Functionalized poly(oxanorbornene)-block-copolymers: Preparation via ROMP/click-methodology

Authors

  • Christian Kluger,

    1. Division of Macromolecular Chemistry, Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9/163/MC, A-1060 Wien, Austria
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  • Wolfgang H. Binder

    Corresponding author
    1. Division of Macromolecular Chemistry, Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9/163/MC, A-1060 Wien, Austria
    • Division of Macromolecular Chemistry, Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9/163/MC, A-1060 Wien, Austria
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Abstract

Block copolymers on basis of poly(oxanorbornenes) bearing functional moieties in their side-chains are prepared via a combination of ROMP-methods and 1,3-dipolar-“click”-reactions. Starting from N-substituted-ω-bromoalkyl-oxanorbornenes and alkyl-/perfluoroalkyl-oxanorbornenes, block copolymers with molecular weights up to 25,000 g mol−1 were generated. Subsequent nucleophilic exchange-reactions yielded the block-copolymers functionalized with ω-azidoalkyl-moieties in one block. The 1,3-azide/alkine-“click” reactions with a variety of terminal alkynes in the presence of a catalyst system consisting of tetrakis(acetonitrile)hexafluorophosphate copper(I) and tris(1-benzyl-5-methyl-1H- [1,2,3]triazol-4-ylmethyl)-amine furnished the substituted block copolymers in high yields, as proven by NMR-spectroscopy. The resulting polymers were investigated via temperature-dependent SAXS-methods, revealing their microphase separated structure as well as their temperature-dependent behavior. The presented method offers the generation of a large set of different block-copolymers from only a small set of starting materials because of the high versatility of the “click” reaction, thus enabling a simple and complete functionalization after the initial polymerization reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 485–499, 2007

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