Functionalization of Single-Walled Carbon Nanotubes with Well-Defined Polymers by Radical Coupling

Polystyrene and poly[( tert -butyl acrylate)- b -styrene] with well-defined molecular weights and polydispersities were prepared by nitroxide-mediated free-radical polymerization. The homopolymers and block copolymers were used to functionalize shortened single-walled carbon nanotubes (SWNTs) through a radical coupling reaction involving polymer-centered radicals generated at 125 °C via loss of the stable free-radical nitroxide capping agent. The resulting polymer−SWNT composites were fully characterized and were found to be highly soluble in a variety of organic solvents. This solubility could also be altered through chemical modification of the appended polymers. The tert -butyl groups of appended poly[( tert -butyl acrylate)- b -styrene] could be removed to produce poly[(acrylic acid)- b -styrene]-functionalized carbon nanotubes. The resulting composite was found to form aggregates in a mixture of chloroform/methanol (v/v: 1/1) as determined by dynamic light scattering.