Polyurea-Functionalized Multiwalled Carbon Nanotubes: Synthesis, Morphology, and Raman Spectroscopy

An in situ polycondensation approach was applied to functionalize multiwalled carbon nanotubes (MWNTs), resulting in various linear or hyperbranched polycondensed polymers [e.g., polyureas, polyurethanes, and poly(urea-urethane)-bonded carbon nanotubes]. The quantity of the grafted polymer can be easily controlled by the feed ratio of monomers. As a typical example, the polyurea-functionalized MWNTs were measured and characterized in detail. The oxidized MWNTs (MWNT-COOH) were converted into acyl chloride-functionalized MWNTs (MWNT-COCl) by reaction with neat thionyl chloride (SOCl2). MWNT-COCl was reacted with excess 1,6-diaminohexane, affording amino-functionalized MWNTs (MWNT-NH2). In the presence of MWNT-NH2, the polyurea was covalently coated onto the surfaces of the nanotube by in situ polycondensation of diisocyanate [e.g., 4,4′-methylenebis(phenylisocyanate)] and 1,6-diaminohexane, followed by the removal of free polymer via repeated filtering and solvent washing. The coated polyurea content can be controlled to some extent by adjusting the feed ratio of the isocyanato and amino groups. The structure and morphology of the resulting nanocomposites were characterized by FTIR, NMR, Raman, confocal Raman, TEM, EDS, and SEM measurements. The polyurea-coated MWNTs showed interesting self-assembled flat-or flowerlike morphologies in the solid state. The signals corresponding to that of the D and G bands of th