WO2002083306A2 - Oligomerisation process and catalyst system - Google Patents

Oligomerisation process and catalyst system Download PDF

Info

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
Application number
PCT/ZA2002/000064
Other languages
French (fr)
Other versions
WO2002083306A3 (en
WO2002083306B1 (en
Inventor
Jacobus Johannes Cronje Grove
David Hedley Morgan
Sianne Lindsay Schwikkard
Barend Christiaan Buurman Bezuidenhoudt
Original Assignee
Sasol Technology (Pty) Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sasol Technology (Pty) Ltd filed Critical Sasol Technology (Pty) Ltd
Priority to AU2002306188A priority Critical patent/AU2002306188A1/en
Publication of WO2002083306A2 publication Critical patent/WO2002083306A2/en
Publication of WO2002083306A3 publication Critical patent/WO2002083306A3/en
Publication of WO2002083306B1 publication Critical patent/WO2002083306B1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04Preparation 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
    • C07C2/06Preparation 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
    • C07C2/08Catalytic processes
    • C07C2/26Catalytic processes with hydrides or organic compounds
    • C07C2/30Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143Catalysts 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04Preparation 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
    • C07C2/06Preparation 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
    • C07C2/08Catalytic processes
    • C07C2/26Catalytic processes with hydrides or organic compounds
    • C07C2/32Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C07C2/34Metal-hydrocarbon complexes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20Olefin oligomerisation or telomerisation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts 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
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/26Chromium
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22Organic 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides 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 invention further provides an aromatic ether component for a trimerisation catalyst system and an oligomerisation process using said catalyst.

Description

OLIGOMERISATION PROCESS AND CATALYST SYSTEM
Field of the Invention
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.
Background to the Invention
The inventors are aware that 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 polymerisation 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 / PAO's), 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 disclosed in US Patent No. 4,668,838, 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 hydrolysed with a specific amount of water and a donor ligand selected from hydrocarbyl isonitriles, amines and ethers; b) European Patent No. 0 416 304 discloses the 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;
c) 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;
d) European Patent. No. 0 706 983 discloses a process for preparing an α-olefin oligomer which comprises oligomerising an α-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;
e) 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
1-hexene is formed; and
g) 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. However, 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.
Summary of the Invention
According to a first aspect of the invention there is provided 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-ethylhexanύate.
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. 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 (see example 11) 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.
Alternativley, 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. 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.
The examples which follow are not intended to limit the invention but rather to show its working by example.
Description of Embodiments of the Invention
Example 1
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
Example 2
The reaction was carried out as per Example 1 except that 0.3 mmol of 2,6- diphenylphenol was used with 0.6 mmol triethyl aluminium. The reaction was performed at 130 °C and 50 barg pressure. The results are summarised in Table
1
Example 3
The reaction was carried out as per example 2 except that the reactor was pressurised to 25 barg. The results are summarised in Table 1
Example 4
The reaction was carried out as per Example 1 except that no 2,6 diphenylphenol was used. The results are summarised in Table 1.
Example 5
The reaction was carried out as per example 1 except that xylene was used as solvent instead of anisole. The results are summarised in Table 1.
Example 6
The reaction was carried out as per example 5 except that no 2,6-diphenylphenol was included. The results are summarised in Table 1. Example 7
The reaction was carried out as per example 1 except that 4-methylanisole was used as solvent. The results are summarised in Table 1.
Example 8
The reaction was carried out as per example 1 except that 4-bromoanisole was used as solvent. The results are summarised in Table 1.
Example 9
The reaction was carried out as per example 1 , except that 1.44 mmol 2,6-di(p- methoxyphenyl)phenol was used as ligand and the reaction was carried out at 120 °C. The results are summarised in Table 1.
Example 10
The reaction was carried out as per example 1, except that 0.87 mmol of 2,6- di(p-tolyl)phenol was used as ligand. The results are summarised in Table 1.
Example 11
The reaction was carried out as per example 1 except that 0.87 mmol of β- Napthol was used as ligand. The results are summarised in Table 1.
Table 1
Figure imgf000012_0001
Figure imgf000013_0001
Magnetic susceptibility measurements using Evans1 method gave the following results for catalyst systems with and without an aromatic ether component.
Figure imgf000013_0002
The above results indicate that a different catalytic system is formed when an aromatic ether is present.
References:
1 ) D.H. Evans: The Determination of the Paramagnetic Susceptibility of Substances in Solution by Nuclear Magnetic Resonance, J. Chem Soc.(1959), 2003-2005

Claims

Claims
1. 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.
2. A catalyst system as claimed in claim 1 , which catalyst system is suitable as an ethylene trimerisation catalyst system.
3. A catalyst system as claimed in any one of the preceding claims, wherein the substituted phenol is a di-substituted phenol.
4. A catalyst system as claimed in any one of the preceding claims, wherein the substituted phenol is a di-aryl-substituted phenol.
5. A catalyst system as claimed in any one of the preceding claims, wherein the substituents on the phenol are linear or branched hydrocarbon groups containing 1 to 30 carbon atoms.
6. A catalyst system as claimed in any one of the preceding claims, wherein the organoaluminium compound is an alkyl aluminium compound.
7. A catalyst system as claimed in any one of the preceding claims, wherein the organoaluminium compound is in the form AI(R)3 in which R is a linear or branched hydrocarbyl group having from 1 to 6 carbon atoms.
8. A catalyst system as claimed in any one of the preceding claims, wherein the substituted phenol is 2,6-diphenylphenol.
9. A catalyst system as claimed in any one of the preceding claims, wherein the organoaluminium compound is an alkyl aluminium compound.
10. A catalyst system as claimed in claim 9, wherein the alkyl aluminium compound is triethylaluminium (TEA).
11. A catalyst system as claimed in any one of the preceding claims, including an aromatic ether.
12. A catalyst system as claimed in claim 11 , wherein the aromatic ether is an alkoxy benzene.
13. A catalyst system as claimed in claim 11 or claim 12, wherein the aromatic ether is a mono alkoxy benzene.
14. A catalyst system as claimed in claim 11, wherein the aromatic ether has the formula Aryl-O-R, in which R is a linear or branched hydrocarbyl radical having 1 to 6 carbon atoms.
15. A catalyst system as claimed in any one of claims 11 to 14, wherein the aromatic ether is selected from one or more of the group including at least methoxy benzene (anisole), 1 ,2-dimethoxy benzene, 1 ,3-dimethoxybenzene, 1 ,4- dimethoxy benzene, dibenzyl ether, and diphenyl ether
16. A catalyst system as claimed in any one of claims 10 to 15, having a chromium:TEA:substituted phenol ratio from 1 :10:8 up to 1 :40:24.
17. A catalyst system as claimed in claim 16, having a chromium:TEA:substituted phenol ratio of 1 :20:24.
18. A process for the trimerisation of ethylene to 1-hexene, said process including the contacting of an ethylene containing stream under oligomerisation reaction conditions with a catalyst system which is prepared from catalyst components selected from the group including at least a chromium source, a substituted phenol, and an organoaluminium compound, said process being carried out in a desired temperature range of 100°C to 140 °C
19. A process as claimed in claim 18, wherein the catalyst components from which the catalyst system is prepared include an aromatic ether.
20. A process as claimed in claim 19, wherein the process is carried out at a temperature of 117°C to 125°C.
21. A process as claimed in claim 20, wherein the process is carried out at a temperature of 120°C.
22. A process as claimed in any one of claims 18 to 20, which is carried out at a pressure of above 10 Barg.
23. A process as claimed in any one of claims 18 to 22, which is carried out at a pressure of above 20 Barg.
24. A process as claimed in claim 23, which is carried out at a pressure of above 30 Barg.
25. A process as claimed in any one of claims 18 to 24, in which the catalyst system is present at an elemental chromium concentration, of less than 0.1 mmol/100ml.
26. A process as claimed in any one of claims 18 to 25, wherein the process is performed by the introduction of an ethylene feedstock into a reactor with the catalyst system already present in the reactor at a temperature in the temperature range of 100°C to 140°C.
27. A method of preparing an oligomerization catalyst system, 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.
28. A method as claimed in claim 27, wherein the suitable medium is an aromatic ether.
29. A method as claimed in claim 28, wherein the aromatic ether is an alkoxy benzene.
30. A method as claimed in claim 28 or claim 29, wherein the aromatic ether is a mono alkoxy benzene.
31. A method as claimed in claim 28, wherein the aromatic ether has the formula Aryl-O-R, in which R is a linear or branched hydrocarbyl radical having 1 to 6 carbon atoms.
32. A method as claimed in any one of claims 28 to 31, wherein the aromatic ether is selected from one or more of the group including at least methoxy benzene (anisole), 1 ,2-dimethoxy benzene, 1 ,3-dimethoxybenzene, 1 ,4- dimethoxy benzene, dibenzyl ether, and diphenyl ether
33. A method as claimed in any one of claims 27 to 32, wherein the chromium:organoaluminium compound substituted phenol ratio is from 1 :10:8 up to 1 :40:24, typically 1 :20:24.
34. A method as claimed in any one of claims 27 to 33, wherein the organoaluminium compound is an alkyl aluminium compound.
35. A method as claimed in claim 34, wherein the alkyl aluminium compound 5 is triethylaluminium (TEA).
36. A method as claimed in any one of claims 27 to 35, wherein the substituted phenol is 2,6-diphenyl phenol.
Q 37. 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.
38. A homogeneous ethylene trimerisation catalyst system component, as 5 claimed in claim 37, wherein the aromatic ether is an alkoxy benzene.
39. A homogeneous ethylene trimerisation catalyst system component, as claimed in claim 37 or claim 38, wherein the aromatic ether is a mono alkoxy benzene. 0
40. A homogeneous ethylene trimerisation catalyst system component, as claimed in any one of claims 37 to 39, wherein the aromatic ether is selected from the group including methoxy benzene (anisole), 1 ,2-dimethoxy benzene, 1 ,3-dimethoxybenzene, 1 ,4-dimethoxy benzene, dibenzyl ether, and diphenyl 5 ether
PCT/ZA2002/000064 2001-04-12 2002-04-12 Oligomerisation process and catalyst system WO2002083306A2 (en)

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
WO2002083306A2 true WO2002083306A2 (en) 2002-10-24
WO2002083306A3 WO2002083306A3 (en) 2003-04-24
WO2002083306B1 WO2002083306B1 (en) 2004-05-27

Family

ID=27501355

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/ZA2002/000064 WO2002083306A2 (en) 2001-04-12 2002-04-12 Oligomerisation process and catalyst system

Country Status (2)

Country Link
AU (1) AU2002306188A1 (en)
WO (1) WO2002083306A2 (en)

Cited By (16)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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)

* Cited by examiner, † Cited by third party
Title
"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)

* Cited by examiner, † Cited by third party
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

Similar Documents

Publication Publication Date Title
US6184428B1 (en) Catalyst and process for ethylene oligomerization
JP4308015B2 (en) Trimerization and oligomerization of olefins using a chromium-based catalyst
JP6921088B2 (en) Antifouling oligomerization catalyst system
KR100518501B1 (en) Process for oligomerizing the catalyst composition and ethylene in particular with 1-butene and / or 1-hexene
EP1915329B2 (en) Oligomerisation of olefinic compounds in the presence of a diluted metal containing activator
EP0668106B1 (en) Olefin production
US4533651A (en) Catalysts for olefin oligomerization and isomerization
EP2328905B2 (en) Ethylene tetramerization catalysts comprising p-n-p ligands
US7361623B2 (en) Trimerisation and oligomerisation of olefins using a chromium based catalyst
WO2002083306A2 (en) Oligomerisation process and catalyst system
US20020177744A1 (en) Linear alpha-olefin dimers possessing substantial linearity
EP1492746A1 (en) Selective coupling of terminal olefins with ethylene to manufacture linear alpha-olefins
US7696397B2 (en) Catalytic composition and its application to olefin oligomerization
AU2600601A (en) Processes for preventing generation of hydrogen halides in an oligomerization product recovery system
JPH01221335A (en) Dimerization of lower alpha-olefin
US5166114A (en) Ethylene dimerization and catalyst therefor
US5260499A (en) Ethylene dimerization and catalyst therefor
US5286696A (en) Ethylene oligomerization and catalyst therefor
US4686315A (en) Oligomerization of ethylene using nickel ylide/alkyl aluminum alkoxide catalyst
US5059739A (en) Hydrogen chloride-free catalyst system for dimerizing and codimerizing olefins
Khamiyev et al. Oligomerization of ethylene in the presence of heterogenized complex catalytic systems based on ionic liquid‐type substituted zirconium phenolates
EP0327743B1 (en) Procedure for manufacturing short-chain linear alpha- olefines from ethylene
KR20210087528A (en) Ligand for production of chromium assisted 1-octene and method for ethylene oligomerization using same
US3644562A (en) Nickel dimerisation catalysts
KR102728965B1 (en) Method for Separating Olefin Oligomerization Products (Variants)

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ CZ DE DE DK DK DM DZ EC EE EE ES FI FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

B Later publication of amended claims

Effective date: 20030212

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase in:

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP