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

Abstract [C12mim][BF4], [C8mim][BF4], and [C4mim][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 [C12mim][BF4] was considerably faster than in [C8mim][BF4] and [C4mim][BF4]. ARGET ATRP of AN in [C12mim][BF4] were better controlled than in [C8mim][BF4] and [C4mim][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 [C12mim][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.