Abstract: | New aromatic diamines were prepared in two steps from 4,5‐dichlorophthalic anhydride and primary amines. The resulting 4,5‐dichlorophthalimide was reacted with 4‐mercaptoaniline, so that the chloroatoms were substituted by the mercapto groups (via the sulfide anions). The new diamines were polycondensed either with the diphenyl ether 3,3′,4,4′‐tetracarboxylic anhydride or with bicyclooctane tetracarboxylic anhydride. These polycondensations were conducted in boiling m‐cresol with azeotropic removal of water. The isolated polyimides were characterized by viscosity measurement, IR‐spectroscopy, elemental analyses, and MALDI‐TOF mass spectrometry. The mass spectra evidenced a high content of cyclic polyimides, indicating nearly perfect reaction conditions. The mass spectra also proved the formation of copolymers containing one diamine with a trialkylamine group in the side chain. High glass transition temperatures but a low crystallization tendency were found by DSC measurements. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6272–6281, 2005 |