I. Synthesis and Properties of Poly(imide-sulfonate)s
N, N``-Bis(hydroxyalkyl) pyromellitic diimides, N, N``-bis(hydroxyphenyl) pyromellitic diimides, N, N``-bis(hydroxyalkyl)-3, 3``, 4, 4``-benzophenonetetra-carboxylic diimides, and N, N``-bis(hydroxyphenyl)-3, 3``, 4, 4``-benzophenonetetracarboxylic diimides were prepared by the reactions of pyromellitic dianhydride or 3, 3``, 4, 4``-benzophenonetetracarboxylic dianhydride with corresponding aminoalcohols or aminophenols.
These diimides were soluble in hot aprotic polar solvents such as DMF, DMAC, NMP, and pyridine and N, N``-bis(hydroxyalkyl) diimides showed higher solubility than N, N``-bis(hydroxyphenyl) diimides.
Characteristic IR absorption bands of these diimides were shown at 3500-3200 $cm^{-1}$ (OH stretching), 1780-1770$cm^{-1}$ and 1730-1700$cm^{-1}$ (imide I bands due to the carbonyl stretchings of imide ring), 1400-1370$cm^{-1}$ (imide II band due to the axial stretching of imide ring), and 1130-1090$cm^{-1}$ (imide III band due to the transverse stretching of imide ring).
These diimides were polycondensed with aromatic disulfonyl chlorides to produce poly(imide-sulfonate)s under various reaction conditions. Amide type solvents such as DMF and DMAC were not adequate reaction media and gave no polymers because of the formation of ammonium salts with aromatic disulfonyl chlorides. The use of triethylamine was also attempted, but it appeared less effective as an acid acceptor than pyridine.
When the polycondation was carried out with 2.0 mmoles of each monomer in 50 ml of pyridine at 80℃ for 24 hr, it gave the best results with respect to yield and viscosity. As expected from the results of model reactions, N, N``-bis(4-hydroxyphenyl)pyromellitic diimide (diimide V) and N, N``-bis[4-hydroxyphenyl]-3, 3``, 4, 4``-ben zophenonetetracarboxylic diimide [diimide X] produced no polymers.
The structures of these poly(imide-sulfonate)s were identified by comparison of infrared spectra with those of mode...