Control of Head/Tail Isomeric Structure in Polyimide and Isomerism-Derived Difference in Molecular Packing and Properties.

Two sequence isomeric poly(amic acid)s (PAAs) are successfully synthesized from 3,3',4,4'-biphenyltetracarboxylic dianhydride and unsymmetrical 5(6)-amino-2-(4-aminobenzene) benzimidazole (PABZ). The syntheses are based on the site-selective reactivity of head/tail amino groups of PABZ and solubility differences of PABZ in good solvent (dimethyl sulfoxide, DMSO) and poor solvent (N-methyl-2-pyrrolidone, NMP). The proton nuclear magnetic resonance (1 H-NMR) results reveal that the content of head tail-head tail (HTHT) bonding units in PAA-DMSO (PAA synthesized in DMSO) is 37%, while this content increases to 54% in PAA-NMP (PAA synthesized in NMP). The wide-angle X-ray diffraction (WAXD) results indicate polyimide (PI)-NMP film with high HTHT content exhibits a semicrystalline structure, while PI-DMSO film is amorphous. Moreover, PI-NMP also shows higher in-plane orientation than PI-DMSO. The ordered molecular packing and higher in-plane orientation of PI-NMP lead to an increase in mechanical properties and a decrease in in-plane thermal expansion coefficient.