Grafting densely-packed poly(n-butyl methacrylate) chains from an iron substrate by aryl diazonium surface-initiated ATRP: XPS monitoring

cited By 66International audiencePoly(n-butyl methacrylate), PBMA, chains were grafted by atom transfer radical polymerization (ATRP) from the surface of iron plates using electrochemically attached initiators based on diazonium salts providing an iron/polyphenylene/PBMA structure. This surface-initiated ATRP procedure was controlled by the addition of a small proportion of Cu++ deactivator, but in the absence of any sacrificial initiator. Combined XPS, IR and AFM experiments provide a powerful means for the characterization of the obtained complex iron/polyphenylene/PBMA layered structure. It is possible to measure the thickness of the brominated aryl structure covalently attached to iron. Concerning the PBMA brushes, their presence on the surface was confirmed by IRRAS. The brominated chain end could be traced by XPS testifying for the ATRP character of the polymerization and the thickness of the polymer brushes was determined. The controlled living ATRP character of the polymerization is confirmed through a linear correlation between the thickness of the layer and the degree of polymerization. Measurement of the grafting density of PBMA chains indicates that they are compactly packed and that, approximately, one brominated aryl chain out of two efficiently initiates ATRP. © 2007 Elsevier B.V. All rights reserved

Novel approach for metallic surface-initiated atom transfer radical polymerization using electrografted initiators based on aryl diazonium salts

cited By 75International audienceThis paper reports on the preparation of poly(methyl methacrylate) (PMMA), poly(n-butyl acrylate) (PBA), and polystyrene (PS) brushes at the surface of conducting materials that were modified by the electrochemical reduction of a brominated aryl diazonium salt BF4-, +N 2-C6H4-CH(CH3)-Br (D1). The grafted organic species -C6H4CH(CH3)-Br was found to be very effective in initiating atom transfer radical polymerization (ATRP) of vinyl monomers. This novel approach combining diazonium salts and ATRP allowed PMMA, PBA, and PS brushes to be grown from the surface of iron electrodes. The polymer films were characterized in terms of their chemical structure by infrared reflection absorption spectroscopy and X-ray photoelectron spectroscopy. Atomic force microscopy studies indicated that the polymer brushes are densely packed. Contact angle measurements of water drops on PS and PMMA brushes were 88.1 ± 2.0 and 70.3 ± 2.1°, respectively, which is consistent with the published wettability data for the corresponding polymer sheets. © 2005 American Chemical Society ́Paris 7