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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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