method relies on building osmotic pressure in oil droplets dispersed in water which acts as semipermeable membrane