Fluoride catalyzes the formation of perfluorinated polyethers such as Krytox. The initial step entails
nucleophilic attack at the middle carbon to give the perfluoropropoxide anion, which in turn attacks another monomer. This process generates a polymer terminated by an
acyl fluoride, which is hydrolyzed to the
carboxylic acid which is decarboxylated with fluorine. The net polymerization reaction can be represented as: :{{chem2|
n + 2 CF3CFCF2O → CF3CF2CF2O(CF(CF3)CF2O)_{
n}CF2CF3 + CO}} Upon heating above 150 °C, HFPO decomposes to
trifluoroacetyl fluoride and
difluorocarbene: : The epoxide of
tetrafluoroethylene is even more unstable with respect to trifluoroacetyl fluoride. In the presence of
Lewis acids the compound rearranges to
hexafluoroacetone (HFA), another important
chemical intermediate. This rearrangement can be of concern during storage as the rearrangement be catalyzed by the material of the storage cylinder's walls and leads to unwanted formation of HFA during storage. As a result of this, 3M recommends using all HFPO shipped in carbon-steel containers within 90 days of shipping.
Methanolysis affords methyl trifluoropyruvate, a reagent useful in organic synthesis: : HFPO is a precursor to
perfluoroalkyl ether sulfonic acids. ==References==