Edge-functionalized graphene nanoplatelets with polystyrene by atom transfer radical polymerization: grafting through carboxyl groups



The surface modifier 3-((4-hydroxybutoxy)dimethylsilyl)propyl methacrylate (CD), which contains a double bond and a hydroxyl group, was synthesized through a coupling reaction of 1,4-butanediol and (3-methacryloxypropyl)dimethylchlorosilane. Subsequently, graphene oxide (GO) was functionalized with different amounts of CD from its edge carboxyl groups. Then, grafting through atom transfer radical polymerization of styrene in the presence of various amounts of the edge-functionalized GO was carried out to evaluate the effect of graphene loading along with graft density. A peak at 3.8 ppm in the 1H NMR spectrum of CD associated with the methylene adjacent to the Si–O group indicated a successful coupling reaction. Attachment of CD on the edges of GO was evaluated using X-ray photoelectron and Fourier transform infrared spectroscopies. Expansion of GO interlayer spacing by functionalization was evaluated using X-ray diffraction. The ordered and disordered crystal structure of carbon was studied using Raman spectroscopy. The close ID/IG values for GO and various kinds of functionalized graphenes show the preserved graphitic crystallite size. Relaxation behaviour of polystyrene chains in the presence of graphene nanoplatelets and also the effect of graft content on chain confinement were studied using differential scanning calorimetry. High-graft-density nanocomposites show higher glass transition temperatures. Morphology of graphene nanoplatelets was studied using scanning electron and transmission electron microscopies. The flat and smooth morphology of graphene nanoplatelets is disturbed and also the transparency of the nanoplatelets decreases during the oxidation and functionalization processes. © 2014 Society of Chemical Industry