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. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 853–861, 2004