Reaction of oligoalcohols with diepoxides: An easy,one‐pot way to star‐shaped,multibranched polymers. II. Poly(ethylene oxide) stars—synthesis and analysis by size exclusion chromatography triple‐detection method

An Erratum has been published for this article in Journal of Polymer Science Part A: Polymer Chemistry (2004) 42(10) 2575‐2576 Starlike, highly branched (A_xB_yA_z) macromolecules having from a few to 100 arms and molar masses up to 10⁵ were prepared in three stages with the one‐pot, arms‐core‐arms method (B_y stands for y molcules of former diepoxides introduced into the core). Oligoalcohols, at least partially converted into their alcoholate counterpart states, reacted with diepoxy compounds giving star‐shaped, highly branched macromolecules. With the properly chosen conditions, complete conversion of both starting components was achieved. In this article homostars built with the first and second generation of poly(ethylene oxide) arms (A_x and A_z, respectively) are described. The number of arms (f) was determined either by direct measurements of the number‐average molcular weight (M_n) of the first and second stars (M_n of arms A_x and A_z is known) or by calculating f from branching indices g and g′ determined from the radius of gyration and the limited viscosity number measured with size exclusion chromatography (SEC) triple detection with TriSEC software. For a few samples, M_n was measured with high‐speed membrane osmometry. The progress of the stars' formation was monitored by ¹H NMR, SEC, and matrix‐assisted laser desorption/ionization time‐of‐flight methods. Functionalization of the ? OH end groups in the second generation of arms was observed by ¹H and/or ³¹P NMR. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1576–1598, 2004