Miktoarm star copolymers of poly(ε-caprolactone) from a novel heterofunctional initiator

Abstract

A novel heterofunctional initiator, synthesized from pentaerythritol in a three step reaction sequence with two ring opening polymerization (ROP) and two atom transfer radical polymerization (ATRP) initiating sites, was used to prepare A2B2 miktoarm star copolymers of poly(ε-caprolactone), PεCL, with polystyrene, PS, poly(methyl methacrylate), PMMA, poly(dimethylaminoethyl methacrylate), PDMAEMA, and poly(2-hydroxyethyl methacrylate), PHEMA. A2B miktoarm stars, A being PεCL or poly(δ-valerolactone), PδVL and B PS were also prepared from ω,ω-dihydroxy-PS, synthesized from ω-Br-PS and serinol, by ROP of εCL or δVL. All polymers were characterized by size exclusion chromatography, 1H NMR spectroscopy, and membrane osmometry. © 2007 Wiley Periodicals, Inc.