Ultra-thin films based on random copolymers containing perfluoropolyether side chains

Random copolymers were synthesised by copolymerizing methylmethacrylate and perfluoropolyetherurethanemethacrylate monomers, differing for the structural unit of the fluorinated chain, its end group and its molecular weight. The copolymers obtained had similar molecular weight and polydispersity, with a fluorine content between 5 and 10% wt/wt; they showed remarkable features such as biphasicity with coexistence of soft domains made of the perfluoropolyether chains and hard domains due to the methylmethacrylate backbone: the glass transition temperature Tg of the soft and hard phases was Tg1 < 90 °C and Tg2 ≅ 110 °C respectively. All the copolymers were highly hydrophobic: water contact angle was always higher than 105°. The copolymers were used for the preparation of ultra thin films by spin coatings: by atomic force microscopy and X-ray reflectivity the thickness was found in the range of 20–400 Å depending on the spinning conditions, in particular the concentration of the spun solutions. The films were also highly smooth, with a roughness lower than 5 Å.

► We describe random methacrylic copolymers with perfluoropolyether side chain.
► The copolymers had a fluorine content of 5–10% wt/wt.
► The copolymers were spin coated and formed hydrophobic films.
► The film thickness was in the range of 20–400 Å.
► The coatings' roughness was always lower than 5 Å.