Selective Alteration of Polymer Surfaces by Thermal Cleavage of Fluorinated Side Chains

We have synthesized a series of fluorinated side chain block copolymers based on either a hydroborated polystyrene-b-polyisoprene or a poly(methyl methacrylate)-b-poly(2-hydroxyethyl methacrylate) backbone. Through polymer-analogous reactions, perfluorinated ester, fluorinated urethane, and fluorinated carbonate side chains were attached to the pendant hydroxyl groups. Their selective thermal degradation behavior was investigated using thermogravimetric analysis (TGA) and thermal desorption mass spectrometry (TDMS). In addition, we investigated the heat- and laser-induced selective alteration of polymer film surfaces by chemically highly selective cleavage of the fluorinated side chains using X-ray photoelectron spectroscopy (XPS), FT-infrared spectroscopy (FT-IR), and contact angle measurements. Finally, we demonstrate the potential to create a laterally patterned surface with different regions of chemically well-defined surface moieties from our fluorinated block copolymers by a “dry” laser process.