A series of poly(amic ester)s, PMm, based on pyromellitic
acid derivatives with long n-alkylene side chains
[−(CH2)
m
H], were synthesized
to prepare low-temperature lyotropic liquid crystalline (LC) precursors
for a fully aromatic rigid-rod polyimide (PI). Highly oriented LC
precursor films (m > 8) were prepared by shearing
at ambient temperature. Although the polydispersity of PMm was not controlled, the PMm solution exhibited
a lyotropic smectic phase in which the main chains were parallel to
the layer normal. After prebaking the lyotropic solution (70 °C),
uniaxial orientation order parameter of the main chain was maintained
at ∼0.5 during heating from 70 to 250 °C before imidization.
Synchrotron radiation wide-angle X-ray diffraction and polarized Fourier
transform infrared spectroscopy revealed that the orientation order
spontaneously increased (0.5–0.9) during imidization (>270
°C), even for free-standing films. This unique phenomenon distinctly
differs from the behavior of conventional amorphous precursors. In
the present case, the rigid PI segments with longer persistence length
spontaneously grow along the n-director of the LC
matrix of the precursor to form highly oriented homogeneous PI films.