ARGET ATRP of acrylonitrile with ionic liquid as reaction media and 1,1,4,7,7-pentamethyldiethylenetriamine as both ligand and reducing agent in the presence of air

[C(12)mim][BF4], [C(8)mim][BF4], and [C(4)mim][BF4] were first applied as reaction media for atom transfer radical polymerization using activators regenerated by electron transfer (ARGET ATRP) of acrylonitrile (AN) with 1,1,4,7,7-pentamethyldiethylenetriamine (PMDETA) as both ligand and reducing agent in the presence of air. The rate of polymerization in [C(12)mim][BF4] was considerably faster than in [C(8)mim][BF4] and [C(4)mim][BF4]. ARGET ATRP of AN in [C(12)mim][BF4] were better controlled than in [C(8)mim][BF4] and [C(4)mim][BF4] under the same experimental conditions. With an increase in the content of PMDETA, the polymerization provided an accelerated reaction rate and a broader polymer molecular weight distribution. A slow polymerization rate and a broad polydispersity index were observed using TMEDA instead of PMDETA as both ligand and reducing agent. There was an obvious induction period with CuCl2 instead of CuBr2 as catalyst. Well-defined PAN-b-PMMA with higher molecular weight at 104,560 and relatively broader distribution at 1.35 was successfully prepared with PAN as macroinitiator via ARGET ATRP in [C(12)mim][BF4] in the presence of air. The resultant fibers were obtained with the fineness at 1.17dtex and the tenacity at 6.03cN . dtex(-1). Copyright (C) 2010 John Wiley & Sons, Ltd.