Abstract: | Fluoroalkyl end‐capped homo‐ and co‐ oligomers containing silsesquioxane segments were prepared by the reactions of fluoroalkanoyl peroxides with the corresponding methacrylate monomer‐bearing silsesquioxane unit (Si‐MMA) and comonomers such as N,N‐dimethylacrylamide (DMAA) and acrylic acid (ACA). These new fluorinated Si‐MMA oligomers were easily soluble in various organic solvents and were able to reduce the surface tension of m‐xylene effectively. The modified poly(methyl methacrylate) [PMMA] and glass surface treated with fluorinated Si‐MMA homo‐oligomers exhibited a strong oleophobicity, although these fluorinated oligomers possess high oleophilic silsesquioxane segments. In contrast, the modified PMMA surface treated with fluorinated Si‐MMA–DMAA cooligomers exhibited a good hydrophilicity with a strong oleophobicity. In a series of fluorinated Si‐MMA oligomers, fluorinated Si‐MMA homo‐oligomers had a relatively high thermal stability. Therefore, these fluoroalkyl end‐capped Si‐MMA oligomers are suggested to have high potential for new functional materials through their unique properties such as a high solubility and surface active properties. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3486–3493, 2002 |