Synthesis of semifluorinated block copolymers by atom transfer radical polymerization

Two sets of styrene-based semifluorinated block copolymers, one with a perfluoroether pendant group and another with a perfluoroalkyl group, were synthesized by atom transfer radical polymerization. Microphase separation of the block copolymers was established by small-angle X-ray scattering and differential scanning calorimetry (DSC). DSC measurements also showed that the perfluoroether-based polymer had a low glass-transition temperature (-44°C). Contact-angle measurements indicated that the semifluorinated block copolymers had low surface energies (ca. 13 mJ/m²). These materials hold promise as low-surface-energy additives or surfactants for supercritical CO₂ applications.