Atom transfer radical polymerization directly from poly(vinylidene fluoride): Surface and antifouling properties

Abstract

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

Improved Permeate Flux of PVDF Ultrafiltration Membrane Containing PVDF-g-PHEA Synthesized via ATRP

“…ATRP is utilized for polymerization of polymers containing halogen atoms and hydrophilic polymers containing styrene, (meth)acrylates, (meth)acrylamides and acrylonitrile structures as the simple polymerization method which does not require strict experiment environment, comparing to other traditional polymerization methods [12,13]. In advance, numerous graft copolymers such as poly(vinylidene fluoride)-graft-poly(ethylene glycol) methyl ether methacrylate (PVDF-g-PEGMA) and poly(vinylidene fluoride)-graft-poly(oxyethylene methacrylate) (PVDF-g-POEM) were successfully made by using ATRP method [14,15].…”

Facile approach to functionalizing polymers with specific chemical groups by an ozone treatment: Preparation of crosslinkable poly(vinylidene fluoride) possessing benzoxazine pendent groups

“…[11][12][13][14] Polymer modification and functionalization are then performed by sequential grafting polymerization initiated with the active groups generated from irradiation. Recently, Chen and coworkers 15,16 reported atom transfer radical polymerization and reversible addition-fragmentation chain transfer polymerization directly initiated from the surface of a PVDF film. However, polymer modification with specific chemical groups, rather than long polymer chains, is not achievable with the irradiation and grafting polymerization method.…”

Synthesis of Terpolymers with Homogeneous Composition by Free Radical Copolymerization of Maleic Anhydride, Perfluorooctyl and Butyl or Dodecyl Methacrylates: Application of the Continuous Flow Monomer Addition Technique

“…Due to their outstanding chemical resistance, thermal stability as well as low friction coefficient and flame retardation [1], fluorinated and partly fluorinated polymers have found many industrial applications, e.g., as friction modifiers [2], anti-fouling coatings [3] or membranes [4,5]. Homopolymerization of fluorinated monomers such as perfluoroolefins, (meth) acrylates with perfluorinated chains or fluorinated styrene derivatives leads to polymers with high fluorine content.…”

“…4 21 ± 2 65 ± 2 14 ± 2 MAH, maleic anhydride; BMA, n-butyl methacrylate; F8H2MA, 1H,1H,2H,2H-perfluorodecyl methacrylate. 1 Determined by 1 H NMR spectroscopy; 2 7 h after the post-addition phase; 3 Conversion calculated for 33 h; 4 As determined from low conversion experiment. The low deviation of incorporated monomers (dF/dt) and its constancy in time seems to be caused by a minimal error in monomer addition rates.…”