Are (Co)Polymers of 1,1,3,3,3-Pentafluoropropene Possible?

The copolymerization and terpolymerization of 1,1,3,3,3-pentafluoropropene (PFP) with various combinations of fluorinated and hydrogenated comonomers were investigated. The chosen fluoromonomers were vinylidene fluoride (VDF), 3,3,3-trifluoropropene (TFP), hexafluoropropene (HFP), perfluoromethylvinyl ether (PMVE), chlorotrifluoroethylene (CTFE) and -butyl-2-trifluoromethacrylate (MAF-TBE), while the hydrocarbon comonomers were vinylene carbonate (VCA), ethyl vinyl ether (EVE) and 3-isopropenyl-α,α-dimethylbenzyl isocyanate (m-TMI). Copolymers of PFP with non-homopolymerizable monomers (HFP, PMVE and MAF-TBE) led to quite low yields, while the introduction of VDF enabled the synthesis of poly(PFP--VDF--M) terpolymers with improved yields.

Novel source of trifluoromethyl radical as efficient initiator for the polymerization of vinylidene fluoride.

A persistent perfluoroalkyl radical (PPFR), perfluoro-3-ethyl-2,4-dimethyl-3-pentyl, is shown to be a good source of •CF(3) radicals and a useful radical capable of initiating the polymerization of vinylidene fluoride (VDF). NMR characterizations of the resulting PVDF homopolymers showed that polymerization of VDF was exclusively initiated by •CF(3) radicals. The addition of •CF(3) radical onto VDF was regioselective leading to CF(3) -CH(2) -CF(2) -PVDF and the CF(3) end-group acted as an efficient label to assess the molecular weights by (19) F NMR spectroscopy.