Copolymerization of ethylene with a vinyl ether bearing a fluorinated group

The copolymerization of ethylene (E) with 1H,1H,2H,2H-perfluorodecyl vinyl ether (FAVE8) by oxidative addition of salicylaldimine ligand to bis(1,5-cyclooctadiene)nickel(0)/methylaluminoxane (MAO) at room temperature and at different ethylene pressures is reported. The homopolymerization of ethylene is known to be highly active with this catalyst in contrast to the fluorinated vinyl ether which does not homopolymerize. The copolymerization of E with FAVE8 led to linear poly(E-co-FAVE8) statistic copolymers that were characterized by means of various techniques. The obtained copolymers, analyzed by FT-IR and solid state NMR spectroscopy, showed a small incorporation of the fluorinated vinyl ether. Three copolymerization reactions were investigated with different ethylene pressures (5, 10 and 50 bar) and the copolymer compositions indicated that the content of FAVE8 units depends on the ethylene pressure. The lower this pressure, the higher the content of such a fluorinated comonomer and for a 50 bar-pressure, no FAVE8 was incorporated. Thermogravimetric and differential scanning calorimetry analyses of these resulting copolymers exhibited high thermal stability, the thermal degradation starting from ca. 300 °C whereas high melting point (Tm = 129 °C) were achieved with these copolymers. Original films processed from these poly(E-co-FAVE8) copolymers illustrated hydrophobic and oleophilic characters as evidenced by water and diiodomethane contact angles of 104° and 49°, respectively.

Graphical abstractThe copolymerization of ethylene (E) with 1H,1H,2H,2H-perfluorodecyl vinyl ether (FAVE8) by oxidative addition of salicylaldimine ligand to bis(1,5 cyclooctadiene)nickel(0)/methylaluminoxane (MAO) at room temperature and at different ethylene pressure is reported. The resulting copolymers showed interesting surface and thermal properties.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Original copolymerization of ethylene (E) with 1H,1H,2H,2H-perfluorodecyl vinyl ether (FAVE8) by nickel complex/methylaluminoxane at different ethylene pressures. ► The copolymerization of E with FAVE8 (the content of FAVE8 units depends on the ethylene pressure) led to linear poly(E-co-FAVE8) statistic copolymers. ► These copolymers were characterized by various spectroscopic and thermal analyses, and valuable surface properties (hydrophobic and oleophilic characters).