Polymer Functionalization of Single-Walled Carbon Nanotubes through Covalent Methods

Abstract

The discovery of nanotubes with unique mechanical, electrical, and thermal properties has led to their use in the development of the next generation of composite materials. However, their poor solubility and dispersion properties in any organic and aqueous solvents limits their potential applications. In order to improve their solubility, single-walled carbon nanotubes (SWNTs) were functionalized along their sidewalls with phenol groups using a 1,3-di^polar cycloaddition reaction. These phenols could be further derivatized with 2-bromoisobutyryl bromide, resulting in the attachment of atom transfer radical polymerization initiators to the sidewalls of the nanotubes. These initiators were found to be active in the polymerization of methyl methacrylate and t-butyl acrylate from the surface of the nanotubes. However, the polymerizations were not controlled, leading to the production of high molecular weight polymeric grafts with relatively large polydispersities. The resulting polymer carrying nanotubes were analyzed by IR, Raman spectroscopy, solid-state NMR, DSC, TEM, and AFM. The nanotubes functionalized with poly(methyl methacrylate) were found to be insoluble in organic solvents, such as THF and CH2CI2. However, the dispersion property of SWNTs in the polymer matrix was improved dramatically. Another monomer t-butyl acrylate (t-BuA) was also polymerized using the same macroinitiators. It was found that the SWNTs functionalized with t-BuA iii were soluble in a variety of organic solvents. The t-butyl groups of these appended polymers could also be removed to produce nanotubes functionalized with poly (acrylic acid), resulting in nanocomposites that are soluble in aqueous solutions. In addition, polystyrene (PS) which was prepared by stable free radical polymerization, was used to functionalize SWNTs through the radical coupling reaction. IR, NMR, TEM, and AFM confirmed that this polystyrene was covalently bonded to the SWNTs. It was also found that the resulting PS-SWNTs composites were quite soluble in organic solvents, such as THF and CH2C12.