Compositions, Halogenated Compositions, Chemical Production and Telomerization Processes
Résumé
The synthesis of original telomers containing 1,1,3,3,3- pentafluoropropene (PFP) RF(C3HF5)nI [with n=1 and 2 and RF =C6F13 or (CF3)2CF] and their cotelomers with general formula : RF{[F2C-CH(CF3)]x- (CH2-CR1R2)y}zI where the monomers used can be: R1=R2=F; vinylidene fluoride H2C=CF2 (VDF); R1=H, R2=CF3); 3,3,3-trifluoropropene CH2=CH(CF3) ( TFP); R1=CF3, R2=CO2 tert-butyl-trifluoromethylacrylate;CH2=C(CF3)CO2 tert-Bu(TFMA), or general formula: RF{[F2C-CH(CF3)]x-(CF2-CR3R4)y}zI where the monomers used can be: R3= F, R4= Cl; chlorotrifluoroethene CF2=CFCl (CTFE); R3= F;R4= CF3;hexafluoropropene F2C=CF(CF3)(HFP); and R3= F;R4= OCF3 - perfluoromethylvinylether F2C=CF(OCF3) (PMVE) are provided. In addition to perfluoroalkyliodides telogens, non-fluorinated chain transfer agents X-Y such as HP(O)(OEt)2, CHCl3, CBrCl3, HSCH2CH2OH were also used. The (co) telomerizations can be carried out thermally or initiated by peroxides or metal complexes in bulk and solution (acetonitrile or 1,1,1,3,3-pentafluorobutane leading to monoadduct and diadduct with a ratio depending on the R0=[RFI]0/[PFP]0 initial molar ratio and the reaction temperature. The amount of monoadduct can be up to 50-60 % versus dimer (30-25%) at temperatures up to 180 °C (thermal) and 150 °C with peroxides as an initiator and R0=[In]0/[M] up to1.5.