Catalytic ethylene polymerisation in carbon dioxide as a reaction medium with soluble nickel(II) catalysts

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2006
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Bastero, Amaia
Franciò, Giancarlo
Leitner, Walter
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A series of neutral NiII salicylaldiminato complexes substituted with perfluorooctyl- and trifluoromethyl groups, [Ni{k2-N,O-6-C(H)=NAr-2,4- R 2C6H2O}(Me)(pyridine)] (6a: Ar=2,6-{4-(F17C8)C6H4}2C6H3, R =I; 6b: Ar=2,6-{4-(F3C)C6H4}2C6H3, R =I; 6c: Ar= 2,6-{3,5-(F3C)2C6H3}2C6H3, R =3,5-(F3C)2C6H3 ; 6d: Ar=2,6-{4-(F17C8)C6H4}2C6H3, R =3,5-(F3C)2-C6H3 ; 6e: Ar=2,6-{3,5-(F3C)2C6H3}2-C6H3, R =I) were studied as catalyst precursors for ethylene polymerisation in supercritical CO2.Catalyst precursors 6a and 6c, which are soluble in scCO2, afford the highest polymer yields, corresponding to 2x 103 turnovers.Semicrystallin e polyethylene (Mn typically 104 gmol -1) is obtained with variable degrees of branching (11 to 24 branches per 1000 carbon atoms, predominantly Me branches) and crystallinities (54 to 21%), depending on the substitution pattern of the catalyst.

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540 Chemie
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carbon dioxide, fluorinated ligands, homogeneous catalysis, nickel, polyethylene, polymerization
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ISO 690BASTERO, Amaia, Giancarlo FRANCIÒ, Walter LEITNER, Stefan MECKING, 2006. Catalytic ethylene polymerisation in carbon dioxide as a reaction medium with soluble nickel(II) catalysts. In: Chemistry - A European Journal. 2006, 12(23), pp. 6110-6116. ISSN 0947-6539. eISSN 1521-3765. Available under: doi: 10.1002/chem.200600499
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@article{Bastero2006Catal-10062,
  year={2006},
  doi={10.1002/chem.200600499},
  title={Catalytic ethylene polymerisation in carbon dioxide as a reaction medium with soluble nickel(II) catalysts},
  number={23},
  volume={12},
  issn={0947-6539},
  journal={Chemistry - A European Journal},
  pages={6110--6116},
  author={Bastero, Amaia and Franciò, Giancarlo and Leitner, Walter and Mecking, Stefan}
}
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    <dcterms:abstract xml:lang="eng">A series of neutral NiII salicylaldiminato complexes substituted with perfluorooctyl- and trifluoromethyl groups, [Ni{k2-N,O-6-C(H)=NAr-2,4- R 2C6H2O}(Me)(pyridine)] (6a: Ar=2,6-{4-(F17C8)C6H4}2C6H3, R =I; 6b: Ar=2,6-{4-(F3C)C6H4}2C6H3, R =I; 6c: Ar= 2,6-{3,5-(F3C)2C6H3}2C6H3, R =3,5-(F3C)2C6H3 ; 6d: Ar=2,6-{4-(F17C8)C6H4}2C6H3, R =3,5-(F3C)2-C6H3 ; 6e: Ar=2,6-{3,5-(F3C)2C6H3}2-C6H3, R =I) were studied as catalyst precursors for ethylene polymerisation in supercritical CO2.Catalyst precursors 6a and 6c, which are soluble in scCO2, afford the highest polymer yields, corresponding to 2x 103 turnovers.Semicrystallin e polyethylene (Mn typically 104 gmol -1) is obtained with variable degrees of branching (11 to 24 branches per 1000 carbon atoms, predominantly Me branches) and crystallinities (54 to 21%), depending on the substitution pattern of the catalyst.</dcterms:abstract>
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