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A series of novel polymers have been prepared by free radical solution polymerization of a variety of hydrocarbon monomers with the (perfluoroalkyl)ethyl methacrylate monomer H2CC(CH3)CO2(CH2)2(CF2) n F, 1 (n̄ ≈ 7.7). Polymers prepared using two different methods of feeding 1 into the reaction mass are discussed. Through a judicious choice of reaction conditions, some control of polymer architecture was exhibited. The resultant (perfluoroalkyl)ethyl methacrylate-containing acrylic polymers were shown to be quite surface active in the solid state. The magnitude of surface activity depends on the monomer 1 feed method. The polymers were formulated into thin films and applied to a variety of surfaces. With levels at 1.5 wt % of 1, water and oil repellent surfaces were created. Water contact angles (advancing) of ∼80−115° and hexadecane contact angles (advancing) of ∼60−70° were observed routinely. In addition, it was observed that the concentration profile of fluorine in the films exhibited a steep gradient normal to the surface when studied by angle-dependent ESCA and secondary ion mass spectroscopic depth profiling.

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The fluorotelomer alcohol F(CF2) n (CH2)2OH (n ≈ 7.8), 2, contains a terminal hydroxyl group that reacts with the isocyanate group of a polyisocyanate cross-linking agent based on the isocyanurate trimer of hexamethylene diisocyanate, 1. The resulting fluorinated isocyanate, 3, contains a urethane linkage and a pendant perfluoroalkyl group. The modified isocyanate, 3, was used to prepare films containing acrylic copolymers with cross-linkable hydroxyl groups. Films were prepared using several varieties of acrylic copolymers with and without the incorporation of small amounts of fluorinated monomers. With regards to surface energy reduction, the initial film properties were excellent. For example, reactive mixtures of 3 with hydrocarbon hydroxyl-containing acrylic copolymers exhibited surfaces enriched with fluorine. Water and hexadecane advancing contact angles were measured to be ∼86° and ∼40° at ∼ 2.3 × 10-2 mole fraction (∼1900 ppm by weight F) of F(CF2) n (CH2)2O−, respectively. Hexadecane contact angles on films of copolymer/isocyanate mixtures containing no fluorine were zero. Mixtures of 3 with fluorinated acrylic copolymers gave surfaces that were enriched with fluorine. The source depended on the surface activities of the respective components. Using mixtures of 3 with the various acrylic copolymers, a variety of surfaces can be constructed. The prepared films were examined by contact angle measurements, electron spectroscopy for chemical analysis and dynamic secondary ion mass spectroscopic depth profiling.