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 tert-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-ter-VDF-ter-M3) terpolymers with improved yields. PFP does not homopolymerize and delays the copolymerizations. All polymers were either amorphous fluoroelastomers or fluorothermoplastics with glass transition temperatures ranging from −56 °C to +59 °C, and they exhibited good thermal stability in air.