Polyimide Fibers Obtained by Spinning Lyotropic Solutions of Rigid-Rod Aromatic Poly(amic ethyl ester)s

Fibers were spun from a lyotropic solution of a high‐molecular‐weight (η = 5.89 g · dL−1), rigid‐rod, fully aromatic polyimide precursor polymer in a dry‐jet, wet‐spinning process in NMP. Acetone was identified as the coagulant of choice since fibers could be drawn extensively in this solvent, resulting in improved mechanical properties (tensile modulus: E = 17 GPa, strength at break: σbreak = 400 MPa, elongation at break: εbreak = 5.3%) and orientation, which was shown by WAXS patterns. SEM images showed a layered, skin‐core morphology without any visible fibrillation. Additional processing of these fibers by step‐wise hot‐drawing up to 400 °C under tension rendered oriented polyimide fibers with excellent mechanical properties. (E = 68 GPa, σbreak = 700 MPa, εbreak = 1%). An analysis of the WAXS diffraction patterns showed an improved orientation of the fibers in the axial and lateral directions; however, probably due to the CF3 side groups, the lateral distance was still too large for crystallization. SEM images of these imidized fibers showed, for the first time, a fibrillar morphology in addition to the typical, skin‐core, sheet‐like morphology. SEM image of the hot‐drawn fiber PI 4 (12). The image shows a skin‐core morphology which was delaminating into ribbons during preparation.