Use of fluorinated maleimide and telechelic bismaleimide for original hydrophobic and oleophobic polymerized networks

The syntheses of original fluorinated maleimide and telechelic bismaleimide bearing C₆F₁₃ and C₆F₁₂ groups, respectively, and their use as reactive additives in photopolymerizable formulations of telechelic poly(propylene glycol) bismaleimide (PPGBMI) are presented. Fluorinated maleimide was synthetized in five steps in 63% overall yield from C₆F₁₃C₂H₄I precursor, whereas the fluorinated bismaleimide was prepared in six steps in 14% overall yield from IC₆F₁₂I. These latter led to fluorinated azido and diazido intermediates that were reduced into the fluorinated amine and diamines in two steps. The condensation of amine and diamine onto maleic anhydride offered an amic acid and a diamic acid, which were subsequently cyclized into fluorinated maleimide and bismaleimide. Formulations of telechelic PPGBMI containing a low concentration of these fluorinated maleimide and bismaleimide were UV cured and the surface properties of the resulting films were investigated. A deep modification of the surface properties was noted when the monomaleimide was used. In all the cases, a selective enrichment of the fluorinated monomer at the film surface was observed. The dependence of the surface properties on the fluorinated maleimide and bismaleimide concentrations were also studied, and showed an asymptotic behavior of the contact angle with only 1.5 wt % of fluorinated maleimide additive, whatever the conditions. This monomaleimide led to better hydrophobic and oleophobic properties of the resulting material than that containing the telechelic one. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3214–3228, 2008