Direct synthesis of well-defined poly[{2-(methacryloyloxy)ethyl} trimethylammonium chloride] brush via surface-initiated atom transfer radical polymerization in fluoroalcohol

Motoyasu Kobayashi, Masami Terada, Yuki Terayama, Moriya Kikuchi, Atsushi Takahara

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A well-defined cationic polymer and polymer brush were simultaneously prepared by copper-catalyzed atom transfer radical polymerization (ATRP) of 2-(methacryloxy)ethyltrimethylammonium chloride (MTAC) in 2,2,2-trifluoroethanol (TFE) at 60 °C initiated with ethyl 2-bromoisobutylate and the corresponding alkylbromide immobilized on silicon wafer. ATRP of MTAC in TFE as well as aqueous solution proceeded quickly but in a poorly controlled manner, leading to a relatively higher molecular weight distribution (MWD) than M w/Mn = 1.3, where Mw and Mn are weight-average and number-average molecular weights, respectively. Addition of a small amount of isopropyl alcohol to the TFE-based reaction mixture reduced the polymerization rate and produced a poly(MTAC) with predictable molecular weight and narrower MWD than 1.19. The Mn of poly(MTAC) was controllable in the range 104-105 g mol-1 based on the molar ratio of monomer and initiator in the feed. The Mn of the brush on a flat silicon wafer matched that of the free poly(MTAC). The graft density of poly(MTAC) was 0.20 chains nm-2. The ATRP of MTAC in TFE/1-ethyl-3-methylimidazolium chloride (EMImCl) also proceeded in a controlled manner at 60 °C, yielding polymers with narrow MWDs (Mw/M n = 1.12-1.13). Analysis of the 13C NMR spectra of the carbonyl region of the resulting poly(MTAC)s revealed that syndiotactic-rich configurations were produced by ATRP of MTAC in aqueous solution, TFE/isopropyl alcohol, and TFE/EMImCl. The solvent effect of TFE and ionic liquid on the tacticity of polymer was negligible.

Original languageEnglish
Pages (from-to)8409-8415
Number of pages7
Issue number20
Publication statusPublished - Oct 26 2010


All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

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