Preparation of H-shaped ABCAB terpolymers by atom transfer radical coupling

Authors

  • Xiaolan Luo,

    1. The Key Laboratory of Molecular Engineering of Polymer, State Education Ministry of China, Department of Macromolecular Science, Fudan University, Shanghai 200433, China
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  • Guowei Wang,

    1. The Key Laboratory of Molecular Engineering of Polymer, State Education Ministry of China, Department of Macromolecular Science, Fudan University, Shanghai 200433, China
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  • Junlian Huang

    Corresponding author
    1. The Key Laboratory of Molecular Engineering of Polymer, State Education Ministry of China, Department of Macromolecular Science, Fudan University, Shanghai 200433, China
    • The Key Laboratory of Molecular Engineering of Polymer, State Education Ministry of China, Department of Macromolecular Science, Fudan University, Shanghai 200433, China
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Abstract

H-shaped ABCAB terpolymers composed of polystyrene (PS) (A), poly(ethylene oxide) (PEO) (B), and poly(tert-butyl acrylate) (PtBA) (C) were prepared by atom transfer radical coupling reaction using ABC star terpolymers as precursors, CuBr and N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA) as catalysts, and nanosize copper as the reducing agent. The synthesis of 3-miktoarm star terpolymer PS-PEO-(PtBA-Br) involved following steps: (1) the preparation of PS with an active and an ethoxyethyl-ptotected hydroxyl group at the same end; (2) the preparation of diblock copolymer PS-b-PEO with ethoxyethyl-protected group at the junction point through the ring-opening polymerization (ROP) of EO; (3) after de-protection of ethoxyethyl group and further modification of hydroxyl group, tBA was polymerized by atom transfer radical polymerization using PS-b-PEO with 2-bromoisobutyryl functional group as macroinitiator. The H-shaped terpolymer could be successfully formed by atom transfer radical coupling reaction in the presence of small quantity of styrene, CuBr/PMDETA, and Cu at 90 °C. The copolymers were characterized by SEC, 1H NMR, and FTIR in detail. The optimized coupling temperature is 90 °C. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 59–68, 2009

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