CA2510801C - Tetramerization of olefins - Google Patents

Tetramerization of olefins Download PDF

Info

Publication number
CA2510801C
CA2510801C CA2510801A CA2510801A CA2510801C CA 2510801 C CA2510801 C CA 2510801C CA 2510801 A CA2510801 A CA 2510801A CA 2510801 A CA2510801 A CA 2510801A CA 2510801 C CA2510801 C CA 2510801C
Authority
CA
Canada
Prior art keywords
methoxyphenyl
phenyl
group
catalyst system
transition metal
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
CA2510801A
Other languages
French (fr)
Other versions
CA2510801A1 (en
Inventor
Kevin Blann
Annette Bollmann
John Thomas Dixon
Arno Neveling
David Hedley Morgan
Hulisani Maumela
Esna Killian
Fiona Millicent Hess
Stefanus Otto
Matthew James Overett
Michael James Green
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sasol Technology Pty Ltd
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
Publication of CA2510801A1 publication Critical patent/CA2510801A1/en
Application granted granted Critical
Publication of CA2510801C publication Critical patent/CA2510801C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • C07C2/36Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
    • 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
    • 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
    • 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
    • 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
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • 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
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • 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
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1865Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
    • B01J31/187Amide derivatives thereof
    • 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
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1875Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
    • B01J31/188Amide derivatives thereof
    • 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
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1885Ligands comprising two different formal oxidation states of phosphorus in one at least bidentate ligand, e.g. phosphite/phosphinite
    • 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
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22Organic complexes
    • B01J31/2204Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • 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
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24Phosphines, 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
    • B01J31/2404Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00Compounds containing elements of Groups 6 or 16 of the Periodic System
    • C07F11/005Compounds containing elements of Groups 6 or 16 of the Periodic System compounds without a metal-carbon linkage
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46Titanium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48Zirconium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/50Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/56Vanadium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/50Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/58Tantalum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62Chromium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/64Molybdenum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/66Tungsten
    • 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
    • B01J31/128Mixtures of organometallic compounds
    • 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
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1608Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
    • 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
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • 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
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/165Polymer immobilised coordination complexes, e.g. organometallic complexes
    • 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
    • C07C2531/24Phosphines
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/26Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
    • C07C2531/34Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of chromium, molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02Ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/03Multinuclear procatalyst, i.e. containing two or more metals, being different or not
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/639Component covered by group C08F4/62 containing a transition metal-carbon bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Abstract

The invention describes a process for tetramerisation of olefins wherein the product stream of the process contains more than 30% of the tetramer olefin.
The process includes the step of contacting an olefinic feedstream with a catalyst system containing a transition metal compound and a heteroatomic ligand.

Description

TETRAMERIZATION OF OLEFINS
Field of the invention:

This invention relates to the oligomerisation of ethylene. More particularly, the invention relates to a tetramerisation process, a catalyst system for tetramerisation of olefins and the identification and use of ligands for a catalyst system for tetramerisation of olefins.
Background of the invention This invention defines a process and catalyst system, that facilitates the production of 1-octene in high selectivity, while avoiding the co-production of significant quantities of butenes, other octene isomers, specific higher oligomers and polyethylene. The catalyst system can also be used for the tetramerisation of other olefins, especially a-olefins.
Despite the well known value of 1-octene, the art does not teach a commercially successful process for the tetramerisation of ethylene to produce 1-octene selectively.
Conventional ethylene oligomerisation technologies produce a range of a olefins following either a Schulz-Flory or Poisson product distribution. By definition, these mathematical distributions limit the mass % of the tetramer that can be formed and make a distribution of products. In this regard, it is known from the prior art (US
patent 6,184,428) that a nickel catalyst comprising a chelating ligand, preferably 2-diphenyl phosphino benzoic acid (DPPBA), a nickel compound, preferably NiC12.6H20, and a catalyst activator, preferably sodium tetraphenylborate, catalyse the oligomerisation of ethylene to yield a mixture of linear olefins. The selectivity towards linear C8 a-olefins is claimed to be 19%. Similarly the Shell Higher Olefins Process (SHOP process, US
patents 3,676,523 and 3,635,937) using a similar catalyst system is reported to typically yield 11 mass % 1-octene in its product mixture (Chem Systems PERP 1997, reports 90-1, 93-6 "Alpha Olefins" and 94/95S12 "Hexene-1 via Ethylene Trimerisation").

Ziegler-type technologies based on trialkylaluminium catalysts, independently developed by Gulf Oil Chemicals Company (Chevron, e.g. DE patent 1,443,927) and Ethyl Corporation (BP/Amoco, e.g. US patent 3,906,053), are also commercially used to oligomerise ethylene to mixtures of olefins that reportedly contain 13-25 mass % 1-octene (Chem Systems PERP 1997, reports 90-1,93-6, "Alpha Olefins" and 94/95S12 "Rexene-1 via Ethylene Trimerisation").

The prior art also teaches that chromium-based catalysts containing heteroatomic ligands with both phosphorus and nitrogen heteroatoms selectively catalyse the trimerisation of ethylene to 1-hexene. Examples of such heteroatomic ligands for ethylene trimerisation include bis(2-diethylphosphino-ethyl) amine (WO 03/053891) as well as (o-methoxyphenyl)2PN(methyl) P(o-methoxyphenyl)2 (WO 02/04119). Both these catalyst systems and processes are very specific for the production of 1-hexene and only yield 1-octene as an impurity (typically less than 3 mass %

of the product mixture as disclosed by WO 02/04119). The coordinating phosphorus heteroatoms in (o-methoxyphenyl)2PN(methyl)P(o-methoxyphenyl)2 (WO 02/04119) are spaced apart by one nitrogen atom. It is believed that the nitrogen atom does not coordinate, at least in the absence of an activator, with the chromium and that without any further electron donating atoms on the ligand that it is a bidentate system. Furthermore it is argued that the polar, or electron donating substituents in the ortho-position of the phenyl groups help form a tridentate system, which is generally believed to enhance selectivity towards 1-hexene formation as reiterated by the inventor of WO
02/04119 in Chem. Commun., 2002,858-859, Cohen, N.A. et al.
"High Activity Trimerisation Catalysts Based On Diphosphine Ligands" by stating "This has led us to hypothesise that the potential for ortho-methoxy groups to act as pendent donors and increase the coordinative saturation of the chromium centre is an important factor". To support their hypothesis, the authors of Chem. Commun., 2002, 858-859, Cohen, N.A. et al. "High Activity Trimerisation Catalysts Based On Diphosphine Ligands" showed that the use of (p-methoxyphenyl)2PN(methyl)P(p-methoxyphenyl)2r a compound without any such ortho-polar substituents on at least one of R1, R2, R3 and R4, as a ligand under catalytic conditions resulted in no catalytic activity towards a-olefins.

WO 02/04119 (Example 16) teaches the production of octenes using a trimerisation of olefins process and catalyst system. In this instance, 1-butene was co-trimerised with two ethylene molecules to give 25% octenes. However, the nature of these octenes was not disclosed and the applicant believes that they consist of a mixture of linear and branched octenes.

The prior art teaches that high 1-octene selectivities cannot be achieved since expansion of the generally accepted seven-membered metallacycle reaction intermediate for ethylene trimerisation (Chem. Commun., 1989, 674, J.R. Briggs "The Selective Trimerization of Ethylene to Hex-1-ene") to a nine-membered metallacycle is unlikely to occur (Organometallics, 2003, 22, 2564; Angew. Chem. Int. Ed., 2003, 42 (7), 808, Blok, A.N.J. et al. "Mechanism of Ethene Trimerization at an ANSA-(Arene)(Cyclopentadienyl) Titanium Fragment"). It is argued that the nine-membered ring is the least favoured medium sized ring and should thus be disfavoured relative to the seven-membered ring (Organometallics, 2003, 22, 2564 Blok, A.N.J. et al.
"Mechanism of Ethene Trimerization at an ANSA-(Arene)(Cyclopentadienyl) Titanium Fragment"). In addition, it is also stated by the same authors that, "if a nine-membered ring formed, it would be more likely to grow to an eleven- or thirteen-membered ring...In other words, one would never expect much octene, but formation of some (linear) decene or dodecene would be more reasonable".
Despite the teaching of the opposite, the applicant has now found a process for selectively producing a tetramerised olefin. The applicant has further found that chromium-based catalysts containing mixed heteroatomic ligands with both nitrogen and phosphorus heteroatoms, with polar substituents on the hydrocarbyl or heterohydrocarbyl groups on the phosphorous atoms, can be used to selectively tetramerise ethylene to 1-octene often in excess of 60 mass%
selectivity. This high 1-octene selectivity cannot be achieved via conventional one-step ethylene oligomerisation or trimerisation technologies which at most yield 25 mass%
1-octene.

Summary of the invention This invention relates to a process for selectively producing tetrameric products.

This invention specifically relates to a process for selectively producing tetrameric products such as 1-octene from olefins such as ethylene.

The invention relates to a process of selectively producing tetrametric products using a transition metal catalyst system containing a heteroatomic ligand.

According to a first aspect of the invention there is provided a process for tetramerisation of olefins wherein the product of the tetramerisat.ion process is an olefin and makes up more than 30% of the product stream of the process.
According to a second aspect of the invention the tetramerisation process includes the step of contacting an olefinic feedstream with a catalyst system which includes a transition metal and a heteroatomic ligand and wherein the product of the tetramerisation process is an olefin and makes up more than 30%
of the product stream of the process.

In one specific aspect, the invention relates to a process for tetramerisation of olefins wherein a product stream of the process contains at least 30% of the tetramer olefin comprising contacting an olefinic feedstream with a catalyst system which comprises the combination of: a transition metal compound;
and a heteroatomic ligand defined by the following general formula (R1)(R2)A-B-C(R3)(R4) wherein A and C are independently an atom selected from the group consisting of phosphorus, arsenic, antimony, bismuth and nitrogen, or phosphorus, arsenic, antimony, bismuth or nitrogen are independently oxidized by S, Se, N or 0, where the valence of A and/or C allows for such oxidation; B is a linking group between A and C; and each of R1, R2, R3 and R4 is independently selected from the group consisting of non-aromatic groups, aromatic homohydrocarbyl groups, and non-aromatic and aromatic heterohydrocarbyl groups; at least one of R1, R2, R3 and has a polar substituent group on a second or further atom from the atom bound to A or C and provided that any polar substituents that R1, R2, R3 and R4 may have are not on the atom adjacent to the atom bound to A or C so as to obtain the desired oligomer(s) in the product stream.

In a further specific aspect, the invention relates to a tetramerisation catalyst system to be used in the above process, comprising: a transition metal compound; and a heteroatomic ligand defined by the following general formula (R1)(R2)A-B-C(R3)(R4) wherein A and C are independently an atom selected from the group consisting of phosphorus, arsenic, antimony, bismuth and nitrogen, or phosphorus, arsenic, antimony, bismuth or nitrogen are independently oxidized by S, Se, N or 0, where the valence of A and/or C allows for such oxidation; B is a linking group between 4a A and C; and each of R', R2, R3 and R4 is independently selected from the group consisting of non-aromatic groups, aromatic homohydrocarbyl groups, and non-aromatic and aromatic heterohydrocarbyl groups; at least one of R1, R2, R3 and R4 has a polar substituent group on a second or further atom from the atom bound to A or C and provided that any polar substituents that R1, R2, R3 and R4 may have are not on the atom adjacent to the atom bound to A or C.

4b In this specification, % will be understood to, be a mass %.

The term tetramerisation" generally refers to the reaction of four, and preferably four identical, olefinic monomer units to yield a linear and/or branched olefin.

By heteroatomic is meant a ligand that contains at least two heteroatoms, which can be the same or different, where the heteroatoms may be selected from phosphorus, arsenic, antimony, sulphur, oxygen, bismuth, selenium or nitrogen.

The feedstream will be. understood to include an olefin to be tetramerised and can be introduced into the process according to the invention in a continuous or batch fashion.
The product stream will be understood to indude a tetramer, which tetramer is produced according to the invention in a continuous or batch fashion.

The feedstream may include an a-olefin and the product stream may include at least 30%, preferably at least 35%, of a tetramerised a-olefin monomer.

The process may indude a process for tetramerisation of a-olefins. Under the term a-olefins is meant all hydrocarbon compounds with terminal double bonds. This definition includes ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-octene and the like.

The process may indude a process for tetrameilsation of a-olefins to selectively yield tetrameric a-olefin products.

The olefinic feedstream may include ethylene and the product stream may include at least 30% 1-octene. The process may be a process for tetramerisation of ethylene.

The invention allows the ligand, catalyst system and/or process conditions to be selected to give a product stream of more than 40%, 50%, or 60% a-olefins. It may be 4c Printed: 05-04-2005. DESC? ZA0300186 preferable, depending on the further use of the product stream, to have such high selectivities of the a-olefin.

The olefinic feedstream may include ethylene and the (C6 + C8) : (C4 + Cio) ratio in the product stream may be more than 2.5:1.

The olefinic feedstream may include ethylene and the C8 : C6 ratio in the product stream is more than 1.

The ethylene may be contacted with the catalyst system at a pressure of greater than 100 kPa (1 barg) and preferably greater than 1000 kPa (10 barg), more preferably greater than 3000 kPa (30 barg).

The heteroatomic ligand may be described by the following general formula (R)õA-B-C(R), where A and C are independently selected from a group which comprises phosphorus, arsenic, antimony, oxygen, bismuth, sulphur, selenium, and nitrogen, and B is a linking group between A and-C, and R is independently selected from any homo or heterohydrocarbyl group of which at least one R group is substituted with a polar substituent and n and m is determined by the respective valence and oxidation state of A and C.

A and/or C may be a potential electron donor for coordination with the transition metal.

An electron donor or electron donating substituent is defined as that entity that donates electrons used in chemical, including dative covalent, bond formation.

The heteroatomic ligand may be described by the following general formula (R')(R2)A-B-C(R3)(R4) where A and C are independently selected from a group which comprises phosphorus, arsenic, antimony, bismuth and nitrogen and B is a linking group between A and C, and R1, R2, R3 and R4 are independently selected from non-aromatic and aromatic, including heteroaromatic, groups of which at least one of R', R2, R3 and R4 is substituted with a polar substituent.

In some embodiments of the process aspect of the invention, up to four of R', R2, R3 and R4 may have substituents on the atom adjacent to the atom bound to A or C.

AMENDS? 14EET 5 In addition to at least one of R', R2, R3 and R4 being substituted with a polar substituent, each of R', R2, R3 and R4 may be aromatic, including heteroaromatic, but preferably not, all of R', R2, R3 and R4, if they all are aromatic, are substituted by any substituent on an atom adjacent to the atom bound to A or C.

In addition to at least one of R', R2, R3 and R4 being substituted with a polar substituent, not more than two of R', R2, R3 and R4, if they are aromatic, may have substituents on the atom adjacent to the atom bound to A or C.

Any polar substituents on R', R2, R3 and R4, if they are aromatic, may preferably not be on the atom adjacent to the atom bound to A or C.

At least one of R', R2, R3 and R4, if aromatic, may be substituted with a polar substituent on the 2" d or further atom from the atom bound to A or C.

Any polar substituent on one or more of R', R2, R3 and R4 may be electron donating.
Polar is defined by IUPAC as an entity with a permanent electric dipole moment. Polar substituents include methoxy, ethoxy, isopropoxy, C3-C20 alkoxy, phenoxy, pentafluorophenoxy, trimethylsiloxy, dimethylamino, methylsuffanyl, tosyt, methoxymethy, methyithiomethyl, 1,3-oxazolyl, methomethoxy, hydroxyl, amino, phosphino, arsino, stibino, sulphate, nitro and the like.

Any of the groups R', R2, R3 and R4 may independently be linked to one or more of each other or to the linking group B to form a cyclic structure together with A and C, A and B
or B and C.

R', R2, R3 and R4 may be independently selected from a group comprising a benzyt, phenyl, tolyl, xyfyl, mesityt, biphenyl, naphthyl, anthracenyt, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, diethylamino, methylethylamino, thiophenyt, pyridyl, thioethyl, thiophenoxy, trimethytsilyl, dimethythydrazyt, methyl, ethyl, ethenyl, propyl, butyl, propenyl, propynyl, cyclopentyl, cyclohexyl, ferrocenyl and tetrahydrofuranyl group.

Preferably, R1, R2, R3 and R4 may independently be selected from a group comprising a phenyl, tolyl, biphenyl, naphthyl, thiophenyl and ethyl group.

A and/or C may be independently oxidised by S, Se, N or 0, where the valence of A and/or C allows for such oxidation.

A and C may be independently phosphorus or phosphorus oxidised by S or Se or N or 0.

B may be selected from any one of a group comprising: organic linking groups comprising a hydrocarbylene, a substituted hydrocarbylene, a heterohydrocarbylene and a substituted heterohydrocarbylene;
inorganic linking groups comprising single atom links; ionic links; and a group comprising methylene, dimethylmethylene, 1,2-ethylene, 1,2-phenylene, 1,2-propylene, 1,2-catecholate, - (CH3) N-N (CH3) -, -B (R5) -, -Si (R5) 2-, -P (R5) - and -N (R5) - where R5 is hydrogen, a hydrocarbyl or substituted hydrocarbyl, a substituted heteroatom or a halogen. Preferably, B may be -N(R5)- and R5 is a hydrocarbyl or a substituted hydrocarbyl group. R5 may be hydrogen or may be selected from the group consisting of alkyl, substituted alkyl, aryl, substituted aryl, aryloxy, substituted aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino, silyl groups or derivatives thereof, and aryl substituted with any of these substituents. Preferably R5 may be an isopropyl, a 1-cyclohexylethyl, a 2-methylcyclohexyl or a 2-octyl group.

B may be selected to be a single atom spacer. A
single atom linking spacer is defined as a substituted or non-substituted atom that is bound directly to A and C.

The ligand may also contain multiple (R),A-B-C(R)m units. Non limiting examples of such ligands include dendrimeric ligands as well as ligands where the individual units are coupled either via one or more of the R groups or via the linking group B. More specific, but non limiting, examples of such ligands may include 1, 2-di- (N (P (4-methoxyphenyl) 2) 2) -benzene, 1, 4-di- (N (P (4-methoxyphenyl) 2) 2) -benzene, N (CH2CH2N (P (4 -methoxyphenyl) 2) 2) 3 and 1,4-di-(P(4-methoxyphenyl)N(methyl)P(4-methoxyphenyl)2)-benzene.

7a The ligands can be prepared using procedures known to one skilled in the art and procedures disdosed in published literature. Examples of ligands are: (3-methoxyphenyl)2PN(methyl)P(3-methoxyphenyt)2, (4-methoxyphenyl)2PN(methyl)P(4 methoxyphenyt)2s - . (3-methoxyphenyl)2PN(isopropyl)P(3-methoxyphenyl)2,(4 methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(2-ethylhexyl)P(4-methoxyphenyl)2, (3-methoxyphenylxphenyl)PN(methyl)P(phenyl)2 and (4-methoxyphenyl)(phenyl)PN(methyl)P(phenyl)2i (3-methoxyphenyl)(phenyl)PN(methyl)P(3-methoxyphenylxphenyl), (4-methoxyphenyl)(phenyl)PN(methyl)P(4-methoxyphenyl)(phenyl), (3-methoxyphenyl)2PN(meth)4)P(phenyl)2 and (4-metho)cyphenyl)2PN(methyl)P(phenyl)2, (4 methoxyphenyl)2PN(1-cydohexylethyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(2-methylcyclohexyl)P(4-methoxyphenyl)2r (4-methoxyphenyl)2PN(decyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(pentyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(benzyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(phenyl)P(4-methoxypheriyl)2, (4- luorophenyl)2PN(methyl)P(4fluorophenyl)2, (2-fluorophenyl)2PN(methyl)P(2-fluorophenyl)2i (4-dimethylamino-phenyl)2PN(methyl)P(4 dimethylamino-phenyl)2i (4-methoxyphenyl)2PN(allyl)P(4-methoxyphenyl)2, (phenyl)2PN(isopropyl)P(2-methoxyphenyl)2, (4(4-methoxyphenyl)-phenyl)2PN(isopropyl)P(4-(4-methoxyphenyl)-phenyl)2 and (4-methoxyphenylXphenyl)PN(isopropyl)P(phenyl)2.

The catalyst system may include an activator and the process may include the step of combining in any order a heteroatomic ligand with a transition metal compound and an activator.

The process may indude the step of generating a heteroatomic coordination complex in situ from a transition metal compound and a heteroatomic ligand. The process may indude the step of adding a pre-formed coordination complex, prepared using a heteroatomic ligand and a transition metal compound, to a reaction mixture, or the step of adding separately to the reactor, a heteroatomic ligand and a transition metal compound such that a heteroatomic coordination complex of a transition metal is generated in situ. By generating a heteroatomic coordination complex in situ is meant that the complex is generated in the medium in which catalysis takes place.
Typically, the heteroatomic coordination complex is generated in situ. Typically, the transition metal compound, and heteroatomic ligand are combined (both in situ and ex situ) to provide metal/Iigand ratios from about 0.01:100 to 10 000:1, and preferably, from about 0.1:1 to 10:1.

The transition metal may be selected from any one of a group comprising chromium, molybdenum, tungsten, titanium, tantalum, vanadium and zirconium, preferably chromium.

The transition metal compound which, upon mixing with the heteroatomic ligand and an activator, catalyses ethylene tetramerisation in accordance with the invention, may be a simple inorganic or organic salt, a co-ordination or organometallic complex and may be selected from any one of a group comprising chromium trichloride tris-tetrahydrofuran complex, (benzene)tricarbonyl chromium, chromium (III) octanoate, chromium hexacarbonyl, chromium (III) acetylacetonoate and chromium (III) 2-ethylhexanoate. The preferred transition metal compounds include chromium (III) acetylacetonoate and chromium (III) 2-ethylhexanoate.

The heteroatomic ligand can be modified to be attached to a polymer chain so that the resulting heteroatomic coordination complex of the transition metal is soluble at elevated temperatures, but becomes insoluble at 25 C. This approach would enable the recovery of the complex from the reaction mixture for reuse and has been used for other catalyst as described by D.E. Bergbreiter et al., J. Am. Chem. Soc., 1987, 109, 177-179. In a similar vein these transition metal complexes can also be immobilised by binding the heteroatomic ligands for example to silica, silica gel, polysiloxane, alumina backbone or the like as demonstrated, for example, by C. Yuanyin et al., Chinese J. React.
Pol., 1992, 1(2), 152-159 for immobilising platinum complexes.

The activator for use in the process may in principle be any compound that generates an active catalyst when combined with the heteroatomic ligand and the transition metal compound. Mixtures of activators may also be used. Suitable compounds include organoaluminium compounds, organoboron compounds, organic salts, such as methyllithium and methylmagnesium bromide, inorganic acids and salts, such as tetrafluoroboric acid etherate, silver tetrafluoroborate, sodium hexafluoroantimonate and the like.

Suitable organoaluminium compounds include compounds of the formula AIR3, where each R is independently a Cl-C12 alkyl, an oxygen containing moiety or a halide, and compounds such as LiAIH4 and the like. Examples include trimethylaluminium (TMA), triethylaluminium (TEA), tri-isobutylaluminium (TIBA), tri-n-octylaluminium, methylaluminium dichloride, ethylaluminium dichloride, dimethylaluminium chloride, diethylaluminium chloride, aluminium isopropoxide, ethylaluminiumsesquichloride, methylaluminiumsesquichloride, and aluminoxanes. Aluminoxanes are well known in the art as typically oligomeric compounds which can be prepared by the controlled addition of water to an alkylaluminium compound, for example trimethylaluminium. Such .
compounds can be linear, cyclic, cages or mixtures thereof. Mixtures of different aluminoxanes may also be used in the process.

Examples of suitable organoboron compounds are boroxines, NaBH4, triethylborane, tris(pentafluoropheny)borane, tributyl borate and the like.

The activator may also be or contain a compound that acts as a reducing or oxidising agent, such as sodium or zinc metal and the like, or oxygen and the like.

The activator may be selected from alkylaluminoxanes such as methylaluminoxane (MAO) and ethylaluminoxane (EAO) as well as modified alkylaluminoxanes such as modified methylaluminoxane (MMAO). Modified methylaluminoxane (a commercial product from Akzo Nobel) contains modifier groups such as isobutyl or n-octyl groups, in addition to methyl groups.

The transition metal and the aluminoxane may be combined in proportions to provide Al/metal ratios from about 1:1 to 10 000:1, preferably from about 1:1 to 1000:1, and more preferably from 1:1 to 300:1.

The process may include the step of adding to the catalyst system a trialkylaluminium compound in amounts of between 0.01 to 1000 mol per mol of alkylaluminoxane.

It should be noted that aluminoxanes generally also contain considerable quantities of the corresponding trialkylaluminium compounds used in their preparation. The presence of these trialkylaluminium compounds in aluminoxanes can be attributed to their incomplete hydrolysis with water. Any quantity of a trialkylaluminium compound quoted in this disclosure is additional to alkylaluminium compounds contained within the aluminoxanes.

The process may include the step of mixing the components of the catalyst system at any temperature between -20 C and 250 C in the presence of an olefin. The applicant has found that the presence of an olefin may stabilise the catalyst system.

The individual components of the catalyst system described herein may be combined simultaneously or sequentially in any order, and in the presence or absence of a solvent, in order to give an active catalyst. The mixing of the catalyst components can be conducted at any temperature between -20 C and 250 C. The presence of an olefin during the mixing of the catalyst components generally provides a protective effect which may result in improved catalyst performance. The preferred temperature range may be between 20 C and 100 C.

The catalyst system, in accordance with the invention, or its individual components, may also be immobilised by supporting it on a support material, for example, silica, alumina, MgCI2, zirconia or mixtures thereof, or on a polymer, for example polyethylene, polypropylene, polystyrene, or poly(aminostyrene). The catalyst can be formed in situ in the presence of the support material, or the support can be pre-impregnated or premixed, simultaneously or sequentially, with one or more of the catalyst components.
In some cases, the support material can also act as a component of the activator. This approach would also facilitate the recovery of the catalyst from the reaction mixture for reuse. The concept was, for example, successfully demonstrated with a chromium-based ethylene trimerisation catalyst by T. Monoi and Y. Sasaki, J. Mol.
Cat.A:Chem., 1987, 109, 177-179. In some cases, the support can also act as a catalyst component, for example where such supports contain aluminoxane functionalities or where the support is capable of performing similar, chemical functions as an aluminoxane, which is for instance the case with IOLATM (a commercial product from Grace Davison).

The reaction products or in other words olefin oligomers, as described herein, may be prepared using the disclosed catalyst system by homogeneous liquid phase reaction in Printed: 05-04-2005 DESC 'ZA0300186 1 the presence or absence of an inert solvent, and/or by slurry reaction where the catalyst system is in a form that displays little or no solubility, and/or a two-phase liquid/liquid reaction, and/or a bulk phase reaction in which neat reagent and/or product olefins serve as the dominant medium, and/or gas phase reaction, using conventional equipment and contacting techniques.

The process may therefore also be carried out in an inert solvent. Any inert solvent that does not react with the activator can be used. These inert solvents may include any saturated aliphatic and unsaturated aliphatic and aromatic hydrocarbon and halogenated hydrocarbon. Typical solvents include, but are not limited to, benzene, toluene, xylene, cumene, heptane, methylcyclohexane, methylcyclopentane, cyclohexane, 1 -hexene, 1 -octene, ionic liquids and the like.

The process may be carried out at pressures from atmospheric to 50000 (500 barg).
Ethylene pressures in the range of 1000-7000 kPa (10-70 barg) are preferred.
Particularly preferred pressures range from 3000-5000 (30-50 barg).

The process may be carried out at temperatures from - 20 C - 250 C.
Temperatures in the range of 15-130 C are preferred. Particularly preferred temperatures range from 35-100 C.

In a preferred embodiment of the invention, the heteroatomic coordination complex and reaction conditions are selected such that the yield of 1-octene from ethylene is greater than 30 mass %, preferably greater than 35 mass %. In this regard yield refers to grams of 1 -octene formed per 100g of total reaction product formed.

In addition to 1 -octene, the process may also yield different quantities of 1 -butene, 1-hexene, methylcyclopentane, methylene cyclopentane, propylcyclopentane, propylene cyclopentane and specific higher oligomers, depending on the nature of the heteroatomic ligand and the reaction conditions. A number of these products cannot be formed via conventional ethylene oligomerisation and trimerisation technologies in the yields observed in the present invention.

AMEM)EP SHEET" 12 Although the catalyst, its individual components, reagents, solvents and reaction products are generally employed on a once-through basis, any of these materials can, and are indeed preferred to be recycled to some extent in order to minimise production costs.

The process may be carried out in a plant which includes any type of reactor.
Examples of such reactors include, but are not limited to, batch reactors, semi-batch reactors and continuous reactors. The plant may include, in combination a) a reactor, b) at least one inlet line into this reactor for olefin reactant and the catalyst system, c) effluent lines from this reactor for oligomerisation reaction products, and d) at least one separator to separate the desired oligomerisation reaction products, wherein the catalyst system may include a heteroatomic coordination complex of a transition metal compound and an activator, as described herein.

In another embodiment of the process the reactor and a separator may be combined to facilitate the simultaneous formation of reaction products and separation of these compounds from the reactor. This process principle is commonly known as reactive distillation. When the catalyst system exhibits no solubility in the solvent or reaction products, and is fixed in the reactor so that it does not exit the reactor with the reactor product, solvent and unreacted olefin, the process principle is commonly known as catalytic distillation.

According to a further aspect of the invention, there is provided a catalyst system, as described above, for the tetramerisation of olefins. The catalyst system may include a heteroatomic ligand as described above and a transition metal. The catalyst system may also include an activator as described above.

The heteroatomic ligand may be described by the following general formula (R)nA-B-C(R)m where A and C are independently selected from a group which comprises phosphorus, arsenic, antimony, oxygen, bismuth, sulphur, selenium, and nitrogen, and B
is a linking group between A and C, and R is independently selected from any homo or heterohydrocarbyl group of which at least one R group is substituted with a polar substituent and n and m is determined by the respective valence and oxidation state of A
and C.

A and/or C may be a potential electron donor for coordination with the transition metal.
An electron donor or electron donating substituent is defined as that entity that donates electrons used in chemical, including dative covalent, bond formation.

The heteroatomic ligand may be described by the following general formula (R')(R2)A-B-C(R3)(R4) where A and C are independently selected from a group which comprises phosphorus, arsenic, antimony, bismuth and nitrogen and B is a linking group between A
and C, and R1, R2, R3 and R4 are independently selected from non-aromatic and aromatic, including heteroaromatic, groups of which at least one of R1, R2, R3 and R4 is substituted with a polar substituent.

In addition to at least one of R1, R2, R3 and R4 being substituted with a polar substituent, each of R1, R2, R3 and R4 may be aromatic, including heteroaromatic, but preferably not all of R1, R2, R3 and R4, if they all are aromatic, are substituted by any substituent on an atom adjacent to the atom bound to A or C.

In addition to at least one of R', R2, R3 and R4 being substituted with a polar substituent, not more than two of R', R2, R3 and R4, if they are aromatic, may have substituents on the atom adjacent to the atom bound to A or C.

Any polar substituents on R1, R2, R3 and R4, if they are aromatic, may preferably not be on the atom adjacent to the atom bound to A or C.

Any polar substituent on one or more of R', R2, R3 and R4 may be electron donating.
Polar is defined as an entity with a permanent electric dipole moment. Polar substituents include methoxy, ethoxy, isopropoxy, C3-C20 alkoxy, phenoxy, pentafluorophenoxy, trimethylsiloxy, dimethylamino, methylsulfanyl, tosyl, methoxymethy, methylthiomethyl, 1,3-oxazolyl, methomethoxy, hydroxyl, amino, phosphino, arsino, stibino, sulphate, nitro and the like.

Any of the groups R1, R2, R3 and R4 may independently be linked to one or more of each other or to the linking group B to form a cyclic structure together with A and C, A and B
or B and C.

R', R2, R3 and R4 may be independently selected from a group comprising a benzyl, phenyl, tolyl, xylyl, mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, diethylamino, methylethylamino, thiophenyl, pyridyl, thioethyl, thiophenoxy, trimethylsilyl, dimethylhydrazyl, methyl, ethyl, ethenyl, propyl, butyl, propenyl, propynyl, cyclopentyl, cyclohexyl, ferrocenyl and tetrahydrofuranyl group.
Preferably, R1, R2, R3 and R4 may independently be selected from a group comprising a phenyl, tolyl, biphenyl, naphthyl, thiophenyl and ethyl group.

A and/or C may be independently oxidised by S, Se, N or 0, where the valence of A
and/or C allows for such oxidation.

A and C may be independently phosphorus or phosphorus oxidised by S or Se or N
or 0.

B may be selected from any one of a group comprising: organic linking groups comprising a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and a substituted heterohydrocarbyl; inorganic linking groups comprising single atom links;
ionic links; and a group comprising methylene, dimethylmethylene, 1,2-ethane, 1,2-phenylene, 1,2-propane, 1,2-catechol, 1,2-dimethylhydrazine, -B(R5)-, -Si(R5)2-, -P(R5)- and -N(R5)-where R5 is hydrogen, a hydrocarbyl or substituted hydrocarbyl, a substituted heteroatom or a halogen. Preferably, B may be -N(R5)- and R5 is a hydrocarbyl or a substituted hydrocarbyl group. R5 may be hydrogen or may be selected from the groups consisting of alkyl, substituted alkyl, aryl, substituted aryl, aryloxy, substituted aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino, silyl groups or derivatives thereof, and aryl substituted with any of these substituents. Preferably R5 may be an isopropyl, a 1-cyclohexylethyl, a 2-methylcyclohexyl or a 2-octyl group.

B may be selected to be a single atom spacer. A single atom linking spacer is defined as a substituted or non-substituted atom that is bound directly to A and C.

The ligand may also contain multiple (R)BA-B-C(R)m units. Not limiting examples of such ligands include dendrimeric ligands as well as ligands where the individual units are coupled either via one or more of the R groups or via the linking group B .
More specific, but not limiting, examples of such ligands may include 1,2-di-(N(P(4-phenyl)2)2)-benzene, 1,4-di-(N(P(4-methoxyphenyl)2)2)-benzene, N(CH2CH2N(P(4-methoxyphenyl)2)2)3 and 1,4-di-(P(4-methoxyphenyl)N(methyl)P(4-methoxyphenyl)2)-benzene.

The ligands can be prepared using procedures known to one skilled in the art and procedures disclosed in published literature. Examples of ligands are: (3-methoxyphenyl)2PN(methyl)P(3-methoxyphenyl)2, (4-methoxyphenyl)2PN(methyl)P(4-methoxyphenyl)2, (3-methoxyphenyl)2PN(isopropyl)P(3-methoxyphenyl)2,(4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(2-ethylhexyl)P(4-methoxyphenyl)2, (3-methoxyphenyl)(phenyl)PN(methyl)P(phenyl)2 and (4-methoxyphenyl)(phenyl)PN(methyl)P(phenyl)2, (3-methoxyphenyl)(phenyl)PN(methyl)P(3-methoxyphenyl)(phenyl), (4-methoxyphenyl)(phenyl)PN(methyl)P(4-methoxyphenyl)(phenyl), (3-methoxyphenyl)2PN(methyl)P(phenyl)2 and (4-methoxyphenyl)2PN(methyl)P(phenyl)2, (4-methoxyphenyl)2PN(1-cyclohexylethyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(2-methylcyclohexyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(decyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(pentyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(benzyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(phenyl)P(4-methoxyphenyl)2, (4-fluorophenyl)2PN(methyl)P(4-fluorophenyl)2, (2-fluorophenyl)2PN(methyl)P(2-fluorophenyl)2, (4-dimethylamino-phenyl)2PN(methyl)P(4-dimethylamino-phenyl)2, (4-methoxyphenyl)2PN(allyl)P(4-methoxyphenyl)2, (phenyl)2PN(isopropyl)P(2-methoxyphenyl)2, (4-(4-methoxyphenyl)-phenyl)2PN(isopropyl)P(4-(4-methoxyphenyl)-phenyl)2 and (4-methoxyphenyl)(phenyl)PN(isopropyl)P(phenyl)2.

The transition metal may be selected from any one of a group comprising chromium, molybdenum, tungsten, titanium, tantalum, vanadium and zirconium, preferably chromium.

The transition metal may be derived from a transition metal compound selected from a simple inorganic or organic salt, a co-ordination or organometallic complex, which may be selected from a group comprising chromium trichloride tris-tetrahydrofuran complex, (benzene)tricarbonyl chromium, chromium (III) octanoate, chromium (III) acetylacetonoate, chromium hexacarbonyl, and chromium (III) 2-ethylhexanoate.
The preferred transition metal compounds include chromium (III) acetylacetonoate and chromium (III) 2-ethylhexanoate.

The transition metal compound and heteroatomic ligand may have metal/ligand ratios from about 0.01:100 to 10 000:1, preferably from about 0.1:1 to 10:1.

The catalyst system may also include an activator as described above.

The activator may in principle be any compound that generates an active catalyst when combined with the heteroatomic ligand and the transition metal compound.
Mixtures of activators may also be used. Suitable compounds include organoaluminium compounds, organoboron compounds, organic salts, such as methyllithium and methylmagnesium bromide, inorganic acids and salts, such as tetrafluoroboric acid etherate, silver tetrafluoroborate, sodium hexafluoroantimonate and the like.

The activator may be selected from alkylaluminoxanes such as methylaluminoxane (MAO) and ethylaluminoxane (EAO) as well as modified alkylaluminoxanes such as modified methylaluminoxane (MMAO). Modified methylaluminoxane (a commercial product from Akzo Nobel) contains modifier groups such as isobutyl or n-octyl groups, in addition to methyl groups. The transition metal and the aluminoxane may be in such proportions relative to each other to provide Al/metal ratios from about 1:1 to 10 000:1, preferably from about 1:1 to 1000:1, and more preferably from 1:1 to 300:1.

The catalyst system may also include a trialkylaluminium compound in amounts of between 0.01 to 100 mol per mol of aluminoxane.

According to an even further aspect of the invention, there is provided a ligand, as described above, for a catalyst system, as described above, for the tetramerisation of olefins.

The invention also extends to the identification and use of ligands suitable for use in a tetramerisation of olefins process or catalyst system.

EXAMPLES OF PERFORMING THE INVENTION

The invention will now be described with reference to the following examples which are not in any way intended to limit the scope of the invention. The individual components of the examples may conceivably be omitted or substituted and, although not necessarily ideal, the invention may conceivably still be performed and these components are not to be taken as essential to the working of the invention.

In the examples that follow all procedures were carried out under inert conditions, using pre-dried reagents. Chemicals were obtained from Sigma-Aldrich or Strem Chemicals unless stated otherwise. All trialkylaluminium and aluminoxane compounds and solutions thereof were obtained from Crompton Gmbh, Akzo Nobel and Albemarle Corporation. In all the examples, the molar mass of methylaluminoxane (MAO) was taken to be 58.016 g/mol, corresponding to the (CH3-Al-O) unit, in order to calculate the molar quantities of MAO used in the preparation of the catalysts described in the examples below. Similarly the molar mass of ethylaluminoxane (EAO) was taken as 72.042 g/mol, corresponding to the (CH3CH2-AI-O) building block, and that of modified methylaluminoxane prepared from a 70:30 mixture of trimethylaluminium and tri-isobutylaluminium as 70.7 g/mol corresponding to the (Meo.7oisonBuo.30-Al-O) unit.
Ethylene oligomerisation products were analysed by GC-MS and GC-FID.

The mixed heteroatomic PNP ligands were made by reacting amines and phosphine chlorides R2PCI as described in (a) Ewart et al, J. Chem. Soc. 1964, 1543; (b) Dossett, S.J. et al, Chem. Commun., 2001, 8, 699; (c) Balakrishna, M.S. et al, J.
Organomet.
Chem. 1990, 390, 2, 203). The respective phosphine chlorides R2PCI were prepared as described in literature (Casalnuovo, A.L. et al, J. Am. Chem. Soc. 1994, 116, 22, 9869;
Rajanbabu, T.V. et al, J. Org. Chem. 1997, 62, 17, 6012).

Example 1 : Preparation of the (4-methoxyphenyl)2PN(isopropyl)P(4-phenyl), ligand Example 1a) : Preparation of N,N-Diisopropylphosphoramide dichloride Diisopropylamine (70 ml, 0.50 mol) in toluene (80 ml) was added to a solution of PCI3 (21.87 ml, 0.25 mol) in toluene (80 ml) at -10 C. The mixture was stirred for two hours and then allowed to warm to room temperature. The solution was stirred for a further hour after which it was filtered through a pad of celite. The product (35 g, 0.17 mol, 68 %) was obtained after removal of the solvent. 31P
{H}
NMR: 170 ppm Example 1b) Preparation of 4-methoxvphenvl-magnesium bromide Magnesium turnings (9.11 g, 0.375 mol) were treated with 4-bromoanisole (9.39 ml, 75 mmol) in THE (100 ml). A vigorous reaction ensued which was cooled in an ice bath.
Once the reaction had dissipated, the reaction mixture was heated under reflux for 2 hours yielding the Grignard reagent.

Example 1c) : Preparation of Bis(4-methoxvphenvl) phosphorus chloride The Grignard reagent was added to N,N-diisopropylphosphoramide dichloride (6.64 ml, 36 mmol) in THE (100 ml) at 0 C. After stirring at room temperature overnight the mixture was diluted with cyclohexane (200 ml) and dry HCI gas was bubbled through the solution for 0.5 hours. After filtration of the precipitate, the solvent was removed to give a mixture of the phosphine chloride and bromide in an 80% yield. This crude product was not isolated and all was used in the next step.

Example Id) Preparation of (4-methoxvphenvl)2PN(isopropyl)P(4-methoxvphenvl)2 To a solution of the crude Bis(4-methoxyphenyl) phosphorus chloride (28.8 mmol calculated from crude reaction mixture) in DCM (80 ml) and triethylamine (15 ml) at 0 C
was added isopropylamine (1.11 ml ,13 mmol). The reaction was stirred for 30 min after I Printed: 05-04-20051 DESC ZA03001861 which the ice bath was removed. After stirring for a total of 14 hrs the solution was filtered to remove the triethylammonium salt formed. The product was isolated after crystallisation in a 77 % yield.31p {H} NMR: 47.4 ppm (broad singlet) Example 2: Ethylene tetramerisation reaction using Cr (III) acetylacetonoate, (4-methoxyphenyl)2PN(methyl)P(4-methoxyphenyl)2 and MAO
A solution of 30.0 mg of (4-methoxyphenyl)2PN(methyl)P(4-methoxyphenyl)2 (0.066 mmol) in 10 ml of toluene was added to a solution of 11.5 mg chromium (III) acetylacetonoate (0.033 mmol) in 10 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80ml) and MAO
(methylaluminoxane, 9.9 mmol) at 60 C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 65 C, while the ethylene pressure was kept at 3000 kPa (30 barg). Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 30 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 10 C. After releasing the excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid wax/polymeric products. These solid products were dried overnight in an oven at 100 C and then weighed to yield 0.2254 g of polyethylene. The GC analyses indicated that the reaction mixture contained 38.50g oligomers. The product distribution of this example is summarised in Table 1.

Example 3: Ethylene tetramerisation reaction using Cr (III) acetylacetonoate, (3-methoxyphenyl)2PN(methyl)P(3-methoxyphenyl)2 and MAO
A solution of 30.0 mg of (3-methoxyphenyl)2PN(methyl)P(3-methoxyphenyl)2 (0.066 mmol) in 10 ml of toluene was added to a solution of 11.5 mg chromium (III) acetylacetonoate (0.033 mmol) in 10 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80m1) and MAO

15 A. EVDE'4O SHEE' 12-11-2004 Printed: 05-04-2005 DESC ZA0300186 , (methylaluminoxane, 9.9 mmol) at 60 C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 65 C, while the ethylene pressure was kept at 3000 kPa (30 barg). Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 30 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 10 C. After releasing the excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid wax/polymeric products. These solid products were dried overnight in an oven at 100 C and then weighed to yield 1.2269 g of polyethylene. The GC analyses indicated that the reaction mixture contained 9.71 g oligomers. The product distribution of this example is summarised in Table 1.

Example 4: Ethylene tetramerisation reaction using Cr (III) acetylacetonoate, (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 and MAO
A solution of 36.1 mg of (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 (0.066 mmol) in 10 ml of toluene was added to a solution of 11.5 mg chromium (III) acetylacetonoate (0.033 mmol) in 10 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80m1) and MAO
(methylaluminoxane, 9.9 mmol) at 60 C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 65 C, while the ethylene pressure was kept at 3000 kPa (30 barg). Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 30 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 10 C. After releasing the excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid wax/polymeric products. These solid products were dried overnight in an oven at 100 C and then weighed to yield 0.7105 g of polyethylene. The GC analyses indicated 1r)i SHED

1:6 Printed: 05-04-2005 { DESC ZA0300186 that the reaction mixture contained 61.33g oligomers. The product distribution of this example is summarised in Table 1.

Example 5: Ethylene tetramerisation reaction using Cr (III) acetylacetonoate, (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 and MAO
A solution of 36.1 mg of (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 (0.066 mmol) in 10 ml of toluene was added to a solution of 11.5 mg chromium (III) acetylacetonoate (0.033 mmol) in 10 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80ml) and MAO
(methylaluminoxane, 9.9 mmol) at 40 C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45 C, while the ethylene pressure was kept at 4500 kPa (45 barg). Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 12 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 10 C. After releasing the excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid wax/polymeric products. These solid products were dried overnight in an oven at 100 C and then weighed to yield 2.3010 g of polyethylene. The GC analyses indicated that the reaction mixture contained 73.53g oligomers. The product distribution of this example is summarised in Table 1.

Example 6: Ethylene tetramerisation reaction using Cr (III) acetylacetonoate, (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 and MAO
A solution of 16.4 mg of (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 (0.03 mmol) in 10 ml of cyclohexane was added to a solution of 5.2 mg chromium (III) acetylacetonoate (0.015 mmol) in 10 ml cyclohexane in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of cyclohexane (80ml) and MAO (methylaluminoxane in toluene, 4.5 mmol) at 40 C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45 C, while the .MIE~J n SHEET 22 17 12 11'-2004 Printed: 05-04-2005 DESC ZA0300186 ethylene pressure was kept at 4500 kPa (45 barg). Thorough mixing was ensured throughout by mixing speeds of 1100 RPM'S using a gas entraining stirrer. The reaction was terminated after 11 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 10 C. After releasing the excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid wax/polymeric products. These solid products were dried overnight in an oven at 100 C and then weighed to yield 1.9168 g of polyethylene. The GC analyses indicated that the reaction mixture contained 62.72g oligomers. The product distribution of this example is summarised in Table 1.

Example 7: Ethylene tetramerisation reaction using Cr (III) acetylacetonoate, (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 and MAO
A solution of 9.8 mg of (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 (0.018 mmol) in 10 ml of toluene was added to a solution of 5.2 mg chromium (III) acetylacetonoate (0.015 mmol) in 10 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80m1) and MAO
(methylaluminoxane, 4.5 mmol) at 40 C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45 C, while the ethylene pressure was kept at 4500 kPa (45 barg). Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 21 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 10 C. After releasing the excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid wax/polymeric products. These solid products were dried overnight in an oven at 100 C and then weighed to yield 0.8280 g of polyethylene. The GC analyses indicated that the reaction mixture contained 69.17 g oligomers. The product distribution of this example is summarised in Table 1.

18 . 1.2-1`1-2004 Printed: 05-04-2005 DESC ZA0300186 Example 8: Ethylene tetramerisation reaction using CrC13.THF3 , (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 and MAO
A solution of 9.8 mg of (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 (0.018 mmol) in 10 ml of toluene was added to a solution of 5.6 mg CrCl3.THF3 (0.015 mmol) in 10 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80ml) and MAO (methylaluminoxane, 4.5 mmol) at 40 C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45 C, while the ethylene pressure was kept at 4500 kPa (45 barg). Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 10 C. After releasing the excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10%
hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid wax/polymeric products. These solid products were dried overnight in an oven at 100 C and then weighed to yield 1.0831 g of polyethylene. The GC analyses indicated that the reaction mixture contained 42.72 g oligomers. The product distribution of this example is summarised in Table 1.

Example 9: Ethylene tetramerisation reaction using Cr (III) 2-ethylhexanoate , (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 and MAO
A solution of 9.8 mg of (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 (0.018 mmol) in 10 ml of toluene was added to a solution of 10.2 mg Cr (III) 2-ethylhexanoate (70% in mineral oil, 0.015 mmol) in 10 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80m1) and MAO (methylaluminoxane, 4.5 mmol) at 40 C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45 C, while the ethylene pressure was kept at 4500 kPa (45 barg). Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer.
The reaction was terminated after ~t Fp IsHFI
1 CA 02510801 2005-06-17 `Ar Printed: 05-04-20W DESC ~ZA0300186', 30 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 10 C. After releasing the excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10%
hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid wax/polymeric products. These solid products were dried overnight in an oven at 100 C and then weighed to yield 1.52 g of polyethylene.
The GC analyses indicated that the reaction mixture contained 61.27 g oligomers.
The product distribution of this example is summarised in Table 1.

Example 10: Ethylene tetramerisation reaction using Cr (III) octanoanoate , (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 and MAO
A solution of 9.8 mg of (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 (0.018 mmol) in 10 ml of toluene was added to a solution of 10.3 mg Cr (III) octanoate (70%
in toluene, 0.015 mmol) in 10 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80ml) and MAO
(methylaluminoxane, 4.5 mmol) at 40 C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45 C, while the ethylene pressure was kept at 4500 kPa (45 barg). Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 40 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 10 C. After releasing the excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid wax/polymeric products. These solid products were dried overnight in an oven at 100 C and then weighed to yield 0.3773 g of polyethylene. The GC analyses indicated that the reaction mixture contained 18.91 g oligomers. The product distribution of this example is summarised in Table 1.

4p~ " SHEET 25 CA 02510801 2005-06-17 iV1`
20 !' 12-11-2004 Printed: '05-04-20051 DESC ZA0300186 Example 11: Ethylene tetramerisation reaction using Cr (III) acetylacetonoate, (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 and MAO
A solution of 6.6 mg of (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 (0.012 mmol) in 10 ml of toluene was added to a solution of 3.5 mg chromium (III) acetylacetonoate (0.015 mmol) in 10 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80ml) and MAO
(methylaluminoxane, 3.0 mmol) at 40 C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45 C, while the ethylene pressure was kept at 4500 kPa (45 barg). Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 30 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 10 C. After releasing the excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid wax/polymeric products. These solid products were dried overnight in an oven at 100 C and then weighed to yield 1.3958 g of polyethylene. The GC analyses indicated that the reaction mixture contained 54.52 g oligomers. The product distribution of this example is summarised in Table 1.

Example 12: Ethylene tetramerisation reaction using Cr (III) acetylacetonoate, (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 and MAO

A solution of 9.8 mg of (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 (0.018 mmol) in 10 ml of toluene was added to a solution of 5.2 mg chromium (III) acetylacetonoate (0.015 mmol) in 10 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80m1) and MAO
(methylaluminoxane in toluene, 2.25 mmol) at 40 C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45 C, while the ethylene pressure was kept at 4500 kPa (45 barg). Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer.
The reaction was terminated after 15 minutes by Printed: 05-04-2005 DESC ZA0300186 discontinuing the ethylene feed to the reactor and cooling the reactor to below 10 C.
After releasing the excess ethylene from the autoclave, the liquid -contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water.
Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid wax/polymeric products. These solid products were dried overnight in an oven at 100 C and then weighed to yield 0.5010 g of polyethylene.
The GC analyses indicated that the reaction mixture contained 70.87 g oligomers.
The product distribution of this example is summarised in Table 1.

Example 13: *Ethylene tetramerisation reaction using Cr (III) acetylacetonoate, (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 and MMAO-3A
A solution of 16.4 mg of (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 (0.03 mmol) in 10 ml of toluene was added to a solution of 5.2 mg chromium (III) acetylacetonoate (0.015 mmol) in 10 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80ml) and MMAO-(modified methylaluminoxane in heptanes, 4.5 mmol) at 40 C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45 C, while the ethylene pressure was kept at 4500 kPa (45 barg). Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 22 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 10 C. After releasing the excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid wax/polymeric products. These solid products were dried overnight in an oven at 100 C and then weighed to yield 1.76 g of polyethylene. The GC analyses indicated that the reaction mixture contained 50.42g oligomers. The product distribution of this example is summarised in Table 1.

a~ 27 Printed: 05-04-2005 DESC ZA0300186 Example 14: Ethylene tetramerisation reaction using Cr (III) acetylacetonoate, (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 and EAO/TMA
A solution of 36.1 mg of (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 (0.066 mmol) in 10 ml of toluene was added to a solution of 5.2 mg chromium (III) acetylacetonoate (0.015 mmol) in 10 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80ml), EAO
(ethylaluminoxane in toluene, 33 mmol) and TMA (trimethylaluminium, 8.25mmol) at 40 C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45 C, while the ethylene pressure was kept at kPa (45 barg). Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 60 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below C. After releasing the excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water.
Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid wax/polymeric products. These solid products were dried overnight in an oven at 100 C and then weighed to yield 0.189 g of polyethylene. The GC analyses indicated that the reaction mixture contained 40.97g oligomers.
The product distribution of this example is summarised in Table 1.

Example 15: Ethylene tetramerisation reaction using Cr (III) acetylacetonoate, (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 and MAO in the presence of H2 o h A solution of 16.4 mg of (4-methoxYphenY1)2PN(isopropYI)P(4 methxYpenY1)2 (0.03 mmol) in 10 ml of toluene was added to a solution of 5.2 mg chromium (III) acetylacetonoate (0.015 mmol) in 10 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80m1) and MAO
(methylaluminoxane in toluene, 4.5 mmol) at 40 C. The pressure reactor was first charged with hydrogen to a pressure of approximately 250 kPa (2.5 barg) and subsequently with ethylene to 4500 kPa (45 barg) after which the reactor temperature was maintained at 45 C, while the ethylene pressure was kept at kPa (45 barg). Thorough mixing was ensured throughout by mixing speeds of 1100 23; 12-11-2004 Printed: 06-04-2005 DESC ' ZA0300186' RPM's using a gas entraining stirrer. The reaction was terminated after 15 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below C. After releasing the excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water.
Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid wax/polymeric products. These solid products were dried overnight in an oven at 100 C and then weighed to yield 1.2060 g of polyethylene.
The GC analyses indicated that the reaction mixture contained 81.51 g oligomers.
The product distribution of this example is summarised in Table 1.

Example 16: Ethylene tetramerisation reaction using Cr (III) acetylacetonoate, (phenyl)2PN(isopropyl)P(2-methoxyphenyl)2 and MAO

A solution of 32.2 mg of (phenyl)2PN(isopropyl)P(2-methoxyphenyl)2 (0.066 mmol) in 10 ml of toluene was added to a solution of 11.5 mg chromium (III) acetylacetonoate (0.033 mmol) in 10 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80ml) and MAO (methylaluminoxane in toluene, 4.5 mmol) at 40 C. The pressure reactor was first charged with ethylene after which the reactor temperature was maintained at 45 C, while the ethylene pressure was kept at 4500 kPa (45 barg). Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 15 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 10 C. After releasing the excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid wax/polymeric products. These solid products were dried overnight in an oven at 100 C and then weighed to yield 6.82 g of polyethylene. The GC analyses indicated that the reaction mixture contained 38.33 g oligomers. The product distribution of this example is summarised in Table 1.

q~ 29 Table 1: Ethylene tetramerisation runs: Examples 2- 16 Total 1-Example Activity Product Solids Liquids Liquid Product Distribution Octene in C8 g prod./g g Wt % Wt % Wt % Wt %
Cr C4 C6 C8 C10 C11+
2 22622 38.72 0.58 99.42 3.2 26.0 50.1 4.2 16.0 93.5 3 6376 10.94 11.21 88.79 2.8 33.8 37.5 1.4 19.5 92.2 4 36156 62.04 1.15 98.08 0.5 39.1 51.5 2.9 5.8 98.8 44301 75.83 3.03 96.97 1.2 24.4 61.1 1.0 10.7 98.0 6 83515 62.64 2.97 97.03 1.0 24.5 54.9 1.0 16.0 97.0 7 90432 69.99 1.18 98.82 1.1 23.2 62.9 0.6 10.9 98.4 8 56365 43.80 2.47 97.53 1.1 24.4 69.3 0.8 3.6 98.9 9 80510 62.79 2.42 97.58 1.3 23.1 62.7 2.6 10.1 98.0 24924 19.29 1.96 98.04 1.0 23.4 67.3 0.9 6.4 98.6 11 107331 55.92 2.50 97.50 1.3 25.4 63.0 1.0 7.8 98.0 12 92214 71.37 0.70 99.30 1.0 23.5 65.4 0.9 3.1 98.6 13 66911 52.18 3.37 96.86 2.0 18.3 65.8 2.7 11.1 98.4 14 23987 41.16 0.46 99.54 2.1 28.3 63.5 1.4 4.5 98.2 106055 82.71 1.46 98.54 1.9 32.6 63.2 1.1 1.1 98.0 16 26310 45.15 15.11 84.89 0.3 36.7 46.3 5.8 10.6 98.5

Claims (54)

CLAIMS:
1. A process for tetramerisation of olefins wherein a product stream of the process contains at least 30% of the tetramer olefin comprising contacting an olefinic feedstream with a catalyst system which comprises the combination of:

- a transition metal compound; and - a heteroatomic ligand defined by the following general formula (R1)(R2)A-B-C(R3)(R4) wherein A and C are independently an atom selected from the group consisting of phosphorus, arsenic, antimony, bismuth and nitrogen, or phosphorus, arsenic, antimony, bismuth or nitrogen are independently oxidized by S, Se, N or O, where the valence of A and/or C allows for such oxidation;

B is a linking group between A and C; and each of R1, R2, R3 and R4 is independently selected from the group consisting of non-aromatic groups, aromatic homohydrocarbyl groups, and non-aromatic and aromatic heterohydrocarbyl groups;

at least one of R1, R2, R3 and R4 has a polar substituent group on a second or further atom from the atom bound to A or C and provided that any polar substituents that R1, R2, R3 and R4 may have are not on the atom adjacent to the atom bound to A or C so as to obtain the desired oligomer(s) in the product stream.
2. The process as claimed in claim 1, wherein each of R1, R2, R3 and R4 is aromatic or heteroaromatic, but not all of R1, R2, R3 and R4 are substituted by a substituent on an atom adjacent to the atom bound to A or C.
3. The process as claimed in claim 2, wherein not more than two of R1, R2, R3 and R4 have substituents on the atom adjacent to the atom bound to A or C.
4. The process as claimed in claim 1, wherein each polar substituent that one or more of R1, R2, R3 and R4 may have is electron donating.
5. The process as claimed in claim 1, wherein the olefinic feedstream comprises an .alpha.-olefin and the product stream comprises at least 30% of a tetramerised .alpha.-olefin monomer.
6. The process as claimed in claim 5, wherein the olefinic feedstream comprises ethylene and the product stream comprises at least 30% 1-octene.
7. The process as claimed in claim 1, wherein the olefinic feedstream comprises ethylene and the product stream comprises C4, C6, C8 and C10 oligomers wherein the (C6+C8):(C4+C10) ratio in said product stream is more than 2.5:1.
8. The process as claimed in claim 1, wherein the olefinic feedstream comprises ethylene and wherein the C8:C6 ratio in the product stream is more than 1.
9. The process as claimed in claim 1, wherein the olefinic feedstream is contacted with the catalyst system at a pressure which is greater than 100 kPa (1 barg).
10. The process as claimed in claim 1, wherein ethylene is contacted with the catalyst system at a pressure of more than 1000 kPa (10 barg).
11. The process as claimed in claim 1, wherein A and/or C are a potential electron donor for coordination with the transition metal.
12. The process as claimed in claim 1, wherein B is selected from the group consisting of an organic linking group consisting of a hydrocarbylene, a substituted hydrocarbylene, a hetero hydrocarbylene or a substituted hetero hydrocarbylene; an inorganic linking group consisting of a single atom linking spacer; and a group consisting of methylene, dimethylmethylene, 1,2-ethylene, 1,2-phenylene, 1,2-propylene, 1,2-catecholate, -(CH3)N-N(CH3)-, -B(R5)-, -Si(R5)2-, -P(R5)- or -N(R5)-, where R5 is hydrogen, a hydrocarbyl or substituted hydrocarbyl, a substituted heteroatom or a halogen.
13. The process as claimed in claim 12, wherein B is a single atom linking spacer.
14. The process as claimed in claim 12, wherein B is -N(R5)-, wherein R5 is a substituent selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, aryloxy, substituted aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino, silyl groups, and aryl substituted with any of these substituents.
15. The process as claimed in claim 1, wherein A and/or C is independently oxidised by S, Se, N or O, where the valence of A and/or C allows for such oxidation.
16. The process as claimed in claim 1, wherein A and C are independently phosphorous or phosphorous oxidised by S or Se or N or O.
17. The process as claimed in claim 1, wherein R1, R2, R3 and R4 are independently selected from the group consisting of benzyl, phenyl, tolyl, xylyl, mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, diethylamino, methylethylamino, thiophenyl, pyridyl, thioethyl, thiophenoxy, trimethylsilyl, dimethylhydrazyl, methyl, ethyl, ethenyl, propyl, butyl, propenyl, propynyl, cyclopentyl, cyclohexyl, ferrocenyl and tetrahydrofuranyl group.
18. The process as claimed in claim 1, wherein the ligand is selected from the group consisting of (3-methoxyphenyl)2PN(methyl)P(3-methoxyphenyl)2, (4-methoxyphenyl)2PN(methyl)P(4-methoxyphenyl)2, (3-methoxyphenyl)2PN(isopropyl)P(3-methoxyphenyl)2, (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(2-ethylhexyl)P(4-methoxyphenyl)2, (3-methoxyphenyl)(phenyl)PN(methyl)P(phenyl)2, (4-methoxyphenyl)(phenyl)PN(methyl)P(phenyl)2, (3-methoxyphenyl)(phenyl)PN(methyl)P(3-methoxyphenyl)(phenyl), (4-methoxyphenyl)(phenyl)PN(methyl)P(4-methoxyphenyl)(phenyl), (3-methoxyphenyl)2PN(methyl)P(phenyl)2, (4-methoxyphenyl)2PN(methyl)P(phenyl)2, (4-methoxyphenyl)2PN(1-cyclohexylethyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(2-methylcyclohexyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(decyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(pentyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(benzyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(phenyl)P(4-methoxyphenyl)2, (4-fluorophenyl)2PN(methyl)P(4-fluorophenyl)2, (3-fluorophenyl)2PN(methyl)P(3-fluorophenyl)2, (4-dimethylamino-phenyl)2PN(methyl)P(4-dimethylamino-phenyl)2, (4-methoxyphenyl)2PN(allyl)P(4-methoxyphenyl)2, (4-(4-methoxyphenyl)-phenyl)2PN(isopropyl)P(4-(4-methoxyphenyl)-phenyl)2 and (4-methoxyphenyl)(phenyl)PN(isopropyl)P(phenyl)2.
19. The process as claimed in claim 1, wherein the catalyst system is prepared by combining in any order the heteroatomic ligand with the transition metal compound and an activator.
20. The process as claimed in claim 19, which comprises a step of adding a pre-formed coordination complex, prepared using the heteroatomic ligand and the transition metal compound, to a reaction mixture containing the activator.
21. The process as claimed in claim 19, which comprises a step of generating a heteroatomic coordination complex in situ from the transition metal compound and a heteroatomic ligand.
22. The process as claimed in claim 1, wherein the transition metal compound is selected from the group consisting of chromium, molybdenum, tungsten, titanium, tantalum, vanadium and zirconium.
23. The process as claimed in claim 22, wherein the transition metal is chromium.
24. The process as claimed in claim 1, wherein the transition metal compound is selected from the group consisting of an inorganic salt, an organic salt, a co-ordination complex and an organometallic complex.
25. The process as claimed in claim 24, wherein the transition metal compound is selected from the group consisting of chromium trichloride tris-tetrahydrofuran complex, (benzene)tricarbonyl chromium, chromium (III) octanoate, chromium (III) acetylacetonoate, chromium hexacarbonyl and chromium (III) 2-ethylhexanoate.
26. The process as claimed in claim 25, wherein the transition metal compound is selected from a complex selected from chromium (III) acetylacetonoate and chromium (III) 2-ethylhexanoate.
27. The process as claimed in claim 1, wherein the transition metal compound and the heteroatomic ligand are combined to provide a transition metal/ligand ratio from about 0.01:100 to 10 000:1.
28. The process as claimed in claim 19, wherein the catalyst system further comprises an activator selected from the group consisting of an organoaluminium compound, an organoboron compound, an organic salt, an inorganic acid and salt.
29. The process as claimed in claim 28, wherein the activator is an alkylaluminoxane.
30. The process as claimed in claim 29, wherein the transition metal compound and the aluminoxane are combined in proportions to provide an Al/transition metal ratio from about 1:1 to 10 000:1.
31. A tetramerisation catalyst system to be used in the process of claim 1, comprising:

- a transition metal compound; and - a heteroatomic ligand defined by the following general formula (R')(R2)A-B-C(R3)(R4) wherein A and C are independently an atom selected from the group consisting of phosphorus, arsenic, antimony, bismuth and nitrogen, or phosphorus, arsenic, antimony, bismuth or nitrogen are independently oxidized by S, Se, N or O, where the valence of A and/or C allows for such oxidation;

B is a linking group between A and C; and each of R1, R2, R3 and R4 is independently selected from the group consisting of non-aromatic groups, aromatic homohydrocarbyl groups, and non-aromatic and aromatic heterohydrocarbyl groups;

at least one of R1, R2, R3 and R4 has a polar substituent group on a second or further atom from the atom bound to A or C and provided that any polar substituents that R1, R2, R3 and R4 may have are not on the atom adjacent to the atom bound to A or C.
32. The catalyst system as claimed in claim 31, wherein each of R1, R2, R3 and R4 is aromatic or heteroaromatic, but not all of R1, R2, R3 and R4 are substituted by a substituent on an atom adjacent to the atom bound to A or C.
33. The catalyst system as claimed in claim 32, wherein not more than two of R1, R2, R3 and R4 have substituents on the atom adjacent to the atom bound to A
or C.
34. The catalyst system as claimed in claim 31, wherein each polar substituent that one or more of R1, R2, R3 and R4 may have is electron donating.
35. The catalyst system as claimed in claim 31, wherein A and/or C are a potential electron donor for coordination with the transition metal.
36. The catalyst system as claimed in claim 31, wherein B is selected from the group consisting of an organic linking group consisting of a hydrocarbylene, a substituted hydrocarbylene, a hetero hydrocarbylene or a substituted hetero hydrocarbylene; an inorganic linking group consisting of a single atom linking spacer;
and a group consisting of methylene, dimethylmethylene, 1,2-ethylene, 1,2-phenylene, 1,2-propylene, 1,2-catecholate, -(CH3)N-N(CH3)-, -B(R5)-, -Si(R5)2-, -P(R5)- or -N(R5)-, where R5 is hydrogen, a hydrocarbyl or substituted hydrocarbyl, a substituted heteroatom or a halogen.
37. The catalyst system as claimed in claim 36, wherein B is a single atom linking spacer.
38. The catalyst system as claimed in claim 36, wherein B is selected to be -N(R5)-, wherein R5 is a substituent selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, aryloxy, substituted aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino, silyl groups, and aryl substituted with any of these substituents.
39. The catalyst system as claimed in claim 31, wherein A and/or C is independently oxidised by S, Se, N or O, where the valence of A and/or C
allows for such oxidation.
40. The catalyst system as claimed in claim 31, wherein A and C are independently phosphorus or phosphorus oxidised by S or Se or N or O.
41. The catalyst system as claimed in claim 31, wherein the ligand is selected from the group consisting of (3-methoxyphenyl)2PN(methyl)P(3-methoxyphenyl)2, (4-methoxyphenyl)2PN(methyl)P(4-methoxyphenyl)2, (3-methoxyphenyl)2PN(isopropyl)P(3-methoxyphenyl)2, (4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(2-ethylhexyl)P(4-methoxyphenyl)2, (3-methoxyphenyl)(phenyl)PN(methyl)P(phenyl)2, (4-methoxyphenyl)(phenyl)PN(methyl)P(phenyl)2, (3-methoxyphenyl)(phenyl)PN(methyl)P(3-methoxyphenyl)(phenyl), (4-methoxyphenyl)(phenyl)PN(methyl)P(4-methoxyphenyl)(phenyl), (3-methoxyphenyl)2PN(methyl)P(phenyl)2, (4-methoxyphenyl)2PN(methyl)P(phenyl)2, (4-methoxyphenyl)2PN(1-cyclohexylethyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(2-methylcyclohexyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(decyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(pentyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(benzyl)P(4-methoxyphenyl)2, (4-methoxyphenyl)2PN(phenyl)P(4-methoxyphenyl)2, (4-fluorophenyl)2PN(methyl)P(4-fluorophenyl)2, (3-fluorophenyl)2PN(methyl)P(3-fluorophenyl)2, (4-dimethylamino-phenyl)2PN(methyl)P(4-dimethylamino-phenyl)2, (4-methoxyphenyl)2PN(allyl)P(4-methoxyphenyl)2, (4-(4-methoxyphenyl)-phenyl)2P N(isopropyl) P(4-(4-methoxyphenyl)-phenyl)2 and (4-methoxyphenyl)(phenyl)PN(isopropyl)P(phenyl)2.
42. The catalyst system as claimed in claim 31, wherein the transition metal compound is selected from the group consisting of chromium, molybdenum, tungsten, titanium, tantalum, vanadium and zirconium.
43. The catalyst system as claimed in claim 42, wherein the transition metal is chromium.
44. The catalyst system as claimed in claim 31, wherein the transition metal compound is selected from the group consisting of an inorganic salt, an organic salt, a co-ordination complex and an organometallic complex.
45. The catalyst system as claimed in claim 44, wherein the transition metal compound is selected from the group consisting of chromium trichloride tris-tetrahydrofuran complex, (benzene)tricarbonyl chromium, chromium (III) octanoate, chromium (III) acetylacetonoate, chromium hexacarbonyl, and chromium (III) 2-ethylhexanoate.
46. The catalyst system as claimed in claim 45, wherein the transition metal is selected from a complex selected from chromium (III) acetylacetonoate and chromium (III) 2-ethylhexanoate.
47. The catalyst system as claimed in claim 31, wherein the transition metal compound and the heteroatomic ligand are combined to provide a transition metal/ligand ratio from about 0.01:100 to 10 000:1..
48. The catalyst system as claimed in claim 31, which further comprises an activator.
49. The catalyst system as claimed in claim 48, wherein the activator is selected from the group consisting of an organoaluminium compound, an organoboron compound, an organic salt, an inorganic acid and salt.
50. The catalyst system as claimed in claim 49, wherein the activator is an alkylaluminoxane.
51. The catalyst system as claimed in claim 50, wherein the alkylaluminoxane is selected from the group consisting of methylaluminoxane (MAO), ethylaluminoxane (EAO), modified alkylaluminoxanes (MMAO), and mixtures thereof.
52. The catalyst system as claimed in claim 50, wherein the transition metal and the aluminoxane are combined in proportions to provide an Al/transition metal ratio from about 1:1 to 10 000:1.
53. The process of claim 28, wherein the activator is methyllithium, methylmagnesium bromide, tetrafluoroboric acid diethylether complex, silver tetrafluoroborate or sodium hexafluoroantimonate.
54. The catalyst system of claim 49, wherein the activator is methyllithium, methylmagnesium bromide, tetrafluoroboric acid diethylether complex, silver tetrafluoroborate or sodium hexafluoroantimonate.
CA2510801A 2002-12-20 2003-12-19 Tetramerization of olefins Expired - Lifetime CA2510801C (en)

Applications Claiming Priority (13)

Application Number Priority Date Filing Date Title
US43540502P 2002-12-20 2002-12-20
ZA2002/10339 2002-12-20
ZA200210339 2002-12-20
US60/435,405 2002-12-20
US47837903P 2003-06-13 2003-06-13
ZA200304632 2003-06-13
US60/478,379 2003-06-13
ZA2003/4632 2003-06-13
US50930903P 2003-10-06 2003-10-06
ZA200307774 2003-10-06
ZA2003/7774 2003-10-06
US60/509,309 2003-10-06
PCT/ZA2003/000186 WO2004056478A1 (en) 2002-12-20 2003-12-19 Tetramerization of olefins

Publications (2)

Publication Number Publication Date
CA2510801A1 CA2510801A1 (en) 2004-07-08
CA2510801C true CA2510801C (en) 2011-11-01

Family

ID=32686408

Family Applications (3)

Application Number Title Priority Date Filing Date
CA2510801A Expired - Lifetime CA2510801C (en) 2002-12-20 2003-12-19 Tetramerization of olefins
CA2510190A Expired - Lifetime CA2510190C (en) 2002-12-20 2003-12-19 Trimerisation of olefins
CA2510194A Expired - Lifetime CA2510194C (en) 2002-12-20 2003-12-19 Tetramerization of olefins

Family Applications After (2)

Application Number Title Priority Date Filing Date
CA2510190A Expired - Lifetime CA2510190C (en) 2002-12-20 2003-12-19 Trimerisation of olefins
CA2510194A Expired - Lifetime CA2510194C (en) 2002-12-20 2003-12-19 Tetramerization of olefins

Country Status (13)

Country Link
US (1) US7511183B2 (en)
EP (3) EP1581341B1 (en)
JP (2) JP2006516265A (en)
KR (3) KR20050100600A (en)
CN (3) CN100548946C (en)
AT (2) ATE477053T1 (en)
AU (3) AU2003297545A1 (en)
BR (6) BRPI0317510B1 (en)
CA (3) CA2510801C (en)
DE (1) DE60331252D1 (en)
ES (1) ES2340483T3 (en)
PL (3) PL377488A1 (en)
WO (3) WO2004056477A1 (en)

Families Citing this family (200)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7273959B2 (en) 2003-10-10 2007-09-25 Shell Oil Company Catalytic trimerization of olefinic monomers
US20050187418A1 (en) 2004-02-19 2005-08-25 Small Brooke L. Olefin oligomerization
US20070043181A1 (en) 2005-08-19 2007-02-22 Knudsen Ronald D 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
US20050187098A1 (en) 2004-02-20 2005-08-25 Knudsen Ronald D. Methods of preparation of an olefin oligomerization catalyst
US7384886B2 (en) 2004-02-20 2008-06-10 Chevron Phillips Chemical Company Lp Methods of preparation of an olefin oligomerization catalyst
EP1765495B1 (en) * 2004-06-18 2011-09-07 Sasol Technology (Pty) Ltd Oligomerisation in the presence of both a tetramerisation catalyst and a further oligomerisation catalyst
BRPI0511007B1 (en) 2004-06-18 2021-03-16 Sasol Technology (Pty) Ltd process to produce an oligomeric product containing octene
JP4982952B2 (en) * 2005-02-14 2012-07-25 住友化学株式会社 Ethylene trimerization catalyst and ethylene trimerization method using the catalyst
JP2006218437A (en) * 2005-02-14 2006-08-24 Sumitomo Chemical Co Ltd Trimerization catalyst of olefin and trimerization method of olefin using it
US7414006B2 (en) * 2005-03-09 2008-08-19 Exxonmobil Chemical Patents Inc. Methods for oligomerizing olefins
ATE475633T1 (en) * 2005-03-09 2010-08-15 Exxonmobil Chem Patents Inc METHOD FOR OLIGOMERIZATION OF OLEFINS
US7259123B2 (en) 2005-04-08 2007-08-21 Shell Oil Company Catalytic trimerization and tetramerization of olefinic monomers
US7323611B2 (en) 2005-06-28 2008-01-29 Sumitomo Chemical Company Limited Process for producing olefin oligomer
JP2007039641A (en) * 2005-06-28 2007-02-15 Sumitomo Chemical Co Ltd Method for producing olefin oligomer
EP1915329B2 (en) 2005-07-12 2016-05-11 Sasol Technology (Pty) Ltd Oligomerisation of olefinic compounds in the presence of a diluted metal containing activator
US7727926B2 (en) 2005-07-21 2010-06-01 Chevron Phillips Chemical Company Lp Diimine metal complexes, methods of synthesis, and method of using in oligomerization and polymerization
US7129304B1 (en) 2005-07-21 2006-10-31 Chevron Phillips Chemical Company Lp Dimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization
US7271121B2 (en) 2005-07-21 2007-09-18 Chevron Phillips Chemical Company Lp Diimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization
US7268096B2 (en) 2005-07-21 2007-09-11 Chevron Phillips Chemical Company Lp Diimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization
US7550639B2 (en) 2005-07-27 2009-06-23 Sumitomo Chemical Company, Limited Process for producing olefin oligomer
JP2007056002A (en) * 2005-07-27 2007-03-08 Sumitomo Chemical Co Ltd Method for producing olefin oligomer
GB0520085D0 (en) * 2005-10-03 2005-11-09 Sasol Tech Pty Ltd Oligomerisation of olefinic compounds in the presence of an oligomerisation catalyst, and a catalyst activator including a halogenated -AR group
US8874477B2 (en) 2005-10-04 2014-10-28 Steven Mark Hoffberg Multifactorial optimization system and method
US20070185357A1 (en) * 2005-11-21 2007-08-09 De Boer Eric J M Catalytic process for the oligomerization of olefinic monomers
CA2629885C (en) * 2005-11-21 2014-06-03 Shell Internationale Research Maatschappij B.V. Catalytic oligomerization of olefinic monomers
US8003839B2 (en) * 2006-02-03 2011-08-23 Exxonmobil Chemical Patents Inc. Process for generating linear apha olefin comonomers
CA2637703A1 (en) * 2006-02-03 2007-08-09 Ineos Europe Limited Transition metal catalysts
WO2007092136A2 (en) 2006-02-03 2007-08-16 Exxonmobil Chemical Patents, Inc. Process for generating alpha olefin comonomers
US7687672B2 (en) 2006-02-03 2010-03-30 Exxonmobil Chemical Patents Inc. In-line process for generating comonomer
US7858833B2 (en) 2006-02-03 2010-12-28 Exxonmobil Chemical Patents Inc. Process for generating linear alpha olefin comonomers
US7982085B2 (en) * 2006-02-03 2011-07-19 Exxonmobil Chemical Patents Inc. In-line process for generating comonomer
CN100443178C (en) * 2006-03-10 2008-12-17 中国石油天然气股份有限公司 Catalyst composition of ethylene oligomerization and the application
US7378537B2 (en) 2006-07-25 2008-05-27 Chevron Phillips Chemical Company Lp Olefin oligomerization catalysts and methods of using same
US8404915B2 (en) * 2006-08-30 2013-03-26 Exxonmobil Chemical Patents Inc. Phosphine ligand-metal compositions, complexes, and catalysts for ethylene trimerizations
US7803886B2 (en) 2006-12-22 2010-09-28 Shell Oil Company Ligands and catalyst systems thereof for the catalytic oligomerization of olefinic monomers
CN101600722B (en) * 2006-12-22 2015-11-25 国际壳牌研究有限公司 For part and the catalyst system of oligomerization of olefinic monomers
WO2008085658A1 (en) 2007-01-08 2008-07-17 Exxonmobil Chemical Patents Inc. Methods for oligomerizing olefins with chromium pyridine thioether catalysts
EP2104679A1 (en) 2007-01-08 2009-09-30 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
KR101074202B1 (en) * 2007-01-18 2011-10-14 에스케이종합화학 주식회사 Ethylene tetramerization catalyst systems and method for preparing 1-octene using the same
KR101095796B1 (en) * 2007-02-08 2011-12-21 에스케이종합화학 주식회사 Ethylene Tetramerization Catalytst Systems for Immobilization and Process Using the Same
CA2583007C (en) 2007-03-29 2015-03-31 Nova Chemicals Corporation Amino phosphine
JP4974732B2 (en) * 2007-03-30 2012-07-11 三井化学株式会社 Method for producing cyclic olefin
MY148530A (en) * 2007-05-28 2013-04-30 Sasol Tech Pty Ltd Two stage activation of oligomerisation catalyst and oligomerisation of olefinic compounds inthe presence of an oligomerisation catalyst so activated
MY148675A (en) 2007-07-11 2013-05-31 Linde Ag Catalyst composition and process for di-, tri-and/or tetramerization of ethylene
KR101057576B1 (en) * 2007-08-16 2011-08-17 에스케이종합화학 주식회사 Selective Ethylene Oligomerization Catalyst System
JP2009072665A (en) * 2007-09-19 2009-04-09 Mitsui Chemicals Inc Catalyst for olefin polymerization, and manufacturing method of ethylene polymer
US8211949B2 (en) 2007-09-24 2012-07-03 Dow Global Technologies Llc Functionalized long-chain olefin mixtures and uses therefor
WO2009060343A1 (en) * 2007-11-07 2009-05-14 Sasol Technology (Proprietary) Limited Process for polymerising or oligomerising a hydrocarbon
CA2705154C (en) * 2007-11-07 2015-12-29 Sasol Technology (Proprietary) Limited Process for polymerising or oligomerising a hydrocarbon
WO2009068157A1 (en) 2007-11-28 2009-06-04 Linde Ag Catalyst composition and process for oligomerization of ethylene
US7902415B2 (en) 2007-12-21 2011-03-08 Chevron Phillips Chemical Company Lp Processes for dimerizing or isomerizing olefins
EP2106854B1 (en) 2008-04-04 2011-05-25 Saudi Basic Industries Corporation Catalyst for oligomerization of ethylene, method for preparation thereof and process for oligomerization using it
JP5208870B2 (en) * 2008-07-11 2013-06-12 三井化学株式会社 Method for producing silylated polyolefin and additive containing silylated polyolefin
CA2639882C (en) 2008-09-29 2016-07-12 Nova Chemicals Corporation Tetramerization
CA2639870A1 (en) * 2008-09-29 2010-03-29 Nova Chemicals Corporation Trimerization
KR101065596B1 (en) * 2009-01-29 2011-09-19 에스케이종합화학 주식회사 High Active and High Selective Ethylene Oligomerization Catalyst, and process for preparing hexene or octene using thereof
US9035119B2 (en) 2009-02-16 2015-05-19 Sasol Technology (Pty) Limited Oligomerisation of olefinic compounds in the presence of an activated oligomerisation catalyst
US8227653B2 (en) 2009-03-27 2012-07-24 Exxonmobil Chemical Patents Inc. Olefin oligomerization reaction processes exhibiting reduced fouling
ES2371218T3 (en) 2009-04-09 2011-12-28 Saudi Basic Industries Corporation COMPOSITION OF CATALYST AND PROCEDURE FOR THE OLIGOMERIZATION OF ETHYLENE.
BR112012008987B1 (en) 2009-10-16 2021-08-24 Sasol Technology (Proprietary) Limited PROCESSES TO SEPARATE A HYDROCARBIDE CURRENT FROM MULTIPLE COMPONENTS AND ETHYLENE OLIGOMERIZATION
IN2012DN03367A (en) 2009-10-19 2015-10-23 Sasol Technolgoy Pty Ltd
CN102107146B (en) * 2009-12-29 2013-10-16 中国石油天然气股份有限公司 Catalyst for synthesizing hexane-1 from ethylene trimerization and application of catalyst
MX359459B (en) 2009-12-31 2018-09-28 Chevron Phillips Chemical Co Lp Phosphinyl amidine compounds, metal complexes, catalyst systems, and their use to oligomerize or polymerize olefins.
WO2011085951A1 (en) 2010-01-15 2011-07-21 Basell Polyolefine Gmbh Oligomerization of olefins
CN102781948A (en) 2010-02-12 2012-11-14 埃南蒂亚有限公司 Enantiomerically enriched aminodiphosphines as ligands for the preparation of catalysts for asymmetric synthesis
RU2541528C2 (en) * 2010-03-03 2015-02-20 ЭсКей ИННОВЭЙШН КО., ЛТД. Highly active and highly selective catalyst of ethylene oligomerisation and method of obtaining hexene or octene with application of said catalyst
CA2703435C (en) * 2010-05-12 2017-05-02 Nova Chemicals Corporation Oligomerization process using a chromium p-n-p catalyst with added alkyl zinc
CA2716714C (en) 2010-10-06 2017-05-16 Nova Chemicals Corporation Tetramerization ligands
WO2012055943A2 (en) 2010-10-28 2012-05-03 Basell Polyolefine Gmbh Oligomerization of olefins
CA2723515C (en) 2010-12-01 2018-05-15 Nova Chemicals Corporation Heat management in ethylene oligomerization
ES2409707T3 (en) 2011-02-16 2013-06-27 Linde Ag Process for preparing a catalytic composition for oligomerization of ethylene and preforming unit of respective catalyst composition
RU2470707C1 (en) * 2011-06-27 2012-12-27 Общество с ограниченной ответственностью "Объединенный центр исследований и разработок" Catalyst for trimerisation of ethylene to 1-hexene, ligand for producing catalyst, method of producing catalyst and method of producing ligand
JP5844636B2 (en) 2011-12-27 2016-01-20 出光興産株式会社 Method for producing α-olefin
US9586872B2 (en) 2011-12-30 2017-03-07 Chevron Phillips Chemical Company Lp Olefin oligomerization methods
AU2013207783B2 (en) 2012-01-13 2017-07-13 Lummus Technology Llc Process for providing C2 hydrocarbons via oxidative coupling of methane and for separating hydrocarbon compounds
CA2765429C (en) 2012-01-25 2019-12-31 Nova Chemicals Corporation P-n-p ligand
KR101846031B1 (en) 2012-03-16 2018-04-05 에스케이이노베이션 주식회사 Catalyst Systems for Preparing 1-Hexene and/or 1-Octene from Ethylene
BR112014027663A2 (en) 2012-05-09 2017-06-27 Sasol Tech Pty Ltd process for the oligomerization of a hydrocarbon
CA2867667C (en) * 2012-05-09 2021-05-25 Sasol Technology (Proprietary) Limited Tetramerisation of ethylene
MY170070A (en) 2012-05-09 2019-07-03 Sasol Tech Pty Ltd Tetramerisation of ethylene
EP2846888B1 (en) 2012-05-09 2016-09-14 Sasol Technology (Proprietary) Limited Separation of components from a multi-component hydrocarbon stream
EP2847149B1 (en) 2012-05-09 2022-01-12 Sasol Technology (Proprietary) Limited Oligomerisation of olefinic compounds with reduced polymer formation
AU2013266250B2 (en) 2012-05-24 2017-07-06 Lummus Technology Llc Oxidative coupling of methane systems and methods
US8865610B2 (en) 2012-06-06 2014-10-21 Chevron Phillips Chemical Company Lp Phosphinyl guanidine compounds, metal salt complexes, catalyst systems, and their use to oligomerize or polymerize olefins
US9670113B2 (en) 2012-07-09 2017-06-06 Siluria Technologies, Inc. Natural gas processing and systems
KR101483248B1 (en) * 2012-11-15 2015-01-16 주식회사 엘지화학 Ligand compound, organic chromium compound, catalyst system for ethylene oligomerization, method for preparign the same, and method for ethylene oligomerization using the same
WO2014089479A1 (en) 2012-12-07 2014-06-12 Siluria Technologies, Inc. Integrated processes and systems for conversion of methane to multiple higher hydrocarbon products
CA2800268C (en) 2012-12-21 2020-02-25 Nova Chemicals Corporation Continuous ethylene tetramerization process
WO2014133005A1 (en) 2013-02-27 2014-09-04 三井化学株式会社 Catalyst for olefin multimerization and method for producing olefin multimer in presence of catalyst for olefin multimerization
CN104059105B (en) * 2013-03-20 2016-06-29 中国石油化工股份有限公司 Ligand compound containing pyridine radicals, the catalyst containing this compound and application thereof
US9546117B2 (en) * 2013-05-09 2017-01-17 Sasol Technology (Proprietary) Limited Tetramerisation of ethylene
MY174705A (en) 2013-05-09 2020-05-08 Sasol Tech Pty Ltd Oligomerisation of ethylene to mixtures of 1-hexene and 1-octene
KR20160006191A (en) * 2013-05-09 2016-01-18 사솔 테크날러지 (프로프라이어터리) 리미티드 Oligomerisation of ethylene to mixtures of 1-hexene and 1-octene
FR3007761B1 (en) * 2013-06-28 2016-02-05 IFP Energies Nouvelles NEW NICKEL COMPLEX AND USE THEREOF IN OLEFIN OLIGOMERIZATION PROCESS
EP2832445A1 (en) * 2013-07-29 2015-02-04 Linde AG Catalyst composition and process for oligomerization of ethylene
CN104415790B (en) * 2013-08-23 2017-06-30 中国石油化工股份有限公司 A kind of catalyst for ethylene tetramerization composition and application
EP2987783A4 (en) * 2013-11-18 2017-02-08 LG Chem, Ltd. Ligand compound, catalyst system for olefin oligomerization, and olefin oligomerization method using same
KR20150058034A (en) * 2013-11-18 2015-05-28 주식회사 엘지화학 Ligand compound, catalyst system for olefin oligomerization, and method for olefin oligomerization using the same
KR101676835B1 (en) * 2013-11-18 2016-11-17 주식회사 엘지화학 Ligand compound, catalyst system for olefin oligomerization, and method for olefin oligomerization using the same
KR101657259B1 (en) * 2013-11-19 2016-09-13 주식회사 엘지화학 Ligand compound, catalyst system for olefin oligomerization, and method for olefin oligomerization using the same
EP3074119B1 (en) 2013-11-27 2019-01-09 Siluria Technologies, Inc. Reactors and systems for oxidative coupling of methane
CA2835683C (en) 2013-12-05 2021-07-06 Nova Chemicals Corporation Ethylene oligomerization with mixed ligands
CA2837590C (en) 2013-12-23 2020-12-15 Nova Chemicals Corporation Continuous ethylene oligomerization with in-situ catalyst preparation
CN106068323B (en) 2014-01-08 2019-09-06 希路瑞亚技术公司 Ethylene at liquid system and method
WO2015106023A1 (en) 2014-01-09 2015-07-16 Siluria Technologies, Inc. Oxidative coupling of methane implementations for olefin production
US10377682B2 (en) 2014-01-09 2019-08-13 Siluria Technologies, Inc. Reactors and systems for oxidative coupling of methane
EP3102616B1 (en) 2014-02-03 2020-10-14 Saudi Basic Industries Corporation Catalyst composition pre-formation unit for preparing a catalyst composition for oligomerization of ethylene
US9175109B1 (en) 2014-05-20 2015-11-03 Chevron Phillips Chemical Company Lp Oligomerization processes and polymer compositions produced therefrom
US10472302B2 (en) 2014-06-18 2019-11-12 Lg Chem, Ltd. Ligand compound, organic chromium compound, catalyst system for oligomerization of olefins, and method for oligomerization of olefins using the catalyst system
BR112017001004A2 (en) 2014-07-24 2017-11-14 Linde Ag catalyst composition, process for ethylene oligomerization and ethylene oligomerization reaction which produces 1-hexene and 1-octene
CN105562098B (en) * 2014-10-08 2018-03-02 中国石油化工股份有限公司 A kind of ethylene oligomerisation catalyst composition and its application
CN105562099B (en) * 2014-10-08 2018-01-23 中国石油化工股份有限公司 A kind of catalyst for ethylene tetramerization composition and ethylene tetramerization method
CN105566036B (en) * 2014-10-13 2018-05-11 中国石油化工股份有限公司 A kind of method of ethylene tetramerization
JP6488638B2 (en) * 2014-10-28 2019-03-27 セントラル硝子株式会社 Method for producing α-fluoroaldehyde equivalents
DK3237363T3 (en) * 2014-12-23 2019-06-24 Sibur Holding Public Joint Stock Co PROCEDURES FOR PREPARING OLIGOMERS OF AN OLEFIN
MX369759B (en) * 2015-01-19 2019-11-20 Evonik Operations Gmbh Combined preparation of butene and octene from ethene.
US9505675B2 (en) 2015-02-09 2016-11-29 Chevron Phillips Chemical Company Lp Deactivation of a process by-product
KR101679515B1 (en) 2015-02-12 2016-11-24 주식회사 엘지화학 Method of preparing catalyst system for oligomerization and catalyst sysyem for oligomerization prepared thereby
BR112017019457A2 (en) 2015-03-13 2018-05-15 Dow Global Technologies Llc olefin oligomerization process with a catalyst comprising a chromium complex with a phosphate-containing binder
US10793490B2 (en) 2015-03-17 2020-10-06 Lummus Technology Llc Oxidative coupling of methane methods and systems
US9334204B1 (en) 2015-03-17 2016-05-10 Siluria Technologies, Inc. Efficient oxidative coupling of methane processes and systems
US20160289143A1 (en) 2015-04-01 2016-10-06 Siluria Technologies, Inc. Advanced oxidative coupling of methane
KR101761395B1 (en) * 2015-04-15 2017-07-25 주식회사 엘지화학 Ligand compound, catalyst system for oligomerization, and method for olefin oligomerization using the same
KR101768194B1 (en) * 2015-05-15 2017-08-16 주식회사 엘지화학 Catalyst composition and method for preparing polyolefin using the same
EP3243847B1 (en) * 2015-05-15 2020-08-26 LG Chem, Ltd. Catalytic composition and method of preparing polyolefin using same
KR20160134464A (en) 2015-05-15 2016-11-23 주식회사 엘지화학 Supported hybrid catalyst system and method for olefin polymerization using the same
KR101757370B1 (en) 2015-06-01 2017-07-12 주식회사 엘지화학 1-Octene composition
KR101757835B1 (en) * 2015-06-12 2017-07-13 주식회사 엘지화학 Ligand compound, organic chromium compound, catalyst system for oligomerization of olefins and method for oligomerization of olefins using the catalyst system
US9328297B1 (en) 2015-06-16 2016-05-03 Siluria Technologies, Inc. Ethylene-to-liquids systems and methods
WO2016205411A2 (en) 2015-06-16 2016-12-22 Siluria Technologies, Inc. Ethylene-to-liquids systems and methods
WO2017010998A1 (en) 2015-07-14 2017-01-19 Chevron Phillips Chemical Company Lp Olefin compositions
US9732300B2 (en) 2015-07-23 2017-08-15 Chevron Phillipa Chemical Company LP Liquid propylene oligomers and methods of making same
KR102058142B1 (en) 2015-09-02 2019-12-20 주식회사 엘지화학 Ligand compound, catalyst system for olefin oligomerization, and method for olefin oligomerization using the same
KR101749542B1 (en) 2015-09-03 2017-06-21 한택규 Process for selective oligomerization of Ethylene
KR20170032766A (en) * 2015-09-15 2017-03-23 주식회사 엘지화학 Method for oligomerization of olefins
WO2017046701A1 (en) 2015-09-16 2017-03-23 Sabic Global Technologies B.V. Process for deactivation of an olefin oligomerization catalyst
US10519077B2 (en) 2015-09-18 2019-12-31 Chevron Phillips Chemical Company Lp Ethylene oligomerization/trimerization/tetramerization reactor
US10513473B2 (en) 2015-09-18 2019-12-24 Chevron Phillips Chemical Company Lp Ethylene oligomerization/trimerization/tetramerization reactor
KR101735687B1 (en) * 2015-09-23 2017-05-15 롯데케미칼 주식회사 Catalyst system for olefin oligomerization, and method for olefin oligomerization using the same
EP3786138A1 (en) 2015-10-16 2021-03-03 Lummus Technology LLC Oxidative coupling of methane
KR101761830B1 (en) * 2015-10-21 2017-07-26 주식회사 엘지화학 Ligand compound, catalyst system for olefin oligomerization, and method for olefin oligomerization using the same
CN105289742B (en) * 2015-11-11 2018-07-13 天津科技大学 For the catalyst of ethylene selectivity oligomerisation, ligand and preparation method thereof
US20190322965A1 (en) 2015-12-04 2019-10-24 Sabic Global Technologies B.V. Process for flushing an oligomerization reactor and oligomerization of an olefin
CN108778479A (en) 2016-03-21 2018-11-09 沙特基础工业全球技术有限公司 Method for handling oligomerization product stream
US10441946B2 (en) * 2016-03-22 2019-10-15 Apalene Technology Co., Ltd. (Hangzhou) Linear alpha-olefin catalysts and preparation and use thereof
EP4071131A1 (en) 2016-04-13 2022-10-12 Lummus Technology LLC Apparatus and method for exchanging heat
WO2017187289A1 (en) 2016-04-25 2017-11-02 Sabic Global Technologies B.V. Process for removing heat from an oligomerization reaction
US10329212B2 (en) 2016-05-27 2019-06-25 Chevron Phillips Chemical Company Lp Reduced polymer formation for selective ethylene oligomerizations
US10414698B2 (en) 2016-05-27 2019-09-17 Chevron Phillips Chemical Company Lp Reduced polymer formation for selective ethylene oligomerizations
KR102545533B1 (en) 2016-05-27 2023-06-21 에스케이이노베이션 주식회사 Oligomerization Catalyst And Process For Preparing Ethylene Oligomer Using Thereof
US10414699B2 (en) 2016-05-27 2019-09-17 Chevron Phillips Chemical Company Lp Process improvements in selective ethylene oligomerizations
FR3051683B1 (en) 2016-05-31 2020-10-09 Ifp Energies Now CATALYTIC COMPOSITION BASED ON CHROME AND A LIGAND BASED ON PHOSPHINE AND ITS USE IN A PROCESS FOR PROCESSING OCTENS
CN106111200B (en) * 2016-06-21 2019-03-12 东南大学 More metal corsslinkings cooperation catalyst and its preparation method and application for uns-dimethylhydrazine degradation
KR102428767B1 (en) 2016-07-14 2022-08-04 에스케이이노베이션 주식회사 Oligomerisation of ethylene
WO2018012792A1 (en) 2016-07-14 2018-01-18 Sk Innovation Co., Ltd. Oligomerization of ethylene
JP6871358B2 (en) * 2016-07-15 2021-05-12 パブリック・ジョイント・ストック・カンパニー・“シブール・ホールディング” Oligomer oligomerization method
US9944661B2 (en) 2016-08-09 2018-04-17 Chevron Phillips Chemical Company Lp Olefin hydroboration
CN106582851B (en) * 2016-10-17 2019-04-30 天津科技大学 Catalytic component and its catalyst for ethylene selectivity oligomerisation
JP6806973B2 (en) 2016-11-02 2021-01-06 アジュ ユニバーシティー インダストリー−アカデミック コーオペレイション ファウンデーションAjou University Industry−Academic Cooperation Foundation Chromium compound, catalyst system using this, and method for producing ethylene oligomer
WO2018118105A1 (en) 2016-12-19 2018-06-28 Siluria Technologies, Inc. Methods and systems for performing chemical separations
EP3558905A1 (en) 2016-12-22 2019-10-30 SABIC Global Technologies B.V. Methods of producing linear alpha olefins
CN110139711A (en) 2016-12-30 2019-08-16 沙特基础工业全球技术有限公司 The preparation method of the homogeneous catalyst of 1- hexene is produced for selectivity
CN110494218A (en) 2016-12-30 2019-11-22 沙特基础工业全球技术有限公司 The preparation method of catalyst solution for the production of selective 1- hexene
CN110114139A (en) 2016-12-30 2019-08-09 沙特基础工业全球技术有限公司 The method of production of linear alhpa olefin
EP3630707B1 (en) 2017-05-23 2023-09-06 Lummus Technology LLC Integration of oxidative coupling of methane processes
US10232339B2 (en) 2017-06-06 2019-03-19 Chevron Phillips Chemical Company Lp Fouling protection for an oligomerization reactor inlet
KR102450815B1 (en) 2017-06-16 2022-10-05 에스케이이노베이션 주식회사 Heteroatomic ligand, oligomerization catalyst containing the same, and production method of oligomer
CA3068805C (en) 2017-07-06 2023-05-16 Mitsui Chemicals, Inc. Olefin oligomerization catalyst and method for producing olefin oligomer in the presence of the same catalyst
US10836689B2 (en) 2017-07-07 2020-11-17 Lummus Technology Llc Systems and methods for the oxidative coupling of methane
US10493442B2 (en) 2017-09-22 2019-12-03 Chevron Phillips Chemical Company Lp Fluorinated N2-phosphinyl amidine compounds, chromium salt complexes, catalyst systems, and their use to oligomerize ethylene
US10183960B1 (en) 2017-09-22 2019-01-22 Chevron Phillips Chemical Company Lp Perfluorohydrocarbyl-N2-phosphinyl amidine compounds, chromium salt complexes, catalyst systems, and their use to oligomerize ethylene
US10294171B2 (en) 2017-09-22 2019-05-21 Chevron Phillips Chemical Company Lp Carbonyl-containing perfluorohydrocarbyl-N2-phosphinyl amidine compounds, chromium salt complexes and their use to oligomerize ethylene
US10464862B2 (en) 2017-09-28 2019-11-05 Chevron Phillips Chemical Company Lp Oligomerization reactions using aluminoxanes
WO2019074304A1 (en) * 2017-10-11 2019-04-18 롯데케미칼 주식회사 Catalyst system for olefin oligomerization and method for preparing olefin oligomer by using same
WO2019074303A1 (en) * 2017-10-11 2019-04-18 롯데케미칼 주식회사 Catalyst system for olefin oligomerization and method for preparing olefin oligomer by using same
WO2019168249A1 (en) 2018-02-27 2019-09-06 에스케이이노베이션 주식회사 Ligand, oligomerization catalyst comprising same, and method for producing ethylene oligomer by using oligomerization catalyst
KR102605188B1 (en) 2018-02-27 2023-11-24 에스케이이노베이션 주식회사 Ligand, Oligomerization Catalyst And Process For Preparing Ethylene Oligomer Using Thereof
EP3805240B1 (en) 2018-06-07 2022-12-14 Ajou University Industry-Academic Cooperation Foundation Bisphosphine ligand compound, chromium compound, ethylene oligomerization catalyst system, and ethylene oligomer preparing method
JP7402241B2 (en) 2019-01-15 2023-12-20 中国石油化工股▲ふん▼有限公司 Halogen-containing compounds and uses, and ethylene oligomerization catalyst compositions and ethylene oligomerization methods, ethylene trimerization methods, and ethylene tetramerization methods
US11306040B2 (en) 2019-01-15 2022-04-19 China Petroleum & Chemical Corporation Halogen-containing compound and use thereof, catalyst composition, and ethylene oligomerization, trimerization and tetramerization methods
KR20210127775A (en) 2019-03-13 2021-10-22 티피씨 그룹 엘엘씨 Flexible manufacturing system for selectively producing different linear alpha olefins
FR3108264B1 (en) 2020-03-19 2022-04-08 Ifp Energies Now Ethylene oligomerization plant to produce alpha-olefins
CN112387311A (en) * 2020-10-22 2021-02-23 杭州小菱科技有限公司 Ethylene oligomerization catalyst system, preparation method and application thereof
CN114409495A (en) * 2020-10-28 2022-04-29 中国石油天然气股份有限公司 Ethylene tetramerization method
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
FR3116739A1 (en) 2020-11-30 2022-06-03 IFP Energies Nouvelles NEW CATALYTIC COMPOSITION BASED ON CHROME COMPRISING AN AROMATIC HYDROCARBON ADDITIVE AND ASSOCIATED METHOD FOR THE OLIGOMERIZATION OF ETHYLENE INTO OCTENE-1
KR102631413B1 (en) 2021-06-15 2024-01-31 한화토탈에너지스 주식회사 Method for ethylene oligomerization
KR20230027512A (en) 2021-08-19 2023-02-28 에스케이이노베이션 주식회사 Chromium catalyst precursors, ethylene oligomerization catalyst comprising the same and process for preparing ethylene oligomer
CN113773430B (en) * 2021-09-13 2023-01-13 万华化学集团股份有限公司 Preparation method of alpha-olefin copolymer
FR3128710A1 (en) 2021-11-02 2023-05-05 IFP Energies Nouvelles Ethylene oligomerization process using a catalytic composition comprising a chromium precursor, a PNP type ligand and an aluminoxane
US11583843B1 (en) 2021-11-08 2023-02-21 Chevron Phillips Chemical Company, Lp Chromium phosphinyl isoindole amidine complexes for tetramerization of ethylene
US11505513B1 (en) 2021-11-08 2022-11-22 Chevron Phillips Chemical Company, Lp Chromium bicyclic phosphinyl amidine complexes for tetramerization of ethylene
US11492305B1 (en) 2021-11-08 2022-11-08 Chevron Phillips Chemical Company, Lp Chromium phosphinyl hydroisoindole amidine complexes for tetramerization of ethylene
CN113996343A (en) * 2021-11-19 2022-02-01 中化泉州石化有限公司 Catalyst composition for preparing 1-octene
KR20230134435A (en) * 2022-03-14 2023-09-21 주식회사 엘지화학 Ligand compound, organic chromium compound and catalyst composition comprising the same
CN115124575B (en) * 2022-06-23 2024-02-27 中国五环工程有限公司 Preparation method of PNP ligand structure Cr (III) metal catalyst
US11639321B1 (en) 2022-08-31 2023-05-02 Saudi Arabian Oil Company Catalyst systems that include meta-alkoxy substituted n-aryl bis-diphosphinoamine ligands
US11623901B1 (en) 2022-08-31 2023-04-11 Saudi Arabian Oil Company Catalyst systems that include silyl ether moieties

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2699457A (en) * 1950-06-21 1955-01-11 Ziegler Karl Polymerization of ethylene
GB1020563A (en) 1961-11-21 1966-02-23 Gulf Research Development Co Process for polymerizing ethylene
US3635937A (en) 1969-11-05 1972-01-18 Shell Oil Co Ethylene polymerization
US3676523A (en) 1971-07-16 1972-07-11 Shell Oil Co Alpha-olefin production
US3906053A (en) 1971-08-10 1975-09-16 Ethyl Corp Process for the production of olefins
US4628138A (en) * 1985-09-20 1986-12-09 Ashland Oil, Inc. Catalyst and process for oligomerization of ethylene
JPH07215896A (en) * 1994-02-04 1995-08-15 Idemitsu Kosan Co Ltd Production of alpha-olefin oligomer
JPH09143228A (en) * 1995-11-22 1997-06-03 Sumitomo Chem Co Ltd Production of ethylene/alpha-olefin copolymer
US6184428B1 (en) 1998-04-22 2001-02-06 Saudi Basic Industries Corporation Catalyst and process for ethylene oligomerization
GB9918635D0 (en) * 1999-08-06 1999-10-13 Bp Chem Int Ltd Polymerisation process
GB0016895D0 (en) 2000-07-11 2000-08-30 Bp Chem Int Ltd Olefin oligomerisation
EP2075242A1 (en) 2001-12-20 2009-07-01 Sasol Technology (Proprietary) Limited Trimerisation and oligomerisation of olefins using a chromium based catalyst

Also Published As

Publication number Publication date
ES2340483T3 (en) 2010-06-04
WO2004056478A1 (en) 2004-07-08
AU2003297544A1 (en) 2004-07-14
AU2003297546A1 (en) 2004-07-14
PL377211A1 (en) 2006-01-23
CN1741851A (en) 2006-03-01
EP1581341B1 (en) 2010-02-10
BR0317510A (en) 2005-11-16
EP1581342A1 (en) 2005-10-05
WO2004056477A1 (en) 2004-07-08
CN100540514C (en) 2009-09-16
ATE477053T1 (en) 2010-08-15
CA2510194A1 (en) 2004-07-08
EP1578531B1 (en) 2010-08-11
EP1581341A1 (en) 2005-10-05
BRPI0317510B1 (en) 2020-01-07
CA2510190A1 (en) 2004-07-08
CN1741850A (en) 2006-03-01
CA2510801A1 (en) 2004-07-08
EP1578531A1 (en) 2005-09-28
CN100548946C (en) 2009-10-14
BRPI0317516B1 (en) 2019-12-17
US20060229480A1 (en) 2006-10-12
KR20060002741A (en) 2006-01-09
AU2003297545A1 (en) 2004-07-14
KR20060002742A (en) 2006-01-09
KR20050100600A (en) 2005-10-19
BR0317516A (en) 2005-11-16
ATE457196T1 (en) 2010-02-15
DE60331252D1 (en) 2010-03-25
JP2006516265A (en) 2006-06-29
BRPI0316870B1 (en) 2019-10-08
BR0316870A (en) 2005-10-25
PL377406A1 (en) 2006-02-06
US7511183B2 (en) 2009-03-31
CA2510190C (en) 2011-10-11
CN1741849A (en) 2006-03-01
PL377488A1 (en) 2006-02-06
CN100548947C (en) 2009-10-14
WO2004056479A1 (en) 2004-07-08
CA2510194C (en) 2012-01-31
EP1578531B9 (en) 2011-02-02
JP2006517528A (en) 2006-07-27
EP1581342B1 (en) 2010-12-15

Similar Documents

Publication Publication Date Title
CA2510801C (en) Tetramerization of olefins
US7297832B2 (en) Tetramerization of olefins
US7525009B2 (en) Trimerisation of olefins
CA2570056C (en) Oligomerisation in the presence of both a tetramerisation catalyst and a further oligomerisation catalyst
CA2570054C (en) Oligomerisation of olefinic compounds in an aliphatic medium
CA2612214C (en) Oligomerisation of olefinic compounds in the presence of a diluted metal containing activator
US20090306442A1 (en) Oligomerisation catalyst with pendant donor groups
EP1931470A2 (en) Oligomerisation of olefinic compounds in the presence of an oligomerisation catalyst, and a catalyst activator including a halogenated organic group
JP2006511625A (en) Tetramerization of olefins
ES2350468T3 (en) OLEFIN TRETRAMERIZATION.
ZA200504750B (en) Tetramerization of olefins
ZA200504749B (en) Tetramerization of olefins
ZA200504706B (en) Trimerisation of olefins

Legal Events

Date Code Title Description
EEER Examination request
MKEX Expiry

Effective date: 20231219