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In this work, we investigated a simple one-step process for the formation of chemical bonds between multi-walled carbon nanotubes (MWCNTs) and benzyl-type side chain radicals generated by UV photolysis of polystyrene derivatives containing the chloromethyl (–CH2Cl) group. Poly(4-chloromethyl)styrene, or styrene/4-(chloromethyl)styrene random copolymer, was mixed with MWCNTs in 1-methyl-2-pyrrolidone and irradiated with ultraviolet (UV) light. Films of polymer/MWCNT mixtures before and after UV irradiation were fabricated, and then examined by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. According to the XPS analysis, the amount of Cl atoms in the mixture was found to decrease upon UV irradiation, indicating that the Cl atoms generated by photolysis of chloromethyl groups escaped from the reaction system in the form of gaseous Cl2. The structural change of CNTs after UV irradiation was also observed by comparing the G/D ratios (the intensity ratio of the G to D bands) of the Raman spectra obtained before and after UV irradiation. Similar phenomena were also confirmed in the case of the polymer/MWCNT mixture containing hydroxylammonium chloride as a dispersant of MWCNTs. These results confirmed the UV-induced covalent bond formation between polymer side chains and MWCNTs

Simple Process for Sidewall Modification of Multi-Walled Carbon Nanotubes with Polymer Side Chain Radicals Generated by Ultraviolet-Induced C–Cl Bond Dissociation of Polystyrene Derivatives