High-strength–high-modulus polyimide fibers I. One-step synthesis of spinnable polyimides

Polyimides with aromatic links are synthesized usually in two steps, but a series of aromatic polyimides with large molecular weights sufficient to produce strong fibers were prepared in one step by the reaction of 3,3′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) with various aromatic diamines. The one-step polycondensation was possible even when BPDA was replaced to some extent by pyromellitic dianhydride, which is a basic component in the conventional two-step method. The copolyimides based on BPDA and mixtures of aromatic diamines were also synthesized in similar manner. For the one-step polycondensation, phenol and some of its derivatives were found to be suitable solvents, while the typical solvent employed in the two-step method, such as N-methyl-2-pyrrolidone, could not be used because of the precipitation of low-molecular weight polyimides. p-Hydroxybenzoic acid proved to be a very efficient accelerator for the conversion of polyamic acids to polyimides.