Daisuke Shirakawa

A new route to perfluorinated vinyl ether monomers: synthesis of perfluoro(alkoxyalkanoyl) fluorides from non-fluorinated compounds

Abstract A new synthetic procedure for the preparation of various perfluoro(alkoxyalkanoyl) fluorides, which are precursors to perfluorinated vinyl ether monomers, from non-fluorinated alkoxyalcohols has been developed. Available perfluoro(alkoxyalkanoyl) fluorides such as perfluoro(2-propoxypropionyl) fluoride, so-called HFPO dimer, can be multiplied by the use of the hydrocarbon counterpart alcohols and fluorine gas as raw materials. In the case that the desired perfluoro(alkoxyalkanoyl) fluoride is not readily available, it can be obtained from its hydrocarbon counterpart alcohol and an available perfluoroacyl fluoride.

A New Route to Perfluoro(Propyl Vinyl Ether) Monomer: Synthesis of Perfluoro(2-propoxypropionyl) Fluoride from Non-Fluorinated Compounds

Perfluoro(2-propoxypropionyl) fluoride (1a), which is the precursor of the perfluorinated propyl vinyl ether (PPVE) monomer of an industrially important perfluoroalkoxy copolymer (PFA), was synthesized by utilizing direct fluorination of the non-fluorinated counterpart for the first time. The partially-fluorinated ester 7 synthesized from the desired perfluorinated acid fluoride 1a itself and the non-fluorinated alcohol 5, which has a carbon skeleton corresponding to the desired compound 1a, was perfluorinated by liquid-phase direct fluorination with elemental fluorine. Degradation of the resulting perfluorinated ester 8 gave 2 mols of the desired acid fluoride 1a. In a sense, this process can be called self-multiplication of a perfluorinated acid fluoride from a non-fluorinated alcohol.