Controlled grafting from poly(vinylidene fluoride) films by surface‐initiated reversible addition–fragmentation chain transfer polymerization

Abstract

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.

Living Radical Polymerization by the RAFT Process—A First Update

“…PVDF-graft-(PMMA-block-PDMAEMA) and PVDF-graft-(PPGEMAblock-PDMAEMA) were prepared. [238] Other papers cover RAFT polymerization of AA/65 from a PVDF surface previously irradiated with an electron beam [115] and graft copolymerization from a PP surface was achieved by gamma-irradiation of a solution of styrene and 1-(2-isocyanatopropan-2-yl)-3-(propen-2-yl)benzene and 38 in the presence of a PP 'lantern'. [239] Several papers report the use of RAFT polymerization to prepare a backbone polymers/macroinitiator for comb polymer synthesis.…”

Preparation and characterization of poly(vinylidene fluoride) (PVDF) based ultrafiltration membranes using nano γ-Al2O3

“…Surface modification and blending techniques are mostly adapted due to their versatile controlling conditions. Surface modification methods include plasma [1][2][3], UV [4][5][6][7], electron beam surface induced grafting polymerization [8][9][10][11], and surface living/controlled radical polymerization [12][13][14][15][16][17][18]. Blending methods usually involve some amphiphilic copolymers, requiring to be synthesized elaborately through atom transfer radical polymerization (ATRP) [19][20][21] or reversible addition-fragmentation chain transfer polymerization (RAFT) [3,22].…”

Toward New Materials Prepared via the RAFT Process: From Drug Delivery to Optoelectronics?

“…They successfully synthesized PHEMA brushes via the RAFT process from the pretreated substrate (O 2 plasma) and claimed that these biointerfaces are very promising [169]. A similar 'grafting-from' strategy was used to tether poly(methyl methacrylate) (PMMA) and poly(ethyelene glycol) monomethacrylate (PEGMA) brushes via the RAFT process on azo-functionalized poly(vinylidene fluoride) (PVDF) surfaces [170]. Another strategy was proposed by Grasselli and Betz using an electron-beam-induced RAFT-mediated graft polymerization.…”