Polymer Brushes via ATRP: Role of Activator and Deactivator in the Surface‐Initiated ATRP of Styrene on Planar Substrates
TL;DR: The role of activator and deactivator species in the surface-initiated atom-transfer radical polymerization of styrene using CuBr/CuBr 2 /pentamethyl-diethylenetriamine as a model system is described in this paper.
Abstract: The role of activator and deactivator species in the surface-initiated atom-transfer radical polymerization of styrene using CuBr/CuBr 2 /pentamethyl-diethylenetriamine as a model system is described. The influence of initially added deactivator with respect to the degree of controlling the layer growth and thickness is studieed. Variation of the activator concentration results in changes of the kinetics as wells as brush thicknesses consistent with the well-known rate laws of ATRP. System used for the generation of polymer brushes via ATRP.
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TL;DR: This data indicates that self-Assembled Monolayers and Walled Carbon Nanotubes with high adhesion to Nitroxide-Mediated Polymerization have potential in the well-Defined Polymer Age.
Abstract: Keywords: Fragmentation Chain-Transfer ; Self-Assembled Monolayers ; Walled Carbon Nanotubes ; Well-Defined Polymer ; Nitroxide-Mediated Polymerization ; Block-Copolymer Brushes ; Poly(Methyl Methacrylate) Brushes ; Transfer Raft Polymerization ; Quartz-Crystal Microbalance ; Poly(Acrylic Acid) Brushes Reference EPFL-REVIEW-148464doi:10.1021/cr900045aView record in Web of Science Record created on 2010-04-23, modified on 2017-05-10
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TL;DR: The generation of polymer brushes by surface-initiated controlled radical polymerization (SI-CRP) techniques has become a powerful approach to tailor the chemical and physical properties of interfaces and has given rise to great advances in surface and interface engineering as mentioned in this paper.
Abstract: The generation of polymer brushes by surface-initiated controlled radical polymerization (SI-CRP) techniques has become a powerful approach to tailor the chemical and physical properties of interfaces and has given rise to great advances in surface and interface engineering. Polymer brushes are defined as thin polymer films in which the individual polymer chains are tethered by one chain end to a solid interface. Significant advances have been made over the past years in the field of polymer brushes. This includes novel developments in SI-CRP, as well as the emergence of novel applications such as catalysis, electronics, nanomaterial synthesis and biosensing. Additionally, polymer brushes prepared via SI-CRP have been utilized to modify the surface of novel substrates such as natural fibers, polymer nanofibers, mesoporous materials, graphene, viruses and protein nanoparticles. The last years have also seen exciting advances in the chemical and physical characterization of polymer brushes, as well as an ev...
681 citations
TL;DR: In this paper, a surface-initiated ATRP of methyl methacrylate mediated by a copper complex was carried out with the initiator-fixed SiPs in the presence of a free initiator.
Abstract: Monodisperse silica particles (SiPs) of diameter between 100 and 1500 nm were surface-modified in a mixture of ethanol/water/ammonia with a newly designed triethoxysilane having an atom transfer radical polymerization (ATRP) initiating site, (2-bromo-2-methyl)propionyloxyhexyltriethoxysilane. The surface-initiated ATRP of methyl methacrylate (MMA) mediated by a copper complex was carried out with the initiator-fixed SiPs in the presence of a “sacrificial” (free) initiator. The polymerization proceeded in a living manner in all examined cases, producing SiPs coated with well-defined PMMA of a target molecular weight up to 480K with a graft density as high as 0.65 chains/nm2. These hybrid particles had an exceptionally good dispersibility in organic solvents. Transmission electron microscopic and atomic force microscopic observations of their monolayers prepared at the air−water interface revealed that they formed an ordered 2-dimensional lattice extending throughout the monolayer.
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Journal Article•
TL;DR: A review of surface-initiated living radical polymerization (LRP) can be found in this article, where a high-density polymer brush has characteristics, in both swollen and dry states, quite different and unpredictable from those of the semi-dilute or moderately dense polymer brushes previously studied.
Abstract: Surface modifications by polymers are becoming increasingly important for various applications ranging from biotechnology to advanced microelectronics. Recent successful applications of living radical polymerization (LRP) made it possible to graft various low-polydispersity polymers including simple homopolymers, end-functionalized polymers, block/random/gradient copolymers, and functional polymers. At the same time, this technique has brought about a striking increase of graft density. Graft chains in such a high-density polymer brush were found to be highly extended in good solvent, even to the order of their full lengths. It was also found that a high-density polymer brush has characteristic properties, in both swollen and dry states, quite different and unpredictable from those of the semi-dilute or moderately dense polymer brushes previously studied. This review highlights the recent development of surface-initiated LRP and the structures, properties, and potential applications of thereby obtainable high-density polymer brushes. It is believed that surface-initiated LRP is opening up a new route to "precision" surface modification.
493 citations
TL;DR: The research activities in the last decade indicate that ATRP has become an essential tool for the design and synthesis of advanced, noble and novel biomaterials.
Abstract: Recent progress in controlled radical polymerizations, in particular atom transfer radical polymerization (ATRP), has provided a unique means for the design and synthesis of bioactive surfaces and functional biomaterials. This review summarizes such recent research activities. The synthesis strategies of bioactive surfaces and biomaterials via ATRP are described in detail. The highly robust and versatile ATRP technique is particularly suited for the preparation of functional bioactive surfaces, including antifouling, antibacterial, stimuli-responsive, biomolecule-coupled and micropatterned surfaces. In addition to bioactive surfaces, ATRP has also been widely used for the preparation of well-structured functional biomaterials, such as micellar delivery systems, hydrogels, cationic gene carriers and polymer–protein conjugates. The research activities in the last decade indicate that ATRP has become an essential tool for the design and synthesis of advanced, noble and novel biomaterials.
363 citations