Zirconium complexes as catalysts for the oligomerisation of ethylene, the role of chelate ligands and the Lewis acid cocatalyst in the generation of the active species

被引:24
作者
Jones, D
Cavell, KJ
Keim, W
机构
[1] Univ Tasmania, Dept Chem, Hobart, Tas 7001, Australia
[2] Rhein Westfal TH Aachen, Inst Tech & Petr Chem, D-52056 Aachen, Germany
关键词
zirconium; oligomerisation; ethylene; catalyst; alpha-olefins; beta-aminoketones;
D O I
10.1016/S1381-1169(98)00144-7
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Highly effective catalysts for the conversion of ethylene into linear cn-olefins may be generated in situ from zirconium tetrachloride, a beta-aminoketone or beta-aminothioketone ligand and an alkylaluminium chloride Lewis acid cocatalyst. Catalysts may also be generated from ZrCl(4) . 2HL adducts (where HL = monodentate, oxygen-bound beta-aminoketones), and from bis-ligand complexes of the type ZrCl(2)L(2) (where L = monovalent, bidentate beta-aminoketones or beta-aminothioketones) on treatment with an alkylaluminium chloride cocatalyst. Product distribution and catalyst activity can be adjusted by ligand substituent variation and/or by the method of catalyst formation. Catalyst systems generated from preformed complexes, ZrCl(2)L(2), were in general significantly more active than those formed in situ or from the bis-ligand adducts, ZrCl(4) . 2HL. Activities of up to 60,000 turnovers/h were obtained with selected complexes. However, in situ mixtures and bis-ligand adducts generally gave a much narrower oligomer distribution, with up to 95% of the oligomers occurring in the C(4)-C(10) range for a number of the systems tested. In situ NMR (nuclear magnetic resonance) tests indicate that complex ligand/cocatalyst interactions are present and that these new oligomerisation systems are active even under very mild conditions, 30 degrees C and 1 atm ethylene. (C) 1999 Published by Elsevier Science B.V. All rights reserved.
引用
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页码:37 / 52
页数:16
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