The synthesis of spherical particles was attained by the direct self-assembly of poly[2-(perfluorooctyl)ethyl acrylate-random-acrylic acid], P(POA-r-AA), and by the indirect self-assembly poly[POA-random-2-(dimethylamino)ethyl acrylate], P(POA-r-DAA), with dicarboxylic acids in supercritical carbon dioxide (scCO2). The copolymers formed spherical particles with hundreds of nanometer diameters in a heterogeneous state at pressures lower than the cloud point pressure. The formation of spherical particles was also dependent on the temperature. The formation of spherical particles could be optimized through varying the solvent quality by the manipulation of the CO2pressure and temperature for the different copolymer compositions. The dynamic light scattering and1H NMR studies demonstrated that the nanospheres had the micellar structures consisting of the CO2-philic POA shells and the CO2-phobic AA or DAA cores including the main chain cores. The nanospheres produced the superhydrophobic surfaces based on the water-proof shells of the POA units.
Nanospheres Prepared by Self-Assembly of Random Copolymers in Supercritical Carbon Dioxide