Summary: Controlled polymerization of N‐isopropylacrylamide (NIPAAM) was achieved by atom transfer radical polymerization (ATRP) using ethyl 2‐chloropropionate (ECP) as initiator and CuCl/tris(2‐dimethylaminoethyl)amine (Me6TREN) as a catalytic system. The polymerization was carried out in DMF:water 50:50 (v/v) mixed solvent at 20 °C. The first order kinetic plot was linear up to 92% conversion. Controlled molecular weights up to 2.2 × 104 and low polydispersities (1.19) were obtained. The living character of the polymerization was also demonstrated by self‐blocking experiments. Block copolymers with N,N‐dimethylacrylamide (DMAAM) and 3‐sulfopropyl methacrylate (SPMA) were successfully prepared.
Molecular weights and polydispersities of polyNIPAAM versus NIPAAM conversion for two different degrees of polymerization.