WO2003004158A2 - 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 Download PDFInfo
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- WO2003004158A2 WO2003004158A2 PCT/ZA2002/000105 ZA0200105W WO03004158A2 WO 2003004158 A2 WO2003004158 A2 WO 2003004158A2 ZA 0200105 W ZA0200105 W ZA 0200105W WO 03004158 A2 WO03004158 A2 WO 03004158A2
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- tetraphenylcyclopenta
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- 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
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- 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
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- 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
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- 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
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- 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
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
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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
- 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
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- 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
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- 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
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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
- B01J31/16—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
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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
- B01J31/26—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
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- 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.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR0210806-2A BR0210806A (en) | 2001-07-02 | 2002-06-27 | Catalytic olefin trimerization system and process for the production of 1-hexene with high selectivity and yield |
EP02757698A EP1404446A2 (en) | 2001-07-02 | 2002-06-27 | Catalyst comprising chromium and a ligand comprising a substituted cyclopentadiene and its use for trimerising olefins |
AU2002323698A AU2002323698A1 (en) | 2001-07-02 | 2002-06-27 | Catalyst comprising chromium and a ligand comprising a substituted cyclopentadiene and its use for trimerising olefins |
Applications Claiming Priority (4)
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US30192501P | 2001-07-02 | 2001-07-02 | |
ZA2001/5422 | 2001-07-02 | ||
US60/301,925 | 2001-07-02 | ||
ZA200105422 | 2001-07-02 |
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WO2003004158A2 true WO2003004158A2 (en) | 2003-01-16 |
WO2003004158A3 WO2003004158A3 (en) | 2004-01-22 |
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PCT/ZA2002/000105 WO2003004158A2 (en) | 2001-07-02 | 2002-06-27 | Catalyst comprising chromium and a ligand comprising a substituted cyclopentadiene and its use for trimerising olefins |
Country Status (4)
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EP (1) | EP1404446A2 (en) |
AU (1) | AU2002323698A1 (en) |
BR (1) | BR0210806A (en) |
WO (1) | WO2003004158A2 (en) |
Cited By (16)
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AU2003237063B2 (en) * | 2002-07-02 | 2009-07-23 | Lg Electronics Inc. | High-density optical disc and method for restricting playback of the high-density optical disc in optical disc apparatus |
US7820581B2 (en) | 2004-02-20 | 2010-10-26 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
US7902415B2 (en) | 2007-12-21 | 2011-03-08 | Chevron Phillips Chemical Company Lp | Processes for dimerizing or isomerizing olefins |
US7910670B2 (en) | 2005-08-19 | 2011-03-22 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
WO2011085951A1 (en) | 2010-01-15 | 2011-07-21 | Basell Polyolefine Gmbh | Oligomerization of olefins |
US7994376B2 (en) | 2004-02-19 | 2011-08-09 | Chevron Phillips Chemical Company Lp | Olefin oligomerization |
US8067609B2 (en) | 2007-01-08 | 2011-11-29 | Exxonmobil Chemical Patents Inc. | Methods for oligomerizing olefins with chromium pyridine thioether catalysts |
US8138348B2 (en) | 2007-01-08 | 2012-03-20 | Exxonmobil Chemical Patents Inc. | Methods for oligomerizing olefins with chromium pyridine mono-oxazoline catalysts |
WO2012055943A2 (en) | 2010-10-28 | 2012-05-03 | Basell Polyolefine Gmbh | Oligomerization of olefins |
US8329608B2 (en) | 2004-02-20 | 2012-12-11 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
US8629280B2 (en) | 2007-01-08 | 2014-01-14 | Exxonmobil Chemical Patents Inc. | Methods for oligomerizing olefins with chromium pyridine ether catalysts |
US8778827B2 (en) | 2007-11-28 | 2014-07-15 | Saudi Basic Industries Corporation | Catalyst composition and process for oligomerization of ethylene |
US9550841B2 (en) | 2004-02-20 | 2017-01-24 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
US9586872B2 (en) | 2011-12-30 | 2017-03-07 | Chevron Phillips Chemical Company Lp | Olefin oligomerization methods |
CN114225968A (en) * | 2022-01-13 | 2022-03-25 | 中化泉州石化有限公司 | Ethylene trimerization catalyst composition |
CN115028509A (en) * | 2022-07-01 | 2022-09-09 | 万华化学集团股份有限公司 | Ethylene oligomerization process with increased reactivity and reduced polymer formation |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0595182A1 (en) * | 1992-10-20 | 1994-05-04 | CHEVRON RESEARCH AND TECHNOLOGY COMPANY, a division of chevron u.s.a. inc. | Selected cyclopentadienyl group VIB metal alpha-olefin polymerization catalysts and process for polymerizing alpha-olefins |
US6127301A (en) * | 1996-06-28 | 2000-10-03 | Sumitomo Chemical Company, Limited | Catalyst system and method for reaction of olefin |
WO2001002323A1 (en) * | 1999-06-30 | 2001-01-11 | Studiengesellschaft Kohle Mbh | Donor ligand-substituted cyclopentadienyl-chrome compounds used as catalysts for oligomerizing alkenes |
WO2001012687A1 (en) * | 1999-08-13 | 2001-02-22 | Basell Polyolefine Gmbh | COPOLYMERS OF ETHYLENE WITH C3-C12 α OLEFINS |
WO2001092346A2 (en) * | 2000-05-25 | 2001-12-06 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst for the production of olefin polymers |
-
2002
- 2002-06-27 AU AU2002323698A patent/AU2002323698A1/en not_active Abandoned
- 2002-06-27 BR BR0210806-2A patent/BR0210806A/en not_active IP Right Cessation
- 2002-06-27 EP EP02757698A patent/EP1404446A2/en not_active Withdrawn
- 2002-06-27 WO PCT/ZA2002/000105 patent/WO2003004158A2/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0595182A1 (en) * | 1992-10-20 | 1994-05-04 | CHEVRON RESEARCH AND TECHNOLOGY COMPANY, a division of chevron u.s.a. inc. | Selected cyclopentadienyl group VIB metal alpha-olefin polymerization catalysts and process for polymerizing alpha-olefins |
US6127301A (en) * | 1996-06-28 | 2000-10-03 | Sumitomo Chemical Company, Limited | Catalyst system and method for reaction of olefin |
WO2001002323A1 (en) * | 1999-06-30 | 2001-01-11 | Studiengesellschaft Kohle Mbh | Donor ligand-substituted cyclopentadienyl-chrome compounds used as catalysts for oligomerizing alkenes |
WO2001012687A1 (en) * | 1999-08-13 | 2001-02-22 | Basell Polyolefine Gmbh | COPOLYMERS OF ETHYLENE WITH C3-C12 α OLEFINS |
WO2001092346A2 (en) * | 2000-05-25 | 2001-12-06 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst for the production of olefin polymers |
Non-Patent Citations (7)
Title |
---|
"ADVANCES IN ORGANOMETALLIC CHEMISTRY" 1991 , ACADEMIC PRESS , NEW YORK, US XP002232569 Janiak, C.; Schumann, H. "Bulky or Supracyclopentadienyl Derivatives in Organometallic Chemistry"; Vol. 33; pages 291-393 page 293 -page 296 page 352 -page 379 * |
CASTELLANI M P ET AL: "SYNTHESIS, REACTIVITIES, MOLECULAR STRUCTURES, AND PHYSICAL PROPERTIES OF PARAMAGNETIC BIS(TETRAPHENYLCYCLOPENTADIENYL) COMPLEXES OF VANADIUM, CHROMIUM, COBALT, AND NICKEL" ORGANOMETALLICS, WASHINGTON, DC, US, vol. 6, no. 8, 1987, pages 1703-1712, XP000953311 ISSN: 0276-7333 * |
DOEHRING A ET AL: "DONOR-LIGAND-SUBSTITUTED CYCLOPENTADIENYLCHROMIUM(III) COMPLEXES: A NEW CLASS OF ALKENE POLYMERIZATION CATALYST 1. AMINO-SUBSTITUTED SYSTEMS" ORGANOMETALLICS, ACS, COLUMBUS, OH, US, vol. 19, no. 4, 21 February 2000 (2000-02-21), pages 388-402, XP001125762 ISSN: 0276-7333 * |
DOEHRING ARNO ET AL: "Donor-ligand-substituted cyclopentadienylchromium(III) complexes: A new class of alkene polymerization catalyst. 2. Phosphinoalkyl-substituted systems" ORGANOMETALLICS, ACS, COLUMBUS, OH, US, vol. 20, no. 11, 28 May 2001 (2001-05-28), pages 2234-2245, XP002225540 * |
HEINEMANN O ET AL: "A facile access to CpCr (acac)Cl and related systems" JOURNAL OF ORGANOMETALLIC CHEMISTRY, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, vol. 553, no. 1-2, 25 February 1998 (1998-02-25), pages 477-479, XP004204947 ISSN: 0022-328X * |
PEUCKER U ET AL: "VINYLIC POLYMERIZATION BY HOMOGENEOUS CHROMIUM (III) CATALYSTS" MACROMOLECULAR: RAPID COMMUNICATIONS, WILEY VCH, WEINHEIM, DE, vol. 19, no. 3, 1 March 1998 (1998-03-01), pages 159-162, XP000766418 ISSN: 1022-1336 * |
SCHUMANN H ET AL: "CYCLOPENTADIENYLTHALLIUM(I) COMPOUNDS WITH BULKY CYCLOPENTADIENYL LIGANDS" JOURNAL OF ORGANOMETALLIC CHEMISTRY, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, vol. 330, no. 3, 1987, pages 347-355, XP009003400 ISSN: 0022-328X * |
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US7910670B2 (en) | 2005-08-19 | 2011-03-22 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
US8067609B2 (en) | 2007-01-08 | 2011-11-29 | Exxonmobil Chemical Patents Inc. | Methods for oligomerizing olefins with chromium pyridine thioether catalysts |
US8138348B2 (en) | 2007-01-08 | 2012-03-20 | Exxonmobil Chemical Patents Inc. | Methods for oligomerizing olefins with chromium pyridine mono-oxazoline catalysts |
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US8778827B2 (en) | 2007-11-28 | 2014-07-15 | Saudi Basic Industries Corporation | Catalyst composition and process for oligomerization of ethylene |
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CN115028509B (en) * | 2022-07-01 | 2024-02-02 | 万华化学集团股份有限公司 | Ethylene oligomerization process with enhanced reactivity and reduced polymer formation |
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EP1404446A2 (en) | 2004-04-07 |
AU2002323698A1 (en) | 2003-01-21 |
BR0210806A (en) | 2004-06-22 |
WO2003004158A3 (en) | 2004-01-22 |
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