Giovanni Simeone

New fluorinated thermoplastic elastomers

New fluorinated thermoplastic elastomers (FTE) with perfluoropolyether (PFPE) blocks have been synthesized by reacting a fluorinated macrodiol with aromatic diisocyanates in the presence of a solvent, followed by subsequent chain extension with low molecular weight aliphatic or aromatic diols. Tensile properties measurements and dynamical-mechanical analysis (DMA) have been carried out and the relationship between chemical structure and final properties has been determined. These new thermoplastic fluorinated polyurethanes show an elastomeric behavior over a wide temperature range (between −75 and 100°C), thanks to their multiphase morphology consisting of a continuous fluorinated phase with a very low Tg (−120°C) and a dispersed high melting hydrogenated hard phase, as verified by a calorimetric and dynamic-mechanical analysis. At the same time, some of the outstanding properties of fluorinated oligomers, such as chemical inertness and low surface tension, are retained in the final polymers. Thanks to these characteristics this new class of polymeric materials provides new opportunities for the application of thermoprocessable elastomers in advanced technological fields.

Perfluoropolyether structures as surface modifying agents of UV-curable systems

New functionalised macromers containing perfluoropolyether (PFPE) structures and methacrylic end groups were synthesised and used as modifying additives for acrylic UV-curable systems. Their chemical structure is Rh-Rf-Rh, where Rh= -CH 2 O-CONH-CH 2 CH 2 OCOC(CH 3 )=CH 2 and Rf=-CF 2 O-(CF 2 CF 2 O) p (CF 2 O) q -CF 2 - with p ≃ q. Notwithstanding their very low concentration, below 0.5 wt.-%, the fluorinated macromers cause a dramatic change of the surface properties of the films, without changing their curing conditions and their bulk properties. X-ray photoelectron spectroscopy (XPS) measurements showed that the macromers are able to concentrate selectively at the surfaces of the films, depending on their chemical structure and on the kind of substrate employed.

Chemical approaches toward the definition of new high-solid and high-performance fluorocoatings

Abstract Hydroxy bifunctional fluoropolyether oligomers (ZDOL) are presented suitable for use as resins or for the preparation of polyurethane, polyester and polyether higher OH functionality resins. The synthesis procedures are described and discussed, and the effect of fluorine content and resin structure on glass transition temperature Tg and viscosity of final resin is stressed. It appears that the highly fluorinated polyether type resins, like the tetraolic derivative (TOL) and its mixtures with ZDOL, are characterized by only one, extremely low Tg and minimum viscosity values. Solvent–resin interactions and criteria for obtaining compatibility with polyisocyanate crosslinkers are discussed, pointing out the key role of hydrogen bonding. High solid coatings (solvent content less than 30%) are obtained by curing with blocked aliphatic polyisocyanates, and a preliminary characterization of final materials based on their thermal transitions and mechanical properties is reported.