Rigid-Rod and Segmented Rigid-Rod Polyimides: Gel/Sol and Liquid Crystalline Transitions, Fibers and Films

Organo-soluble rigid-rod and segmented rigid-rod polyimides and their copolyimides exhibit isotropic solutions in hot m-cresol, but form gels upon cooling. A lyotropic liquid crystal phase is observed below the gel/sol transition. Mechanical gel formation is caused by liquid-liquid phase separation, while the liquid crystal phase may be formed through a nucleation process after gelation. High performance fibers can be spun from the hot isotropic solutions using a dry-jet wet spinning method. After the fibers are drawn at high temperatures, they display tensile strength higher than 3.2 GPa and an initial modulus higher than 130 GPa. In particular, the fibers retain relatively high mechanical properties at elevated temperatures. Solution casted films exhibit very low thermal expansion coefficients and dielectric constants. Their structure, morphology and property relationships will also be discussed.