Abstract: | Supramolecular complexes of alkali metals were used as catalysts in the polymerization of isoprene via a two‐electron‐transfer mechanism. The obtained polyisoprene, having a living end group, was subsequently used to initiate methyl methacrylate polymerization in tetrahydrofuran. Polyisoprene–poly(methyl methacrylate) block copolymers were obtained, and their structure was established with 1H NMR, gel permeation chromatography, differential scanning calorimetry, and experiments of selective extraction. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1086–1092, 2006 |