Polymer Brushes via Controlled, Surface‐Initiated Atom Transfer Radical Polymerization (ATRP) from Graphene Oxide

Abstract

A method for growing polymers directly from the surface of graphene oxide is demonstrated. The technique involves the covalent attachment of an initiator followed by the polymerization of styrene, methyl methacrylate, or butyl acrylate using atom transfer radical polymerization (ATRP). The resulting materials were characterized using a range of techniques and were found to significantly improve the solubility properties of graphene oxide. The surface-grown polymers were saponified from the surface and also characterized. Based on these results, the ATRP reactions were determined to proceed in a controlled manner and were found to leave the structure of the graphene oxide largely intact.

From Self-Assembled Monolayers to Coatings: Advances in the Synthesis and Nanobio Applications of Polymer Brushes

“…X-ray Photoelectron Spectroscopy (XPS) can also be used for surface characterization as it probes a depth of ~10 nm. Most often XPS is used to confirm brush growth, to study surface chemical composition of the brush and to determine surface densities of bound molecules on the brush [138][139][140][141][142]. XPS has also been used for initiator-coated surfaces, however most of these studies have been limited to qualitative confirmation of the presence of initiator groups [143][144][145][146].…”

The Prospective Two-Dimensional Graphene Nanosheets: Preparation, Functionalization and Applications

“…Therefore, it is necessary to first disperse the graphene or GO nanosheets in an organic solvent, followed by polymer blending in the organic solvent. Therefore, the functionalization of graphene or GO sheets has been carried out in order to change the surface properties of nanosheets, making them more lipophilic and consequently dispersible in organic solvents [24,[68][69][70][71][72][73][74][75]. Ruoff et al [69,70] reported that GO can be chemically functionalized with isocyanate, and dispersed in organic solvents, followed by blending with polystyrene and a chemical reduction step.…”

“…Compared with unmodified counterparts, the alkyl attached graphene shows a largely enhanced lipophilicity, and remarkably improvement of dispersion in the nonpolar solvents and polypropylene matrix can be achieved. Other kinds of polymer matrix composites with graphene-based additives, including poly (methyl methacrylate) [71,72], epoxy [73][74][75][76], polyester [77], silicone foam [78], polyurethane [79,80], poly (vinyldiene fluoride) [81], and polycarbonate [82] have also been reported. Melting processing method is another route for polymer processing, which is widely applied in industry area and very suitable for nanocomposite preparation through the addition of graphene-based additives into polymer matrix.…”

Functionalized Graphene Nanocomposites

“…After the addition of the initiating agent to the surface of GO is possible to perform the controlled growth of polymer chains via ATRP (Figure 6). Another approach is the surface modification of carboxylic groups of GO with diamines through the formation of amide groups, allowing the functionalization of GO with terminal amine groups, that also able to establish chemical bonds with the ATRP initiators (Fang, Wang et al 2009;Lee, Dreyer et al 2010). Fig.…”

“…From the previous discussion it is obvious that the GO modification with PMMA via ATRP acts as a reinforcement agent of the PMMA matrix. This strategy can be further exploited to grow a large range of polymers from the GO surface only by changing the monomer, for example styrene (Fang, Wang et al 2009;Fang, Wang et al 2010;Lee, Dreyer et al 2010), 2-(dimethylamine) ethyl methacrylate (DMAEMA ) ), butylacrilate (Lee, Dreyer et al 2010;Li, Liu et al 2010) are just some of the monomers already used. The versatility of this mechanism also allows the controlled growth of copolymers; if the free radical polymerization remains active, it will allow the growth of another polymer chain just by shifting to the desired monomer.…”