Preparation of ABC miktoarm star terpolymer containing poly(ethylene glycol), polystyrene,and poly(tert‐butylacrylate) arms by combining diels–alder reaction,atom transfer radical,and stable free radical polymerization routes

The ABC type miktoarm star terpolymer was prepared utilizing “core‐in” and “core‐out” methods via combination of Diels–Alder reaction (DA), stable free radical polymerization (SFRP), and atom transfer radical polymerization (ATRP). First, in DA reaction, poly(ethylene glycol)‐maleimide (PEG‐maleimide) precursor was reacted with succinic acid anthracen‐9‐ylmethyl ester 3‐(2‐bromo‐2‐methyl‐propionyloxy)‐2‐methyl‐2‐[2‐phenyl‐2‐(2,2,6,6‐tetramethyl‐piperidin‐1‐yloxy)‐ethoxy‐carbonyl]‐propyl ester, 8 , to give DA adduct, 9 , which has appropriate functional groups for SFRP and ATRP. Second, a previously obtained 9 was used as a macroinitiator for SFRP of styrene at 125 °C. As a third step, this PEG‐polystyrene (PEG‐PSt) precursor with a bromine functionality in the core was employed as a macroinitiator for ATRP of tert‐butylacrylate (tBA) in the presence of Cu(I)Br and pentamethyldiethylenetriamine at 80 °C to give ABC type miktoarm star terpolymer (PEG‐PSt‐PtBA) with controlled molecular weight and low polydispersity (M_w/M_n < 1.27). The obtained polymers were characterized by gel permeation chromatography and ¹H NMR. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 499–509, 2006