Synthesis of spherical particles by self-assembly of poly[2-(perfluorooctyl)ethyl acrylate-co-acrylic acid] in supercritical carbon dioxide

Spherical particles were prepared from poly[2-(perfluorooctyl)ethyl acrylateco-acrylic acid] random copolymers (P(POA-co-AA)) by self-assembly in supercritical carbon dioxide (scCO2). The P(POA-co-AA) copolymers with 9:1, 8:2, 7:3, and 6:4 molar ratios of the POA/AA unit completely dissolved in scCO2, however, the solubility was dependent on the POA/AA ratio. The copolymer with the higher AA content had a lower solubility. The scanning electron microscopy (SEM) observations revealed that the spherical particles were obtained in a heterogeneous state at pressures lower than the cloud point pressure. Dynamic light scattering and 1H NMR studies demonstrated that the copolymers formed random copolymer micelles consisting of the shells of the CO2-philic POA units and the cores of the CO2-phobic AA units and main chains. It was found that the formation of spherical particles could be optimized by the manipulation of the CO2 pressure and temperature for the different compositions of the copolymers.