The crystal structures and thermal shrinkage properties of aromatic polyimide fibers

Abstract

Three aromatic polyimides based on 3,3′,4,4′-biphenyl-tetracarboxylic dianhydride (BPDA) and three different diamines 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (PFMB), 2,2′-dimethyl-4, 4′-diaminophenyl (DMB) or 3,3′-dimethylbenzidine (OTOL) have been synthesized. These polyimides are soluble in hotp-chlorophenol,m-cresol or other phenolic solvents. Fibers have been spun from isotropic solutions using a dry-jet wet spinning method. The as-spun fibers generally exhibit low tensile properties, and can be drawn at elevated temperatures (>380° C) up to a draw ratio of 10 times. Remarkable increases in tensile strength and modulus are achieved after drawing and annealing. The crystal structures of highly drawn fibers were determinedvia wide angle X-ray diffraction (WAXD). The crystal unit cell lattices have been determined to be monoclinic for BPDA-PFMB and triclinic for both BPDA-DMB and BPDA-OTOL. Thermomechanical analysis (TMA) was used to measure thermal shrinkage stress and strain. A selfelongation has been found in the temperature region around 450°C. This phenomenon can be explained as resulting from the structural development in the fibers as evidencedvia WAXD observations.