Homogeneous Phase Copolymerizations of Vinylidene Fluoride and Hexafluoropropene in Supercritical Carbon Dioxide

Copolymerizations of vinylidene fluoride (VDF) and hexafluoropropene (HFP) were carried out in homogeneous phase with supercritical carbon dioxide up to complete VDF conversion using conventional peroxide initiators. The HFP monomer feed ratios, fHFP, were varied between 0.65 and 0.20. Depending on fHFP amorphous or semi‐crystalline copolymers were obtained. fHFP also determines the minimum pressure required to allow for homogeneous phase reactions. For example, HFP‐rich copolymerizations in 70 wt.‐% CO2 at 100 °C require a pressure of around 500 bar. Further, bulk copolymerizations in homogenous phase were feasible for fHFP = 0.65 at 900 bar up to complete VDF conversion. Copolymerizations in the presence of perfluorinated hexyl iodide carried out at 75 °C gave access to low dispersity polymers. Due to homogeneous phase conditions the use of any surfactants or fluorinated cosolvent is avoided. magnified image