Preparation of brush-like crystals of poly[2,6-(1,4-phenylene)-benzobisimidazole]

Poly2,6-(1,4-phenylene)-benzobisimidazole] (PPBI) crystals were prepared by using reaction-induced crystallization of oligomers during solution polymerization of 1,2,4,5-tetraaminobenzene and diphenyl terephthalate. Polymerizations were carried out at a monomer concentration of 4.3 × 10⁻² mol L⁻¹ at 350 °C for 6 h. Brush-like PPBI crystals were obtained in a mixture of structural isomers of dibenzyltoluene, in which many needle-like crystals came out vertically from the surface of the ribbon-like crystals. Average width and thickness of the ribbon-like crystals were 0.75 μm and 0.11 μm, respectively. And average length and diameter of the needle-like crystals were 0.36 μm and 50 nm, respectively. The brush-like crystals possessed high crystallinity and exhibited good thermal resistance. The ribbon-like crystals were formed by the crystallization of imidazole oligomers at an initial stage of polymerization, and then the needle-like crystals grew from the surface of the ribbon-like crystals. Polymerization occurred on the crystals when the oligomers were crystallized, leading to the high molecular weight PPBI crystals.