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Heteroarm H-shaped terpolymers through the combination of the Diels–Alder reaction and controlled/living radical polymerization techniques



Heteroarm H-shaped terpolymers (PS)(PtBA)–PEO–(PtBA)(PS) and (PS)(PtBA)–PPO–(PtBA)(PS) [where PS is polystyrene, PtBA is poly(tert-butyl acrylate), PEO is poly(ethylene oxide), and PPO is poly(propylene oxide)], containing PEO or PPO as a backbone and PS and PtBA as side arms, were prepared via the combination of the Diels–Alder reaction and atom transfer radical and nitroxide-mediated radical polymerization routes. Commercially available PEO or PPO containing bismaleimide end groups was reacted with a compound having an anthracene functionality, succinic acid anthracen-9-yl methyl ester 3-(2-bromo-2-methylpropionyloxy)-2-methyl-2-[2-phenyl-2-(2,2,6,6-tetramethylpiperidin-1-yloxy)ethoxycarbonyl]propyl ester, with a Diels–Alder reaction strategy. The obtained macroinitiator with tertiary bromide and 2,2,6,6-tetramethylpiperidin-1-oxy functional end groups was used subsequently in the atom transfer radical polymerization of tert-butyl acrylate and in the nitroxide-mediated free-radical polymerization of styrene to produce heteroarm H-shaped terpolymers with moderately low molecular weight distributions (<1.31). The polymers were characterized with 1H NMR, ultraviolet, gel permeation chromatography, and differential scanning calorimetry. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3947–3957, 2006