In situ preparation and continuous fiber spinning of poly(p-phenylene benzobisoxazole) composites with oligo-hydroxyamide-functionalized multi-walled carbon nanotubes

A graft-from approach has been performed to achieve covalent functionalization of multi-walled carbon nanotubes (MWNTs) with oligo-hydroxyamide (oHA). Pristine MWNT was first oxidized to MWNT-COOH and then functionalized to MWNT-COCl by acyl chloride. MWNT-COCl was copolymerized with oHA to produce oHA-grafted MWNTs (MWNT-oHA). The thickness of the oHA shell in MWNT-oHA is about 7.5 nm. MWNT-oHA has a remarkable solubility in polar solvents and a good thermal stability because characteristic dehydrative ring closure occurs upon heating and forms a thermally more stable benzoxazole component. MWNT-oHA has been further covalently incorporated with a rigid-rod polymer matrix, poly(p-phenylene benzobisoxazole) (PBO), through in situ polymerization. Continuous PBO-MWNT composite fibers with different MWNT compositions have been fabricated using dry-jet wet-spinning technique. The structure and morphology of PBO-MWNT composite fibers have been characterized and their mechanical, thermal, conducting properties have been investigated. The tensile modulus, tensile strength, and thermal stability of PBO-MWNT composite fibers have been improved because of a good dispersion and high alignment of MWNTs in PBO as well as enhanced interfacial interaction between these two components. Furthermore, increased conductivity has been discovered in the PBO-MWNT composite films and the inner core of the composite fibers; however, not on the outer surface. The phenomena can be interpreted using percolation model together with the heterogeneous fiber morphology and nanotube distribution over the cross-section of the fiber.