WO2002083306A2 - Oligomerisation process and catalyst system - Google Patents
Oligomerisation process and catalyst system Download PDFInfo
- Publication number
- WO2002083306A2 WO2002083306A2 PCT/ZA2002/000064 ZA0200064W WO02083306A2 WO 2002083306 A2 WO2002083306 A2 WO 2002083306A2 ZA 0200064 W ZA0200064 W ZA 0200064W WO 02083306 A2 WO02083306 A2 WO 02083306A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst system
- aromatic ether
- substituted phenol
- ether
- benzene
- Prior art date
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Classifications
-
- 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
- C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
-
- 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
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- C07C2531/14—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
-
- 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 an oligomerisation catalyst system, such as a trimerisation catalyst system for trimerisation of ethylene to 1-hexene, to a method of preparation of said catalyst system, and to a process using said catalyst system.
- an oligomerisation catalyst system such as a trimerisation catalyst system for trimerisation of ethylene to 1-hexene
- the inventors are aware that the oligomerisation of olefins, primarily ⁇ - olefins, with chromium catalysts has been extensively studied. More specifically, a number of 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 polymerisation 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 / PAO's), 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:
- European Patent No. 0 668 105 discloses a process to trimerise ethylene to 1-hexene comprising contacting ethylene with a stabilized catalyst system comprising a chromium source, a pyrrole- containing compound, a metal alkyl and an aromatic compound;
- European Patent. No. 0 706 983 discloses a process for preparing an ⁇ -olefin oligomer which comprises oligomerising an ⁇ -olefin in a saturated hydrocarbon solvent in the presence of a chromium-based catalyst system comprising a combination of at least a chromium compound, an amine or metal amide, an alkylaluminium compound and a non-coordinating Lewis acid-containing compound based on an element selected from groups IIIB, IVB, VB and VIB of the periodic table;
- European Patent No. 0 699 648 discloses 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; f) US Patent No.
- 5,811 ,618 discloses 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 stibine coordination complex of a chromium salt, such that
- US Patent No. 6,031 , 145 discloses a catalyst system for the oligomerisation of ethylene to 1-butene or 1-hexene where in the catalytic composition is prepared using a pre-prepared chromium compound mixed with a pre-prepared aryloxy aluminium of a specified formula, and a hydrocarbyl aluminium selected from a specified group.
- This catalyst composition is active at the 0.1 mmol concentration level
- Heterogeneous catalyst systems are often selected over homogeneous catalyst systems due to relative ease of recovering and recycling such catalyst systems.
- the process of trimerisation of ethylene using chromium catalysts supported on an inorganic oxide has problems of insufficient activity, poor selectivity towards the intended trimeric product and leads to unsatisfactory levels of polyethylene by-product.
- a catalyst system, a method for preparing the catalyst system, and a process using the catalyst system is proposed with high activity and C6 selectivity for the trimerisation of ethylene to 1-hexene, typically the proposed system comprises a chromium source, a substituted phenol, and an alkyl aluminium compound.
- a catalyst system for the oligomerisation of olefins which catalyst system is prepared from catalyst components selected from the group including at least a chromium source, a substituted phenol, and an organoaluminium compound.
- the catalyst system may be a catalyst system for the trimerisation of ethylene to 1-hexene.
- the chromium source may be a chromium(lll) complex, a chromium (II) or chromium (III) salt, or a chromium salt with a different oxidation number which contains one or more identical or different anions such as halides, carboxylates, and acetylacetonates.
- the chromium source may preferably be chromium tris-2-ethylhexan ⁇ ate.
- the substituted phenol may be a di-substituted phenol.
- the substituted phenol may be a di-aryl-substituted phenol.
- the substituents on the phenol may be the same or different, linear or branched, hydrocarbyl groups containing 1 to 30 carbon atoms, for example alkyl, cycloalkyl, alkenyl, aryl, or substituted aralkyl, aryl or cycloalkyl.
- the substituted phenol may preferably be 2,6-diphenylphenol.
- the organoaluminium compound may be an alkyl aluminium compound.
- the organoaluminium compound may be in the form AI(R) 3 in which R is a linear or branched hyrocarbyl group having from 1 to 6 carbon atoms.
- the organoaluminium compound may preferably be triethylaluminium. Also known as TEA.
- the abovementioned catalyst system may be prepared by the mixing of the above-mentioned catalyst system components in a suitable solvent
- the catalyst system may include an aromatic ether.
- the aromatic ether may be an alkoxy benzene.
- the aromatic ether may be a mono alkoxy benzene.
- the aromatic ether may have the formula Aryl-O-R, in which R is a linear or branched hydrocarbyl radical having 1 to 6 carbon atoms.
- R is a linear or branched hydrocarbyl radical having 1 to 6 carbon atoms.
- the aryl group may be substituted or unsubstituted.
- Non limiting examples of aromatic ethers useful for the invention include methoxy benzene (anisole), 1 ,2-dimethoxy benzene, 1 ,3-dimethoxybenzene, 1,4- dimethoxy benzene, dibenzyl ether and diphenyl ether
- the aromatic ether may take the part of a solvent in the catalyst system to which it is added.
- the aromatic ether may however act as a co-catalyst, ligand or serve as a stabilizer of any complex formed.
- Magnetic susceptibility measurements using the Evans method indicate that a different catalytic system is formed when an aromatic ether is present than when it is not present.
- the chromium:TEA:substituted phenol ratio may be from 1:10:8 up to 1 :40:24, typically 1:20:24.
- the invention extends to a process for the trimerisation of ethylene to 1-hexene, said process including contacting an ethylene containing feed under oligomerisation reaction conditions to a catalyst system as described above, said process being carried out in a temperature range of 100°C to 140 °C .
- the process may be carried out at a temperature of 117°C to 125°C.
- the process may be carried out at a temperature of 120°C.
- the process may be carried out at a pressure of above 10 Barg, more specifically above 20 Barg, or even more specifically above 30 Barg.
- the process may be carried out by the introduction of an ethylene feedstock into a reactor with the catalyst system already present in the reactor at a temperature in said temperature range.
- the catalyst system may be present in the trimerisation reaction mixture at a concentration of chromium of less than 0.1 mmol, based on elemental chromium.
- the chromium (III) salt, substituted phenol and alkyl aluminium compound may be combined in a mixing container, such as a Schlenk tube, in a suitable solvent. This mixture may then be added to a reactor, such as a Parr reactor, at the appropriate temperature and pressurised with ethylene to form 1-hexene as the reaction product of trimerisation.
- each component may be added individually to the reactor at the appropriate temperature, in the appropriate solvent and pressurised with ethylene.
- the invention extends also to a method of preparing an oligomerization catalyst system substantially as described above, said method including at least the step of contacting in any order in a suitable medium: a substituted phenol; an organoaluminium compound; and a chromium source.
- the suitable medium may be an aromatic ether.
- the aromatic ether may be an alkoxy benzene.
- the aromatic ether may be a mono alkoxy benzene.
- the aromatic ether may have the formula Aryl-O-R, in which R is a linear or branched hydrocarbyl radical having 1 to 6 carbon atoms.
- R is a linear or branched hydrocarbyl radical having 1 to 6 carbon atoms.
- the aryl group may be substituted or unsubstituted.
- Non limiting examples of aromatic ethers useful for the invention include methoxy benzene (anisole), 1,2-dimethoxy benzene, 1,3-dimethoxybenzene, 1,4- dimethoxy benzene, dibenzyl ether and diphenyl ether
- the aromatic ether may take the part of a solvent in the catalyst system to which it is added.
- the aromatic ether may however act as a co-catalyst, ligand or serve as a stabilizer of any complex formed.
- the chromium source may be a chromium(lll) complex, a chromium (II) or chromium (III) salt, a chromium salt with a different oxidation number which contains one or more identical or different anions such as halides, carboxylates, and acetylacetonates.
- the chromium source may be chromium tris-2-ethylhexanoate.
- the substituted phenol may be a di-substituted phenol.
- the substituted phenol may be a di-aryl-substituted phenol.
- the substituents on the phenol may be the same or different, linear or branched, hydrocarbyl groups containing 1 to 30 carbon atoms, for example alkyl, cycloalkyl, alkenyl, aryl, or substituted aralkyl, aryl or cycloalkyl.
- the substituted phenol may be 2,6-diphenylphenol.
- the organoaluminium compound may be an alkyl aluminium compound.
- the organoaluminium compound may be in the form AI(R) 3 in which R is a linear or branched hyrocarbyl group having from 1 to 6 carbon atoms.
- the alkyl aluminium compound may be triethylaluminium, also known as TEA.
- the chromium:organoaluminium:substituted phenol ratio may be from 1 :10:8 up to 1 :40:24, typically 1:20:24.
- the catalyst system may be prepared at a temperature selected to be selective for a desired product, for example, 1-hexene.
- the invention extends to a homogeneous-ethylene-trimerisation-catalyst-system component, which component includes an aromatic ether having the formula Aryl-O-R, in which R is a linear or branched hydrocarbyl radical having 1 to 6 carbon atoms.
- the component is especially useful for catalyst systems including chromium complexes, substituted phenols and alkyl aluminium compounds
- the aromatic ether may be an alkoxy benzene.
- the aromatic ether may be a mono alkoxy benzene.
- Non limiting examples of aromatic ethers useful. for the invention include methoxy benzene (anisole), 1,2-dimethoxy benzene, 1 ,3-dimethoxybenzene, 1 ,4- dimethoxy benzene, dibenzyl ether and diphenyl ether
- the component may take the part of a solvent in the catalyst system to which it is added.
- the component may however act as a co-catalyst, ligand or serve as a stabilizer of any complex formed.
- a catalyst system was prepared in a 100 ml Schlenk tube using 0.06 mmol chromium tris-2-ethylhexanoate, 0.87 mmol 2,6-diphenylphenol and 1.2 mmol triethyl aluminium (1.6M in cyclohexane) in 20 ml of anisole. This was added at 130 deg. C to a 300 ml Parr autoclave containing 80 ml of anisole. The reactor was pressurised to 37.5 bar with ethylene, which was fed to the reactor on demand. After 30 minutes the reactor was depressurised, the polymer separated from the liquid product by filtration, and the liquid product was analysed (GC). The results are summarised in Table 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2002306188A AU2002306188A1 (en) | 2001-04-12 | 2002-04-12 | Oligomerisation process and catalyst system |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US28341901P | 2001-04-12 | 2001-04-12 | |
US28341701P | 2001-04-12 | 2001-04-12 | |
US60/283,417 | 2001-04-12 | ||
ZA2001/3047 | 2001-04-12 | ||
US60/283,419 | 2001-04-12 | ||
ZA200103047 | 2001-04-12 | ||
ZA2001/3049 | 2001-04-12 | ||
ZA200103049 | 2001-04-12 |
Publications (3)
Publication Number | Publication Date |
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WO2002083306A2 true WO2002083306A2 (en) | 2002-10-24 |
WO2002083306A3 WO2002083306A3 (en) | 2003-04-24 |
WO2002083306B1 WO2002083306B1 (en) | 2004-05-27 |
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PCT/ZA2002/000064 WO2002083306A2 (en) | 2001-04-12 | 2002-04-12 | Oligomerisation process and catalyst system |
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WO (1) | WO2002083306A2 (en) |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7060848B2 (en) | 2002-04-24 | 2006-06-13 | Symyx Technologies, Inc. | Bridged bi-aromatic catalysts, complexes, and methods of using the same |
US7091292B2 (en) | 2002-04-24 | 2006-08-15 | Symyx Technologies, Inc. | Bridged bi-aromatic catalysts, complexes, and methods of using the same |
US7241715B2 (en) | 2002-04-24 | 2007-07-10 | Symyx Technologies, Inc. | Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom |
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 |
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 |
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 |
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 |
WO2022023027A1 (en) * | 2020-07-30 | 2022-02-03 | IFP Energies Nouvelles | Novel chromium-based catalytic composition and associated method for the trimerisation of ethylene to hexene-1 |
WO2022023028A1 (en) * | 2020-07-30 | 2022-02-03 | IFP Energies Nouvelles | Ethylene oligomerisation process comprising in situ preparation of the catalytic composition |
FR3116738A1 (en) * | 2020-11-30 | 2022-06-03 | IFP Energies Nouvelles | NEW CATALYTIC COMPOSITION BASED ON CHROMIUM COMPRISING AN AROMATIC ETHER ADDITIVE AND ASSOCIATED PROCESS FOR THE OLIGOMERIZATION OF ETHYLENE INTO OCTENE-1 |
Citations (5)
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---|---|---|---|---|
US3081286A (en) * | 1956-11-19 | 1963-03-12 | Collier Carbon & Chemical Co | Polymerization of olefines with a group va or vla metal oxide-aluminum trialkyl-alkanol catalyst |
US4668838A (en) * | 1986-03-14 | 1987-05-26 | Union Carbide Corporation | Process for trimerization |
US5731487A (en) * | 1993-03-12 | 1998-03-24 | Sumitomo Chemical Company, Limited | Process for producing olefin having a terminal double bond |
US6031145A (en) * | 1997-06-17 | 2000-02-29 | Institut Francais Du Petrole | Catalytic composition and process for oligomerising ethylene in particular to 1-butene and/or 1-hexene |
US6127301A (en) * | 1996-06-28 | 2000-10-03 | Sumitomo Chemical Company, Limited | Catalyst system and method for reaction of olefin |
-
2002
- 2002-04-12 WO PCT/ZA2002/000064 patent/WO2002083306A2/en not_active Application Discontinuation
- 2002-04-12 AU AU2002306188A patent/AU2002306188A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US3081286A (en) * | 1956-11-19 | 1963-03-12 | Collier Carbon & Chemical Co | Polymerization of olefines with a group va or vla metal oxide-aluminum trialkyl-alkanol catalyst |
US4668838A (en) * | 1986-03-14 | 1987-05-26 | Union Carbide Corporation | Process for trimerization |
US5731487A (en) * | 1993-03-12 | 1998-03-24 | Sumitomo Chemical Company, Limited | Process for producing olefin having a terminal double bond |
US6127301A (en) * | 1996-06-28 | 2000-10-03 | Sumitomo Chemical Company, Limited | Catalyst system and method for reaction of olefin |
US6031145A (en) * | 1997-06-17 | 2000-02-29 | Institut Francais Du Petrole | Catalytic composition and process for oligomerising ethylene in particular to 1-butene and/or 1-hexene |
Non-Patent Citations (2)
Title |
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"ACROS CHIMICA Catalogue Handbook of Fine Chemicals 1994-1995" , ACROS CHIMICA XP002224816 page 559 * |
BUDAVARI ET AL. (EDS.): "THE MERCK INDEX, 12th Edition" 1996 , MERCK&CO , WHITEHOUSE STATION, NJ XP002224815 compound nos. 707,1167, 7442,10089 on pages 113,190,1225 and 1697 * |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7091292B2 (en) | 2002-04-24 | 2006-08-15 | Symyx Technologies, Inc. | Bridged bi-aromatic catalysts, complexes, and methods of using the same |
US7241714B2 (en) | 2002-04-24 | 2007-07-10 | Symyx Technologies, Inc. | Bridged bi-aromatic catalysts, complexes, and methods of using the same |
US7241715B2 (en) | 2002-04-24 | 2007-07-10 | Symyx Technologies, Inc. | Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom |
US7659415B2 (en) | 2002-04-24 | 2010-02-09 | Symyx Solutions, Inc. | Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom |
US7060848B2 (en) | 2002-04-24 | 2006-06-13 | Symyx Technologies, Inc. | Bridged bi-aromatic catalysts, complexes, and methods of using the same |
US7994376B2 (en) | 2004-02-19 | 2011-08-09 | Chevron Phillips Chemical Company Lp | Olefin oligomerization |
US8329608B2 (en) | 2004-02-20 | 2012-12-11 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
US7820581B2 (en) | 2004-02-20 | 2010-10-26 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
US9550841B2 (en) | 2004-02-20 | 2017-01-24 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
US8993822B2 (en) | 2004-02-20 | 2015-03-31 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
US7910670B2 (en) | 2005-08-19 | 2011-03-22 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
US8138348B2 (en) | 2007-01-08 | 2012-03-20 | Exxonmobil Chemical Patents Inc. | Methods for oligomerizing olefins with chromium pyridine mono-oxazoline catalysts |
US8629280B2 (en) | 2007-01-08 | 2014-01-14 | Exxonmobil Chemical Patents Inc. | Methods for oligomerizing olefins with chromium pyridine ether catalysts |
US8067609B2 (en) | 2007-01-08 | 2011-11-29 | Exxonmobil Chemical Patents Inc. | Methods for oligomerizing olefins with chromium pyridine thioether catalysts |
US7902415B2 (en) | 2007-12-21 | 2011-03-08 | Chevron Phillips Chemical Company Lp | Processes for dimerizing or isomerizing olefins |
US9586872B2 (en) | 2011-12-30 | 2017-03-07 | Chevron Phillips Chemical Company Lp | Olefin oligomerization methods |
WO2022023027A1 (en) * | 2020-07-30 | 2022-02-03 | IFP Energies Nouvelles | Novel chromium-based catalytic composition and associated method for the trimerisation of ethylene to hexene-1 |
WO2022023028A1 (en) * | 2020-07-30 | 2022-02-03 | IFP Energies Nouvelles | Ethylene oligomerisation process comprising in situ preparation of the catalytic composition |
FR3112969A1 (en) * | 2020-07-30 | 2022-02-04 | IFP Energies Nouvelles | NEW CATALYTIC COMPOSITION BASED ON CHROMIUM AND ASSOCIATED PROCESS FOR THE TRIMERIZATION OF ETHYLENE INTO HEXENE-1 |
FR3113054A1 (en) * | 2020-07-30 | 2022-02-04 | IFP Energies Nouvelles | METHOD FOR THE OLIGOMERIZATION OF ETHYLENE COMPRISING THE IN SITU PREPARATION OF THE CATALYTIC COMPOSITION |
FR3116738A1 (en) * | 2020-11-30 | 2022-06-03 | IFP Energies Nouvelles | NEW CATALYTIC COMPOSITION BASED ON CHROMIUM COMPRISING AN AROMATIC ETHER ADDITIVE AND ASSOCIATED PROCESS FOR THE OLIGOMERIZATION OF ETHYLENE INTO OCTENE-1 |
Also Published As
Publication number | Publication date |
---|---|
WO2002083306A3 (en) | 2003-04-24 |
WO2002083306B1 (en) | 2004-05-27 |
AU2002306188A1 (en) | 2002-10-28 |
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