Fluorinated Polymeric Multilayers by Off‐Stoichiometric Thiol‐Ene Photopolymerization

Abstract This article reports the synthesis of a novel perfluoropolyalkylether (PFPAE) vinylether monomer and its use as a comonomer in the thiol‐ene photopolymerization of a trifunctional thiol together with a trifunctional vinylether. The crosslinked copolymers are obtained in the form of few mm thick layers and characterized. By changing the thiol/ene ratio, the polymers are optimized to tailor their surface composition and obtain adhesion between two thick layers despite the presence of the fluorinated monomer. The final bilayered structures are adhesive, and appeared chemically resistant, with good dimensional stability: therefore, these fluorinated thiol–ene based copolymers are likely to be of interest for applications based on layer‐by‐layer processes, such as additive manufacturing and microfluidics.