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Published online by Cambridge University Press: 15 February 2011
The thermal curing chemistry of a fluorinated polyamic acid based on 6FDA (hexafluoroisopropylidene bis(phthalic anhydride)) and APBP (4,4′-bis(4-aminophenoxy)biphenyl) was studied by thermal-IR spectroscopy. Anhydride formation was observed at intermediate cure temperatures and maximized at approximately 220°C. The degree of anhydride formation was affected by the solvent, being least in 2-methoxyethyl ether and increasing in the solvent order: 2-methoxyethyl ether < NMP < 2-(2-ethoxy)ethoxyethanol. In addition to the back reaction of amic acid to anhydride and amine, at least one additional mechanism of anhydride formation is observed. The onset of the second mechanism of anhydride formation is coincident with the onset of imidization, which leads us to propose that water generated by imidization can react with anhydride during the curing process, before escaping from the film, to form diacid. Cyclization of diacid to anhydride is proposed as the second mechanism of anhydride formation.