ARGET ATRP of 2-(dimethylamino)ethyl methacrylate as an intrinsic reducing agent

A study was conducted to initiate ARGET ATRP of DMAEMA by ethyl 2-bromoisobutyrate (EBiB) and catalyzed by a low level of CuCl 2/tris(2-pyridyl)methyl)amine (TPMA) complex in the presence of N2 and in the presence of limited air. It was observed that all reactions proceeded well, indicating that TPMA formed a stable complex and DMAEMA was unable to replace the ligand. The polymerizations were conducted without adding external reducing agents, while both polymerizations were well controlled, producing polymers with predictable controlled molecular weights and low polydispersities. It was also observed that polydispersity decreased with increase in monomer conversion. The study also demonstrated that a Cu deactivator, resulting from radical termination needs to be continuously regenerated to a Cu activator in ARGET ATRP, by an excess of reducing agents.