Organosoluble star polymers from a cyclodextrin core

Well‐defined star polymers were synthesized with a combination of the core‐first method and atom transfer radical polymerization. The control of the architecture of the macroinitiator based on β‐cyclodextrin bearing functional bromide groups was determined by ¹³C NMR, fast atom bombardment mass spectrometry, and elemental analysis. In a second step, the polymerization of the tert‐butyl acrylate monomer was optimized to avoid a star–star coupling reaction and allowed the synthesis of a well‐defined organosoluble polymer star. The determination of the macromolecular dimensions of these new star polymers by size exclusion chromatography/light scattering was in agreement with the structure of armed star polymers in a large range of predicted molecular weights. This article describes a new approach to polyelectrolyte star polymers by postmodification of poly(tert‐butyl acrylate) by acrylic arm hydrolysis in a water‐soluble system. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5186–5194, 2005