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Anionic polymerization of ethylene oxide with cryptates as counterions: 2
Authors:Alain Deffieux  Ernest Graf  Sylvie Boileau
Affiliation:Laboratoire de Chimie Macromoléculaire associé au CNRS, Université Pierre et Marie Curie, T. 44, 4, place Jussieu, 75 230 Paris Cedex 05, France;Institut Le Bel, Université Louis Pasteur, 4, rue Blaise Pascal, 67 000 Strasbourg, France;Laboratoire de Chimie Macromoléculaire associé au CNRS, Collège de France, 11, place Marcelin Berthelot, 75 231 Paris Cedex 05, France
Abstract:A kinetic study of the anionic polymerization of ethylene oxide has been made in tetrahydrofuran at 20°C, with the cryptate Cs+ + TC] as counterion, TC] being a spheroidal macrotricyclic ligand. Conductance measurements have been made on THF solutions of ?4BCs + TC]. Ionic associations higher than cryptated ion pairs are negligible for living end concentrations lower than 3 × 10?4 moll?1. k± and the alkoxide ion pair dissociation constant KD were determined from both sets of kinetic data obtained with and without added salt knowing the value of k? from kinetic data performed with K+ + 222] as counterion. Free alkoxide ions are about twenty times more reactive than cryptated caesium ion pairs.
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