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Synthesis of Aqueous Polyethylene Dispersions with Electron-Deficient Neutral Nickel(II) Catalysts with Enolatoimine Ligands

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2007

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Yu, Sze-Man
Berkefeld, Andreas

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https://doi.org/10.1021/ma061804n
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Macromolecules. 2007, 40(3), pp. 421-428. ISSN 0024-9297. eISSN 1520-5835. Available under: doi: 10.1021/ma061804n

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A series of new, electron-poor neutral κ2-N,O chelated Ni(II) complexes were studied for ethylene polymerization in aqueous emulsion. Complexes based on enolatoimine ligands bearing electron-withdrawing trifluoromethyl and trifluoroacetyl groups [κ2-N,O-{2,6-R2C6H3NC(H)C(COCF3)C(O)CF3}]Ni(L)Me (4a, R = iPr, L = pyridine; 4b, R = 3,5-(CF3)2C6H3, L = pyridine; 5b, R = 3,5-(CF3)2C6H3, L = PPh3) were prepared. The complexes are very active in aqueous emulsions, with 1.4 × 104 TO h-1 for 4a (50 °C) and 1.9 × 104 TO h-1 for 4b (70 °C), affording stable polyethylene dispersions. The phosphine complex 5b is active in the absence of a phosphine scavenger, with similar activities as 4b. Polyethylenes of typically Mw 3 × 104 g mol-1 (Mw/Mn 2.0−2.5) with 25−50 branches per 1000 carbon atoms and Tm 94−112 °C are obtained.

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ISO 690YU, Sze-Man, Andreas BERKEFELD, Inigo GÖTTKER-SCHNETMANN, Gerhard MÜLLER, Stefan MECKING, 2007. Synthesis of Aqueous Polyethylene Dispersions with Electron-Deficient Neutral Nickel(II) Catalysts with Enolatoimine Ligands. In: Macromolecules. 2007, 40(3), pp. 421-428. ISSN 0024-9297. eISSN 1520-5835. Available under: doi: 10.1021/ma061804n
BibTex
@article{Yu2007-02Synth-42126,
  year={2007},
  doi={10.1021/ma061804n},
  title={Synthesis of Aqueous Polyethylene Dispersions with Electron-Deficient Neutral Nickel(II) Catalysts with Enolatoimine Ligands},
  number={3},
  volume={40},
  issn={0024-9297},
  journal={Macromolecules},
  pages={421--428},
  author={Yu, Sze-Man and Berkefeld, Andreas and Göttker-Schnetmann, Inigo and Müller, Gerhard and Mecking, Stefan}
}
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    <dcterms:abstract xml:lang="eng">A series of new, electron-poor neutral κ&lt;sup&gt;2&lt;/sup&gt;-N,O chelated Ni(II) complexes were studied for ethylene polymerization in aqueous emulsion. Complexes based on enolatoimine ligands bearing electron-withdrawing trifluoromethyl and trifluoroacetyl groups [κ&lt;sup&gt;2&lt;/sup&gt;-N,O-{2,6-R&lt;sub&gt;2&lt;/sub&gt;C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;3&lt;/sub&gt;NC(H)C(COCF&lt;sub&gt;3&lt;/sub&gt;)C(O)CF&lt;sub&gt;3&lt;/sub&gt;}]Ni(L)Me (4a, R =&lt;sup&gt; i&lt;/sup&gt;Pr, L = pyridine; 4b, R = 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;, L = pyridine; 5b, R = 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;, L = PPh&lt;sub&gt;3&lt;/sub&gt;) were prepared. The complexes are very active in aqueous emulsions, with 1.4 × 10&lt;sup&gt;4&lt;/sup&gt; TO h&lt;sup&gt;-1&lt;/sup&gt; for 4a (50 °C) and 1.9 × 10&lt;sup&gt;4&lt;/sup&gt; TO h&lt;sup&gt;-1&lt;/sup&gt; for 4b (70 °C), affording stable polyethylene dispersions. The phosphine complex 5b is active in the absence of a phosphine scavenger, with similar activities as 4b. Polyethylenes of typically Mw 3 × 10&lt;sup&gt;4 &lt;/sup&gt;g mol&lt;sup&gt;-1&lt;/sup&gt; (M&lt;sub&gt;w&lt;/sub&gt;/M&lt;sub&gt;n&lt;/sub&gt; 2.0−2.5) with 25−50 branches per 1000 carbon atoms and T&lt;sub&gt;m&lt;/sub&gt; 94−112 °C are obtained.</dcterms:abstract>
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