ARGET ATRP of Methyl Acrylate with Inexpensive Ligands and ppm Concentrations of Catalyst

Abstract

A simple and versatile polymerization technique via activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) of methyl acrylate (MA) with inexpensive commercially available ligands, including diethylenetriamine (DETA), N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA), and tris(2-aminoethyl)amine (TREN), is reported. Catalytic amounts of catalyst were utilized achieving ppm levels of CuIIBr2/L in the presence of a zerovalent copper metal (i.e., copper powder or wire) at 25 °C. High molecular weight poly(methyl acrylate) (PMA) could also be obtained with Mn > 1.5 million and Mw/Mn ∼ 1.25. A “map” was generated, illustrating minimal catalyst concentrations (i.e., copper and ligand) required over a range of targeted degrees of polymerization with various ligands. Several conclusions were made: (1) lower catalyst concentrations require higher targeted degrees of polymerization to produce equally controlled polymerizations, (2) higher catalyst concentrations are necessa...