WO2012055943A2 - Oligomérisation d'oléfines - Google Patents

Oligomérisation d'oléfines Download PDF

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WO2012055943A2
WO2012055943A2 PCT/EP2011/068809 EP2011068809W WO2012055943A2 WO 2012055943 A2 WO2012055943 A2 WO 2012055943A2 EP 2011068809 W EP2011068809 W EP 2011068809W WO 2012055943 A2 WO2012055943 A2 WO 2012055943A2
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carbon atoms
aryl
alkyl
crc
radicals
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WO2012055943A3 (fr
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Katrin Schuhen
Reynald Chevalier
Sandro Gambarotta
Khalid Albahily
Sebastiano Licciulli
Robbert Duchateau
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Basell Polyolefine Gmbh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts 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
    • B01J31/1845—Catalysts 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
    • B01J31/1865—Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
    • B01J31/187—Amide derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic System
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/64—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/66—Tungsten
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene

Definitions

  • the present invention relates to oligomenzation of olefins, including oligomenzation process, catalyst system for oligomenzation and a transition metal complex which can be used in a catalyst system for oligomenzation of olefins.
  • Oligomers, and especially a-olefins are used in polymerization processes often as monomers or comonomers to prepare polyolefins having interesting properties.
  • WO 2002/041 19 A1 disclosing a catalyst for trimerization of ethylene which comprises a source of chromium, molybdenum and tungsten and a ligand containing at least one phosphorous, arsenic or antimony atom bound to at least one heterohydrocarbyl group. Further examples are disclosed in US 5,81 1 ,618 A1 , WO
  • WO 2004/056478 A1 and WO 2004/056479 A1 a process for preparing 1-octene as the major component is disclosed, wherein a complex comprises a ligand having a phosphorus- nitrogen-phosphorus basic structure.
  • a discussion of the catalytic process is described in J. Am. Chem. Soc, 2004, 126 (45), 14712-14713 and J. Am. Chem. Soc, 2005, 127 (30), 10723-10730.
  • Catalysts having similar basic structures are also disclosed in Organometallics 2006, 25 (3), 715-718 and Organometallics 2007, 26 (10), 2782-2787. The cocatalyst influence on one of these complexes has been examined in Organometallics 2007, 26(10), 2561-2569.
  • a general problem of nearly all oligomerization processes is the production of polymer additionally to the oligomers leading to reactor fouling during industrial set-ups for oligomerization systems.
  • this object is achieved by a transition metal complex comprising at least one ligand system L with a nitrogen-phosphorus-nitrogen-structural element wherein phosphorus is pentavalent, a catalytic system comprising the transition metal compound, and a process for oligomerization carried out in the presence of this catalyst system.
  • the ligand system L is represented by the following formula (A)
  • R 1 , R 2 , R 3 , R 4 , and R 5 are identical or different and are each, independently of one another, hydrogen, halogen, CrC 50 -alkyl, C 2 -C 50 -alkenyl, C6-C5o-aryl, alkylaryl or arylalkyl having from 1 to 50 carbon atoms in the alkyl part and 6 to 50 carbon atoms in the aryl part, C1-C50- alkoxy, or C 6 -C 50 -aryloxy, wherein the organic radicals R 1 , R 2 , R 3 , R 4 , and R 5 may also be substituted by halogens, CrC 50 -alkoxy, C 6 -C 50 -aryloxy or SiR 6 3 and the radicals R 1 , R 2 , R 3 , R 4 , and R 5 and their substituents may also contain heteroatoms selected from N, P, O or S, R 6 are each, independently of one another, hydrogen, CrC 50
  • R 1 , R 2 , R 3 , R 4 , and R 5 are identical or different and are each, independently of one another, hydrogen, halogen, CrC 50 -alkyl, preferably C Cio-alkyl, C 2 -C 50 -alkenyl, preferably C 2 -Ci 0 - alkenyl, C 6 -C 50 -aryl, preferably C 5 -Ci 4 -aryl, CrC 50 -alkoxy, preferably d-Ci 0 -alkoxy, or C6-C 50 -aryloxy, preferably C 6 -Ci 4 -aryloxy or alkylaryl having from 1 to 50 carbon atoms in the alkyl part and 6 to 50 carbon atoms in the aryl part, preferably from 1 to 10 carbon atoms in the alkyl part and from 6 to 14 carbon atoms in the aryl part.
  • Each alkyl moiety and each alkenyl moiety may be branched or unbranched.
  • the organic radicals R 1 , R 2 , R 3 , R 4 , and R 5 may also be substituted by halogens, .i.e. by fluorine, bromine, chlorine, or iodine, CrC 50 - alkoxy, preferably C Cio-alkoxy, C 6 -C 50 -aryloxy preferably C 6 -Ci 4 -aryloxy or SiR 6 3 and R 1 , R 2 , R 3 , R 4 , and R 5 and their substituents may also contain heteroatoms selected from N, P, O or S.
  • R 2 and R 5 are identical or different and are each, independently of one another C C 5 o-alkyl, preferably C Ci 0 -alkyl, C 2 -C 5 o-alkenyl, preferably C 2 -Ci 0 -alkenyl, C 6 -C 5 o-aryl, preferably C 6 -Ci 4 -aryl, or alkylaryl having from 1 to 50 carbon atoms in the alkyl part and 6 to 50 carbon atoms in the aryl part, preferably from 1 to 10 carbon atoms in the alkyl part and from 6 to 14 carbon atoms in the aryl part.
  • Each alkyl moiety and each alkenyl moiety may be branched or unbranched.
  • the organic radicals R 2 and R 5 may also be substituted by halogens, .i.e. by fluorine, bromine, chlorine, or iodine, CrC 50 -alkoxy, preferably C Ci 0 - alkoxy, C 6 -C 50 -aryloxy preferably C 6 -Ci 4 -aryloxy or SiR 6 3 and R 2 and R 5 and their substituents may also contain heteroatoms selected from N, P, O or S. Especially preferred are R 2 and R 5 being tert-buty, isopropyl or phenyl.
  • z may be 0 or 1. If z is 0 the ligand is anionic, while in case z is 1 the ligand is neutral. In case z is 1 , R 1 is preferably hydrogen. Preferably z is 0.
  • R 3 and R 4 are identical or different and are each, independently of one another, C 6 -C 50 -aryl, preferably C 6 -Ci 4 -aryl, or alkylaryl having from 1 to 50 carbon atoms in the alkyl part and 6 to 50 carbon atoms in the aryl part, preferably from 1 to 10 carbon atoms in the alkyl part and from 6 to 14 carbon atoms in the aryl part.
  • Each alkyl moiety and each alkenyl moiety may be branched or unbranched.
  • the organic radicals R 3 and R 4 may also be substituted by halogens, .i.e.
  • R 3 and R 4 and their substituents may also contain heteroatoms selected from N, P, O or S. Especially preferred are R 3 and R 4 being phenyl.
  • the radicals R 6 in organosilicon substituents SiR 6 3 can be the same or different are each, independently of one another, hydrogen, CrC 50 -alkyl, preferably C Cio-alkyl, C 2 -C 50 -alkenyl, preferably C 2 -Ci 0 -alkenyl, C 6 -C 50 -aryl, C 6 -Ci 4 -aryl, arylalkyl or alkylaryl having from 1 to 50, preferably 1 to 10 carbon atoms in the alkyl part and 6 to 50, preferably 6 to 14 carbon atoms in the aryl part, CrC 50 -alkoxy, preferably C Cio-alkoxy or C6-C50— aryloxy, preferably C 6 -Ci 4 -aryloxy, where two radicals R 6 may also be joined to form a 5- or 6-membered ring.
  • radicals R 6 are trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, tritert-butylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl.
  • Preferred radicals R 6 are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, methoxy, ethoxy, propoxy, butoxy, benzyl, phenyl, ortho-dialkyl- or dichloro-substituted phenyls, trialkyl- or trichloro-substituted phenyls, naphthyl, biphenyl and anthranyl.
  • alkyl refers to a branched or unbranched saturated hydrocarbon group containing 1 to 50 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like. Generally, alkyl groups herein may contain 1 to 10 carbon atoms.
  • alkenyl refers to a branched or unbranched, cyclic or acyclic hydrocarbon group containing 2 to 50 carbon atoms and at least one double bond, such as ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, and the like.
  • alkenyl groups herein contain 2 to 10 carbon atoms.
  • aromatic is used in its usual sense, including unsaturation that is delocalized across several bonds around a ring.
  • aryl refers to a group containing an aromatic ring.
  • Aryl groups herein include groups containing a single aromatic ring or multiple aromatic rings that are fused together, linked covalently, or linked to a common group such as a methylene or ethylene moiety. More specific aryl groups contain one aromatic ring or two or three fused or linked aromatic rings, e.g. phenyl, naphthyl, biphenyl, anthracenyl, or phenanthrenyl.
  • Aryl groups include 6 to 50 atoms other than hydrogen, typically 6 to 14 atoms other than hydrogen.
  • multi- ring moieties are substituents and in such embodiments the multi-ring moiety can be attached at an appropriate atom.
  • naphthyl can be 1-naphthyl or 2-naphthyl
  • anthracenyl can be 1-anthracenyl, 2-anthracenyl or 9-anthracenyl
  • phenanthrenyl can be 1 -phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, or 9- phenanthrenyl.
  • alkoxy intends an alkyl group bound through a single, terminal ether linkage; that is, an "alkoxy” group may be represented as -O-alkyl where alkyl is as defined above.
  • aryloxy is used in a similar fashion, and may be represented as - O-aryl, with aryl as defined below.
  • hydroxyl refers to -OH.
  • halo and halogen are used in the conventional sense to refer to a chloro, bromo, fluoro or iodo radical.
  • heteroatoms selected from N, P, O or S refer to a molecule or molecular fragment in which one or more carbon atoms is replaced with a heteroatom.
  • alkyl it refers to an alkyl substituent that is heteroatom-containing.
  • cycles containing a heteroatom one or more carbon atoms in a ring is replaced with a heteroatom, that is, an atom other than carbon, i.e. nitrogen, oxygen, sulfur, phosphorus.
  • aryl containing heteroatoms refers to an aryl radical that includes one or more heteroatoms in the aromatic ring.
  • heteroaryl groups include groups containing heteroaromatic rings such as thiophene, pyridine, pyrazine, isoxazole, pyrrazole, pyrrole, furan, thiazole, oxazole, imidazole, isothiazole, oxadiazole, triazole, and benzo-fused analogues of these rings, such as indole, carbazole, benzofuran, benzothiophene and the like.
  • heteroaromatic rings such as thiophene, pyridine, pyrazine, isoxazole, pyrrazole, pyrrole, furan, thiazole, oxazole, imidazole, isothiazole, oxadiazole, triazole, and benzo-fused analogues of these rings, such as indole, carbazole, benzofuran, benzothiophene and the like.
  • pentavalent is meant that phosphorus
  • M 1 is an element of group 3 to 10 of the Periodic Table of the Elements
  • L is a ligand system with a nitrogen-phosphorus-nitrogen-structural element wherein phosphorus is pentavalent
  • o 1 or 2
  • X are the same or different and are each halogen, CrC 20 -alkyl, C 2 -C 2 o-alkenyl, C 6 -C 22 - aryl, alkylaryl or arylalkyi group having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 22 carbon atoms in the aryl radical, -OR 7 or -NR 7 R 8 , wherein two radicals X may also be joined to one another, and wherein R 7 and R 8 are each independently C Cio-alkyl, C 6 -Ci 4 -aryl, alkylaryl, arylalkyi, fluoroalkyl or fluoroaryl each having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 22, carbon atoms in the aryl radical,
  • n is a natural number from 0 to 5
  • n 1 , 2, or 3;
  • M 1 is a transition metal of group 3 to 10 of the periodic table of the elements or the lanthanides
  • M 1 is preferably an element of group 3, 4, 5 or 6 of the Periodic Table of the Elements or the lanthanides, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, preferably chromium, molybdenum or tungsten, particularly preferably chromium.
  • the radicals X are identical or different, preferably identical, with two radicals X also being able to be joined to one another.
  • X is preferably halogen, for example fluorine, chlorine, bromine, iodine, most preferably chlorine, C C 20 -, preferably CrC 4 -alkyl, in particular methyl, C 2 -C 20 -, preferably C 2 -C 4 -alkenyl, C 5 -C 22 -, preferably C 5 -Ci 0 -aryl, an alkylaryl or arylalkyi group having from 1 to 10, preferably from 1 to 4, carbon atoms in the alkyl radical and from 5 to 22, preferably from 5 to 10, carbon atoms in the aryl radical, -OR 7 or -NR 7 R 8 , preferably -OR 7 , where two radicals X, preferably two radicals -OR 7 , may also be joined to one another.
  • radicals X it is also possible for two radicals X to form a substituted or unsubstituted diene ligand, in particular a 1 ,3-diene ligand.
  • the radicals R 7 and R 8 are each C1-C10-, preferably CrC 4 -alkyl, C5-C15-, preferably C 5 -Ci 0 -aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each having from 1 to 10, preferably from 1 to 4, carbon atoms in the alkyl radical and from 5 to 22, preferably from 5 to 10, carbon atoms in the aryl radical.
  • Most preferably X is chlorine, methyl, or 1 ,3-butadiene.
  • the variable m is a number from 0 to 5.
  • the number m of the ligands X depends on the oxidation state of the transition metal M 1 .
  • the oxidation state of the transition metals M 1 in catalytically active complexes is usually known to those skilled in the art. E.g. chromium, molybdenum and tungsten are very probably present in the oxidation state +3 and titanium, zirconium, hafnium and vanadium in the oxidation state 4, with titanium and vanadium also being able to be present in the oxidation state 3.
  • M 1 is preferably chromium in the oxidation states 2, 3 and 4.
  • the complex may have more than one metal center, i.e. a di- or trimetallic cluster may be formed. In case R 1 is present the complex generally is neutral, i.e. p is 0. In case R 1 is not present, the ligand has a negative charge.
  • the complex may comprise a countercation, which may be retained as a part of the complex or cluster. The countercation may be partially solvated. However, it is also possible that a countercation unconnected to the cluster is present.
  • M 1 is an element of group 3 to 10 of the Periodic Table of the Elements
  • L is a ligand system with a nitrogen-phosphorus-nitrogen-structural element wherein phosphorus is pentavalent
  • o 1 or 2
  • X are the same or different and are each halogen, d-C 2 o-alkyl, C 2 -C 2 o-alkenyl, C 6 -C 2 2- aryl, alkylaryl or arylalkyl group having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 22 carbon atoms in the aryl radical, -OR 7 or -NR 7 R 8 , wherein two radicals X may also be joined to one another, and wherein R 7 and R 8 are each independently C Cio-alkyl, C 6 -Ci 4 -aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 22, carbon atoms in the aryl radical,
  • n is a natural number from 0 to 5
  • n 1 , 2, or 3;
  • M 2 is an element of group 1 of the Periodic Table of the Elements
  • Y is a neutral ligand
  • q is a number from 0 to 3.
  • the complex may further comprise neutral ligands which solvate the countercation and are represented by Y in formula (Bll).
  • Y are selected from the groups of nitriles, isocyanides, alcohols, ethers, amines, acid amides, lactames and sulfones; e.g. acetonitrile (CH 3 CN), diethylether (DEE), dimethylether (DME), water (H 2 0), or acetone.
  • cyclic ligands can be used, e.g. tetrahydrofurane (THF), dioxane, pyridine, imidazole or thiophene.
  • M 2 is an element of group 1 of the Periodic Table of the Elements, i.e. Li, Na, K, Rb, Cs, wherein M 2 preferably is Li.
  • Complex 3 is instead dimeric with three chlorine atoms bridging the two transition metals.
  • the chromium metal displays a square pyramidal coordination geometry.
  • the present invention further refers to a catalyst system for the oligomerization of olefins, which comprises
  • At least one transition metal compound comprising a ligand system L with a nitrogen- phosphorus-nitrogen-structural element wherein phosphorus is pentavalent and
  • the above catalyst system may either be formed prior to use in an oligomerization reaction, or it may be formed in situ by adding the individual components thereof to the reaction mixture.
  • the oligomerization catalyst system may also be formed in-situ by mixing
  • transition metal precursor being a chromium precursor
  • examples for a metal precursor of the present invention are chromium salts in oxidation state +II or +III , preferably THF adducts of chromium(ll) and chromium(lll) salts.
  • Examples for these chromium precursors are (THF) 3 CrMeCI 2 , (THF) 3 CrCI 3 , (Mes) 3 Cr(THF), [ ⁇ TFA ⁇ 2 Cr(OEt 2 )] 2 , (THF) 3 CrPh 3 , Cr(NMe 3 ) 2 CI 3 , CrCI 3 , Cr(acac) 3 , Cr(2-ethylhexanoate) 3 , Cr(neopentyl) 3 (THF) 3 , Cr(CH 2 -C 6 H 4 -o-NMe 2 ) 3 , Cr(TFA) 3 , Cr(CH(SiMe 3 ) 2 ) 3 , Cr(Mes) 2 (THF) 3 , Cr(Mes) 2 (THF), Cr(Mes)CI(THF) 2 , Cr(Mes)CI(THF) 0 5 , Cr(p-tolyl)CI 2 (THF) 3 , Cr(di
  • chromium precursors are (THF) 3 CrCI 3 , CrCI 3 , Cr(acac) 3 , CrCI 2 (THF) 2 .
  • THF tetrahydrofurane
  • Me methyl
  • TFA trifluoroacetate
  • Et ethyl
  • Ph phenyl
  • acac acetylacetonato.
  • a cocatalysts is also present in the invention. Suitable activators for the types of catalyst mentioned are generally known.
  • Lewis acids or Bronstedt may be used. Examples for Lewis acids are boranes or alanes, such as alkyl aluminum, aluminum halogenide, aluminum alcoholate, boron organic compounds, boron halogenides, boronic acid esters or boron or aluminum compounds, comprising halogen as well as alkyl, aryl or alcoholate, as well as mixtures thereof or the triphenyl methyl cation.
  • Further cocatalysts to the above are lithium alkyles or magnesium organic compounds, such as Grignard reagents or partly hydrolyzed boron organic compounds.
  • Preferred cocatalysts are aluminoxanes. It is possible to use, for example, the compounds described in WO 00/31090 1. Particularly suitable aluminoxanes are open-chain or cyclic aluminoxane compounds of the general formulae (CI) or (CM)
  • R c is each, independently of one another, a d-C 6 -alkyl group, preferably a ethyl, butyl or isobutyl group, and
  • s is an integer from 1 to 40, preferably from 4 to 25.
  • a particularly suitable aluminoxane compound is methylaluminoxane.
  • Grignard reagents especially preferred are unsaturated Gringard reagents such as vinyl magnesium chloride.
  • Suitable components are, for example, also strong, uncharged Lewis acids, ionic compounds having Lewis-acid cations or an ionic compounds containing Bronsted acids as cations. Examples are tris(pentafluorophenyl)borane,
  • the catalyst system may further comprise, a metal compound of general formula (D),
  • M D (R D1 ) t (R D2 ) u (R D3 ) v (D) is lithium, sodium, potassium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, thallium, zinc, preferably lithium, sodium, potassium, magnesium, boron, aluminum or zinc and in particular lithium, magnesium, boron or aluminum,
  • R D3 are each hydrogen, halogen, C1—C1 0 — alkyl, C 6 -Ci 5 -aryl, alkylaryl, arylalkyl or alkoxy each having from 1 to 20 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, or alkoxy with C1—C1 0 — alkyl or C 6 -Ci 5 -aryl, is an integer from 1 to 3 are integers from 0 to 2, with the sum t+u+v corresponding to the valence of M D It is also possible to use mixtures of various metal compounds of the formula (D).
  • Particularly preferred metal compounds of the formula (D) are methyllithium, ethyllithium, n-butyllithium, methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium,
  • the partial hydrolysis products of aluminum alkyls with alcohols can also be used.
  • a metal compounds of general formula (D) are used, it is preferably comprised in the catalyst system in such an amount that the molar ratio of M D from formula (D) to the sum of all metals of catalyst components of formula (B), of cocatalyst and of components of formula (D) is from 3000: 1 to 0.1 : 1 , preferably from 800:1 to 0.2: 1 and particularly preferably from 100: 1 to 1 :1.
  • catalyst system comprising oligomerization catalyst components of formula (B) and the cocatalyst, (e.g. an aluminoxane) in solid form.
  • catalyst at least one of transition metal compound and cocatalyst are applied to a solid support. Transition metal complex, and the cocatalyst can be immobilized independently of one another, e.g. in succession or simultaneously.
  • the support component can firstly be brought into contact with the cocatalyst or cocatalysts or the support component can firstly be brought into contact with the transition metal complex.
  • Preactivation of the transition metal complex by means of one or more cocatalysts prior to mixing with the support is also possible.
  • the immobilization is generally carried out in an inert solvent which can be removed by filtration or evaporation after the immobilization.
  • the solid can be washed with suitably inert solvents such as aliphatic or aromatic hydrocarbons and dried.
  • suitably inert solvents such as aliphatic or aromatic hydrocarbons
  • the support component preference is given to using finely divided supports which can be any organic or inorganic solid.
  • the support component can be a porous support such as talc, a sheet silicate such as montmorillonite, mica or an inorganic oxide or a finely divided polymer powder (e.g. polyolefin or a polymer having polar functional groups).
  • the inorganic support can be subjected to a thermal treatment, e.g. to remove adsorbed water.
  • a drying treatment is generally carried out at temperatures in the range from 50 to 1000°C, preferably from 100 to 600°C, with drying at from 100 to 200°C preferably being carried out under reduced pressure and/or under a blanket of inert gas (e.g.
  • the inorganic support can be calcined at temperatures of from 200 to 1000°C to produce the desired structure of the solid and/or set the desired OH concentration on the surface.
  • the support can also be treated chemically using customary dessicants such as metal alkyls preferably aluminum alkyls, chlorosilanes or SiCI 4 , or else methylaluminoxane. Appropriate treatment methods are described, for example, in WO 00/31090 B1.
  • the invention further refers to a process for olefin oligomerization, especially trimerization, carried out in the presence of a catalyst system as defined above.
  • trimerization means catalytic reaction of a single olefinic monomer or a mixture of olefinic monomers to give products derived from the reaction(s) of three olefinic monomers, as distinct from polymerization.
  • Trimerization includes the case where all the monomer units in the trimerization product are identical, where the trimerization product is made from two different olefins (i.e. two equivalents of one monomer react with two equivalents of a second monomer), and also where three different monomer units react to yield the product.
  • a reaction involving more than one monomer is often referred to as co- trimerization.
  • trimerization generally refers to the reaction of three, and preferably three identical, olefinic monomer units or a-olefins to yield a linear and/or branched olefin.
  • a-olefinic monomer units or 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. Trimerization of ethylene is preferred.
  • tetramerization means catalytic reaction of a single olefinic monomer or a mixture of olefinic monomers to give products derived from the reaction(s) of four olefinic monomers.
  • oligomerization means catalytic reaction of a single olefinic monomer or a mixture of olefinic monomers to give products enriched in those constituents derived from the reaction(s) of 2 to 15 olefinic monomers.
  • the cocatalyst or cocatalysts can in each case be used in any amounts based on the complexes of the catalyst composition of the invention. They are preferably used in an excess or in stoichiometric amounts, in each case based on the complex which they activate.
  • the amount of cocatalyst(s) to be used depends on the type of the cocatalyst(s). In general, the molar ratio of transition metal complex to cocatalyst can be from 1 :0.1 to 1 : 10000, preferably from 1 :1 to 1 :2000.
  • Suitable olefinic monomers, or combinations thereof for use in the trimerization process of the present invention are hydrocarbon olefins, for example, ethylene, C 3 -C 2 o a-olefins, internal olefins, vinylidene olefins, cyclic olefins and dienes, propylene, 1-butene, 1-pentene, 1-hexene, 4-methylpentene-1 , 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1- dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1- octadecene, 1-nonadecene, 1-eicosene, styrene, 2-butene, 2-ethyl-1-hexene, cyclohex
  • Olefins with a polar functionality such as methyl (meth)acrylate, vinyl acetate, ⁇ , ⁇ -undecenol and the like, may also be used.
  • the preferred monomer is ethylene.
  • Mixtures of these monomers may also be used, for example a 1- butene unit and two ethylene units may be co-trimerised to form C 8 olefins, or 1-hexene and ethylene co-trimerised to Ci 0 olefins, or 1-dodecene and ethylene co-tetramerised to Ci 6 olefins. Combinations of these co-trimerization reactions may be performed simultaneously, especially when one or more of the monomers are produced in-situ (e.g.
  • a mixture of ethylene and butene can be used to form mixtures containing predominantly hexenes, octenes, and decenes.
  • Techniques for varying the distribution of products from these reactions include controlling process conditions (e.g. concentration, reaction temperature, pressure, residence time) and properly selecting the design of the process and are well known to those skilled in the art.
  • Olefinic monomers or mixtures of olefinic monomers for oligomerization may be substantially pure or may contain olefinic impurities.
  • One embodiment of the process of the invention comprises the oligomerization, preferably trimerization of olefin-containing waste streams from other chemical processes or other stages of the same process.
  • any diluent or solvent that is an olefin, a mixture of olefins, or is substantially inert under oligomerization conditions may be employed.
  • the preferred diluents or solvents are aliphatic and aromatic hydrocarbons and halogenated hydrocarbons such as, for example, isobutane, pentane, toluene, xylene, ethylbenzene, cumene, mesitylene, heptane, cyclohexane, methylcyclohexane, 1-hexene, 1- octene, chlorobenzene, dichlorobenzene, and the like, and mixtures such as isopar.
  • aliphatic and aromatic hydrocarbons and halogenated hydrocarbons such as, for example, isobutane, pentane, toluene, xylene, ethylbenzene, cumene, mesitylene, heptane, cyclohexane, methylcyclohexane, 1-hexene, 1- octene, chlorobenzene, dichlorobenzene, and the like
  • the oligomerization can be carried out in a known manner in bulk, in suspension, in the gas phase or in a supercritical medium in the customary reactors used for the oligomerization or polymerization of olefins. It can be carried out batchwise or continuously in one or more stages. High-pressure oligomerization processes in tube reactors or autoclaves, solution processes, suspension processes, stirred gas-phase processes or gas-phase fluidized-bed processes are all possible.
  • the oligomerizations are usually carried out at temperatures in the range from -60 to 350°C and under pressures of from 0.5 to 4000 bar.
  • the mean residence times are usually from 0.5 to 5 hours, preferably from 0.5 to 3 hours.
  • the advantageous pressure and temperature ranges for carrying out the oligomerizations usually depend on the oligomerization method. In the case of high-pressure oligomerization processes, which are usually carried out at pressures of from 1000 to 4000 bar, in particular from 2000 to 3500 bar, high oligomerization temperatures are generally also set.
  • Advantageous temperature ranges for these high- pressure oligomerization processes are from 200 to 320°C, in particular from 220 to 290°C.
  • a temperature which is at least a few degrees below the softening temperature of the oligomer is generally set. In particular, temperatures of from 50 to 180°C, preferably from 70 to 120°C, are set in these oligomerization processes.
  • the oligomerization temperatures are generally in the range from -20 to 115°C, and the pressure is generally in the range from 1 to 100 bar.
  • the solids content of the suspension is generally in the range from 10 to 80%.
  • the oligomerization can be carried out batchwise, e.g. in stirring autoclaves, or continuously, e.g. in tube reactors, preferably in loop reactors. Particular preference is given to employing the Phillips PF process as described in US-A 3 242 150 and US-A 3 248 179.
  • oligomerization is generally carried out in the range from 30 to 125°C.
  • the oligomerization and co-oligomerization reactions of the present invention can be performed under a range of process conditions that are readily apparent to those skilled in the art: as a homogeneous liquid phase reaction in the presence or absence of an inert hydrocarbon diluent such as toluene or heptanes; as a two-phase liquid/liquid reaction; as a slurry process where the catalyst is in a form that displays little or no solubility; as a bulk process in which essentially neat reactant and/or product olefins serve as the dominant medium; as a gas-phase process in which at least a portion of the reactant or product olefin(s) are transported to or from a supported form of the catalyst via the gaseous state.
  • the oligomerization reactions may be performed in the known types of gas-phase reactors, such as circulating bed, vertically or horizontally stirred-bed, fixed-bed, or fluidized-bed reactors, liquid-phase reactors, such as plug-flow, continuously stirred tank, or loop reactors, or combinations thereof.
  • gas-phase reactors such as circulating bed, vertically or horizontally stirred-bed, fixed-bed, or fluidized-bed reactors
  • liquid-phase reactors such as plug-flow, continuously stirred tank, or loop reactors, or combinations thereof.
  • a wide range of methods for effecting product, reactant, and catalyst separation and/or purification are known to those skilled in the art and may be employed: distillation, filtration, liquid-liquid separation, slurry settling, extraction, etc. It is within the scope of this invention that an oligomerization product, preferably a
  • trimerization product might also serve as a reactant (e.g. 1-octene, produced via the trimerization of ethylene, might be converted to tetradecene products via a subsequent co- trimerization reaction with ethylene.
  • a reactant e.g. 1-octene, produced via the trimerization of ethylene, might be converted to tetradecene products via a subsequent co- trimerization reaction with ethylene.
  • An example of an "in situ” process is the production of branched polyethylene, which is prepared by the oligomerization catalyst added in any order such that the active catalytic species is/are at some point present in a reactor.
  • the catalyst is generally supported and metered and transferred into the oligomerization zone in the form of a particulate solid either as a dry powder (e.g. with an inert gas, ethylene or an olefin) or as a slurry.
  • a particulate solid either as a dry powder (e.g. with an inert gas, ethylene or an olefin) or as a slurry.
  • an optional cocatalyst can be fed to the oligomenzation zone, for example as a solution, separately from or together with the solid catalyst.
  • Such methods generally involve agitating (e.g. by stirring, vibrating or fluidizing) a bed of catalyst, or a bed of the target polymer (i.e. polymer having the same or similar physical properties to that which it is desired to make in the polymerization process) containing a catalyst, and feeding thereto a stream of monomer (under conditions such that at least part of the monomer oligomerizes in contact with the catalyst in the bed.
  • the bed is generally cooled by the addition of cool gas (e.g. recycled gaseous monomer) and/or volatile liquid (e.g. a volatile inert hydrocarbon, or gaseous monomer which has been condensed to form a liquid).
  • the polymer produced in, and isolated from, gas phase processes forms directly a solid in the oligomenzation zone and is free from, or substantially free from liquid.
  • any liquid is allowed to enter the polymerization zone of a gas phase polymerization process the quantity of liquid in the oligomenzation zone is small in relation to the quantity of polymer present.
  • This is in contrast to "solution phase” processes wherein the oligomer is formed dissolved in a solvent, and "slurry phase” processes wherein the polymer forms as a suspension in a liquid diluent.
  • the gas phase process can be operated under batch, semi-batch, or so-called “continuous" conditions. It is preferred to operate under conditions such that monomer is continuously recycled to an agitated oligomenzation zone containing oligomenzation catalyst, make-up monomer being provided to replace oligomerized monomer, and continuously or
  • the process can be operated, for example, in a vertical cylindrical reactor equipped with a perforated distribution plate to support the bed and to distribute the incoming fluidizing gas stream through the bed.
  • the fluidizing gas circulating through the bed serves to remove the heat of oligomenzation from the bed and to supply monomer for oligomenzation in the bed.
  • the fluidizing gas generally comprises the monomer(s) normally together with some inert gas (e.g.
  • the hot fluidizing gas emerging from the top of the bed is led optionally through a velocity reduction zone (this can be a cylindrical portion of the reactor having a wider diameter) and, if desired, a cyclone and or filters to disentrain fine solid particles from the gas stream.
  • the hot gas is then led to a heat exchanger to remove at least part of the heat of oligomerization.
  • Catalysts are preferably fed continuously or at regular intervals to the bed.
  • the bed comprises flu disable polymer which is preferably similar to the target polymer.
  • Oligomer is produced continuously within the bed by the oligomerization of the monomer(s).
  • the process is generally operated at relatively low pressure, for example, at 10 to 50 bars, and at temperatures for example, between 50 and 135°C.
  • the temperature of the bed is maintained below the sintering temperature of the fluidized oligomer to avoid problems of agglomeration.
  • the heat evolved by the exothermic oligomerization reaction is normally removed from the oligomerization zone (i.e. the fluidized bed) by means of the fluidizing gas stream as described above.
  • the hot reactor gas emerging from the top of the bed is led through one or more heat exchangers wherein the gas is cooled.
  • the cooled reactor gas, together with any make-up gas, is then recycled to the base of the bed.
  • the hot recycle gas from the bed enters the heat exchanger, the volatile liquid can condense out.
  • the volatile liquid is separated from the recycle gas and reintroduced separately into the bed.
  • the volatile liquid can be separated and sprayed into the bed.
  • the volatile liquid is recycled to the bed with the recycle gas.
  • the volatile liquid can be condensed from the fluidizing gas stream emerging from the reactor and can be recycled to the bed with recycle gas, or can be separated from the recycle gas and then returned to the bed.
  • the oligomerization catalyst is preferably (but optionally) added before the polymerization catalyst such that the desired primary monomer to comonomer(s) ratio is established prior to introduction of the polymerization catalyst.
  • the desired comonomer composition at start-up may however be achieved through introduction of fresh comonomer feed or through judicious initiation of the trimerization reaction before or during oligomerization catalyst introduction.
  • PLgel 10 ⁇ MIXED-B column set at 135 °C using 1 ,2,4-trichlorobenzene as solvent.
  • the liquid product mixtures were analyzed by using a CP 9000 gas chromatograph (GC) equipped with a 30 mL x 0.32 mm id, capillary CP volamine column and a FID detector. All single-point experiments were performed in duplicate. The yield was determined by 1 H-NMR spectroscopy (Varian Mercury 400 MHz spectrometer).
  • Infrared spectra were recorded on an ABB Bomem FTIR instrument from Nujol mulls prepared in a Vacuum-Amosphere dry box. Samples for magnetic susceptibility were pre-weighed inside a dry box equipped with an analytical balance and measured on a Johnson Matthey Magnetic Susceptibility balance. Elemental analysis was carried out with a Perkin-Elmer 2400 CHN analyzer. Data for X-ray crystal structure determination were obtained with a Bruker diffractometer equipped with a 1 K Smart CCD area detector. Diethyl aluminum chloride and triethyl aluminum were purchased from Strem and were used as received.
  • Methylaluminoxane (MAO, 10% in toluene) and vinyl magnesium bromide (1.6 M in tetrahydrofuran) were purchased from Aldrich.
  • n 3 (Ph)N-P(Ph) 2 -N(Ph) was prepared according to the procedure described by Henri-Jean Cristau, Jouanin, Isabelle, and Taillefer, Marc in Journal of Organometallic Chem. 584 (1999), 68-72 and by Cristau, Henri-Jean and Garcia, Chantal in Synthesis (Stuttgart) 1990, 315-317.
  • the ligand c/ ' s- ⁇ f-Bu(H)NP ⁇ -N]tBu ⁇ 2 PN (H)fBu ⁇ was prepared according to Organometallics 2005, 24, 5214.
  • Polymerizations were carried out in either 200 ml_ high-pressure Buchi reactors containing a heating/cooling jacket. A pre-weighed amount of catalyst was dissolved in 100 ml_ of toluene under N 2 and injected into the preheated reactor already charged with cocatalyst and toluene (total volume 100ml). Solutions were heated using a thermostatic bath and charged with ethylene, maintaining the pressure throughout the run. Polymerizations were quenched by releasing the pressure and addition of EtOH and HCI. The polymers obtained were isolated by filtration, sonicated with a solution of HCI, rinsed and thoroughly dried prior to measuring the mass.

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Abstract

L'invention concerne un composé de métal de transition comprenant au moins un système ligand L comportant un élément structural azote-phosphore-azote dans lequel le phosphore est pentavalent, le système catalyseur pour l'oligomérisation d'oléfines comprenant un tel complexe de métal de transition, et le processus d'oligomérisation de monomères oléfiniques s'effectuant en présence du système catalyseur.
PCT/EP2011/068809 2010-10-28 2011-10-27 Oligomérisation d'oléfines WO2012055943A2 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108264591A (zh) * 2016-12-30 2018-07-10 中国石油天然气股份有限公司 一种烯烃聚合催化剂的主催化剂及其制备方法、烯烃聚合催化剂

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3242150A (en) 1960-03-31 1966-03-22 Phillips Petroleum Co Method and apparatus for the recovery of solid olefin polymer from a continuous path reaction zone
US3248179A (en) 1962-02-26 1966-04-26 Phillips Petroleum Co Method and apparatus for the production of solid polymers of olefins
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
US5811618A (en) 1991-10-16 1998-09-22 Amoco Corporation Ethylene trimerization
WO2000031090A1 (fr) 1998-11-25 2000-06-02 Targor Gmbh Monohalogenures de metallocene
WO2002004119A1 (fr) 2000-07-11 2002-01-17 Bp Chemicals Limited Trimerisation d'olefines par utilisation d'un catalyseur comprenant une source de chrome, de molybdene ou de tungstene et un ligand contenant au moins un atome de phosphore, d'arsenic ou d'antimoine, qui est lie a au moins un groupe (hetero)hydrocarbyle
US20020035029A1 (en) 2000-09-29 2002-03-21 Tosoh Corporation Catalyst for trimerization of ethylene and process for trimerizing ethylene using the catalyst
WO2003004158A2 (fr) 2001-07-02 2003-01-16 Sasol Technology (Proprietary) Limited Trimerisation et oligomerisation d'olefines au moyen d'un catalyseur au chrome
WO2003053890A1 (fr) 2001-12-20 2003-07-03 Sasol Technology (Pty) Ltd Trimerisation et oligomerisation d'olefines par utilisation d'un catalyseur a base de chrome
WO2004056479A1 (fr) 2002-12-20 2004-07-08 Sasol Technology (Pty) Ltd Tetramerisation d'olefines
WO2009006979A2 (fr) 2007-07-11 2009-01-15 Linde Ag Composition de catalyseur et procédé de di-, tri- et/ou tétramérisation de l'éthylène

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3242150A (en) 1960-03-31 1966-03-22 Phillips Petroleum Co Method and apparatus for the recovery of solid olefin polymer from a continuous path reaction zone
US3248179A (en) 1962-02-26 1966-04-26 Phillips Petroleum Co Method and apparatus for the production of solid polymers of olefins
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
US5811618A (en) 1991-10-16 1998-09-22 Amoco Corporation Ethylene trimerization
WO2000031090A1 (fr) 1998-11-25 2000-06-02 Targor Gmbh Monohalogenures de metallocene
WO2002004119A1 (fr) 2000-07-11 2002-01-17 Bp Chemicals Limited Trimerisation d'olefines par utilisation d'un catalyseur comprenant une source de chrome, de molybdene ou de tungstene et un ligand contenant au moins un atome de phosphore, d'arsenic ou d'antimoine, qui est lie a au moins un groupe (hetero)hydrocarbyle
US20020035029A1 (en) 2000-09-29 2002-03-21 Tosoh Corporation Catalyst for trimerization of ethylene and process for trimerizing ethylene using the catalyst
WO2003004158A2 (fr) 2001-07-02 2003-01-16 Sasol Technology (Proprietary) Limited Trimerisation et oligomerisation d'olefines au moyen d'un catalyseur au chrome
WO2003053890A1 (fr) 2001-12-20 2003-07-03 Sasol Technology (Pty) Ltd Trimerisation et oligomerisation d'olefines par utilisation d'un catalyseur a base de chrome
WO2004056479A1 (fr) 2002-12-20 2004-07-08 Sasol Technology (Pty) Ltd Tetramerisation d'olefines
WO2004056478A1 (fr) 2002-12-20 2004-07-08 Sasol Technology (Pty) Limited Tetramerisation d'olefines
WO2009006979A2 (fr) 2007-07-11 2009-01-15 Linde Ag Composition de catalyseur et procédé de di-, tri- et/ou tétramérisation de l'éthylène

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
ANGEW. CHEM. INT. ED., vol. 47, 2008, pages 5816 - 5819
CRISTAU, HENRI-JEAN, GARCIA, CHANTAL, SYNTHESIS (STUTTGART, 1990, pages 315 - 317
HENRI-JEAN CRISTAU, JOUANIN, ISABELLE, TAILLEFER, MARC, JOURNAL OF ORGANOMETALLIC CHEM., vol. 584, 1999, pages 68 - 72
J. AM. CHEM. SOC., vol. 126, no. 45, 2004, pages 14712 - 14713
J. AM. CHEM. SOC., vol. 127, no. 30, 2005, pages 10723 - 10730
ORGANOMETALLICS, vol. 24, 2005, pages 5214
ORGANOMETALLICS, vol. 25, no. 3, 2006, pages 715 - 718
ORGANOMETALLICS, vol. 26, no. 10, 2007, pages 2561 - 2569
ORGANOMETALLICS, vol. 26, no. 10, 2007, pages 2782 - 2787
ORGANOMETALLICS, vol. 27, 2008, pages 5708 - 5711

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108264591A (zh) * 2016-12-30 2018-07-10 中国石油天然气股份有限公司 一种烯烃聚合催化剂的主催化剂及其制备方法、烯烃聚合催化剂
CN108264591B (zh) * 2016-12-30 2021-08-31 中国石油天然气股份有限公司 一种烯烃聚合催化剂的主催化剂及其制备方法、烯烃聚合催化剂

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