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The potential of Cu(I)Cl/2,2′-bipyridine catalysis in a triblock copolymer preparation by atom transfer radical polymerization

Authors

  • Bohumil Masař,

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    1. Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovsky Sq. 2, 162 06 Prague 6, Czech Republic
    • Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovsky Sq. 2, 162 06 Prague 6, Czech Republic
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  • Petr Vlček,

    1. Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovsky Sq. 2, 162 06 Prague 6, Czech Republic
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  • Jaroslav Kříž

    1. Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovsky Sq. 2, 162 06 Prague 6, Czech Republic
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Abstract

The ability of atom transfer radical polymerization (ATRP) in the sequential synthesis of triblock copolymers was examined using Cu(I)Cl/2,2′-bipyridine catalysis at 110°C in toluene, starting from PMMA macroinitiators terminated with the C-Br group. The PMMAs were prepared by living anionic or group transfer polymerization (GTP), followed by bromination of the respective active site with Br2 or N-bromosuccinimide (NBS). The yield of the terminal bromination in the products of both living polymerizations was 60–64% at best, compared with the yield of the bromination of 1-methoxy-(1-trimethylsilyloxy)prop-1-ene (a model of the GTP active site) with NBS, as found by 1H-NMR. The PMMA macroinitiators prepared were utilized to start the sequential ATRP, finally affording PMMA-b-PBuA-b-PSt (Mn69,100), PMMA-b-PSt-b-PBuA (Mn21,300) and PMMA-b-PSt-b-PMMA (Mn35,200), which have not yet been synthesized by ATRP. After the second block has been formed, the Br-unterminated part of PMMA macroinitiator was removed by extraction or repeated precipitation. In the third (last) sequence polymerization, induction periods were observed. The first two triblock copolymers were free of precursors and have Mw/Mn values 1.5–1.6 (SEC). In the course of the last step of PMMA-b-PSt-b-PMMA synthesis, the content of the PMMA-b-PSt precursor slowly decreased with increasing MMA conversion. Still, at ≈90% MMA conversion, about 10–15% of the precursor remained in the product. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3514–3522, 2001

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