Reverse ATRP of ethyl acrylate with ionic liquids as reaction medium

Abstract

Abstract Novel ionic liquids, [C 12 mim][BF 4 ], [C 8 mim][BF 4 ] and [C 4 mim][BF 4 ], were firstly used as the reaction media for reverse atom transfer radical polymerization of ethyl acrylate (EA) initiated by azobisisobutyronitrile (AIBN) with CuBr 2 and N , N , N ′, N ″, N ″-pentamethyl diethylene triamine (PMDETA) as catalyst and ligand. Compared with the polymerization in [C 8 mim][BF 4 ] and [C 4 mim][BF 4 ], the polymerization in [C 12 mim][BF 4 ] not only showed better control of molecular weight and narrower molecular weight distribution but also provided more rapid reaction rate with the ratio of [EA]:[AIBN]:[CuBr 2 ]:[PMDETA] at 400:1:3:4. Block copolymer PEA-b-PSt was obtained via a conventional ATRP process in [C 12 mim][BF 4 ] by using the resulting PEA as macroinitiator. [C 12 mim][BF 4 ] and CuBr 2 /PMDETA could be easily recycled and reused and had no effect on the living nature of reverse atom transfer radical polymerization of EA.