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

Abstract

Abstract A novel ligand, N , N , N ′, N ′, N ″‐penta (methyl acrylate) diethylenetriamine (MA 5 ‐DETA), was synthesized by the reaction of diethylenetriamine with methyl acrylate in almost quantitive yield. The polymerizations of methyl methacrylate with MA 5 ‐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/MA 5 ‐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/MA 5 ‐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/MA 5 ‐DETA/EBiB showed a better‐controlled nature. Moreover, the addition of CuBr 2 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