LAUSR

Abstract Coordination crosslinking, as the kind of strongest supramolecular interaction, has been widely introduced into flexible polymer chains, including rubbers and aerogels, while that in rigid-rod polymer is much rare, due to the difficulty in rigid-rod macromolecules' configuration change. Moreover, the exact coordination structure inside those polymers is not clear. Herein, this coordination interaction was incorporated into a traditional rigid-rod polymer, aramid fiber, by Cu2+-benzimidazole coordination reaction, through the careful control of the dynamic reaction conditions, and the structural/performance relationships of fiber and its composites are detailed studied. It is seen that two different coordination structures, S-coordination style (Cu2+ coordination with single benzimidazole unit) and M-coordination style (Cu2+ coordination with multiple benzimidazole units from different macromolecular chains), could be both obtained inside fiber, using different solvents as the reaction medium. Moreover, using reaction kinetics equilibrium, we presented a mathematical method to investigate those two coordination structures in detail, including their average coordination numbers of Cu2+ and reaction equilibrium constant (K). Further, the experimental results show that the fiber with average coordination number of 2 exhibits a comprehensive improved performance in heat/solvent resistance, fluorescence emission as well as fiber's transverse properties, with the corresponding increase of 54.2% and 47.1% for its composites interfacial properties and compressive strength, compared with untreated fiber.