The direct preparation of grafting polymer brushes from commercial poly (vinylidene fluoride) (PVDF) films with surface‐initiated atom transfer radical polymerization (ATRP) is demonstrated. The direct initiation of the secondary fluorinated site of PVDF facilitated grafting of the hydrophilic monomers from the PVDF surface. Homopolymer brushes of 2‐(N,N‐dimethylamino)ethyl methacrylate (DMAEMA) and poly (ethylene glycol) monomethacrylate (PEGMA) were prepared by ATRP from the PVDF surface. The chemical composition and surface topography of the graft‐functionalized PVDF surfaces were characterized by X‐ray photoelectron spectroscopy, attenuated total reflectance/Fourier transform infrared spectroscopy, and atomic force microscopy. A kinetic study revealed a linear increase in the graft concentration of poly[2‐(N,N‐dimethylamino)ethyl methacrylate] (PDMAEMA) and poly[poly(ethylene glycol) monomethacrylate] (PPEGMA) with the reaction time, indicating that the chain growth from the surface was consistent with a controlled or living process. The living chain ends were used as macroinitiators for the synthesis of diblock copolymer brushes. The water contact angles on PVDF films were reduced by the surface grafting of DMAEMA and PEGMA. Protein adsorption experiments revealed a substantial antifouling property of PPEGMA‐grafted PVDF films and PDMAEMA‐grafted PVDF films in comparison with the pristine PVDF surface. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3434–3443, 2006

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A reversible addition-fragmentation chain transfer (RAFT) polymerization technique was applied to graft polymerize brushes of poly(methyl methacrylate) (PMMA) and poly(poly(ethylene glycol) monomethacrylate) (PPEGMA) from poly(vinylidene fluoride) (PVDF) surfaces. PVDF surfaces were exposed to aqueous LiOH, followed by successive reductions with NaBH 4 and DIBAL-H to obtain hydroxyl functionality. Azo-functionalities, as surface initiators for grafting, were immobilized on the PVDF surfaces by esterification of 4,4 0 -azobis(4-cyanopentanoic acid) and the surface hydroxyl groups. The chemical composition and surface topography of the graftfunctionalized PVDF surfaces were characterized by X-ray photoelectron spectroscopy, attenuated total reflectance-FTIR spectroscopy, and atomic force microscopy. Kinetics studies revealed a linear increase in the graft concentration of PMMA and PPEGMA with the reaction time, indicating that the chain growth from the surface was consistent with a ''controlled'' or ''living'' process. The living chain ends were used as the macroinitiator for the synthesis of diblock copolymer brushes. Water contact angles on PVDF films were reduced by surface grafting of PEGMA and MMA.

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Grafting of polymer brushes from the poly(vinylidene fluoride) (PVDF) surfaces was carried out. The active species, such as peroxide and hydroperoxide, on the surface were generated via ultraviolet (UV) irradiation pretreatment in nitrogen, followed by air exposure. Homopolymer brushes of methyl methacrylate (MMA) were prepared by the surface-initiated free radical polymerization from the peroxide initiators on the PVDF surface. The peroxides formed on UV-treated and air-exposed PVDF surfaces were determined quantitatively by the reaction with 2,2-diphenyl-1-picrylhydrazyl (DPPH) in toluene. The chemical composition and topography of the graft-functionalized PVDF surfaces were characterized by X-ray photoelectron spectroscopy (XPS), attenuated total reflectance (ATR) FT-IR spectroscopy, and atomic force microscopy (AFM). ATR FT-IR revealed an increase in the graft concentration of poly(methyl methacrylate) (PMMA) on PVDF surfaces with an increase of the UV irradiation pretreatment time. Water contact angles on PVDF surfaces were reduced by surface grafting of PMMA.