Abstract

AbstractThis article discusses the characterization of arborescent (hyperbranched) polyisobutylenes (arb‐PIBs) by size exclusion chromatography and differential scanning calorimetry, in comparison with linear PIB standards. The radius of gyration (〈r〉1/2 = Rz), measured from the angle dependence of light scattering of high‐molecular‐weight arb‐PIBs, was significantly larger than the hydrodynamic radius (Rh) from size exclusion chromatography/viscometry, and the Rh values were significantly smaller than Rh of linear PIBs. The glass‐transition temperature of arb‐PIBs having a branch molecular weight higher than the critical entanglement molecular weight was dependent on both the total number‐average molecular weight and BR up to BR ∼ 15. A modified Fox–Flory equation is proposed to describe the effect of architecture on the thermal transition. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1770–1776, 2006

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