Controlled/living radical polymerization. Atom transfer radical polymerization using multidentate amine ligands

TLDR: In this article, three multidentate amines, tetramethylethylenediamine (TMEDA), N,N,NN, N',N' and N'N' were used as new ligands in the copper mediated atom transfer radical polymerization (ATRP) of styrene, methyl acrylate and methyl methacrylate.

Abstract: Three multidentate amines, tetramethylethylenediamine (TMEDA), N,N,N‘,N‘,N‘‘-pentamethyldiethylenetriamine (PMDETA) and 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA) have been successfully used as new ligands in the copper mediated atom transfer radical polymerization (ATRP) of styrene, methyl acrylate and methyl methacrylate. All the polymerizations were well controlled with a linear increase of molecular weights (Mn) with conversion and relatively low polydispersities throughout the reactions. Compared to the 2,2‘-bipyridine (bipy) based ligands, most multidentate amines are less expensive and the polymerization mixtures are less colored. In particular, the use of the tridentate PMDETA and the tetradentate HMTETA as the ligands resulted in faster polymerization rates for styrene and methyl acrylate than those using bipy as the ligand. This may be in part attributed to the fact that the coordination complexes between copper and the simple amines have lower redox potentials than the copper−bipy co...