DEGRADATION OF PERFLUOROPOLYETHERS CATALYZED BY ALUMINUM-OXIDE

Thermal stabilities of perfluoropolyethers, Fomblin Z, Fomblin Y, Krytox, and Demnum in the presence of Al2O3 were examined. Fomblin Z was found to degrade at 200-degrees-C in two stages, the slow first stage, and the vigorous second stage leading to complete loss of fluid. It is concluded that oxide-to-halide conversion occurs on Al2O3 surface during the first stage. The second stage is attributed to a catalytic process induced by Lewis acid AlF3. Based on NMR and mass spectroscopic evidences the following reaction mechanism is advanced for the second stage: (1) a bidentate linkage is formed between an acidic aluminum and two oxygen atoms of an acetal unit (-O-CF2-O-) of Fomblin Z chains, and (2) the partial positive charge thus developed at the acetal carbon induces a fluorine atom transfer from the adjacent CF2 unit onto the acetal carbon and results in chain scission with transformation of the acetal sector into a methoxy end-group (-O-CF3) and the adjacent unit into either an acylfluoride end-group (FCO-CF2-), or a fluoroformate end-group (FCO-O-CF2-). Lacking acetal units Krytox and Demnum are stable against this degradation process. In the case of Fomblin Y, owing to the paucity of acetal units, no reaction was observed when heated in the presence of Al2O3; when heated with AlCl3, removal of acetal units and consequential formation of functional end-groups were observed.