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

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 (M_w/M_n'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 M_w/M_n = 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 M_w/M_n'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