Abstract: A PA-F polymer film is formed using a mixture of 1,4-bis (trifluoromethyl) benzene (TFB) and a halogen initiator. This mixture is provided to a low pressure reactor containing a metal catalyst. The reactor is operated at a sufficient temperature to form a reactive monomer by a chemical reaction at the surface of the catalyst. The reactive monomer is condensed on the surface of a substrate cooled to a temperature sufficiently low to induce polymerization of the reactive monomer to form a PA-F polymer film. In general, the proportion of halogen initiator is about 0.25 to 50% by volume relative to the total volume of the TFB/halogen initiator mixture. The reactor is operated at a temperature of about 200.degree. to 700.degree. C. and a pressure of less than about one torr. In addition, the surface of the substrate is maintained at a temperature of about -30.degree. C. to room temperature.