作者：Li Zhou, Chao Gao, Dandan Zhu, Weijian Xu, Fanqing Frank Chen, Amit Palkar, Luis Echegoyen, Eri
关键字：ATRP (atom transfer radical polymerization)，cycloaddition，functionalization，grafting nano-onions
论文来源：期刊
具体来源：Chem-Eur J 2009, 15, 1389-1396
发表时间：2009年
Facile functionalization of multilayer fullerenes (carbon nano-onions, CNOs) was carried out by [2+ 1] cycloaddition of nitrenes. The products were further derivatized by using the "grafting from" strategy of in situ ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP). Using one-step nitrene chemistry with high-energy reagents, such as azidoethanol and azidoethyl 2-bromo-2-methyl propanoate, in N-methyl -2-pyrrolidone at 160 degrees C for 16 h, hydroxyl and bromide functionalities were introduced onto the surfaces of CNOs. These hydroxyl CNOs (CNO-OH) and bromic CNOs (CNO-Br) were extensively characterized by various techniques such as thermal gravimetric analysis (TGA), transmission electron microscopy (TEM), Raman spectroscopy and X-ray photo electron spectroscopy (XPS). TGA measurements indicated that the surface hydroxyl and bromide group density reached 1.49 and 0.49 mmolg(-1), respectively. The as-functionalized CNOs showed much better solubility in solvents than pristine CNOs. The CNO-OH were also observed to fluoresce at lambda = 453 nm in water. The CNO-OH and CNO-Br can be conveniently utilized as macroinitiators to conduct surface-initiated in-situ polymerizations. Poly(E-caprolactone) (PCL, 45wt%) and polystyrene (PS, 60wt%) were then grafted from surfaces of CNOs through the ROP of E-caprolactone with the macroinitiator CNO-OH and the ATRP of styrene with the macroinitiator CNO-Br, respectively. The structures and morphology of the resulting products were characterized by H-1 NMR, scanning electron microscopy (SEM), TEM, and atomic force microscopy (AFM). The polymer functionalized CNOs have good solubility/dispersibility in common organic solvents. The facile and scalable functionalization approaches can pave the way for the comprehensive investigation of chemistry of CNOs and fabrication of novel CNO-based nanomaterials and nanodevices.