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
收藏
页码:37 / 52
页数:16
相关论文
共 64 条
[31]   LINEAR ALPHA-OLEFINS BY CATALYTIC OLIGOMERIZATION OF ETHYLENE [J].
LANGER, AW .
JOURNAL OF MACROMOLECULAR SCIENCE-CHEMISTRY, 1970, A 4 (04) :775-&
[32]  
LANGER AW, 1983, Patent No. 4409414
[33]  
LANGER AW, 1984, Patent No. 4486615
[34]   DITHIOLE SERIES .2. REACTIONS OF 1,2- AND 1,3-DITHIOLIUM SALTS WITH NUCLEOPHILIC REAGENTS [J].
LEAVER, D ;
MCKINNON, DM ;
ROBERTSO.WA .
JOURNAL OF THE CHEMICAL SOCIETY, 1965, (JAN) :32-&
[35]   DITHIOLE SERIES .1. SYNTHESIS OF 1,2- AND 1,3-DITHIOLIUM SALTS [J].
LEAVER, D ;
ROBERTSON, WAH ;
MCKINNON, DM .
JOURNAL OF THE CHEMICAL SOCIETY, 1962, (DEC) :5104-&
[36]  
LIU HQ, 1991, MAKROMOL CHEM, V192, P2111
[37]  
LIU HQ, 1991, MAKROMOL CHEM, V192, P2125
[38]  
Marks T.J, 1996, U.S. Patent, Patent No. 5500398
[39]  
MARKS TJ, 1996, Patent No. 960319
[40]   STABILITIES OF BIVALENT METAL COMPLEXES OF SOME B-KETOIMINES [J].
MARTIN, DF ;
MARTIN, BB ;
JANUSONIS, GA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1961, 83 (01) :73-+