Catalytic Chain Transfer Polymerization to Functional Reactive End Groups for Controlled Free Radical Growth

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2020
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10.1021/acs.macromol.0c00241
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Macromolecules ; 53 (2020), 7. - pp. 2362-2368. - American Chemical Society (ACS). - ISSN 0024-9297. - eISSN 1520-5835
Abstract
Alkoxyamine-functionalized silane functions as a chain transfer reagent in ethylene polymerization catalyzed by cationic palladium diimine complexes, without significant adverse effects in productivity or yield. Under conditions of limited chain transfer by β-hydride elimination, this approach highly selectively results in alkoxyamine-terminated hyperbranched polyethylenes (PEs) and multiple (up to 5) functionalized PE chains per active metal site. Stoichiometric NMR spectroscopic investigations indicate that the first chain transfer generates a saturated chain end, while all following polymer chains are initiated by (functionalized) silyl groups. Alkoxyamine-functionalized hyperbranched PEs obtained by this approach are suitable precursors for nitroxide-mediated radical polymerizations. This allows for harnessing different chain growth mechanisms (catalytic insertion/free radical) for generation of PE–polyacrylate and PE–polystyrene block copolymers.
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ISO 690STADLER, Sonja M., Inigo GÖTTKER-SCHNETMANN, Amelie S. FUCHS, Stephan R. R. FISCHER, Stefan MECKING, 2020. Catalytic Chain Transfer Polymerization to Functional Reactive End Groups for Controlled Free Radical Growth. In: Macromolecules. American Chemical Society (ACS). 53(7), pp. 2362-2368. ISSN 0024-9297. eISSN 1520-5835. Available under: doi: 10.1021/acs.macromol.0c00241
BibTex
@article{Stadler2020-04-14Catal-49434,
  year={2020},
  doi={10.1021/acs.macromol.0c00241},
  title={Catalytic Chain Transfer Polymerization to Functional Reactive End Groups for Controlled Free Radical Growth},
  number={7},
  volume={53},
  issn={0024-9297},
  journal={Macromolecules},
  pages={2362--2368},
  author={Stadler, Sonja M. and Göttker-Schnetmann, Inigo and Fuchs, Amelie S. and Fischer, Stephan R. R. and Mecking, Stefan}
}
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