New fluorinated, polyfunctional propenyl ether functionalized resins were synthesized, and their behavior in cationic photopolymerization was investigated. The photopolymerization proceeded efficiently with a high double-bond conversion (> 90%), giving rise to UV-cured coatings characterized by low glass-transition temperatures (-33 degrees C <= glass-traiasition temperature <= -15 degrees C) and hydrophobic surface properties. A fluorinated additive was also employed as a reactive additive in the cationic photopolymerization of trirnethylolpropane tripropenyl. ether, increasing the double-bond conversion, polymer network flexibility, thermal stability, and surface hydrophobicity. (c) 2006 Wiley Periodicals, Inc.