Stereospecific polymerization of perfluoroolefins

Preliminary results of research work in the field of stereospecific polymerization of fluorine‐containing olefins are reported. It is shown for the first time that ZIEGLER‐NATTA type catalysts may be used for polymerizing fully fluorinated olefins. By employing catalysts based on titanium tetraalcoholates and alkylaluminum derivatives, in halogenated solvents, slow conversion to crystalline polymers was obtained from tetrafluoroethylene and hexafluoropropylene. To the new crystalline polyhexafluoropropylene, whose main properties are described, an isotactic structure can probably be assigned. Some features of the stereospecific polymerization of perfluoroolefins are reported and briefly discussed.