Atom Transfer Radical Polymerization Using Activators Regenerated by Electron Transfer of Acrylonitrile in 1-(1-Ethoxycarbonylethyl)-3-methylimidazolium Hexafluorophosphate

Atom transfer radical polymerization using activators regenerated by electron transfer (ARGET ATRP) of acrylonitrile (AN) was first approached with 1-(1-ethoxycarbonylethyl)-3-methylimidazolium tetrafluoroborate ([ecemim][BF4]) as reaction medium and tin(II) bis(2-ethylhexanoate) (Sn(EH)2) as reducing agent in the presence of air. When compared with in bulk, an obvious increase of polymer isotacticity was observed for ARGET ATRP of AN in 1-(1-ethoxycarbonylethyl)-3-methylimidazolium hexafluorophospate ([ecemim][PF6]), the reaction rate of ARGET ATRP of AN in [ecemim][PF6] was higher and the polymerization process was better controlled. The block copolymer polyacrylonitrile-block-poly(methyl methacrylate) with molecular weight at 69,750, distribution at 1.34, and isotacticity at 0.36 was successfully obtained in [ecemim][PF6]. [Ecemim][PF6] and the catalyst system were recycled and reused and had no effect on the living nature of polymerization. © 2010 Wiley Periodicals, Inc.