Photoresponsive poly(methyl methacrylate)2–(polystyrene)2 miktoarm star copolymer containing an azobenzene moiety at the core

We prepared a novel miktoarm star copolymer with an azobenzene unit at the core via combination of atom transfer radical polymerization (ATRP) and nitroxide‐mediated free radical polymerization (NMP) routes. For this purpose, first, mikto‐functional initiator, 3, with tertiary bromide (for ATRP) and 2,2,6,6‐tetramethylpiperidin‐1‐yloxy (TEMPO) (for NMP) functionalities and an azobenzene moiety at the core was synthesized. The initiator 3 thus obtained was used in the subsequent living radical polymerization routes such as ATRP of MMA and NMP of St, respectively, to give A2B2 type miktoarm star copolymer, (PMMA)2‐(PSt)2 with an azobenzene unit at the core with controlled molecular weight and low polydispersity (Mw/Mn < 1.15). The photoresponsive properties of 3 and (PMMA)2‐(PSt)2 miktoarm star copolymer were investigated.