Living Aqueous Microemulsion Polymerization of Ethylene with Robust Ni(II) Phosphinophenolato Catalysts

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2021
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urn:nbn:de:bsz:352-2-jh5capdzbn735
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10.1021/jacs.1c10488
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Journal of the American Chemical Society ; 143 (2021), 49. - pp. 20605-20608. - American Chemical Society (ACS). - ISSN 0002-7863. - eISSN 1520-5126
Abstract
Due to chain transfer events being competitive with chain growth, ethylene polymerization by P,O-chelated Ni(II) complexes usually affords low molecular weight polymers or oligomers. We now show that appropriately bulky substituted phosphinophenolato Ni(II) can polymerize in a living fashion, virtually devoid of chain transfer. Aqueous polymerizations with microemulsions of [κ2-P,O-2-(2-(2',6'-(MeO)2C6H3)C6H4)(Ph)P-6-(3',5'-(CF3)2C6H3)C6H3O-NiMe(pyridine)] (3) at 30 °C yield polyethylenes with narrow molecular weight distributions (Mw/Mn 1.02 to 1.34) and ultrahigh molecular weights (up to 2 × 106) in the form of aqueous nanoparticle dispersions. Catalyst stability and activity are maintained up to 70 °C in water.
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ISO 690LIN, Fei, Tobias O. MORGEN, Stefan MECKING, 2021. Living Aqueous Microemulsion Polymerization of Ethylene with Robust Ni(II) Phosphinophenolato Catalysts. In: Journal of the American Chemical Society. American Chemical Society (ACS). 143(49), pp. 20605-20608. ISSN 0002-7863. eISSN 1520-5126. Available under: doi: 10.1021/jacs.1c10488
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@article{Lin2021-12-15Livin-55985,
  year={2021},
  doi={10.1021/jacs.1c10488},
  title={Living Aqueous Microemulsion Polymerization of Ethylene with Robust Ni(II) Phosphinophenolato Catalysts},
  number={49},
  volume={143},
  issn={0002-7863},
  journal={Journal of the American Chemical Society},
  pages={20605--20608},
  author={Lin, Fei and Morgen, Tobias O. and Mecking, Stefan}
}
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    <dcterms:abstract xml:lang="eng">Due to chain transfer events being competitive with chain growth, ethylene polymerization by P,O-chelated Ni(II) complexes usually affords low molecular weight polymers or oligomers. We now show that appropriately bulky substituted phosphinophenolato Ni(II) can polymerize in a living fashion, virtually devoid of chain transfer. Aqueous polymerizations with microemulsions of [κ&lt;sup&gt;2&lt;/sup&gt;-P,O-2-(2-(2',6'-(MeO)&lt;sub&gt;2&lt;/sub&gt;C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;3&lt;/sub&gt;)C6H4)(Ph)P-6-(3',5'-(CF&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;3&lt;/sub&gt;)C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;3&lt;/sub&gt;O-NiMe(pyridine)] (3) at 30 °C yield polyethylenes with narrow molecular weight distributions (M&lt;sub&gt;w&lt;/sub&gt;/M&lt;sub&gt;n&lt;/sub&gt; 1.02 to 1.34) and ultrahigh molecular weights (up to 2 × 10&lt;sup&gt;6&lt;/sup&gt;) in the form of aqueous nanoparticle dispersions. Catalyst stability and activity are maintained up to 70 °C in water.</dcterms:abstract>
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