Journal of Polymer Science Part B: Polymer Physics, Vol.32, No.16, 2705-2713, 1994
Crystal-Structure, Morphology, and Phase-Transitions in Aromatic Polyimide Oligomers .3. Poly(1,4-Phenyleneoxy-1,3-Phenylene Pyromellitimide)
An aromatic polyimide oligomer, poly(1,4-phenyleneoxy-1,3-phenylene pyromellitimide) (PMDA-3,4’ODA), was synthesized from pyromellitic dianhydride (PMDA) and 3,4’-oxydianiline (3,4’-ODA) via a melt-polymerization method. This method permits growth of PMDA-3,4’-ODA lamellar crystals and the crystal structure can be studied via electron diffraction (ED) and wide-angle x-ray diffraction (WAXD) experiments. Our structure analysis indicates that this polyimide possesses a two-chain orthorhombic crystal lattice with dimensions of a = 0.848, b = 0.562, and c = 3.365 nm. It has also been found that poly(amic acid) precursors with little imidization possess the same ab lateral lattice packing, but statistical departure from the ordered packing along the c-direction. Upon increasing the degree of imidization through annealing at elevated temperatures, the order along the c-axis was progressively enhanced. Increasing the annealing temperature caused the di mensions of the a- and the b-axes to expand while the crystal correlation lengths decreased laterally. Simultaneously the dimension of the c-axis shrinks with an increase of the crystal correlation length along the chain direction. Crystal morphological study via transmission electron microscopy (TEM) indicates a mainly lamellar crystal texture with different thicknesses depending upon the polymerization conditions. The end lamellar surface is usually smooth. After annealing at elevated temperatures, the lamellar end surfaces become rough, which may be due to chain motion along the c-axis. The annealed PMDA-3,4’-ODA lamellar crystals still show a large amount of defects.
Keywords:X-RAY