Interfacial aspects of polymer brushes prepared on conductive substrates by aryl diazonium salt surface‐initiated ATRP

Abstract

This article describes the use of aryl diazonium salts to attach halogenated functional groups that initiate atom transfer radical polymerization (ATRP) at the surface of conductive substrates. The interest of this procedure lies in the fact that aryl diazonium salts permit the grafting of high-density initiators within a few minutes of electrochemical surface treatment, and subsequently promote the growth of very compact polymer chains.Several brominated aryl groups were tested for surface-initiating ATRP of styrene and methacrylates. The chemical structure of the polymer brushes was characterized by high-resolution XPS. Particularly, it is shown that grafting of poly(tert-butyl methacrylate), PtBMA, from the surface of glassy carbon plates followed by hydrolysis resulted in carboxylated, tethered chains that were characterized in terms of hydrophilicity and propensity to uptake silver cations.

Hydrophilic Polymer Brush Layers on Stainless Steel Using Multilayered ATRP Initiator Layer

“…The need to protect industrial metal surfaces from scaling, fouling, and corrosion has initiated several research works in pursuit of robust polymer-based modification onto stainless steel surfaces. Techniques such as grafting to , grafting from , and layer-by-layer deposition have been examined previously. − Notably the covalent attachment of polymer chains via SI-ATRP technique have been reported on stainless steel surfaces using different types of ATRP initiator layer structuresmethoxysilanes, phosphonic acids, catechols, and electropolymerized layer. − Alternatively, multilayered ATRP initiator layer was employed on conducting surfaces including carbon, stainless steel, and other metal oxides using electrochemical reduction of aryldiazonium tetrafluoroborate salts. − All previous works have employed mechanical/electrochemical polishing of stainless steel prior to polymer modification to eliminate grain boundary roughness. However, polishing methods are not always practically implementabledue to cost, sample geometry, and variation in surface chemical compositionnecessitating the investigation of chemical homogeneity of the coating method along the grain boundary regions.…”

On Surface-Initiated Atom Transfer Radical Polymerization Using Diazonium Chemistry To Introduce the Initiator Layer

“…Surface functional groups of polymeric materials such as cellulose, chitosan, poly(ether imide), and graphene oxide have also been chemically modified to introduce ATRP initiators. Recently, aryldiazonium-based compounds − have been successfully employed to introduce initiators on conducting substrates such as metals and glassy carbon (GC) through an electrochemical approach. In contrast to initiators formed by self-assembly process, the diazonium approach results in a randomly oriented multilayer structure with thickness ranging from a few nanometers to micrometers, depending on the choice of diazonium salt and experimental conditions.…”

Surface confined atom transfer radical polymerization: access to custom library of polymer-based hybrid materials for speciality applications

“…Like CNTs, the methodology of oxidation of a carbon surface, followed by coupling of an ATRP initiator has been used to functionalize other carbon-based materials with ATRP initiating moieties followed by polymer graing via SC-ATRP such as carbon black NPs, 115 nanodiamond particles, 116 graphitic carbon nanobers, 117 pure carbon spheres, 118 and ultra nanocrystalline diamond lms 100 and glassy carbon substrates. 119 5.1.5. Synthetic polymer surface.…”