Multi-functionalization of poly(vinylidene fluoride) membranes via combined “grafting from” and “grafting to” approaches

PVDF-g-[PBIEM-co-PPMA] graft copolymers were first synthesized in a "grafting from" process, involving thermally induced graft copolymerization of two inimers, 2-(2-bromoisobutyryloxy)ethyl methacrylate (BIEM) and propargyl methacrylate (PMA), from ozone-preactivated poly(vinylidene fluori...

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Bibliographic Details
Published in:Soft matter 2011-01, Vol.7 (23), p.11133-11143
Main Authors: Cai, Tao, Wang, Rong, Yang, Wen Jing, Lu, Shengjie, Neoh, Koon-Gee, Kang, En-Tang
Format: Article
Language:English
Subjects:
Addition polymerization
Bacteria
Brushes
Fluorides
Grafting
Membranes
Polymerization
Polyvinylidene fluorides
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Summary:PVDF-g-[PBIEM-co-PPMA] graft copolymers were first synthesized in a "grafting from" process, involving thermally induced graft copolymerization of two inimers, 2-(2-bromoisobutyryloxy)ethyl methacrylate (BIEM) and propargyl methacrylate (PMA), from ozone-preactivated poly(vinylidene fluoride) (PVDF) chains. Microporous membranes were fabricated from the PVDF-g-[PBIEM-co-PPMA] copolymers by phase inversion in an aqueous medium. The tertiary C-Br groups of BIEM repeat units and the propargyl groups of PMA repeat units on the PVDF-g-[PBIEM-co-PPMA] membrane and pore surfaces provided the respective functionalities for the "grafting from" process involving surface-initiated atom transfer radical polymerization (ATRP) of the viologen-containing monomer, N-benzyl-N[prime or minute]-(4-vinylbenzyl)-4,4[prime or minute]-bipyridium dichloride (BVbpy), and the "grafting to" process involving alkyne-azide click reaction with azido-terminated poly(N-isopropylacrylamide) (PNIPAM-N3), prepared a priori via reversible addition-fragmentation chain transfer (RAFT) polymerization. The resulting PVDF-g-[P(BIEM-g-PBVbpy)-co-P(PMA-click-PNIPAM)] membrane exhibited both redox- and temperature-dependent permeability to aqueous solutions. Alternatively, metal ions, such as Ag, Au or Pt ions, can be immobilized and reduced within the viologen-containing PBVbpy brushes on the PVDF-g-[P(BIEM-g-PBVbpy)-co-PPMA] membrane. The functionalized PVDF-g-[P(BIEM-g-PBVbpy)-co-PPMA]-Ag membrane surfaces were shown to be effective in reducing bacterial adhesion and fouling under continuous-flow conditions.
ISSN:1744-683X
1744-6848
DOI:10.1039/c1sm06039b