N,N,N′,N′,N″‐penta(methyl acrylate)diethylenetriamine: A novel ligand for atom transfer radical polymerization of methyl methacrylate

Abstract A novel ligand, N,N,N′,N′,N″‐penta (methyl acrylate) diethylenetriamine (MA5‐DETA), was synthesized by the reaction of diethylenetriamine with methyl acrylate in almost quantitive yield. The polymerizations of methyl methacrylate with MA5‐DETA as the ligand and α,α‐dichlorotoluene (DCT) and ethyl 2‐bromoisobutyrate (2‐EBiB) as the initiators, respectively, under different conditions were examined. The polymerization with CuCl/MA5‐DETA/DCT was closely controlled in bulk and gave polymers with quite narrow molecular weight distributions (Mw/Mn's) of 1.16–1.29. The polymerization with the system CuBr/MA5‐DETA/EBiB in bulk gave high activity. However, the system was not well controlled and gave the polymers with Mw/Mn = 1.35–1.53. The solution polymerization in anisole with CuBr/MA5‐DETA/EBiB showed a better‐controlled nature. Moreover, the addition of CuBr2 into the aforementioned system can further improve its controllability. The Mw/Mn's of the resulting polymers ranged from 1.11 to 1.21. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1963–1969, 2004