Polymer brushes with single-walled carbon nanotubes (SWNT) as backbones were synthesized by grafting n-butyl methacrylate (nBMA) from the ends and sidewalls of SWNT via atom transfer radical polymerization (ATRP). Carboxylic acid groups on SWNT were formed by nitric acid oxidation. The ATRP initiators were covalently attached to the SWNT by esterification of 2-hydroxyethyl 2'-bromopropionate with carboxylic acid groups. Methyl 2-bromopropionate (MBP) was added as free initiator during the brush preparation to control growth of the brushes and to monitor the polymerization kinetics. Size-exclusion chromatography (SEC) results show that the molecular weight of free poly(n-butyl methacrylate) (PnBMA) increased linearly with nBMA monomer conversion. PnBMA cleaved from the SWNT after high conversion had the same molecular weight as PnBMA produced in solution. Thermogravimetric analyses (TGA) show that the amount of PnBMA grown from the SWNT increased linearly with the molecular weight of the free PnBMA. The most highly PnBMA-functionalized SWNT dissolve in 1,2-dichlorobenzene, chloroform, and tetrahydrofuran, and solubility increases with the amount of PnBMA bound to SWNT. Near-infrared and Raman spectra indicate that the side walls of the SWNT were lightly functionalized by the nitric acid treatment and that the degree of functionalization of the SWNT did not change significantly during the formation of initiator or during the polymerization. Atomic force microscopy (AFM) images show contour lengths of the SWNT brushes on a mica surface from 200 nm to 2.0 microm and an average height of the backbone of 2-3 nm, indicating that the bundles of original SWNT were broken into individual tubes by functionalization and polymerization.

Single-walled carbon nanotubes (SWNT) were functionalized with polystyrene (PSt) by grafting to and grafting from methods. PSt-N3 with designed molecular weight and narrow molecular weight distribution was synthesized by atom transfer radical polymerization (ATRP) of styrene (St) followed by end group transformation and then added to SWNT. The grafting from functionalization was achieved by ATRP of St using 2-bromopropionate groups immobilized SWNT as initiator. Methyl 2-bromopropionate (MBP) was added as free initiator to control the chain propagation on SWNT during the polymerization. Raman and near-IR spectra show that PSt was covalently attached to the sidewalls of SWNT by the grafting to approach, and the degree of functionalization was about 1 in 48 SWNT carbon atoms as determined by thermogravimetric analyses (TGA). In the grafting from approach, size exclusion chromatography (SEC) results show that the molecular weight of free St increased linearly with St conversion, and the PSt cleaved from the SWNT after high conversion had the same molecular weight as the PSt produced in solution. TGA show that the amount of PSt grafted from the SWNT increased linearly with the molecular weight of the free PSt. By both methods, the final functionalized SWNT dissolved well in organic solvents, and the original SWNT bundles were broken into very small ropes or even individual tubes as revealed by AFM.

Oxidation of single-walled carbon nanotubes (SWNTs) with nitric acid increases their dispersability in water, methanol, and N,N-dimethylformamide. Two oxidation protocols, sonication in 8 M HNO 3 at 40 °C and reflux in 2.6 M HNO 3 , have been examined using SWNTs produced by the CoMoCat, HiPco, and pulsed laser vaporization (PLV) methods. The dispersability of all types of nanotubes increased substantially after 1 h of sonication and after 2-4 h of reflux. Longer treatments resulted in little further improvement in dispersability and at reflux degraded the SWNTs. Stable dispersions of CoMoCat SWNTs in DMF at concentrations as high as 0.4 g/L were achieved without the use of surfactants or polymers. Raman spectroscopy showed greater covalent functionalization of the SWNTs by the reflux procedure than by the sonication procedure. Concurrent with improved dispersability, oxidation resulted in smaller diameters and shorter lengths as determined from AFM images, which show mostly bundles rather than individual tubes. The lengths of SWNTs after oxidation decreased in the order PLV > HiPco > CoMoCat. Recommendations for the method of conditioning of the various types of SWNTs depend on their intended use.