Aerosol direct fluorination of esters and the synthesis of perfluorinated olefins

A series of perfluoroesters were synthesized utilizing the aerosol direct fluorination technique. In all cases the starting material was the hydrocarbon analog of the perfluorinated ester. The following compounds were synthesized: F-Methyl F-4-Methoxybutanoate, F-4-Methoxybutanoyl Fluoride, F-Methyl F-4-Ethoxybutanoate, F-4-Ethoxybutanoyl Fluoride, F-Methyl F-4,4-Dimethylpentanoate, F-4,4-Dimethylpentanoyl Fluoride, F-Methyl F-4-[2-Methoxyethoxy]butanoate, F-4-[2-Methoxyethoxy]butanoyl fluoride. Perfluorinated methyl esters and acid fluorides were produced from all esters that were fluorinated due to cleavage of the ester linkage. The resulting perfluorinated methyl esters and perfluorinated acid fluorides were converted into perfluorinated olefins via decarboxylation of the sodium salts derived by basic hydro lysis. The following perfluorinated olefins were synthesized; F-3-Methoxypropene, F-3-Ethoxypropene, F-3,3-Dimethylbutene, F-3-[2-Methoxyethoxyjpropene. These compounds were synthesized to provide perfluorinated precursors for sulfonic acids. The resulting perfluorinated sulfonic acids will be tested as electro lytes for electrolytic fuel cells. All compounds synthesized were characterized by infrared spectroscopy, electron impact and chemical ionization mass spectrometry and both ¹⁹F and ¹H nuclear magnetic resonance spectroscopy.

Continuous modifcations were made to the direct aerosol fluorination system while synthesizing the above compounds to maximize the throughput yields and effluent concentrations of perfluorinated products.