Grafting of poly(ethylene oxide) onto C60 fullerene using macroazo initiators

In order to improve the solubility of C60 fullerene in conventional solvents, grafting of hydrophilic poly(ethylene oxide) (PEO) by utilizing the radical-trapping nature of C60 fullerene was investigated. Macroazo initiators containing a poly(ethylene oxide) unit, known as Azo-PEO, were prepared at various molecular weights by the reaction of 4,4′-azobis(4-cyanopentanoyl chloride) with poly(ethylene glycol) methyl ether. PEO radicals formed by thermal decomposition of Azo-PEO were successfully trapped by C60 fullerene to give PEO-grafted C60 fullerene. Their structures were confirmed by FT-IR spectroscopy, size exclusion chromatography, UV–vis spectroscopy, and differential scanning calorimetry. When Azo-PEO with low-molecular weight was reacted with C60 fullerene, a bis-adduct, C60-(PEO)2, and a tetrakis-adduct, C60-(PEO)4, were formed. In contrast, in reactions with Azo-PEO of higher molecular weight, only the bis-adduct was formed, and no formation of the tetrakis-adduct was observed. The structure of bis-adduct was found to be 1,4-type. The solubility of C60 fullerene in water, THF, methanol, and other conventional organic solvents was remarkably improved by grafting of PEO. In addition, the thermal stability of PEO was dramatically increased by grafting onto C60 fullerene.