EP1404446A2 - Catalyst comprising chromium and a ligand comprising a substituted cyclopentadiene and its use for trimerising olefins - Google Patents

Catalyst comprising chromium and a ligand comprising a substituted cyclopentadiene and its use for trimerising olefins

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Publication number
EP1404446A2
EP1404446A2 EP02757698A EP02757698A EP1404446A2 EP 1404446 A2 EP1404446 A2 EP 1404446A2 EP 02757698 A EP02757698 A EP 02757698A EP 02757698 A EP02757698 A EP 02757698A EP 1404446 A2 EP1404446 A2 EP 1404446A2
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European Patent Office
Prior art keywords
diene
chromium
catalyst system
ligand
tetraphenylcyclopenta
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EP02757698A
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German (de)
French (fr)
Inventor
Jacobus Johannes Cronje Grove
Hamdani Ahmed Mahomed
Louisa Griesel
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Sasol Technology Pty Ltd
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Sasol Technology Pty Ltd
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Publication of EP1404446A2 publication Critical patent/EP1404446A2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0231—Halogen-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C07C2/34—Metal-hydrocarbon complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/122—Metal aryl or alkyl compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes

Definitions

  • This invention relates to a hydrocarbon conversion catalyst system and the use thereof in a hydrocarbon conversion process, such as the oligomerisation or trimerisation of olefins, for example, ethylene.
  • oligomerisation of olefins primarily ⁇ -olefins
  • chromium catalysts have been developed and used to trimerise olefins.
  • the trimerisation of ethylene to 1 -hexene is significant since, in addition to its use as a specific chemical, 1 -hexene is extensively used in polymerization processes either as a monomer or co-monomer.
  • the trimeric products derived from longer chain olefins could be well utilized as synthetic lubricants (e.g. polyalphaolefins / PAOs), as well as various other applications such as components of drilling muds, and as feedstock to prepare detergents and plasticizers.
  • chromium-based processes for the trimerisation of ethylene to 1- hexene include:
  • olefins are trimerised by passing the olefin in contact with a catalyst comprising the reaction product of a chromium compound, an organoaluminium compound hydrolyzed with a specific amount of water and a donor ligand selected from hydrocarbyl isonitriles, amines and ethers (US Patent No. 4,668,838); b) Trimerisation of olefins by chromium-containing compounds, such as, for example, chromium pyrrolides that are prepared by forming a mixture of a chromium salt, a metal amide and an electron pair donor solvent, such as, for example, an ether.
  • chromium catalysts can be used either unsupported or supported on an inorganic oxide (European Patent No. 0
  • catalytic composition is obtained by mixing at least one chromium compound with at least one aryloxy aluminium compound with general formula R ⁇ AI(R'0)3-n where R is a linear or branched hydrocarbyl radical containing 1 to 30 carbon atoms, RO is an aryloxy radical containing 6 to 80 carbon atoms and n is a whole which can take the values 0,1 or 2, and with at least one other hydrocarbyl aluminium compound selected from tris(hydocarbyl)alumi ⁇ ium compound or chlorinated or brominated hydrocarbyl aluminium compounds (US Patent No. 6,031 ,145);
  • a process for producing 1 -hexene which comprises trimerising ethylene in a 1 -hexene solvent in the presence of a catalyst system obtainable by contacting in a 1 -hexene solvent a chromium-containing compound, trialkylaluminium or dialkylaluminium hydride, a pyrrole compound or derivative thereof and a group 13 (III B) or group 14 (IV B) halogen compound (European Patent No. 0 699 648);
  • a process for the trimerisation of ethylene comprising reacting ethylene, using a catalyst comprising an aluminoxane and a polydentate phosphine, arsenic and/or antimony coordination complex of a chromium salt, such that 1-hexene is formed (US Patent No. 5,811,618).
  • a process for the trimerisation of olefins comprising contacting a monomeric olefin or mixture of olefins under trimerisation conditions with a catalyst which comprises a source of chromium, molybdenum or tungsten; a ligand containing at least one phosphorous, arsenic or antimony atom bound to at least one hydrocarbyl group having a polar substituent, but excluding the case where all such polar substituents are phosphane, arsane or stibane groups; and optionally an activator (WO Patent No. 02/04119)
  • chromium-based processes for the trimerisation of ethylene are centred around catalyst systems that contain a pyrrole ligand in order to achieve the required selectivity and activity towards the formation of the desired products.
  • a pyrrole source any pyrrole derivative containing a NH functionality is used as a ligand in the reaction.
  • This invention recognizes the need for a catalyst system, which eliminates the need for using a pyrrole or related heteroaromatic analogues to achieve the required selectivity towards the formation of the desired products.
  • a trimerisation catalyst system which includes a chromium source and a ligand comprising a substituted five membered carbocyclic ring or derivatives thereof.
  • the five membered carbocyclic ring may be a substituted cyclopentadiene derivative of the general formula, CsR n H ⁇ - ⁇ , wherein each R is a substituent and n is an integer from 1 to 5.
  • the catalyst system may include a combination of at least a chromium source, a metal alkyl, a halogen source, and a substituted cyclopentadiene ligand.
  • the catalyst system of the invention attempts to address the need for using a pyrrole or related heteroaromatic analogues to achieve the required selectivity towards the formation of the desired products without compromising the advantages associated with the known homogeneous systems.
  • the process may be carried out at pressures from 5 to 80 barg.
  • the process may be carried out at temperatures from 25 °C to 150 °C
  • the chromium source of said catalyst system may consist of one or more organic and/or inorganic chromium compounds, with the chromium oxidation state ranging from 0 to 6.
  • the chromium compounds may suitably be expressed by the general formula CrXn, wherein X can be the same or different and represents an organic or inorganic radical, group or compound, and n is an integer from 0 to 6.
  • Typical organic radicals may have from about 1 to 20 carbon atoms per radical, and are selected from the group consisting of alkyl, alkoxy, ester, ketone and/or amido radicals.
  • Typical organic compounds include, but are not limited to an amine compound, a phosphine compound, a phosphine oxide compound ⁇ nitrosyl group and/or an ether compound.
  • Examples of the inorganic radicals may include halides, nitrates and sulfates.
  • Specific examples of chromium sources may include chromium(lll)acetylacetonate, chromium (III) acetate, chromium (III) pyrrolides, chromium (III) 2,2,6,6-tetramethylheptadionate, chromium (III) tris(2-ethylhexanoate), bis( ⁇ /, ⁇ f-bis(trimethylsilyl)benzamidinato) chromium (III) chloride, trichlorotris(4-isopropylpyridine) chromium (III), trichloro ( ⁇ , ⁇ , ⁇ ', ⁇ ', ⁇ "-pentamethyldiethylenetriamine) chromium (III), chromium (III) chloride, bis-(2-dimethylphosphino-ethyl)ethyl ⁇ hosphine chrom
  • a ligand for an trimerisation catalyst system which includes a chromium source, the ligand comprising a substituted five membered carbocyclic ring or derivatives thereof.
  • the ligand may be a substituted cyclopentadiene derivative of the general formula, CsR ⁇ H ⁇ - n , wherein each R is a substituent and n is an integer from 0 to 5.
  • the substituents may independently be selected from the group consisting of alkyl, aryl, aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, silyl, aminocarbonyl, carbonylamino, dialkylamino, or derivatives thereof, or aryl substituted with any of these substituents.
  • aryl group is a phenyl group and n is an integer from 0 to 5.
  • cyclopentadiene ligands may include 1,2,3,4- tetraphenylcyclopenta-1 ,3-diene, 1 ,2,3,4,5-pentaphenylcyclopenta-l ,3-diene, 1 ,2,3,4,5-pentabenzylcyclopenta-l ,3-diene, 5-methyl-1 ,2,3,4- tetraphenylcyclopenta-1 ,3-diene, 1 ,3-diphenylcyclopenta-1 ,3-diene, 1-phenyl- 2,3,4,5-tetrapropylcyclopenta-1 ,3-diene, 1 ,4,5-triphenylcyclopenta-l ,3-diene, 1 ,2,3,4-tetraphenyM ,3-cyclopentadienyl-dimethyl-f-butylsilane, 5-benzyl- 1 ,2, 3, 4-tetraphenylcyclopenta-1 ,3-diene
  • cyclopentadiene refers to a compound containing a 5-membered, carbocycle.
  • Derivatives of cyclopentadiene may include substituted cyclopentadienes and/or any heteroleptic or homoleptic metal cyclopentadienyl complexes or salts.
  • the cyclopentadiene containing ligand may be either affirmatively added to the catalyst system, to the reaction mixture, or generated in-situ.
  • cyclopentadiene-containing compounds suitable to form or generate ligands include, but are not limited to 1,2,3,4,5- pentaphenylcyclopentadiene, lithium 1 ,2,3,4,5-pentaphenylcyclopentadienide, diethyl-aluminium-1 ,2,3,4,5-pentaphenylcyclopentadienide, 1 ,3- diphenylcyclopentadiene, lithium 1 ,3-diphenylcyclopentadienide, diethylaluminium-1 ,3-diphenylcyclopentadienide, 1 ,2,3,4- tetraphenylcyclopentadiene, lithium 1 ,2,3,4-tetraphenylcyclopentadienide, diethyl-aluminium-1 ,2,3,4-tetraphenylcyclopentadienide or derivatives thereof or the like.
  • a metal alkyl may also be present in the catalyst system.
  • the metal alkyl may be any heteroleptic or homoleptic metal alkyl compound. One or more metal alkyls can be used. Typically the alkyl ligand(s) is any saturated aliphatic radical. The alkyl ligand(s) on the metal may be aliphatic or aromatic. The metal alkyl may have any number of carbon atoms, but typically less than about 20 carbon atoms per molecule.
  • metal alkyl compounds examples include, but are not limited to, alkyl aluminium compounds, hydrolyzed alkyl aluminium compounds (aluminoxanes), alkyl boron compounds, alkyl magnesium compounds, alkyl zinc compounds and/or alkyl lithium compounds.
  • the metal alkyl is an alkyl aluminium compound, hydrolyzed alkyl aluminium compound and/or alkyl boron compound.
  • the metal alkyl is an alkyl aluminium compound, expressed by the following formulae: AiXnR3-n and RnAIOR3- n , wherein n is an integer, R is an alkyl group and X is a halogen atom.
  • alkyl aluminium compound is advantageous to activity.
  • Specific alkyl aluminium compounds may include trimethyl aluminium, triethyl aluminium, tripropyl aluminium, tributyl aluminium, triisobutyl aluminium, diethyl aluminium chloride, diethyl aluminium bromide, diethyl aluminium ethoxide, ethyl aluminium dichloride, ethyl aluminium sesquichloride, or the like, and mixtures thereof.
  • a halogen source may also be present in the catalyst system.
  • the halogen source may be any organic or inorganic halogen containing compound.
  • the halogen compound is a halogen containing hydrocarbon.
  • the hydrocarbon can have any number of carbon atoms, but for economic reasons under present economic conditions, typically less than about 20 carbon atoms per molecule.
  • Examples of the afore-mentioned compounds include, hexachloroethane, trichloroethane, tetrachloroethane, 1-bromobutane and diethylaluminiumchloride.
  • halogen compound is advantageous in catalyst system activity and reduces the quantity of undesirable by-product polymer.
  • the catalyst system may also contain a hydrocarbon compound as solvent for the homogeneous catalyst system.
  • the hydrocarbon compound may be any saturated or unsaturated aliphatic hydrocarbon compound.
  • the hydrocarbon compound can have any number of carbon compounds per molecule, but usually contain less than 20 carbon atoms due to commercial availability and end-use.
  • Typical unsaturated hydrocarbon compounds include, but are not limited to 1- hexene, 1,3-butadiene, 1,4-cyclo-octadiene, benzene, toluene, ethylbenzene, xylene, acetonitrile and the like.
  • Further saturated hydrocarbon compounds include, but are not limited to cyclohexane, hexane, heptane, and the like.
  • Example 1 Ethylene trimerisation using 1,2,3,4,5-pentaphenylcyclopenta- 1, 3-diene (1) as the ligand.
  • the catalyst system was prepared as follows: 0.0417 mmol of chromium(lll) ethylhexanoate was combined with 0.125 mmol of 1,2,3,4,5- pentaphenylcyclopenta-1 ,3-diene, 0.21 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane.
  • the catalyst complex was activated by adding 3.75 mmol of triethylaluminium at room temperature for a period of 2-5 min.
  • a catalyst activity of 30 300 g product/g Cr/ hour was observed.
  • the selectivity towards C ⁇ products was 91 mass%, while the selectivity observed towards 1 -hexene formation was 73 mass %.
  • the polymeric side product obtained from the above reaction comprised 1 mass % of the reaction products.
  • Example 2 The procedure described in example 1 was followed except that 90 ml cyclohexane and 10ml of 1-heptene, was charged to the pressure reactor.
  • Example 3 The procedure in example 1 was followed except that 1.4ml of
  • 2,6-di-te/f-butylpyridine was also charged to the pressure reactor together with the 90 ml of cyclohexane, and the ethylene pressure was kept at 43 barg.
  • Example 4 The procedure in example 1 was followed except that 1.87 mmol of triethylaluminium was used to activate the catalyst.
  • Example 5 The procedure in example 1 was followed except that the catalyst system was prepared as follows: 0.0208 mmol of chromium(lll) ethylhexanoate was combined with 0.0208 mmol of 1,2,3,4,5- pentaphenylcyclopenta-1 ,3-diene, 0.052 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane. The catalyst complex was activated by adding 0.468 mmol of triethylaluminium at room temperature for a period of 2-5 min.
  • Example 6 The procedure in example 5 was followed except that the reaction was conducted at 100°C.
  • Example 7 The procedure in example 5 was followed except that the pressure reactor was fitted with a gas entrainment stirrer and baffles and the reaction was conducted at 100°C
  • Example 8 The procedure in example 1 was followed except that the reaction was conducted at 50°C and 45 barg.
  • Example 9 The procedure in example 8 was followed except that the reaction was conducted at 30°C
  • Example 10 The procedure in example 5 was followed except that 0.94 mmol of triethylaluminium was used and the reaction was conducted at 70°C.
  • Example 11 The procedure in example 5 was followed except that 0.936 mmol of triethylaluminium was used, the reaction was conducted at 70°C and 20 barg.
  • Example 12 The procedure in example 1 was followed except that the catalyst system was prepared as follows: 0.0417 mmol of chromium(lll) ethylhexanoate was combined with 0.0417 mmol of 1,2,3,4,5- pentaphenylcyclopenta-1 ,3-diene, 0.104 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane. The catalyst complex was activated by adding 2.30 mmol of triethylaluminium at room temperature for a period of 2-5 min and transferred to a pressure reactor. The reactor was first pressurised with H2 to 1.5 barg and subsequently with ethylene to a pressure of 50 barg which was maintained throughout the reaction.
  • Example 13 The procedure in example 12 was followed except that the reactor was not pressurised with 1.5 barg H 2 before the addition of ethylene to the reactor.
  • Example 14 Ethylene trimerisation using 1 ,2,3,4-tetraphenylcyclopenta-l ,3- diene (2) as the ligand. General workup conditions and stirring speeds from example 1 apply.
  • the catalyst system was prepared as follows: 0.0833 mmol of chromium(lll) ethylhexanoate was combined with 0.25 mmol of 1,2,3,4- tetraphenylcyclopenta-1, 3-diene and 0.42 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane.
  • the catalyst complex was activated by adding 3.75 mmol of triethylaluminium at room temperature for a period of 2-5 min.
  • Example 15 Ethylene trimerisation using 1-phenyl-2,3,4,5- tetrapropylcyclopenta-1 , 3-diene (3) as the ligand. General workup conditions and stirring speeds from example 1 apply.
  • the catalyst system was prepared as follows: 0.0417 mmol of chromium(lll) ethylhexanoate was combined with 0.0417 mmol of 1 -phenyl-2, 3,4,5- tetrapropylcyclopenta-1 ,3-diene (3) and 0.10 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane. The catalyst complex was activated by adding 1.88 mmol of triethylaluminium at room temperature for a period of 2-5 min.
  • Example 16 Ethylene trimerisation using 1 ,4,5-triphenylcyclopenta-1 , 3-diene (4) as the ligand. General workup conditions and stirring speeds from example 1 apply.
  • the catalyst system was prepared as follows: 0.0833 mmol of chromium(lll) ethylhexanoate was combined with 0.25 mmol of 1,4,5-triphenylcyclopenta- 1, 3-diene (4) and 0.42 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane.
  • the catalyst complex was activated by adding 3.75 mmol of triethylaluminium at room temperature for a period of 2-5 min. This solution, together with an additional 90 ml cyclohexane, was charged to a pressure reactor. The reactor temperature was maintained at 120°C, while the ethylene pressure was kept at 42 barg.
  • Example 17 Ethylene trimerisation using 1,2,3,4-tetraphenyl-1,3- cyclopentadienyl-dimethyl-f-butylsilane (5) as the ligand.
  • General workup conditions and stirring speeds from example 1 apply.
  • Example 18 Ethylene trimerisation using 5-methyl-1 ,2,3,4- tetraphenylcyclopenta-l, 3-diene (6) as the ligand. General workup conditions and stirring speeds from example 1 apply.
  • Example 19 Ethylene trimerisation using 5-benzyl-1 ,2,3,4- tetraphenylcyclopenta-l ,3-diene (7) as the ligand.
  • General workup conditions and stirring speeds from example 1 apply.
  • the catalyst system was prepared as follows: 0.0208 mmol of chromium(lll) ethylhexanoate was combined with 0.0208 mmol of 5-benzyl-1 ,2,3,4- tetraphenylcyclopenta-l, 3-diene (7), 0.052 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane.
  • the catalyst complex was activated by adding 0.94 mmol of triethylaluminium at room temperature for a period of 2-5 min.
  • Example 20 Ethylene trimerisation using 1,2,3,4,5-pentabenzylcyclopenta- 1, 3-diene (8) as the ligand.
  • General workup conditions and stirring speeds frona example 1 apply.
  • the procedure in example 19 was followed except that the ligand was changed to 1 ,2,3,4,5-pentabenzylcyclopenta-1 ,3-diene (8).
  • Example 21 Ethylene trimerisation using 1,2,3,4-tetraphenyl-5-p- tolylcyclopenta-1, 3-diene (9) as the ligand.
  • General workup conditions and stirring speeds from example 1 apply.
  • the catalyst system was prepared as follows: 0.0208 mmol of chromium(lll) ethylhexanoate was combined with 0.062 mmol of 1 ,2,3,4-tetraphenyl-5-p- tolylcyclopenta-1 , 3-diene (9), 0.052 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane.
  • the catalyst complex was activated by adding 0.47 mmol of triethylaluminium at room temperature for a period of 2-5 min.
  • Example 22 The procedure in example 21 was followed except that the reaction was conducted at 100°C
  • Example 23 The procedure in example 21 was followed except that 0.94 mmol of triethylaluminium was used and the reaction was conducted at 70°C
  • Example 24 Ethylene trimerisation using 5-mesityl-1 ,2,3,4- tetraphenylcyclopenta-l ,3-diene (10) as the ligand. General workup conditions and stirring speeds from example 1 apply.
  • the catalyst system was prepared as follows: 0.0208 mmol of chromium(lll) ethylhexanoate was combined with 0.042 mmol of 5-mesityl-1 ,2,3,4- tetraphenylcyclopenta-l ,3-diene (10), 0.052 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane.
  • the catalyst complex was activated by adding 0.47 mmol of triethylaluminium at room temperature for a period of 2-5 min. This solution, together with an additional 90 ml cyclohexane, was charged to a pressure reactor fitted with a gas entrainment stirrer and baffles. The reactor temperature was maintained at 100°C, while the ethylene pressure was kept at 50 barg.
  • Example 25 Ethylene trimerisation using 5-(4'-f-butylphenyl)-1 ,2,3,4- tetraphenylcyclopenta-l ,3-diene (11) as the ligand.
  • General workup conditions and stirring speeds from example 1 apply.
  • the catalyst system was prepared as follows: 0.0208 mmol of chromium(lll) ethylhexanoate was combined with 0.062 mmol of 5-(4'-f-butylphenyl)-1 ,2,3,4- tetraphenylcyclopenta-l ,3-diene (11), 0.052 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane.
  • the catalyst complex was activated by adding 0.47 mmol of triethylaluminium at room temperature for a period of 2-5 min.
  • Example 26 The procedure in example 25 was followed except that 0.94 mmol of triethylaluminium was used and the reaction was conducted at 70°C
  • Example 27 Ethylene trimerisation using 5-(4'-chlorophenyl)-1 ,2,3,4- tetraphenylcyclopenta-l ,3-diene (12) as the ligand.
  • General workup conditions and stirring speeds from example 1 apply.
  • the catalyst system was prepared as follows: 0.0208 mmol of chromium(lll) ethylhexanoate was combined with 0.062 mmol of 5-(4'-chlorophenyl)-1 ,2,3,4- tetraphenylcyclopenta-l ,3-diene (12), 0.052 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane.
  • the catalyst complex was activated by adding 0.94 mmol of triethylaluminium at room temperature for a period of 2-5 min. This solution, together with an additional 90 ml cyclohexane, was charged to a pressure reactor. The reactor temperature was maintained at 120°C, while the ethylene pressure was kept at 50 barg.
  • Example 28 The procedure in example 27 was followed except that the reaction was conducted at 70°C.
  • Example 29 The procedure in example 27 was followed except that the ligand was changed to 5-(4'-fluorophenyl)-1 ,2,3,4-tetraphenylcyclopenta-l ,3- diene (13).
  • Example 30 The procedure in example 27 was followed except that the ligand was changed to 5-(4'-fluorophenyl)-1 ,2,3,4-tetraphenylcyclopenta-l ,3- diene (13) and the reaction was conducted at 70°C.
  • Example 31 The procedure in example 27 was followed except that the ligand was changed to 5-(pentafluorophenyl)-1,2,3,4-tetraphenylcyclopenta- 1 ,3-diene (14).
  • Example 32 The procedure in example 27 was followed except that the ligand was changed to 5-(pentafluorophenyl)-1,2,3,4-tetraphenylcyclopenta- 1 ,3-diene (14) and the reaction was conducted at 70°C
  • Example 33 The procedure in example 27 was followed except that the ligand was changed to 1,2,3,4-tetraphenyl-5-(phenylethynyl)-cyclopenta-1,3- diene (15).
  • Example 34 Ethylene trimerisation using 2,3,4,5-tetraphenyl-2,4- cyclopentadienol (16) as the ligand. General workup conditions and stirring speeds from example 1 apply.
  • the catalyst system was prepared as follows: 0.0833 mmol of chromium(lll) ethylhexanoate was combined with 0.25 mmol of 2,3,4,5-tetraphenyl-2,4- cyclopentadienol (16), 0.42 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane.
  • the catalyst complex was activated by adding 3.75 mmol of triethylaluminium at room temperature for a period of 2-5 min.
  • Example 35 Ethylene trimerisation using a mixture of (1,3) and (1,4)-di-f- butylcyclopenta-1 ,3-diene (17) as the ligand.
  • General workup conditions and stirring speeds from example 1 apply.
  • the catalyst system was prepared as follows: 0.0417 mmol of chromium(lll) ethylhexanoate was combined with 0.125 mmol of (1,3)(1,4)-di-f- butylcyclopenta-1, 3-diene (17), 0.21 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane.
  • the catalyst complex was activated by adding 3.75 mmol of triethylaluminium at room temperature for a period of 2-5 min.
  • Example 36 The procedure in example 35 was followed except that the ligand was changed to 1,3-di-f-butyl-cyclopentadienyltrimethylsilane (18).
  • Example 37 Ethylene trimerisation using pentakis(4-f-butylphenyl)- cyclopenta-1 , 3-diene (19) as the ligand. General workup conditions and stirring speeds from example 1 apply.
  • the catalyst system was prepared as follows: 0.0417 mmol of chromium(lll) ethylhexanoate was combined with 0.834 mmol of pentakis(4-f-butylphenyl)- cyclopenta-1 ,3-diene (19), 0.104 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane. The catalyst complex was activated by adding 1.87 mmol of triethylaluminium at room temperature for a period of 2-5 min.

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Abstract

A trimerisation catalyst system includes a chromium source and a ligand comprising a substituted five membered carbocyclic ring or derivatives thereof. The five membered carbocyclic ring is a substituted cyclopentadiene derivative of the general Formula, C5RnH6-n wherein each R is a substituent and n is an integer from 1 to 5. The catalyst system further includes a halogen source and a metal alkyl.

Description

TRIMERISING AND OLIGOMERISING OLEFINS USING A CHROMIUM
BASED CATALYST
FIELD OF THE INVENTION
This invention relates to a hydrocarbon conversion catalyst system and the use thereof in a hydrocarbon conversion process, such as the oligomerisation or trimerisation of olefins, for example, ethylene.
BACKGROUND OF THE INVENTION
The oligomerisation of olefins, primarily α-olefins, with chromium catalysts has been extensively studied. More specifically, a number of chromium catalysts have been developed and used to trimerise olefins. In this regard, the trimerisation of ethylene to 1 -hexene is significant since, in addition to its use as a specific chemical, 1 -hexene is extensively used in polymerization processes either as a monomer or co-monomer. Furthermore, the trimeric products derived from longer chain olefins could be well utilized as synthetic lubricants (e.g. polyalphaolefins / PAOs), as well as various other applications such as components of drilling muds, and as feedstock to prepare detergents and plasticizers.
Known chromium-based processes for the trimerisation of ethylene to 1- hexene include:
a) A process in which olefins are trimerised by passing the olefin in contact with a catalyst comprising the reaction product of a chromium compound, an organoaluminium compound hydrolyzed with a specific amount of water and a donor ligand selected from hydrocarbyl isonitriles, amines and ethers (US Patent No. 4,668,838); b) Trimerisation of olefins by chromium-containing compounds, such as, for example, chromium pyrrolides that are prepared by forming a mixture of a chromium salt, a metal amide and an electron pair donor solvent, such as, for example, an ether. These chromium catalysts can be used either unsupported or supported on an inorganic oxide (European Patent No. 0
416 304);
c) A process for oligomerising ethylene to produce 1 -butene and/or 1 -hexene wherein catalytic composition is obtained by mixing at least one chromium compound with at least one aryloxy aluminium compound with general formula RπAI(R'0)3-n where R is a linear or branched hydrocarbyl radical containing 1 to 30 carbon atoms, RO is an aryloxy radical containing 6 to 80 carbon atoms and n is a whole which can take the values 0,1 or 2, and with at least one other hydrocarbyl aluminium compound selected from tris(hydocarbyl)alumiπium compound or chlorinated or brominated hydrocarbyl aluminium compounds (US Patent No. 6,031 ,145);
d) A process for producing 1 -hexene which comprises trimerising ethylene in a 1 -hexene solvent in the presence of a catalyst system obtainable by contacting in a 1 -hexene solvent a chromium-containing compound, trialkylaluminium or dialkylaluminium hydride, a pyrrole compound or derivative thereof and a group 13 (III B) or group 14 (IV B) halogen compound (European Patent No. 0 699 648);
e) A process for the trimerisation of ethylene, said process comprising reacting ethylene, using a catalyst comprising an aluminoxane and a polydentate phosphine, arsenic and/or antimony coordination complex of a chromium salt, such that 1-hexene is formed (US Patent No. 5,811,618).
f) A process for the trimerisation of olefins comprising contacting a monomeric olefin or mixture of olefins under trimerisation conditions with a catalyst which comprises a source of chromium, molybdenum or tungsten; a ligand containing at least one phosphorous, arsenic or antimony atom bound to at least one hydrocarbyl group having a polar substituent, but excluding the case where all such polar substituents are phosphane, arsane or stibane groups; and optionally an activator (WO Patent No. 02/04119)
Many of the known chromium-based processes for the trimerisation of ethylene are centred around catalyst systems that contain a pyrrole ligand in order to achieve the required selectivity and activity towards the formation of the desired products. As the pyrrole source, any pyrrole derivative containing a NH functionality is used as a ligand in the reaction.
The prior art catalyst systems and processes suffer from various drawbacks, including but not limited to, the need for using a pyrrole or related heteroaromatic analogues to achieve the required selectivity towards the formation of the desired products.
SUMMARY OF THE INVENTION
This invention recognizes the need for a catalyst system, which eliminates the need for using a pyrrole or related heteroaromatic analogues to achieve the required selectivity towards the formation of the desired products.
Thus, according to a first aspect of the invention, there is provided a trimerisation catalyst system, which includes a chromium source and a ligand comprising a substituted five membered carbocyclic ring or derivatives thereof.
The five membered carbocyclic ring may be a substituted cyclopentadiene derivative of the general formula, CsRnHβ-π, wherein each R is a substituent and n is an integer from 1 to 5.
The catalyst system may include a combination of at least a chromium source, a metal alkyl, a halogen source, and a substituted cyclopentadiene ligand. The catalyst system of the invention attempts to address the need for using a pyrrole or related heteroaromatic analogues to achieve the required selectivity towards the formation of the desired products without compromising the advantages associated with the known homogeneous systems.
According to a second aspect of the invention there is provided a process by which 1 -hexene can be produced in a high selectivity and yield by the trimerisation of ethylene under trimerisation conditions of temperature and pressure in the presence of an ethylene trimerisation catalyst system comprising a combination of at least a chromium source, a metal alkyl, a halogen source and a substituted cyclopentadiene ligand.
The process may be carried out at pressures from 5 to 80 barg.
The process may be carried out at temperatures from 25 °C to 150 °C
The chromium source of said catalyst system may consist of one or more organic and/or inorganic chromium compounds, with the chromium oxidation state ranging from 0 to 6.
The chromium compounds may suitably be expressed by the general formula CrXn, wherein X can be the same or different and represents an organic or inorganic radical, group or compound, and n is an integer from 0 to 6.
Typical organic radicals may have from about 1 to 20 carbon atoms per radical, and are selected from the group consisting of alkyl, alkoxy, ester, ketone and/or amido radicals.
Typical organic compounds include, but are not limited to an amine compound, a phosphine compound, a phosphine oxide compound^ nitrosyl group and/or an ether compound.
Examples of the inorganic radicals may include halides, nitrates and sulfates. Specific examples of chromium sources may include chromium(lll)acetylacetonate, chromium (III) acetate, chromium (III) pyrrolides, chromium (III) 2,2,6,6-tetramethylheptadionate, chromium (III) tris(2-ethylhexanoate), bis(Λ/,Λf-bis(trimethylsilyl)benzamidinato) chromium (III) chloride, trichlorotris(4-isopropylpyridine) chromium (III), trichloro (Λ,Λ,Λ ',Λ ',Λ "-pentamethyldiethylenetriamine) chromium (III), chromium (III) chloride, bis-(2-dimethylphosphino-ethyl)ethylρhosphine chromium (III), (2- dimethylphosphino-ethyl)(3-dimethylphosphinopropyl)methylphosphine chromium (III) chromium (III) naphthenate, chromium (II) acetate, chromium (II) pyrrolides, chromium (II) bis(2-ethylhexanoate) and/or chromium (II) chloride.
According to a third aspect of the invention, there is provided a ligand for an trimerisation catalyst system which includes a chromium source, the ligand comprising a substituted five membered carbocyclic ring or derivatives thereof.
The ligand may be a substituted cyclopentadiene derivative of the general formula, CsRπHβ-n, wherein each R is a substituent and n is an integer from 0 to 5.
The substituents may independently be selected from the group consisting of alkyl, aryl, aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, silyl, aminocarbonyl, carbonylamino, dialkylamino, or derivatives thereof, or aryl substituted with any of these substituents.
Typically the aryl group is a phenyl group and n is an integer from 0 to 5.
Specific examples of cyclopentadiene ligands may include 1,2,3,4- tetraphenylcyclopenta-1 ,3-diene, 1 ,2,3,4,5-pentaphenylcyclopenta-l ,3-diene, 1 ,2,3,4,5-pentabenzylcyclopenta-l ,3-diene, 5-methyl-1 ,2,3,4- tetraphenylcyclopenta-1 ,3-diene, 1 ,3-diphenylcyclopenta-1 ,3-diene, 1-phenyl- 2,3,4,5-tetrapropylcyclopenta-1 ,3-diene, 1 ,4,5-triphenylcyclopenta-l ,3-diene, 1 ,2,3,4-tetraphenyM ,3-cyclopentadienyl-dimethyl-f-butylsilane, 5-benzyl- 1 ,2, 3, 4-tetraphenylcyclopenta-1 ,3-diene, 1 ,2,3,4-tetraphenyl-5-p- tolylcyclopenta-1 ,3-diene, 5-mesityl-1 ,2,3,4-tetraphenylcyclopenta-1 ,3-diene, 5-(4'-f-butylphenyl)-1 ,2,3,4-tetraphenylcyclopenta-l ,3-diene, 5-(4'- chlorophenyl)-1 ,2,3,4-tetraphenylcyclopenta-1 ,3-diene, 5-(4'-fluorophenyl)- 1 ,2,3,4-tetraphenylcyclopenta-l ,3-diene, 5-(pentafluorophenyl)-1 ,2,3,4- tetraphenylcyclopenta-l ,3-diene, 1 ,2,3,4-tetraphenyl-5-(phenylethynyl) cyclopenta-1 ,3-diene, 2,3,4,5-tetraphenyl-2,4-cyclopentadienol, (1 ,3)(1 ,4)-di-t- butylcyclopenta-1 ,3-diene, 1 ,3-di-f-butyl-cyclopentadienyltrimethylsilane, pentakis(4'-t-butylphenyl) cyclopenta-1 ,3-diene and/ or derivatives thereof.
The term "cyclopentadiene" refers to a compound containing a 5-membered, carbocycle. Derivatives of cyclopentadiene may include substituted cyclopentadienes and/or any heteroleptic or homoleptic metal cyclopentadienyl complexes or salts.
The cyclopentadiene containing ligand may be either affirmatively added to the catalyst system, to the reaction mixture, or generated in-situ.
Examples of cyclopentadiene-containing compounds suitable to form or generate ligands include, but are not limited to 1,2,3,4,5- pentaphenylcyclopentadiene, lithium 1 ,2,3,4,5-pentaphenylcyclopentadienide, diethyl-aluminium-1 ,2,3,4,5-pentaphenylcyclopentadienide, 1 ,3- diphenylcyclopentadiene, lithium 1 ,3-diphenylcyclopentadienide, diethylaluminium-1 ,3-diphenylcyclopentadienide, 1 ,2,3,4- tetraphenylcyclopentadiene, lithium 1 ,2,3,4-tetraphenylcyclopentadienide, diethyl-aluminium-1 ,2,3,4-tetraphenylcyclopentadienide or derivatives thereof or the like.
A metal alkyl may also be present in the catalyst system.
The metal alkyl may be any heteroleptic or homoleptic metal alkyl compound. One or more metal alkyls can be used. Typically the alkyl ligand(s) is any saturated aliphatic radical. The alkyl ligand(s) on the metal may be aliphatic or aromatic. The metal alkyl may have any number of carbon atoms, but typically less than about 20 carbon atoms per molecule.
Examples of the afore-mentioned metal alkyl compounds include, but are not limited to, alkyl aluminium compounds, hydrolyzed alkyl aluminium compounds (aluminoxanes), alkyl boron compounds, alkyl magnesium compounds, alkyl zinc compounds and/or alkyl lithium compounds. Preferably, the metal alkyl is an alkyl aluminium compound, hydrolyzed alkyl aluminium compound and/or alkyl boron compound.
Typically the metal alkyl is an alkyl aluminium compound, expressed by the following formulae: AiXnR3-n and RnAIOR3-n, wherein n is an integer, R is an alkyl group and X is a halogen atom.
The use of said alkyl aluminium compound is advantageous to activity.
Specific alkyl aluminium compounds may include trimethyl aluminium, triethyl aluminium, tripropyl aluminium, tributyl aluminium, triisobutyl aluminium, diethyl aluminium chloride, diethyl aluminium bromide, diethyl aluminium ethoxide, ethyl aluminium dichloride, ethyl aluminium sesquichloride, or the like, and mixtures thereof.
A halogen source may also be present in the catalyst system.
The halogen source may be any organic or inorganic halogen containing compound.
Typically the halogen compound is a halogen containing hydrocarbon. The hydrocarbon can have any number of carbon atoms, but for economic reasons under present economic conditions, typically less than about 20 carbon atoms per molecule. Examples of the afore-mentioned compounds include, hexachloroethane, trichloroethane, tetrachloroethane, 1-bromobutane and diethylaluminiumchloride.
The use of said halogen compound is advantageous in catalyst system activity and reduces the quantity of undesirable by-product polymer.
The catalyst system may also contain a hydrocarbon compound as solvent for the homogeneous catalyst system. The hydrocarbon compound may be any saturated or unsaturated aliphatic hydrocarbon compound. The hydrocarbon compound can have any number of carbon compounds per molecule, but usually contain less than 20 carbon atoms due to commercial availability and end-use.
Typical unsaturated hydrocarbon compounds include, but are not limited to 1- hexene, 1,3-butadiene, 1,4-cyclo-octadiene, benzene, toluene, ethylbenzene, xylene, acetonitrile and the like. Further saturated hydrocarbon compounds include, but are not limited to cyclohexane, hexane, heptane, and the like.
Table 1
The invention is now described by way of non limiting examples.
The liquid product weight distribution for this and all other examples are given in Tablel and the structure and names of ligands used, are given in Table 2.
All procedures were carried out under inert conditions, using pre-dried reagents.
Examples of performing the invention:
Example 1: Ethylene trimerisation using 1,2,3,4,5-pentaphenylcyclopenta- 1, 3-diene (1) as the ligand.
The catalyst system was prepared as follows: 0.0417 mmol of chromium(lll) ethylhexanoate was combined with 0.125 mmol of 1,2,3,4,5- pentaphenylcyclopenta-1 ,3-diene, 0.21 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane. The catalyst complex was activated by adding 3.75 mmol of triethylaluminium at room temperature for a period of 2-5 min.
This solution, together with an additional 90 ml cyclohexane, was transferred to a pressure reactor, fitted with a mechanical stirrer. The reactor was charged with ethylene where after the reactor temperature was maintained at 120°C, while the ethylene pressure was kept at 50 barg. Thorough mixing was ensured by mixing speeds of 1100 RPM's. Thirty minutes later the reaction was terminated by the injection of 1-butanol/water into the pressure reactor. After releasing ethylene from the autoclave, the by product polymers in the reaction were separated by filtration and the product/solvent phase was analysed by GC
A catalyst activity of 30 300 g product/g Cr/ hour was observed. The selectivity towards Cβ products was 91 mass%, while the selectivity observed towards 1 -hexene formation was 73 mass %. The polymeric side product obtained from the above reaction comprised 1 mass % of the reaction products.
Example 2: The procedure described in example 1 was followed except that 90 ml cyclohexane and 10ml of 1-heptene, was charged to the pressure reactor.
Example 3: The procedure in example 1 was followed except that 1.4ml of
2,6-di-te/f-butylpyridine was also charged to the pressure reactor together with the 90 ml of cyclohexane, and the ethylene pressure was kept at 43 barg.
Example 4: The procedure in example 1 was followed except that 1.87 mmol of triethylaluminium was used to activate the catalyst.
Example 5: The procedure in example 1 was followed except that the catalyst system was prepared as follows: 0.0208 mmol of chromium(lll) ethylhexanoate was combined with 0.0208 mmol of 1,2,3,4,5- pentaphenylcyclopenta-1 ,3-diene, 0.052 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane. The catalyst complex was activated by adding 0.468 mmol of triethylaluminium at room temperature for a period of 2-5 min.
Example 6: The procedure in example 5 was followed except that the reaction was conducted at 100°C.
Example 7: The procedure in example 5 was followed except that the pressure reactor was fitted with a gas entrainment stirrer and baffles and the reaction was conducted at 100°C
Example 8: The procedure in example 1 was followed except that the reaction was conducted at 50°C and 45 barg. Example 9: The procedure in example 8 was followed except that the reaction was conducted at 30°C
Example 10: The procedure in example 5 was followed except that 0.94 mmol of triethylaluminium was used and the reaction was conducted at 70°C.
Example 11: The procedure in example 5 was followed except that 0.936 mmol of triethylaluminium was used, the reaction was conducted at 70°C and 20 barg.
Example 12: The procedure in example 1 was followed except that the catalyst system was prepared as follows: 0.0417 mmol of chromium(lll) ethylhexanoate was combined with 0.0417 mmol of 1,2,3,4,5- pentaphenylcyclopenta-1 ,3-diene, 0.104 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane. The catalyst complex was activated by adding 2.30 mmol of triethylaluminium at room temperature for a period of 2-5 min and transferred to a pressure reactor. The reactor was first pressurised with H2 to 1.5 barg and subsequently with ethylene to a pressure of 50 barg which was maintained throughout the reaction.
Example 13: The procedure in example 12 was followed except that the reactor was not pressurised with 1.5 barg H2 before the addition of ethylene to the reactor.
Example 14: Ethylene trimerisation using 1 ,2,3,4-tetraphenylcyclopenta-l ,3- diene (2) as the ligand. General workup conditions and stirring speeds from example 1 apply.
The catalyst system was prepared as follows: 0.0833 mmol of chromium(lll) ethylhexanoate was combined with 0.25 mmol of 1,2,3,4- tetraphenylcyclopenta-1, 3-diene and 0.42 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane. The catalyst complex was activated by adding 3.75 mmol of triethylaluminium at room temperature for a period of 2-5 min.
This solution, together with an additional 90 ml cyclohexane, was charged to a pressure reactor. The reactor temperature was maintained at 130°C, while the ethylene pressure was kept at 35 barg.
Example 15: Ethylene trimerisation using 1-phenyl-2,3,4,5- tetrapropylcyclopenta-1 , 3-diene (3) as the ligand. General workup conditions and stirring speeds from example 1 apply.
The catalyst system was prepared as follows: 0.0417 mmol of chromium(lll) ethylhexanoate was combined with 0.0417 mmol of 1 -phenyl-2, 3,4,5- tetrapropylcyclopenta-1 ,3-diene (3) and 0.10 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane. The catalyst complex was activated by adding 1.88 mmol of triethylaluminium at room temperature for a period of 2-5 min.
This solution, together with an additional 90 ml cyclohexane, was charged to a pressure reactor. The reactor temperature was maintained at 120°C, while the ethylene pressure was kept at 50 barg.
Example 16: Ethylene trimerisation using 1 ,4,5-triphenylcyclopenta-1 , 3-diene (4) as the ligand. General workup conditions and stirring speeds from example 1 apply.
The catalyst system was prepared as follows: 0.0833 mmol of chromium(lll) ethylhexanoate was combined with 0.25 mmol of 1,4,5-triphenylcyclopenta- 1, 3-diene (4) and 0.42 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane. The catalyst complex was activated by adding 3.75 mmol of triethylaluminium at room temperature for a period of 2-5 min. This solution, together with an additional 90 ml cyclohexane, was charged to a pressure reactor. The reactor temperature was maintained at 120°C, while the ethylene pressure was kept at 42 barg.
Example 17: Ethylene trimerisation using 1,2,3,4-tetraphenyl-1,3- cyclopentadienyl-dimethyl-f-butylsilane (5) as the ligand. General workup conditions and stirring speeds from example 1 apply.
The procedure in example 15 was followed except that the ligand was changed to 1 ,2,3,4-tetrapheny ,3-cyclopentadienyl-dimethyl-f-butylsilane (5).
Example 18: Ethylene trimerisation using 5-methyl-1 ,2,3,4- tetraphenylcyclopenta-l, 3-diene (6) as the ligand. General workup conditions and stirring speeds from example 1 apply.
The procedure in example 16 was followed except that the ligand was changed to 5-methyl-1 ,2,3,4-tetraphenylcyclopenta-l, 3-diene (6) and the reactor pressure was maintained at 45 barg.
Example 19: Ethylene trimerisation using 5-benzyl-1 ,2,3,4- tetraphenylcyclopenta-l ,3-diene (7) as the ligand. General workup conditions and stirring speeds from example 1 apply.
The catalyst system was prepared as follows: 0.0208 mmol of chromium(lll) ethylhexanoate was combined with 0.0208 mmol of 5-benzyl-1 ,2,3,4- tetraphenylcyclopenta-l, 3-diene (7), 0.052 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane. The catalyst complex was activated by adding 0.94 mmol of triethylaluminium at room temperature for a period of 2-5 min.
Example 20: Ethylene trimerisation using 1,2,3,4,5-pentabenzylcyclopenta- 1, 3-diene (8) as the ligand. General workup conditions and stirring speeds frona example 1 apply. The procedure in example 19 was followed except that the ligand was changed to 1 ,2,3,4,5-pentabenzylcyclopenta-1 ,3-diene (8).
Example 21: Ethylene trimerisation using 1,2,3,4-tetraphenyl-5-p- tolylcyclopenta-1, 3-diene (9) as the ligand. General workup conditions and stirring speeds from example 1 apply.
The catalyst system was prepared as follows: 0.0208 mmol of chromium(lll) ethylhexanoate was combined with 0.062 mmol of 1 ,2,3,4-tetraphenyl-5-p- tolylcyclopenta-1 , 3-diene (9), 0.052 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane. The catalyst complex was activated by adding 0.47 mmol of triethylaluminium at room temperature for a period of 2-5 min.
This solution, together with an additional 90 ml cyclohexane, was charged to a pressure reactor. The reactor temperature was maintained at 120°C, while the ethylene pressure was kept at 50 barg.
Example 22: The procedure in example 21 was followed except that the reaction was conducted at 100°C
Example 23: The procedure in example 21 was followed except that 0.94 mmol of triethylaluminium was used and the reaction was conducted at 70°C
Example 24: Ethylene trimerisation using 5-mesityl-1 ,2,3,4- tetraphenylcyclopenta-l ,3-diene (10) as the ligand. General workup conditions and stirring speeds from example 1 apply.
The catalyst system was prepared as follows: 0.0208 mmol of chromium(lll) ethylhexanoate was combined with 0.042 mmol of 5-mesityl-1 ,2,3,4- tetraphenylcyclopenta-l ,3-diene (10), 0.052 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane. The catalyst complex was activated by adding 0.47 mmol of triethylaluminium at room temperature for a period of 2-5 min. This solution, together with an additional 90 ml cyclohexane, was charged to a pressure reactor fitted with a gas entrainment stirrer and baffles. The reactor temperature was maintained at 100°C, while the ethylene pressure was kept at 50 barg.
Example 25: Ethylene trimerisation using 5-(4'-f-butylphenyl)-1 ,2,3,4- tetraphenylcyclopenta-l ,3-diene (11) as the ligand. General workup conditions and stirring speeds from example 1 apply.
The catalyst system was prepared as follows: 0.0208 mmol of chromium(lll) ethylhexanoate was combined with 0.062 mmol of 5-(4'-f-butylphenyl)-1 ,2,3,4- tetraphenylcyclopenta-l ,3-diene (11), 0.052 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane. The catalyst complex was activated by adding 0.47 mmol of triethylaluminium at room temperature for a period of 2-5 min.
This solution, together with an additional 90 ml cyclohexane, was charged to a pressure reactor. The reactor temperature was maintained at 100°C, while the ethylene pressure was kept at 50 barg.
Example 26: The procedure in example 25 was followed except that 0.94 mmol of triethylaluminium was used and the reaction was conducted at 70°C
Example 27: Ethylene trimerisation using 5-(4'-chlorophenyl)-1 ,2,3,4- tetraphenylcyclopenta-l ,3-diene (12) as the ligand. General workup conditions and stirring speeds from example 1 apply.
The catalyst system was prepared as follows: 0.0208 mmol of chromium(lll) ethylhexanoate was combined with 0.062 mmol of 5-(4'-chlorophenyl)-1 ,2,3,4- tetraphenylcyclopenta-l ,3-diene (12), 0.052 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane. The catalyst complex was activated by adding 0.94 mmol of triethylaluminium at room temperature for a period of 2-5 min. This solution, together with an additional 90 ml cyclohexane, was charged to a pressure reactor. The reactor temperature was maintained at 120°C, while the ethylene pressure was kept at 50 barg.
Example 28: The procedure in example 27 was followed except that the reaction was conducted at 70°C.
Example 29: The procedure in example 27 was followed except that the ligand was changed to 5-(4'-fluorophenyl)-1 ,2,3,4-tetraphenylcyclopenta-l ,3- diene (13).
Example 30: The procedure in example 27 was followed except that the ligand was changed to 5-(4'-fluorophenyl)-1 ,2,3,4-tetraphenylcyclopenta-l ,3- diene (13) and the reaction was conducted at 70°C.
Example 31: The procedure in example 27 was followed except that the ligand was changed to 5-(pentafluorophenyl)-1,2,3,4-tetraphenylcyclopenta- 1 ,3-diene (14).
Example 32: The procedure in example 27 was followed except that the ligand was changed to 5-(pentafluorophenyl)-1,2,3,4-tetraphenylcyclopenta- 1 ,3-diene (14) and the reaction was conducted at 70°C
Example 33: The procedure in example 27 was followed except that the ligand was changed to 1,2,3,4-tetraphenyl-5-(phenylethynyl)-cyclopenta-1,3- diene (15).
Example 34: Ethylene trimerisation using 2,3,4,5-tetraphenyl-2,4- cyclopentadienol (16) as the ligand. General workup conditions and stirring speeds from example 1 apply.
The catalyst system was prepared as follows: 0.0833 mmol of chromium(lll) ethylhexanoate was combined with 0.25 mmol of 2,3,4,5-tetraphenyl-2,4- cyclopentadienol (16), 0.42 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane. The catalyst complex was activated by adding 3.75 mmol of triethylaluminium at room temperature for a period of 2-5 min.
This solution, together with an additional 90 ml cyclohexane, was charged to a pressure reactor. The reactor temperature was maintained at 120°C, while the ethylene pressure was kept at 50 barg.
Example 35: Ethylene trimerisation using a mixture of (1,3) and (1,4)-di-f- butylcyclopenta-1 ,3-diene (17) as the ligand. General workup conditions and stirring speeds from example 1 apply.
The catalyst system was prepared as follows: 0.0417 mmol of chromium(lll) ethylhexanoate was combined with 0.125 mmol of (1,3)(1,4)-di-f- butylcyclopenta-1, 3-diene (17), 0.21 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane. The catalyst complex was activated by adding 3.75 mmol of triethylaluminium at room temperature for a period of 2-5 min.
This solution, together with an additional 90 ml cyclohexane, was charged to a pressure reactor. The reactor temperature was maintained at 120°C, while the ethylene pressure was kept at 50 barg.
Example 36: The procedure in example 35 was followed except that the ligand was changed to 1,3-di-f-butyl-cyclopentadienyltrimethylsilane (18).
Example 37: Ethylene trimerisation using pentakis(4-f-butylphenyl)- cyclopenta-1 , 3-diene (19) as the ligand. General workup conditions and stirring speeds from example 1 apply.
The catalyst system was prepared as follows: 0.0417 mmol of chromium(lll) ethylhexanoate was combined with 0.834 mmol of pentakis(4-f-butylphenyl)- cyclopenta-1 ,3-diene (19), 0.104 mmol of hexachloroethane and stirred at room temperature for 30 minutes in 30 ml of dry cyclohexane. The catalyst complex was activated by adding 1.87 mmol of triethylaluminium at room temperature for a period of 2-5 min.
This solution, together with an additional 90 ml cyclohexane, was charged to a pressure reactor. The reactor temperature was maintained at 120°C, while the ethylene pressure was kept at 50 barg.

Claims

Claims:
1. A trimerisation catalyst system, which includes a chromium source and a ligand comprising a substituted five membered carbocyclic ring or derivatives thereof.
2. A catalyst system as claimed in claim 1 , wherein the five membered carbocyclic ring is a substituted cyclopentadiene derivative of the general formula, Cβ nHβ-ni wherein each R is a substituent and n is an integer from 1 to 5.
3. A catalyst system as claimed in claim 1 or claim 2, wherein the catalyst system is for the selective trimerisation of ethylene to 1 -hexene.
4. A catalyst system as claimed in any one claims 1 to 3, which include, in combination with the ligand and the chromium source, one or more metal alkyls expressed by the following formulae: AIXnR3-n and RnAIOR3-n, wherein n is an integer from 0 - 3, X is a halogen atom, R is an alkyl group and the alkyl has less than about 20 carbon atoms per molecule.
5. A catalyst system as claimed in claim 4, which include a halogen source, which is selected from a group of compounds, which include hexachloroethane, trichloroethane, tetrachloroethane, 1 -bromobutane and/ or diethylaluminiumchloride.
6. A catalyst system as claimed in any one of claims 1 to 5, wherein the chromium source is selected from a group including chromium(lll)acetylacetonate, chromium (III) acetate, chromium (III) pyrrolides, chromium (III) 2,2,6,6-tetramethylheptadionate, chromium (III) tris(2-ethylhexanoate), bis(Λ/,Λ/,-bis(trimethylsilyl)benzamidinato) chromium (III) chloride, trichlorotris(4-isopropylpyridine) chromium (III), trichloro (^^Λ/^/V^Λ '-pentamethyldiethylenetriamine) chromium (III), chromium (III) chloride, bis-(2-dimethylphosphino-ethyl)ethylphosphine chromium (III), (2- dimethylphosphino-ethyl)(3-dimethylphosphinopropyl)methylphosphine chromium (III) chromium (III) naphthenate, chromium (II) acetate, chromium (II) pyrrolides, chromium (II) bis(2-ethylhexanoate) and/or chromium (II) chloride.
7. A catalyst system as claimed in any one of claims 2 to 6, wherein the substituents, R, are independently selected from the group which includes alkyl, aryl, arylalkyl, aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, silyl, aminocarbonyl, carbonylamino, dialkylamino, and/ or derivatives thereof, and/ or aryl substituted with any of these substituents.
8. A catalyst system as claimed in claim 7, wherein the aryl or arylalkyl group is selected from a phenyl, benzyl, tolyl, f-butylphenyl, chlorophenyl, fluorophenyl or pentafluorophenyl group.
9. A catalyst system as claimed in claim 2, wherein n is 5 and the aryl group a phenyl.
10. A catalyst system as claimed in claim 1 or 2, wherein the ligand is selected from the group which includes 1 ,2,3,4-tetraphenylcyclopenta-l ,3- diene, 1, 2,3,4, 5-pentaphenylcyclopenta-1 , 3-diene, 1,2,3,4,5- pentabenzylcyclopenta-1 ,3-diene, 5-methyl-1 ,2,3,4-tetraphenylcyclopenta-l ,3- diene, 1,3-diphenylcyclopenta-1 ,3-diene, 1-phenyl-2,3,4,5- tetrapropylcyclopeπta-1 ,3-diene, 1 ,4,5-triphenylcyclopenta-1 ,3-diene, 1 ,2,3,4- tetraphenyl-1 ,3-cyclopentadienyl-dimethyl-f-butylsilane, 5-benzyl-1 ,2,3,4- tetraphenylcyclopenta-1 ,3-diene, 1 ,2,3,4-tetraphenyl-5-p-tolylcyclopenta-1 ,3- diene, 5-mesityl-1 ,2,3,4-tetraphenylcyclopenta-l ,3-diene, 5-(4'-f-butylphenyl)- 1 ,2,3,4-tetraphenylcyclopenta-l ,3-diene, 5-(4'-chlorophenyl)-1 ,2,3,4- tetraphenylcyclopenta-l ,3-diene, 5-(4'-fluorophenyl)-1 ,2,3,4- tetraphenylcyclopenta-l ,3-diene, 5-(pentafluorophenyl)-1 ,2,3,4- tetraphenylcyclopenta-1 ,3-diene, 1 ,2,3,4-tetraphenyl-5-(phenylethynyl) cyclopenta-1 ,3-diene, 2,3,4,5-tetraphenyl-2,4-cyclopentadienol, (1,3)(1 ,4)-di-t- butylcyclopenta-1 ,3-diene, 1 ,3-di-f-butyl-cyclopentadienyltrimethylsilane, pentakis(4'-t-butylphenyl) cyclopenta-1 ,3-diene and/ or derivatives thereof.
11. A catalyst system as claimed in any one of claims 4 to 10, wherein the metal alkyl is selected from a group of compounds which include alkyl aluminium compounds, hydrolyzed alkyl aluminium compounds (aluminoxanes), alkyl boron compounds, alkyl magnesium compounds, alkyl zinc compounds and/or alkyl lithium compounds.
12. A catalyst system as claimed in claim 11, wherein the metal alkyl is selected from a group of alkyl aluminium compounds which include trimethyl aluminium, triethyl aluminium, tripropyl aluminium, tributyl aluminium, triisobutyl aluminium, diethyl aluminium chloride, diethyl aluminium bromide, diethyl aluminium ethoxide, ethyl aluminium dichloride, ethyl aluminium sesquichloride, and mixtures thereof.
13. A catalyst system as claimed in any one of claims 1 to 12, wherein the catalyst system is a homogeneous catalyst system, which includes a hydrocarbon compound as solvent for the homogeneous catalyst system.
14. A catalyst system as claimed in claim 13, wherein the hydrocarbon compound as the solvent is an unsaturated hydrocarbon compound, which is selected from a group, which includes 1 -hexene, 1,3-butadiene, 1,4-cyclo- octadiene, benzene, toluene, ethylbenzene, xylene and/ or acetonitrile.
15. A catalyst system as claimed in claim 13, wherein the hydrocarbon compound as the solvent is a saturated hydrocarbon compound, which is selected from a group, which includes cyclohexane, hexane and/ or heptane.
16. A process for producing 1 -hexene in a high selectivity and yield by the trimerisation of ethylene under trimerisation conditions of a temperature ranging between 25 °C and 150 °C and a pressure ranging between 5 and 80 barg, in the presence of an ethylene trimerisation catalyst system which includes a chromium source and a ligand comprising a substituted five membered carbocyclic ring or derivatives thereof.
17. A process as claimed in claim 16, wherein the carbocyclic ring ligand is a substituted cyclopentadiene, which is either affirmatively added to the catalyst system, to the reaction mixture, or generated in-situ.
18. A process as claimed in claim 17, wherein the ligand is formed or generated by the compounds selected from a group, which includesl, 2,3,4,5- pentaphenylcyclopentadiene, lithium 1 ,2,3,4,5-pentaphenylcyclopentadienide, diethyl-aluminium-1 ,2,3,4,5-pentaρhenylcyclopentadienide, 1 ,3- diphenylcyclopentadiene, lithium 1 ,3-diphenylcyclopentadienide, diethylaluminium-1 ,3-diphenylcyclopentadienide, 1 ,2,3,4- tetraphenylcyclopentadiene, lithium 1 ,2,3,4-tetraphenylcyclopentadienide, diethyl-aluminium-1 ,2,3,4-tetraphenylcyclopentadienide or the like.
19. A ligand for a trimerisation catalyst system which includes a chromium source, the ligand comprising a substituted five membered carbocyclic ring or derivatives thereof.
20. A ligand as claimed in claim 19, wherein the catalyst system is for the substantially selective trimerisation of ethylene to 1 -hexene.
21. A ligand as claimed in claim 19 or claim 20, wherein the ligand is a substituted cyclopentadiene derivative of the general formula, CsRnHβ-n, wherein each R is a substituent and n is an integer from 1 to 5.
22. A ligand as claimed in claim 21, wherein the substituents, R, are independently selected from the group, which includes alkyl, aryl, arylalkyl, aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, silyl, aminocarbonyl, carbonylamino, dialkylamino, or derivatives thereof, or aryl substituted with any of these substituents.
23. A ligand as claimed in claim 22, wherein the aryl or arylalkyl group is selected from a phenyl, benzyl, tolyl, f-butylphenyl, chlorophenyl, fluorophenyl or pentafluorophenyl group.
24. A ligand as claimed in claim 23, wherein n is 5 and the aryl group a phenyl.
25. A ligand as claimed in claim 22, wherein the silyl group is selected from a dimethyl-f-butylsilane or trimethylsilane group.
26. A ligand as claimed in claim 22, wherein the ligand is selected from the group which includes 1 ,2,3,4-tetraphenylcyclopenta-l ,3-diene, 1,2,3,4,5- pentaphenylcyclopenta-1 ,3-diene, 1 ,2,3,4,5-pentabenzylcyclopenta-1 ,3-diene, 5-methyl-1 ,2,3,4-tetraphenylcyclopenta-l ,3-diene, 1 ,3-diphenylcyclopenta- 1 ,3-diene, 1-ρhenyl-2,3,4,5-tetrapropylcyclopenta-1 ,3-diene, 1 ,4,5- triphenylcyclopenta-1 ,3-diene, 1 ,2,3,4-tetraphenyl-1 ,3-cyclopentadienyl- dimethyl-f-butylsilane, 5-benzyl-1 ,2,3,4-tetraphenylcyclopenta-l ,3-diene, 1 ,2,3,4-tetraphenyl-5-p-tolylcyclopenta-1 ,3-diene, 5-mesityl-1 ,2,3,4- tetraphenylcyclopenta-l ,3-diene, δ-^'-f-butylpheny -l ,2,3,4- tetraphenylcyclopenta-l ,3-diene, 5-(4'-chlorophenyl)-1 ,2,3,4- tetraphenylcyclopenta-l ,3-diene, 5-(4'-fluorophenyl)-1 ,2,3,4- tetraphenylcyclopenta-l ,3-diene, 5-(pentafluorophenyl)-1 ,2,3,4- tetraphenylcyclopenta-1 ,3-diene, 1 ,2,3,4-tetraphenyl-5-(phenylethynyl) cyclopenta-1 ,3-diene, 2,3,4,5-tetraphenyl-2,4-cyclopentadienoJ, (1 ,3)(1 ,4)-di-t- butylcyclopenta-1 ,3-diene (mixture), 1,3-di-f-butyl- cyclopentadienyltrimethylsilane, pentakis(4'-t-butylphenyl) cyclopenta-1 ,3- diene and/ or derivatives thereof.
27. A trimerisation catalyst system substantially as described herein.
28. A process for producing 1 -hexene substantially as described herein.
29. A ligand for a trimerisation catalyst system substantially as described herein.
EP02757698A 2001-07-02 2002-06-27 Catalyst comprising chromium and a ligand comprising a substituted cyclopentadiene and its use for trimerising olefins Withdrawn EP1404446A2 (en)

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