Reevaluation of Tetrahydrophthalic Anhydride as an End Cap for Improved Oxidation Resistance in Addition Polyimides

Several substituted 1,2,3,6-tetrahydrophthalic anhydride end caps, including the 3-phenyl, 3-methoxy, 3-trimethylsilyloxy, and 3,6-diphenyl analogues, were synthesized via the Diels−Alder condensation of the corresponding butadienes and maleic anhydride. These anhydrides, as well as the commercially available 3-hydro and 4-methyl analogues, were each ground up together with methylenedianiline in a 2:1 ratio and heated gradually from 204 to 371 °C, with the thermolysis followed by NMR. Generally speaking, a transformation via monoimide to bisimide was observed in the lower temperature range, followed by competition between cross-linking and aromatization. We believe that this competition produces a substantial percentage of aromatic product, with the concomitant lowering of the relative amount of cross-linking and is responsible for both improved thermooxidative stability of tetrahydrophthalic end-capped polyimides and their substantial frangibility. The thermolysis of the tetrahydrophthalimides under an inert atmosphere dramatically lowers the amount of aromatization; hence, the mechanism for aromatization is an oxidative one.