Polymer grafting on graphene layers by controlled radical polymerization

In situ controlled radical polymerization (CRP) is considered as an important approach to graft polymer brushes with controlled grafting density, functionality, and thickness on graphene layers. Polymers are tethered with chain end or through its backbone to the surface or edge of graphene layers with two in situ polymerization methods of “grafting from” and “grafting through” and also a method based on coupling reactions known as “grafting to”. The “grafting from” method relies on the propagation of polymer chains from the surface- or edge-attached initiators. The “grafting through” method is based on incorporation of double bond-modified graphene layers into polymer chains through the propagation reaction. The “grafting to” technique involves attachment of pre-fabricated polymer chains to the graphene substrate. Here, physical and chemical attachment approaches are also considered in polymer-modification of graphene layers. Combination of CRP mechanisms of reversible activation, degenerative (exchange) chain transfer, atom transfer, and reversible chain transfer with various kinds of grafting reactions makes it possible to selectively functionalize graphene layers. The main aim of this review is assessment of the recent advances in the field of preparation of polymer-grafted graphene substrates with well-defined polymers of controlled molecular weight, thickness, and polydispersity index. Study of the opportunities and challenges for the future works in controlling of grafting density, site-selectivity in grafting, and various topologies of the brushes with potential applications in stimuli-responsive surfaces, polymer composites, Pickering emulsions, coating technologies, and sensors is also considered. [Display omitted] •Polymer-grafting on graphene layers was reported by in situ controlled radical polymerization or coupling reactions,•In situ polymerization consists of “grafting from” and “grafting through” methods,•Coupling reactions is commonly known as “grafting to” method.•The “grafting from” method results in higher grafting densities,•Controlling grafting density, site-selectivity in grafting, and various topologies of the brushes are the targets,•Applications in smart surfaces, polymer composites, Pickering emulsions, colloidal systems, coatings, and sensors are considered.