WO2019105843A1 - New catalytic composition based on nickel, a phosphorus compound and a sulfonic acid, and use thereof for the oligomerization of olefins - Google Patents

New catalytic composition based on nickel, a phosphorus compound and a sulfonic acid, and use thereof for the oligomerization of olefins Download PDF

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Publication number
WO2019105843A1
WO2019105843A1 PCT/EP2018/082220 EP2018082220W WO2019105843A1 WO 2019105843 A1 WO2019105843 A1 WO 2019105843A1 EP 2018082220 W EP2018082220 W EP 2018082220W WO 2019105843 A1 WO2019105843 A1 WO 2019105843A1
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nickel
composition according
chloride
groups
alkyl
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French (fr)
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Typhène MICHEL
Pierre-Alain Breuil
Emmanuel Pellier
Helene Olivier-Bourbigou
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IFP Energies Nouvelles
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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
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • 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
    • 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
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • 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
    • C07C2531/025—Sulfonic acids
    • 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

Definitions

  • the present invention relates to a new nickel-based catalytic composition and its use in chemical transformation reactions and in particular in a process for oligomerization of an olefinic feedstock.
  • the invention also relates to a process for oligomerizing an olefinic feedstock comprising bringing said feedstock into contact with the nickel-based composition according to the invention and in particular a process for the selective dimerization of ethylene by purpose. 1-ene using said nickel-based composition according to the invention.
  • Ni (0) nickel precursor with a zero oxidation state
  • phosphine phosphine
  • Bronsted acid have in particular been described in patents US Pat. No. 5,237,118, US Pat. No. 4,478,747 and DE 10303931.
  • R 8 is selected from alkyl DC 20, heteroalkyl, Ci-C 20 aryl, C 5 -C 30 heteroaryl and C 4 -C 30 .
  • An advantage of the catalytic composition according to the present invention is to have a good efficiency / selectivity pair for the dimerization of ethylene to but-1-ene.
  • heteroatom an atom different from carbon and hydrogen.
  • a heteroatom may be selected from oxygen, sulfur, nitrogen, phosphorus, silicon and halides such as fluorine, chlorine, bromine or iodine.
  • Alkyl is understood to mean a hydrocarbon chain comprising from 1 to 20 carbon atoms, DC 2 o alkyl noted, saturated or unsaturated, linear or branched, non-cyclic, cyclic or polycyclic, substituted or unsubstituted.
  • C 1 -C 6 alkyl is an alkyl selected from methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, hexyl and cyclohexyl.
  • alkoxy is meant a monovalent radical consisting of an alkyl group bonded to an oxygen atom such as the groups CH 3 0-, C 2 H 5 O-, C 3 H 7 O-.
  • aryloxy is meant a monovalent radical consisting of an aryl group bonded to an oxygen atom such as the group C 6 H 5 O-.
  • Heteroalkyl group is understood to mean an alkyl group comprising between 1 and 20 carbon atoms and at least one heteroatom chosen from oxygen (O), sulfur (S), nitrogen (N) and silicon (Si), denoted C 1 -C 20 heteroalkyl.
  • aryl group is meant an aromatic group, mono- or polycyclic, fused or otherwise, substituted or unsubstituted, comprising between 5 and 30 carbon atoms, denoted aryl C 5 -C 3 o.
  • Heteroaryl group an aromatic group comprising between 4 and 30 carbon atoms and at least within at least one aromatic ring, a heteroatom chosen from oxygen (O), sulfur (S), nitrogen (N) and silicon (Si), denoted C 4 -C 30 heteroaryl.
  • Ni (II) is understood to mean a nickel-based compound with a +11 oxidation state.
  • the present invention therefore relates to a catalytic composition
  • a catalytic composition comprising, and preferably consisting of:
  • R 8 is selected from alkyl DC 20, heteroalkyl, Ci-C 20 aryl, C 5 -C 30 heteroaryl and C 4 -C 30 .
  • the aluminum-based compound is chosen from at least one compound, taken alone or as a mixture, of general formula AIR 1 R 2 R 3 in which the groups R 1 , R 2 and R 3 , which are identical or different linear or branched, are independently selected from hydrogen, alkyl groups in CC 20, CC 20 alkoxy, aryloxy and C 5 -C 30.
  • the groups R 1 , R 2 and R 3 are chosen from alkyl and alkyloxy groups, said groups preferably comprise between 1 and 15 carbon atoms, preferably between 1 and 10 carbon atoms, preferably between 1 and 6 carbon atoms and very preferably between 1 and 4 carbon atoms.
  • said groups preferably comprise between 5 and 20 carbon atoms, preferably between 5 and 15 carbon atoms, and preferably between 5 and 10 carbon atoms. carbon atoms.
  • one of the groups R 1 , R 2 and R 3 is a hydrogen.
  • At least one of the groups R 1 , R 2 and R 3 is independently selected from alkyl and alkyloxy groups.
  • said groups are chosen from methyl, ethyl, propyl, n-butyl, sobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl and octyl, and from the corresponding alkyloxy groups.
  • At least one of the groups R 1 , R 2 and R 3 is independently selected from aryloxy groups.
  • said group is phenoxy.
  • the one or more aluminum-based compounds are chosen from trimethylaluminium, triethylaluminium, tripropylaluminium, tri-n-butylaluminium, triisobutylaluminium, tri-tert-butylaluminium, trihexylaluminium, trioctylaluminium, diethylethoxyaluminium, dimethylethoxyaluminium, and preferably the aluminum-based compound is diethylethoxyaluminium.
  • the molar ratio of the aluminum-based compound to the nickel precursor, denoted Al / Ni is between 0.5 and 100.0, preferably between 3.0 and 90.0, preferably between 10 and 10. , 0 and 80.0, preferably between 1 and 50.0, preferably between 11.0 and 60.0, preferably between 15.0 and 50.0, preferably between 1.5 and 25.0, very preferably between 1.5 and 20.0, and even more preferably between 2.0 and 15.0.
  • the phosphorus compound corresponds to the general formula P (A 1 R 4 ) (A 2 R 5 ) (A 3 R 6 ) in which: - A 1 , A 2 and A 3 , identical or different, are independently selected from S, NR 7 or a covalent bond between the phosphorus atom and a carbon atom or a hydrogen atom,
  • R 4, R 5 and R 6, identical or different, linked or not to each other, are independently selected from hydrogen, an alkyl group o CC 2, CC 2 o heteroalkyl, aryl, C 5 -C 3 o and C 4 -C 30 heteroaryl,
  • the R 7 group is independently selected from hydrogen, alkyl Ci-C 2 o, heteroalkyl, Ci-C 2 o aryl, C 5 -C 30 heteroaryl and C 4 -C 30.
  • the groups A 1 , A 2 and A 3 which may be identical or different, are chosen from NR 7 and a covalent bond between the phosphorus atom and a carbon atom or a hydrogen atom, and preferably a covalent bond between the phosphorus atom and a carbon atom or a hydrogen atom.
  • the group R 7 is chosen from alkyl and heteroalkyl groups, comprising between 1 and 15 carbon atoms, preferably between 1 and 10 carbon atoms and preferably between 1 and 6 carbon atoms.
  • R 4 , R 5 and R 6 are chosen from alkyl and heteroalkyl groups, said groups preferably comprise between 1 and 15 carbon atoms, preferably between 1 and 10 carbon atoms and, preferably, between 1 and 6 carbon atoms.
  • R 4 , R 5 and R 6 are chosen from aryl and heteroaryl groups, said groups preferably comprise between 4 and 20 carbon atoms, preferably between 4 and 15 carbon atoms, and preferably between 4 and 15 carbon atoms. and 10 carbon atoms.
  • At least one of the groups R 4 , R 5 and R 6 is independently selected from methyl, ethyl, propyl, propyl, n-butyl, sobutyl, tert-butyl, pentyl, hexyl, heptyl and octyl groups.
  • the groups R 4 , R 5 and R 6 are identical.
  • the molar ratio between the phosphorus compound and the nickel precursor, denoted P / Ni is between 0.1 and 20.0, preferably between 5 and 19.0, preferably between 10.0 and 18, 0, preferably between 11.0 and 17.0, preferably between 0.2 and 10.0, preferably between 0.5 and 8.0, and even more preferably between 0.8 and 5.0.
  • the sulfonic acid is of formula R 8 S0 3 H wherein R 8 is selected from an alkyl group Ci-C 2 o, heteroalkyl, Ci-C 2 o aryl, C 5 -C 3 o and C 4 -C 30 heteroaryl.
  • R 8 when R 8 is chosen from an alkyl or heteroalkyl group, R 8 comprises between 1 and 15 carbon atoms, preferably between 1 and 10 carbon atoms and preferably between 1 and 6 carbon atoms.
  • R 8 when R 8 is chosen from an aryl or heteroaryl group, R 8 comprises between 4 and 20 carbon atoms, preferably between 4 and 15 carbon atoms and preferably between 4 and 10 carbon atoms.
  • R 8 comprises at least one fluorine atom, preferably between 1 and 10 fluorine atoms, preferably between 1 and 6 fluorine atoms, preferably between 2 and 6 fluorine atoms and very preferably between 3 and 6 fluorine atoms. and 6 fluorine atoms.
  • the sulphonic acid is chosen from p-toluenesulphonic acid, benzenesulphonic acid, naphthalenesulphonic acid, methanesulphonic acid, trifluoromethanesulphonic acid, 4-fluorobenzenesulphonic acid and pentafluorobenzenesulphonic acid.
  • the molar ratio of the sulphonic acid relative to the phosphorus compound, denoted RS0 3 H / P is between 0.1 and 20.0, preferably between 0.2 and 10.0, preferably between 0.3 and 8.0, very preferably between 0.4 and 5.0, and even more preferably between 0.6 and 2.0.
  • the catalytic composition comprises at least one nickel precursor with a +11 degree of oxidation.
  • the precursor of nickel (II) is chosen from nickel (II) chloride, nickel (II) chloride (dimethoxyethane), nickel bromide (II), nickel (II) bromide (dimethoxyethane) , nickel fluoride (II), nickel iodide (II), nickel (II) sulphate, nickel (II) carbonate, nickel (II) dimethylglyoxime, nickel (II) hydroxide , nickel (II) hydroxyacetate, nickel (II) oxalate, nickel (II) carboxylates such as, for example, nickel (II) 2-ethylhexanoate, nickel (II) alkoxides, such as Ni (CH 2 CH 2 O 2 CH 2 CH 2 OCH 3) 2, chlorinated nickel (II) alkoxides, such as, for example, Ni (OCH 3 ) Cl, nickel (II) alkoxides, such as, for example, Ni (OE), nickel (
  • the composition comprises, and preferably consists of:
  • a pre-catalytic mixture which has previously been formed and preferably consists of: at least one nickel precursor of oxidation state +11 o at least one phosphorus compound of general formula P (A 1 R 4 ) (A 2 R) 5 ) (A 3 R 6 ) in which ⁇ A 1, A 2 and A 3, identical or different, are independently selected from S, NR 7 or a covalent bond between the phosphorus atom and a carbon atom or a hydrogen atom,
  • R 4 groups, R 5 and R 6, identical or different, linked or not to each other are independently selected from hydrogen, alkyl DC 20, heteroalkyl, Ci-C 2 o aryl, C 5 -C 3 o and C 4 -C 30 heteroaryl,
  • the R 7 group is independently selected from hydrogen, alkyl DC 20, heteroalkyl, Ci-C 20 aryl, C 5 -C 30 heteroaryl and C 4 -C 30 and o at least one sulfonic acid of formula General R 8 S0 3 H, wherein R 8 is selected from an alkyl group Ci-C 20 heteroalkyl CC 20 aryl, C 5 -C 30 heteroaryl and C 4 -C 3Q.
  • the catalyst composition according to the invention can be formulated by preparing a mixture comprising the Ni (II) precursor, the phosphorus compound, the sulfonic acid and the aluminum compound.
  • the catalyst composition is formulated by preparing a precatalytic mixture comprising the Ni (II) precursor, the phosphorus compound and the sulfonic acid prior to contacting with the aluminum compound.
  • each constituent of the catalytic composition or mixture of constituents can be used in a solvent.
  • the precatalytic mixture consists of the Ni (II) precursor, a phosphorus compound, the sulfonic acid and at least one solvent.
  • - ethers alcohols, halogenated solvents and hydrocarbons, saturated or unsaturated, cyclic or not, aromatic or not, comprising between 1 and 20 carbon atoms, preferably between 1 and 15 carbon atoms and preferably between 4 and 15 carbon atoms, ionic liquids.
  • the solvent is selected from pentane, hexane, cyclohexane, methylcyclohexane, heptane, butane or isobutane, cycloocta-1,5-diene, benzene, toluene, ortho -xylene, mesitylene, ethylbenzene, diethyl ether, tetrahydrofuran, 1,4-dioxane, dichloromethane, dichloroethane, chlorobenzene, dichlorobenzene, methanol, ethanol, pure or in mixture and liquids ionic.
  • the solvent is an unsaturated hydrocarbon
  • it may advantageously be chosen from the products of the oligomerization reaction.
  • the solvent is an ionic liquid
  • it is advantageously chosen from N-butyl-pyridinium hexafluorophosphate, N-ethyl-pyridinium tetrafluoroborate, pyridinium fluorosulfonate and butyl-3-methyl-1 tetrafluoroborate.
  • Another object of the invention relates to the implementation of the catalyst composition according to the invention in a process for oligomerization of olefins and in particular dimerization of ethylene to but-1-ene.
  • Oligomerization is defined as the conversion of a monomeric unit into a compound or mixture of unsaturated compounds of general formula C p H 2p in which p is between 4 and 80, preferably between 4 and 50, preferably between 4 and 50. and 26 and more preferably between 4 and 14.
  • the olefins used in the oligomerization process are olefins having between 2 and 10 carbon atoms.
  • said olefins are chosen from ethylene, propylene, n-butenes and n-pentenes, alone or as a mixture, pure or diluted.
  • said olefins are diluted, said olefins are diluted with one or more alkane (s) or any other petroleum fraction, such as they are found in "cuts" from petroleum refining or petrochemical processes, such as catalytic cracking or steam cracking.
  • alkane s
  • any other petroleum fraction such as they are found in "cuts" from petroleum refining or petrochemical processes, such as catalytic cracking or steam cracking.
  • Said olefins can come from non-fossil resources such as biomass.
  • the olefins used in the oligomerization process according to the invention can be produced from alcohols and in particular by dehydration of alcohols.
  • the olefin used in the oligomerization process is ethylene.
  • the nickel concentration used in the oligomerization process is between 10 12 and 1 mol / L, and preferably between 10 9 and 0.4 mol / L.
  • the oligomerization process may advantageously be carried out in the presence of a solvent as described above.
  • the oligomerization process advantageously operates at a total pressure of between 0.1 and 20.0 MPa, preferably between 0.1 and 15.0 MPa, and preferably between 0.5 and 8.0 MPa, and a temperature between -40 and 250 ° C, preferably between -20 ° C and 150 ° C, preferably between 20 ° C and 100 ° C, and preferably between 30 to 80 ° C.
  • the heat generated by the reaction can be removed by any means known to those skilled in the art.
  • the oligomerization process and in particular the dimerization of ethylene to but-1-ene can be carried out continuously.
  • the constituents of the catalytic composition according to the invention are injected into a stirred reactor by conventional mechanical means or by an external recirculation, in which the olefin reacts, preferably with a control of the temperature.
  • the solutions comprising the precatalytic mixture and the aluminum compound are injected into a stirred reactor by mechanical means. conventional or by external recirculation, in which the olefin reacts, preferably with a temperature control.
  • the catalytic composition may be neutralized at the end of the process by any means known to those skilled in the art.
  • the following examples illustrate the invention without limiting its scope.
  • the nickel precursor (II) used is nickel 2-ethylhexanoate, denoted Ni (2-EH) 2 .
  • the phosphorus compound used is chosen from tricyclohexylphosphine, denoted PCy 3 , triphenylphosphine, denoted PPh 3 , and tributylphosphine, denoted Pn-Bu 3.
  • the sulphonic acid used is trifluoromethanesulphonic acid, denoted CF 3 SO 3 H.
  • the carboxylic acid used is trifluoroacetic acid, denoted CF 3 CO 2 H.
  • the aluminum-based compound used is chosen from triethylaluminium, noted AIEt 3 , triisobutylaluminium, noted Al / Bu 3 , and diethylethoxyaluminium, noted AIEt 2 (OEt).
  • the activity of the catalyst system (kg / (g Ni .h)) is expressed by weight of ethylene consumed (in kg) per gram of nickel implemented per hour.
  • a solution of the precatalytic mixture (precursor of Ni (II), phosphorus compound and acid) in a volume dilution solvent (V d ) is introduced into the reactor.
  • the total volume of solvent is 100 mL.
  • the reactor is pressurized with 3.0 MPa of ethylene at 45 ° C. and at a stirring of 1000 rpm. After the defined reaction time, the mixture is cooled to 30 ° C, the reactor is depressurized. The liquid phase obtained is weighed, neutralized and analyzed in GC. The gas phase is accounted for and analyzed in GC.
  • the catalyst composition is carried out with molar ratios P / Ni equal to 2.0, RS0 3 H / P equal to 1.0, and Al / Ni equal to 2.5, according to the general protocol, for 65 minutes.
  • the aluminum-based compound used is Al Et 3
  • the acid is CF 3 SO 3 H
  • the phosphorus compound is PCy 3
  • the catalyst composition is carried out with P / Ni molar ratios equal to 3.0, RS0 3 H / P equal to 1.0 and Al / Ni equal to 2.5, according to the general protocol, for 97 minutes.
  • the activity of the catalyst system amounted to 6.1 kg / (g Ni .h).
  • the aluminum-based compound used is Al Et 3
  • the acid is CF 3 SO 3 H
  • the phosphorus compound is PCy 3
  • the catalyst composition is carried out with molar ratios P / Ni equal to 2.0, RS0 3 H / P equal to 0.5 and Al / Ni equal to 2.5, according to the general protocol, for 90 minutes.
  • the activity of the catalyst system was 4.8 kg / (g Ni .h).
  • the aluminum compound used is AIEt 3
  • the acid is CF 3 CO 2 H
  • the phosphorus compound is PCy 3
  • the solvent is toluene
  • V d 5.0 mL.
  • the catalyst composition is carried out with molar ratios P / Ni equal to 2.0, RC0 2 H / P equal to 1.0 and Al / Ni equal to 2.5, according to the general protocol, for 60 minutes.
  • Example 5 according to the invention
  • the catalyst composition is carried out with molar ratios P / Ni equal to 2.0, RS0 3 H / P equal to 1.0 and Al / Ni equal to 2.5, according to the general protocol, for 120 minutes.
  • the activity of the catalyst system was 14.1 kg / (g Ni .h).
  • the catalyst composition is carried out with molar ratios P / Ni equal to 2.0, RS0 3 H / P equal to 1.0 and Al / Ni equal to 2.5, according to the general protocol, for 90 minutes.
  • the activity of the catalyst system amounted to 21.4 kg / (g Ni .h).
  • the catalyst composition is carried out with molar ratios P / Ni equal to 2.0, RS0 3 H / P equal to 1.0 and Al / Ni equal to 5.0, according to the general protocol, for 90 minutes.
  • the catalyst composition is carried out with molar ratios P / Ni equal to 2.0, RS0 3 H / P equal to 1.0 and Al / Ni equal to 5.0, according to the general protocol, for 50 minutes.
  • the activity of the catalyst system amounted to 47.6 kg / (g Ni .h).
  • the catalyst composition is carried out with molar ratios P / Ni equal to 0, RS0 3 H / Ni equal to 2.5 and Al / Ni equal to 2.5, according to the general protocol, for 60 minutes.
  • the activity of the catalyst system is 28.0 kg / (g Ni .h).
  • the catalyst composition is carried out with molar ratios P / Ni equal to 1.0, RS0 3 H / P equal to 1.0 and Al / Ni equal to 2.5, according to the general protocol, for 60 minutes.
  • the activity of the catalyst system was 18.2 kg / (g Ni .h).
  • the aluminum compound used is AIEt 3
  • the phosphorus compound is PCy 3
  • the catalyst composition is carried out with molar ratios P / Ni equal to 1.0, RS0 3 H / Ni equal to 0 and Al / Ni equal to 2.5, according to the general protocol, for 30 minutes.
  • the selectivities are expressed as weight percentages.
  • the selectivity to butenes (denoted C4), hexenes (denoted C6) and octenes (denoted C8) corresponds to the amount of oligomer C4, C6 and C8, respectively, relative to the other products formed during the reaction.
  • the selectivity to but-1-ene (denoted 1-C4) corresponds to the amount of but-1-ene relative to the C4 oligomers.

Abstract

The invention relates to a new catalytic composition comprising a Ni(II) precursor, a phosphorus compound, a sulfonic acid, and an aluminum-based compound, as well as to the use of said composition in chemical transformation reactions and in particular in a process for the oligomerization of an olefinic feedstock.

Description

NOUVELLE COMPOSITION CATALYTIQUE A BASE DE NICKEL, D’UN COMPOSE PHOSPHOREE ET D’UN ACIDE SULFONIQUE ET SON UTILISATION POUR  NOVEL CATALYTIC COMPOSITION BASED ON NICKEL, PHOSPHORUS COMPOUND AND SULFONIC ACID AND USE THEREOF
L’OLIGOMERISATION DES OLEFINES  OLIGOMERIZATION OF OLEFINS
Domaine technique de l'invention Technical field of the invention
La présente invention concerne une nouvelle composition catalytique à base de nickel et son utilisation dans des réactions de transformation chimique et en particulier dans un procédé d'oligomérisation d'une charge oléfinique. The present invention relates to a new nickel-based catalytic composition and its use in chemical transformation reactions and in particular in a process for oligomerization of an olefinic feedstock.
L’invention concerne également un procédé d'oligomérisation d'une charge d'oléfinique comprenant la mise en contact de ladite charge avec la composition à base de nickel selon l'invention et en particulier un procédé de dimérisation sélective de l’éthylène en but-l-ène mettant en oeuvre ladite composition à base de nickel selon l'invention. The invention also relates to a process for oligomerizing an olefinic feedstock comprising bringing said feedstock into contact with the nickel-based composition according to the invention and in particular a process for the selective dimerization of ethylene by purpose. 1-ene using said nickel-based composition according to the invention.
Art antérieur Prior art
La dimérisation de l'éthylène en butènes par un catalyseur homogène à base de nickel est étudiée depuis 1950. Plusieurs systèmes catalytiques à base de nickel et utilisant notamment des ligands de type phosphine ont été développés. The dimerization of ethylene to butenes by a homogeneous nickel-based catalyst has been studied since 1950. Several nickel-based catalytic systems, in particular using phosphine-type ligands, have been developed.
Des systèmes catalytiques constitués d'un précurseur de nickel à un degré d'oxydation zéro, noté Ni(0), de phosphine et d'acide de Bronsted ont notamment été décrits dans les brevets US 5237118, US 4487847 et DE 10303931. Le coût du Ni(0) et les difficultés liées à sa mise en oeuvre du fait de son instabilité, le rendent peu intéressant pour une exploitation à l'échelle industrielle. Catalytic systems consisting of a nickel precursor with a zero oxidation state, denoted Ni (0), phosphine and Bronsted acid have in particular been described in patents US Pat. No. 5,237,118, US Pat. No. 4,478,747 and DE 10303931. The cost Ni (0) and the difficulties related to its implementation because of its instability, make it unattractive for exploitation on an industrial scale.
D'autres systèmes catalytiques constitués d'un précurseur de nickel à un degré d'oxydation +11, noté Ni(ll), et d'un composé à base d'aluminium sont décrits dans les brevets US 4242531 et FR 1547921. L'emploi de phosphine ou encore d'acide carboxylique a également été envisagé dans les brevets FR 1588162 et US 5245097, respectivement. La mise en oeuvre de ces compositions dans des procédés de dimérisation de l'éthylène conduit à l'obtention de mélange de butènes avec une faible sélectivité en but-l-ène. Other catalytic systems consisting of a nickel precursor with a +11 oxidation state, denoted Ni (II), and an aluminum-based compound are described in US Pat. No. 4,274,231 and US Pat. No. 1,547,921. use of phosphine or carboxylic acid has also been envisaged in FR 1588162 and US 5245097, respectively. The use of these compositions in ethylene dimerization processes leads to the production of a mixture of butenes with a low selectivity to but-1-ene.
Il existe donc un besoin de développer de nouvelles compositions catalytiques plus performantes en termes de rendement et de sélectivité pour la dimérisation de l'éthylène en but-l-ène. De manière surprenante, la demanderesse a mis en évidence que l'emploi d'une composition catalytique comprenant un précurseur de Ni(ll), un composé phosphoré, un acide sulfonique et un composé à base d'aluminium permet une amélioration du rendement en butènes, s'accompagnant d'une forte sélectivité en faveur du but-l-ène. There is therefore a need to develop new catalytic compositions that are more efficient in terms of yield and selectivity for the dimerization of ethylene to but-1-ene. Surprisingly, the Applicant has demonstrated that the use of a catalyst composition comprising a precursor of Ni (II), a phosphorus compound, a sulfonic acid and an aluminum-based compound makes it possible to improve the yield of butenes. , accompanied by a strong selectivity in favor of the goal-l-ene.
Objet de l'invention Object of the invention
La demanderesse a, dans ses recherches, mis au point une nouvelle composition catalytique comprenant : The applicant has, in his research, developed a new catalytic composition comprising:
• au moins un composé à base d'aluminium de formule générale AIR1R2R3 dans lequel les groupements R1, R2 et R3, identiques ou différents, linéaires ou ramifiés, sont choisis indépendamment parmi un hydrogène, les groupements alkyles en C C20, alkoxy en C C20 et aryloxy en C5-C3o, At least one aluminum-based compound of general formula AIR 1 R 2 R 3 in which the groups R 1 , R 2 and R 3 , which are identical or different, linear or branched, are chosen independently from a hydrogen, the alkyl groups DC 20, DC 20 alkoxy, aryloxy and C 5 -C 3 o,
• au moins un précurseur de nickel de degré d'oxydation +11, At least one nickel precursor of oxidation state +11,
• au moins un composé phosphoré de formule générale P(A1R4)(A2R5)(A3R6) dans lequel o A1, A2 et A3, identiques ou différents, sont choisis indépendamment parmi S, NR7 ou une liaison covalente entre l'atome de phosphore et un atome de carbone ou un atome d'hydrogène, o les groupements R4, R5 et R6, identiques ou différents, liés ou non entre eux, sont choisis indépendamment parmi un hydrogène, un groupement alkyle en C C20, hétéroalkyle en Ci-C20, aryle en C5-C3o et hétéroaryle en C4-C30, o le groupement R7 est choisi indépendamment parmi un hydrogène, un groupement alkyle en C C20, hétéroalkyle en C C20, aryle en C5-C30 et hétéroaryle en C4-C30, et At least one phosphorus compound of general formula P (A 1 R 4 ) (A 2 R 5 ) (A 3 R 6 ) in which o A 1 , A 2 and A 3 , which are identical or different, are chosen independently from S, NR 7 or a covalent bond between the phosphorus atom and a carbon atom or a hydrogen atom, o the R 4 , R 5 and R 6 groups , which are identical or different, whether or not they are linked together, are chosen independently from among hydrogen, alkyl group CC 20, heteroalkyl, Ci-C 20 aryl, C 5 -C 3 o and heteroaryl, C 4 -C 30, where the R 7 group is independently selected from hydrogen, alkyl group CC 20, CC 20 heteroalkyl, aryl, C 5 -C 30 heteroaryl, C 4 -C 30, and
• au moins un acide sulfonique de formule générale R8S03H, dans lequel R8 est choisi parmi un groupement alkyle en C C20, hétéroalkyle en Ci-C20, aryle en C5-C30 et hétéroaryle en C4-C30. • at least one sulfonic acid of the general formula R 8 S0 3 H, wherein R 8 is selected from alkyl DC 20, heteroalkyl, Ci-C 20 aryl, C 5 -C 30 heteroaryl and C 4 -C 30 .
Un avantage de la composition catalytique selon la présente invention est de présenter un bon couple rendement/sélectivité pour la dimérisation de l'éthylène en but-l-ène. Définitions et Abréviations An advantage of the catalytic composition according to the present invention is to have a good efficiency / selectivity pair for the dimerization of ethylene to but-1-ene. Definitions and Abbreviations
Il est précisé que, dans toute cette description, les expressions « compris(e) entre ... et ... » « comprenant entre ... et ... » doivent s'entendre comme incluant les bornes citées. It is specified that, throughout this description, the expressions "included between ... and ..." "comprising between ... and ..." must be understood as including the quoted boundaries.
On entend par hétéroatome, un atome différent du carbone et de l’hydrogène. Un hétéroatome peut être choisi parmi l'oxygène, le soufre, l'azote, le phosphore, le silicium et les halogénures tels que le fluor, le chlore, le brome ou l'iode. By heteroatom is meant an atom different from carbon and hydrogen. A heteroatom may be selected from oxygen, sulfur, nitrogen, phosphorus, silicon and halides such as fluorine, chlorine, bromine or iodine.
On entend par groupement alkyle, une chaîne hydrocarbonée comprenant entre 1 et 20 atomes de carbone, noté alkyle en C C2o, saturée ou non, linéaire ou ramifiée, non cyclique, cyclique ou polycyclique, substituée ou non. Par exemple, on entend par alkyle en Ci-C6, un alkyle choisi parmi les groupements méthyle, éthyle, propyle, butyle, pentyle, cyclopentyle, hexyle et cyclohexyle. Alkyl is understood to mean a hydrocarbon chain comprising from 1 to 20 carbon atoms, DC 2 o alkyl noted, saturated or unsaturated, linear or branched, non-cyclic, cyclic or polycyclic, substituted or unsubstituted. For example, C 1 -C 6 alkyl is an alkyl selected from methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, hexyl and cyclohexyl.
On entend par alkoxy, un radical monovalent constitué d'un groupement alkyle lié à un atome d'oxygène tel que les groupements CH30-, C2H50-, C3H70-. By alkoxy is meant a monovalent radical consisting of an alkyl group bonded to an oxygen atom such as the groups CH 3 0-, C 2 H 5 O-, C 3 H 7 O-.
On entend par aryloxy, un radical monovalent constitué d'un groupement aryle lié à un atome d'oxygène tel que le groupement C6H50-. By aryloxy is meant a monovalent radical consisting of an aryl group bonded to an oxygen atom such as the group C 6 H 5 O-.
On entend par groupement hétéroalkyle, un groupement alkyle comprenant entre 1 et 20 atomes de carbone et au moins un hétéroatome choisi parmi l'oxygène (O), le soufre (S), l'azote (N) et le silicium (Si), noté hétéroalkyle en Ci-C20. Heteroalkyl group is understood to mean an alkyl group comprising between 1 and 20 carbon atoms and at least one heteroatom chosen from oxygen (O), sulfur (S), nitrogen (N) and silicon (Si), denoted C 1 -C 20 heteroalkyl.
On entend par groupement aryle, un groupement aromatique, mono ou polycyclique, fusionné ou non, substitué ou non, comprenant entre 5 et 30 atomes de carbone, noté aryle en C5-C3o. By aryl group is meant an aromatic group, mono- or polycyclic, fused or otherwise, substituted or unsubstituted, comprising between 5 and 30 carbon atoms, denoted aryl C 5 -C 3 o.
On entend par groupement hétéroaryle, un groupement aromatique comprenant entre 4 et 30 atomes de carbone et au moins au sein d'au moins un noyau aromatique, un hétéroatome choisi parmi l'oxygène (O), le soufre (S), l'azote (N) et le silicium (Si), noté hétéroaryle en C4-C30. Heteroaryl group, an aromatic group comprising between 4 and 30 carbon atoms and at least within at least one aromatic ring, a heteroatom chosen from oxygen (O), sulfur (S), nitrogen (N) and silicon (Si), denoted C 4 -C 30 heteroaryl.
On entend par Ni(ll) un composé à base de nickel à un degré d'oxydation +11. Ni (II) is understood to mean a nickel-based compound with a +11 oxidation state.
Les rapports molaires cités dans la présente invention notamment par rapport au précurseur de nickel et par rapport au composé phosphoré sont entendus et exprimés respectivement par rapport au nombre de moles de nickel et par rapport au nombre de moles du composé phosphoré apportées dans la composition catalytique. détaillée de l'invention The molar ratios cited in the present invention in particular with respect to the nickel precursor and with respect to the phosphorus compound are understood and expressed respectively with respect to the number of moles of nickel and relative to the number of moles of the phosphorus compound added to the catalytic composition. Detailed description of the invention
Dans le sens de la présente invention, les différents modes de réalisation présentés peuvent être utilisés seul ou en combinaison les uns avec les autres, sans limitation de combinaison. In the sense of the present invention, the various embodiments presented can be used alone or in combination with each other, without limitation of combination.
La présente invention concerne donc une composition catalytique comprenant, et de préférence constitué de : The present invention therefore relates to a catalytic composition comprising, and preferably consisting of:
• au moins un composé à base d'aluminium de formule générale AIR1R2R3 dans lequel les groupements R1, R2 et R3, identiques ou différents, linéaires ou ramifiés, sont choisis indépendamment parmi un hydrogène, les groupements alkyles en Ci-C2o, alkoxy en C C2o et aryloxy en C5-C3o, At least one aluminum-based compound of general formula AIR 1 R 2 R 3 in which the groups R 1 , R 2 and R 3 , which are identical or different, linear or branched, are chosen independently from a hydrogen, the alkyl groups C 1 -C 2 o, alkoxy CC 2 o and aryloxy C 5 -C 3 o,
• au moins un précurseur de nickel de degré d'oxydation +11, At least one nickel precursor of oxidation state +11,
• au moins un composé phosphoré de formule générale P(A1R4)(A2R5)(A3R6) dans lequel o A1, A2 et A3, identiques ou différents, sont choisis indépendamment parmi S, NR7 ou une liaison covalente entre l'atome de phosphore et un atome de carbone ou un atome d'hydrogène, o les groupements R4, R5 et R6, identiques ou différents, liés ou non entre eux, sont choisis indépendamment parmi un hydrogène, un groupement alkyle en C C2o, hétéroalkyle en Ci-C20, aryle en C5-C3o et hétéroaryle en C4-C30, o le groupement R7 est choisi indépendamment parmi un hydrogène, un groupement alkyle en Ci-C20, hétéroalkyle en Ci-C20, aryle en C5-C30 et hétéroaryle en C4-C30, et At least one phosphorus compound of general formula P (A 1 R 4 ) (A 2 R 5 ) (A 3 R 6 ) in which o A 1 , A 2 and A 3 , which are identical or different, are chosen independently from S, NR 7 or a covalent bond between the phosphorus atom and a carbon atom or a hydrogen atom, o the R 4 , R 5 and R 6 groups , which are identical or different, whether or not they are linked together, are chosen independently from among hydrogen, alkyl group 2 CC o heteroalkyl Ci-C 20 aryl, C 5 -C 3 o and heteroaryl, C 4 -C 30, where the R 7 group is independently selected from hydrogen, an alkyl group Ci-C 20 heteroalkyl Ci-C 20 aryl, C 5 -C 30 heteroaryl and C 4 -C 30, and
• au moins un acide sulfonique de formule générale R8S03H, dans lequel R8 est choisi parmi un groupement alkyle en C C20, hétéroalkyle en Ci-C20, aryle en C5-C30 et hétéroaryle en C4-C30. • at least one sulfonic acid of the general formula R 8 S0 3 H, wherein R 8 is selected from alkyl DC 20, heteroalkyl, Ci-C 20 aryl, C 5 -C 30 heteroaryl and C 4 -C 30 .
Le composé à base d'aluminium The aluminum-based compound
Selon l'invention, le composé à base d'aluminium est choisi parmi au moins un composé, pris seul ou en mélange, de formule générale AIR1R2R3 dans lequel les groupements R1, R2 et R3, identiques ou différents, linéaires ou ramifiés, sont choisis indépendamment parmi un hydrogène, les groupements alkyles en C C20, alkoxy en C C20 et aryloxy en C5-C30. Lorsque au moins un des groupements R1, R2 et R3 est choisi parmi les groupements alkyle et alkyloxy, lesdits groupements comprennent de préférence entre 1 et 15 atomes de carbone, de préférence entre 1 et 10 atomes de carbone, de manière préférée entre 1 et 6 atomes de carbone et de manière très préférée entre 1 et 4 atomes de carbone. According to the invention, the aluminum-based compound is chosen from at least one compound, taken alone or as a mixture, of general formula AIR 1 R 2 R 3 in which the groups R 1 , R 2 and R 3 , which are identical or different linear or branched, are independently selected from hydrogen, alkyl groups in CC 20, CC 20 alkoxy, aryloxy and C 5 -C 30. When at least one of the groups R 1 , R 2 and R 3 is chosen from alkyl and alkyloxy groups, said groups preferably comprise between 1 and 15 carbon atoms, preferably between 1 and 10 carbon atoms, preferably between 1 and 6 carbon atoms and very preferably between 1 and 4 carbon atoms.
Lorsque au moins un des groupements R1, R2 et R3 est choisi parmi les aryloxy, lesdits groupements comprennent de préférence entre 5 et 20 atomes de carbone, de préférence entre 5 et 15 atomes de carbone et de manière préférée entre 5 et 10 atomes de carbone. When at least one of the groups R 1 , R 2 and R 3 is chosen from aryloxy, said groups preferably comprise between 5 and 20 carbon atoms, preferably between 5 and 15 carbon atoms, and preferably between 5 and 10 carbon atoms. carbon atoms.
De préférence, un des groupements R1, R2 et R3 est un hydrogène. Preferably, one of the groups R 1 , R 2 and R 3 is a hydrogen.
De préférence, au moins un des groupements R1, R2 et R3 est choisi indépendamment parmi les groupements alkyles et alkyloxy. De manière très préférée lesdits groupements sont choisis parmi méthyle, éthyle, propyle, n-butyle, /sobutyle, sec-butyl, ferf-butyle, pentyle, hexyle, heptyle, octyle, et parmi les groupements alkyloxy correspondants. Preferably, at least one of the groups R 1 , R 2 and R 3 is independently selected from alkyl and alkyloxy groups. In a very preferred manner, said groups are chosen from methyl, ethyl, propyl, n-butyl, sobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl and octyl, and from the corresponding alkyloxy groups.
De préférence, au moins un des groupements R1, R2 et R3 est choisi indépendamment parmi les groupements aryloxy. De manière très préférée, ledit groupement est le phenoxy. Preferably, at least one of the groups R 1 , R 2 and R 3 is independently selected from aryloxy groups. In a very preferred manner, said group is phenoxy.
Avantageusement, le ou les composés à base d'aluminium sont choisis parmi le triméthylaluminium, le triéthylaluminium, le tripropylaluminium, le tri-n-butylaluminium, le triisobutylaluminium, le tri- tert-butylaluminium, le trihexylaluminium, le trioctylaluminium, le diéthyléthoxyaluminium, le diméthyléthoxyaluminium, et de manière préférée le composé à base d'aluminium est le diéthyléthoxyaluminium. Advantageously, the one or more aluminum-based compounds are chosen from trimethylaluminium, triethylaluminium, tripropylaluminium, tri-n-butylaluminium, triisobutylaluminium, tri-tert-butylaluminium, trihexylaluminium, trioctylaluminium, diethylethoxyaluminium, dimethylethoxyaluminium, and preferably the aluminum-based compound is diethylethoxyaluminium.
De préférence, le rapport molaire du composé à base d'aluminium sur le précurseur de nickel, noté Al/Ni, est compris entre 0,5 et 100,0, de préférence entre 3,0 et 90,0, de préférence entre 10,0 et 80,0, de préférence entre 1 et 50,0, de préférence entre 11,0 et 60,0, de préférence entre 15,0 et 50,0, de manière préférée entre 1,5 et 25,0, de manière très préférée entre 1,5 et 20,0, et de manière encore plus préférée entre 2,0 et 15,0.
Figure imgf000006_0001
Preferably, the molar ratio of the aluminum-based compound to the nickel precursor, denoted Al / Ni, is between 0.5 and 100.0, preferably between 3.0 and 90.0, preferably between 10 and 10. , 0 and 80.0, preferably between 1 and 50.0, preferably between 11.0 and 60.0, preferably between 15.0 and 50.0, preferably between 1.5 and 25.0, very preferably between 1.5 and 20.0, and even more preferably between 2.0 and 15.0.
Figure imgf000006_0001
Selon l'invention, le composé phosphoré répond à la formule générale P(A1R4)(A2R5)(A3R6) dans laquelle : - A1, A2 et A3, identiques ou différents, sont choisis indépendamment parmi S, NR7 ou une liaison covalente entre l'atome de phosphore et un atome de carbone ou un atome d'hydrogène, According to the invention, the phosphorus compound corresponds to the general formula P (A 1 R 4 ) (A 2 R 5 ) (A 3 R 6 ) in which: - A 1 , A 2 and A 3 , identical or different, are independently selected from S, NR 7 or a covalent bond between the phosphorus atom and a carbon atom or a hydrogen atom,
- les groupements R4, R5 et R6, identiques ou différents, liés ou non entre eux, sont choisis indépendamment parmi un hydrogène, un groupement alkyle en C C2o, hétéroalkyle en C C2o, aryle en C5-C3o et hétéroaryle en C4-C30, - the groups R 4, R 5 and R 6, identical or different, linked or not to each other, are independently selected from hydrogen, an alkyl group o CC 2, CC 2 o heteroalkyl, aryl, C 5 -C 3 o and C 4 -C 30 heteroaryl,
- le groupement R7 est choisi indépendamment parmi un hydrogène, un groupement alkyle en Ci-C2o, hétéroalkyle en Ci-C2o, aryle en C5-C30 et hétéroaryle en C4-C30. - the R 7 group is independently selected from hydrogen, alkyl Ci-C 2 o, heteroalkyl, Ci-C 2 o aryl, C 5 -C 30 heteroaryl and C 4 -C 30.
De préférence, les groupements A1, A2 et A3, identiques ou différents, sont choisis parmi NR7 et une liaison covalente entre l'atome de phosphore et un atome de carbone ou un atome d'hydrogène, et de manière préférée est une liaison covalente entre l'atome de phosphore et un atome de carbone ou un atome d'hydrogène. Preferably, the groups A 1 , A 2 and A 3 , which may be identical or different, are chosen from NR 7 and a covalent bond between the phosphorus atom and a carbon atom or a hydrogen atom, and preferably a covalent bond between the phosphorus atom and a carbon atom or a hydrogen atom.
De préférence le groupement R7, est choisi parmi les groupements alkyle et hétéroalkyle, comprenant entre 1 et 15 atomes de carbone, de préférence entre 1 et 10 atomes de carbone et de manière préférée entre 1 et 6 atomes de carbone. Preferably, the group R 7 is chosen from alkyl and heteroalkyl groups, comprising between 1 and 15 carbon atoms, preferably between 1 and 10 carbon atoms and preferably between 1 and 6 carbon atoms.
Lorsque au moins un des groupements R4, R5 et R6 est choisi parmi les groupements alkyle et hétéroalkyle, lesdits groupements comprennent de préférence entre 1 et 15 atomes de carbone, de préférence entre 1 et 10 atomes de carbone et de manière préférée entre 1 et 6 atomes de carbone. When at least one of the groups R 4 , R 5 and R 6 is chosen from alkyl and heteroalkyl groups, said groups preferably comprise between 1 and 15 carbon atoms, preferably between 1 and 10 carbon atoms and, preferably, between 1 and 6 carbon atoms.
Lorsque au moins un des groupements R4, R5 et R6 est choisi parmi les aryles et les hétéroaryles lesdits groupements comprennent de préférence entre 4 et 20 atomes de carbone, de préférence entre 4 et 15 atomes de carbone et de manière préférée entre 4 et 10 atomes de carbone. When at least one of the groups R 4 , R 5 and R 6 is chosen from aryl and heteroaryl groups, said groups preferably comprise between 4 and 20 carbon atoms, preferably between 4 and 15 carbon atoms, and preferably between 4 and 15 carbon atoms. and 10 carbon atoms.
De préférence, au moins un des groupements R4, R5 et R6 est choisi indépendamment parmi les groupements méthyle, éthyle, propyle, /sopropyle, n-butyle, /sobutyle, ferf-butyle, pentyle, hexyle, heptyle, octyle, cyclopentyle, cyclohexyle, cyclooctyle, cyclododécyle, adamantyle, norbornyle, phényle, benzyle, o-tolyle, m-tolyle, p-tolyle, mésityle, 3,5-diméthylphényle, 4-n-butylphényle, 4- méthoxyphényle, 2-méthoxyphényle, 3-méthoxyphényle, 4-méthoxyphényle, 2-isopropoxyphényle, 4-méthoxy-3,5-diméthylphényle, 3,5-ditert-butyl-4-méthoxyphényle, 4-chlorophényle, 3,5- di(trifluorométhyl)phényle, benzyle, naphtyle, bisnaphtyle, pyridyle, bisphényle, furanyle, thiophényle. Dans un mode de réalisation préféré, un des groupements R4, R5 et R6 est un hydrogène. Preferably, at least one of the groups R 4 , R 5 and R 6 is independently selected from methyl, ethyl, propyl, propyl, n-butyl, sobutyl, tert-butyl, pentyl, hexyl, heptyl and octyl groups. cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, adamantyl, norbornyl, phenyl, benzyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-n-butylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-isopropoxyphenyl, 4-methoxy-3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 4-chlorophenyl, 3,5-di (trifluoromethyl) phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl, thiophenyl. In a preferred embodiment, one of R 4 , R 5 and R 6 is hydrogen.
Dans un autre mode de réalisation préféré, les groupements R4, R5 et R6 sont identiques. In another preferred embodiment, the groups R 4 , R 5 and R 6 are identical.
De préférence, le rapport molaire entre le composé phosphoré et le précurseur de nickel, noté P/Ni, est compris entre 0,1 et 20,0, de préférence entre 5 et 19,0, de préférence entre 10,0 et 18,0, de préférence entre 11,0 et 17,0, de préférence entre 0,2 et 10,0, de préférence entre 0,5 et 8,0, et de manière encore plus préférée entre 0,8 et 5,0. Preferably, the molar ratio between the phosphorus compound and the nickel precursor, denoted P / Ni, is between 0.1 and 20.0, preferably between 5 and 19.0, preferably between 10.0 and 18, 0, preferably between 11.0 and 17.0, preferably between 0.2 and 10.0, preferably between 0.5 and 8.0, and even more preferably between 0.8 and 5.0.
Acide sulfonique Sulfonic acid
Selon l'invention, l'acide sulfonique est de formule R8S03H dans lequel R8 est choisi parmi un groupement alkyle en Ci-C2o, hétéroalkyle en Ci-C2o, aryle en C5-C3o et hétéroaryle en C4-C30. According to the invention, the sulfonic acid is of formula R 8 S0 3 H wherein R 8 is selected from an alkyl group Ci-C 2 o, heteroalkyl, Ci-C 2 o aryl, C 5 -C 3 o and C 4 -C 30 heteroaryl.
De préférence, lorsque R8 est choisi parmi un groupement alkyle ou hétéroalkyle, R8 comprend entre 1 et 15 atomes de carbone, de préférence entre 1 et 10 atomes de carbone et de manière préférée entre 1 et 6 atomes de carbone. Preferably, when R 8 is chosen from an alkyl or heteroalkyl group, R 8 comprises between 1 and 15 carbon atoms, preferably between 1 and 10 carbon atoms and preferably between 1 and 6 carbon atoms.
De préférence, lorsque R8 est choisi parmi un groupement aryle ou hétéroaryle, R8 comprend entre 4 et 20 atomes de carbone, de préférence entre 4 et 15 atomes de carbone et de manière préférée entre 4 et 10 atomes de carbone. Preferably, when R 8 is chosen from an aryl or heteroaryl group, R 8 comprises between 4 and 20 carbon atoms, preferably between 4 and 15 carbon atoms and preferably between 4 and 10 carbon atoms.
De préférence, R8 comprend au moins un atome de fluor, de préférence entre 1 et 10 atomes de fluor, de préférence entre 1 et 6 atomes de fluor, de manière préférée entre 2 et 6 atomes de fluor et de manière très préférée entre 3 et 6 atomes de fluor. Preferably, R 8 comprises at least one fluorine atom, preferably between 1 and 10 fluorine atoms, preferably between 1 and 6 fluorine atoms, preferably between 2 and 6 fluorine atoms and very preferably between 3 and 6 fluorine atoms. and 6 fluorine atoms.
De préférence, l'acide sulfonique est choisi parmi l'acide p-toluènesulfonique, l'acide benzènesulfonique, l'acide naphtalènesulfonique, l'acide méthanesulfonique, l'acide trifluorométhanesulfonique, l'acide 4-fluorobenzènesulfonique, l'acide pentafluorobenzènesulfonique. Preferably, the sulphonic acid is chosen from p-toluenesulphonic acid, benzenesulphonic acid, naphthalenesulphonic acid, methanesulphonic acid, trifluoromethanesulphonic acid, 4-fluorobenzenesulphonic acid and pentafluorobenzenesulphonic acid.
De préférence, le rapport molaire de l'acide sulfonique par rapport au composé phosphoré, noté RS03H/P, est compris entre 0,1 et 20,0, de préférence entre 0,2 et 10,0, de manière préférée entre 0,3 et 8,0, de manière très préférée entre 0,4 et 5,0, et de manière encore plus préférée entre 0,6 et 2,0. Précurseur de nickel Preferably, the molar ratio of the sulphonic acid relative to the phosphorus compound, denoted RS0 3 H / P, is between 0.1 and 20.0, preferably between 0.2 and 10.0, preferably between 0.3 and 8.0, very preferably between 0.4 and 5.0, and even more preferably between 0.6 and 2.0. Nickel precursor
Selon l'invention, la composition catalytique comprend au moins un précurseur de nickel de degré d'oxydation +11. According to the invention, the catalytic composition comprises at least one nickel precursor with a +11 degree of oxidation.
De préférence, le précurseur de nickel(ll) est choisi parmi le chlorure de nickel(ll), le chlorure de nickel(ll)(diméthoxyéthane), le bromure de nickel(ll), le bromure de nickel(ll)(diméthoxyéthane), le fluorure de nickel(ll), l’iodure de nickel(ll), le sulfate de nickel(ll), le carbonate de nickel(ll), le diméthylglyoxime de nickel(ll), l’hydroxyde de nickel(ll), l’hydroxyacétate de nickel(ll), l’oxalate de nickel(ll), les carboxylates de nickel(ll) tels que par exemple le 2-éthylhexanoate de nickel(ll), les alcoolates de nickel(ll) tel que par exemple le Ni(0CH2CH20CH2CH20CH3)2, les alcoolates de nickel(ll) chlorés tel que par exemple le Ni(OCH3)CI, les alcoolates carboxylates de nickel(ll) tel que par exemple le Ni(OEt)(OOCCH3), les phénates de nickel(ll), les naphténates de nickel(ll), l’acétate de nickel(ll), le trifluoroacétate de nickel(ll), le triflate de nickel(ll), le stéarate de nickel(ll), le formate de nickel(ll), l’acétylacétonate de nickel(ll), l’hexafluoroacétylacétonate de nickel(ll), le chlorure de p- allylnickel(ll), le bromure de n-allylnickel(ll), le dimère du chlorure de méthallylnickel(ll), l’hexafluorophosphate de q3-allylnickel(ll), l’hexafluorophosphate de q3-méthallylnickel(ll), le 1,5- cyclooctadiényle de nickel(ll), le Ni(cyclopentadiényl)2, le (cyclopentadiényl)NiCI, le NiCI2(sulfolane), le NiCI2(POBu3)2, le NiCI2(PBu3)2, le N iCI2(PPh3)2, le NiCI2(PCy3)2, le Ni(SCN)2(PBu3)2, le Ni(SCN)2(PPh3)2, le NiCI2(TMEDA), le NiCI2(pyridine)2, les xanthates de nickel(ll) et les dicarbamates de nickel(ll) sous leur forme hydratée ou non, pris seul ou en mélange. Preferably, the precursor of nickel (II) is chosen from nickel (II) chloride, nickel (II) chloride (dimethoxyethane), nickel bromide (II), nickel (II) bromide (dimethoxyethane) , nickel fluoride (II), nickel iodide (II), nickel (II) sulphate, nickel (II) carbonate, nickel (II) dimethylglyoxime, nickel (II) hydroxide , nickel (II) hydroxyacetate, nickel (II) oxalate, nickel (II) carboxylates such as, for example, nickel (II) 2-ethylhexanoate, nickel (II) alkoxides, such as Ni (CH 2 CH 2 O 2 CH 2 CH 2 OCH 3) 2, chlorinated nickel (II) alkoxides, such as, for example, Ni (OCH 3 ) Cl, nickel (II) alkoxides, such as, for example, Ni (OEt) ( OOCCH 3 ), nickel (II) phenates, nickel (II) naphthenates, nickel (II) acetate, nickel triflouroacetate (II), nickel triflate (II), nickel stearate ( 11), nickel (II) formate, nickel (II) acetylacetonate, nickel (II) hexafluoroacetylacetonate, p-allylnickel (II) chloride, n-allylnickel (II) bromide, methallylnickel (II) chloride dimer, q 3 -allylnickel (II) hexafluorophosphate , 3 -methallyl nickel (11) hexafluorophosphate, nickel (II) 1,5-cyclooctadienyl, Ni (cyclopentadienyl) 2 , (cyclopentadienyl) NiCl, NiCl 2 (sulfolane), NiCl 2 (POBu 3 ) 2 , NiCl 2 (PBu 3 ) 2 , N iCl 2 (PPh 3 ) 2 , NiCl 2 (PCy 3 ) 2 , Ni (SCN) 2 (PBu 3 ) 2 , Ni (SCN) 2 (PPh 3 ) 2 , NiCI 2 (TMEDA), NiCI 2 (pyridine) 2 , nickel xanthates (II) and nickel (II) dicarbamates in their hydrated form or not, taken alone or as a mixture.
Dans un mode préféré, la composition comprend, et de préférence, est constituée de : In a preferred embodiment, the composition comprises, and preferably consists of:
• au moins un composé à base d'aluminium de formule générale AIR1R2R3 dans lequel les groupements R1, R2 et R3, identiques ou différents, linéaires ou ramifiés, sont choisis indépendamment parmi un hydrogène, les groupements alkyles en C C20, alkoxy en C C20 et aryloxy en C5-C30, At least one aluminum-based compound of general formula AIR 1 R 2 R 3 in which the groups R 1 , R 2 and R 3 , which are identical or different, linear or branched, are chosen independently from a hydrogen, the alkyl groups DC 20, DC 20 alkoxy, aryloxy and C 5 -C 30,
• un mélange précatalytique préalablement formé comprenant et, de préférence, constitué de : o au moins un précurseur de nickel de degré d'oxydation +11, o au moins un composé phosphoré de formule générale P(A1R4)(A2R5)(A3R6) dans lequel ■ A1, A2 et A3, identiques ou différents, sont choisis indépendamment parmi S, NR7 ou une liaison covalente entre l'atome de phosphore et un atome de carbone ou un atome d'hydrogène, A pre-catalytic mixture which has previously been formed and preferably consists of: at least one nickel precursor of oxidation state +11 o at least one phosphorus compound of general formula P (A 1 R 4 ) (A 2 R) 5 ) (A 3 R 6 ) in which ■ A 1, A 2 and A 3, identical or different, are independently selected from S, NR 7 or a covalent bond between the phosphorus atom and a carbon atom or a hydrogen atom,
■ les groupements R4, R5 et R6, identiques ou différents, liés ou non entre eux, sont choisis indépendamment parmi un hydrogène, un groupement alkyle en C C20, hétéroalkyle en Ci-C2o, aryle en C5-C3o et hétéroaryle en C4-C30, ■ the R 4 groups, R 5 and R 6, identical or different, linked or not to each other, are independently selected from hydrogen, alkyl DC 20, heteroalkyl, Ci-C 2 o aryl, C 5 -C 3 o and C 4 -C 30 heteroaryl,
■ le groupement R7 est choisi indépendamment parmi un hydrogène, un groupement alkyle en C C20, hétéroalkyle en Ci-C20, aryle en C5-C30 et hétéroaryle en C4-C30 et o au moins un acide sulfonique de formule générale R8S03H, dans lequel R8 est choisi parmi un groupement alkyle en Ci-C20, hétéroalkyle en C C20, aryle en C5-C30 et hétéroaryle en C4-C3Q. ■ the R 7 group is independently selected from hydrogen, alkyl DC 20, heteroalkyl, Ci-C 20 aryl, C 5 -C 30 heteroaryl and C 4 -C 30 and o at least one sulfonic acid of formula General R 8 S0 3 H, wherein R 8 is selected from an alkyl group Ci-C 20 heteroalkyl CC 20 aryl, C 5 -C 30 heteroaryl and C 4 -C 3Q.
Formulation de la composition catalytique Formulation of the catalytic composition
La composition catalytique selon l'invention peut être formulée en préparant un mélange comprenant le précurseur de Ni(ll), le composé phosphoré, l'acide sulfonique et le composé à base d'aluminium. The catalyst composition according to the invention can be formulated by preparing a mixture comprising the Ni (II) precursor, the phosphorus compound, the sulfonic acid and the aluminum compound.
De préférence, la composition catalytique est formulée en préparant un mélange précatalytique comprenant le précurseur de Ni(ll), le composé phosphoré et l'acide sulfonique préalablement à sa mise en contact avec le composé à base d'aluminium. Preferably, the catalyst composition is formulated by preparing a precatalytic mixture comprising the Ni (II) precursor, the phosphorus compound and the sulfonic acid prior to contacting with the aluminum compound.
De façon préférée, chaque constituant de la composition catalytique ou mélange de constituants peut être mis en oeuvre dans un solvant. Preferably, each constituent of the catalytic composition or mixture of constituents can be used in a solvent.
De préférence, le mélange précatalytique est constitué du précurseur de Ni(ll), d'un composé phosphoré, de l'acide sulfonique et d'au moins un solvant. Preferably, the precatalytic mixture consists of the Ni (II) precursor, a phosphorus compound, the sulfonic acid and at least one solvent.
Le ou les solvants sont avantageusement choisis parmi The solvent or solvents are advantageously chosen from
- les éthers, les alcools, les solvants halogénés et les hydrocarbures, saturés ou insaturés, cycliques ou non, aromatiques ou non, comprenant entre 1 et 20 atomes de carbone, de préférence entre 1 et 15 atomes de carbone et de préférence entre 4 et 15 atomes de carbone, les liquides ioniques. - ethers, alcohols, halogenated solvents and hydrocarbons, saturated or unsaturated, cyclic or not, aromatic or not, comprising between 1 and 20 carbon atoms, preferably between 1 and 15 carbon atoms and preferably between 4 and 15 carbon atoms, ionic liquids.
De préférence, le solvant est choisi parmi le pentane, l'hexane, le cyclohexane, le méthylcyclohexane, l'heptane, le butane ou l'isobutane, le cycloocta-l,5-diène, le benzène, le toluène, l'ortho-xylène, le mésitylène, l'éthylbenzène, le diéthyl éther, le tétrahydrofurane, le 1,4-dioxane, le dichlorométhane, le dichloroéthane, le chlorobenzène, le dichlorobenzène, le méthanol, l'éthanol, purs ou en mélange et les liquides ioniques. Preferably, the solvent is selected from pentane, hexane, cyclohexane, methylcyclohexane, heptane, butane or isobutane, cycloocta-1,5-diene, benzene, toluene, ortho -xylene, mesitylene, ethylbenzene, diethyl ether, tetrahydrofuran, 1,4-dioxane, dichloromethane, dichloroethane, chlorobenzene, dichlorobenzene, methanol, ethanol, pure or in mixture and liquids ionic.
Dans le cas où le solvant est un hydrocarbure insaturé, il peut être avantageusement choisi parmi les produits de la réaction d'oligomérisation. In the case where the solvent is an unsaturated hydrocarbon, it may advantageously be chosen from the products of the oligomerization reaction.
Dans le cas où le solvant est un liquide ionique, il est avantageusement choisi parmi l’hexafluorophosphate de N-butyl-pyridinium, le tétrafluoroborate de N-éthyl-pyridinium, le fluorosulfonate de pyridinium, le tétrafluoroborate de butyl-3-méthyl-l-imidazolium, l'amidure de bis-trifluorométhane-sulfonyle de butyl-3-méthyl-l-imidazolium, l'amidure de bis-trifluorométhane- sulfonyle de triéthylsulfonium, l’hexafluoro-antimonate de butyl-3-méthyl-l-imidazolium, l’hexa- fluorophosphate de butyl-3-méthyl-l-imidazolium, le trifluoroacétate de butyl-3-méthyl-l- imidazolium, le trifluorométhylsulfonate de butyl-3-méthyl-l-imidazolium, l’hexafluorophosphate de triméthyl-phénylammonium et le tétrafluoroborate de tétrabutylphosphonium, le chlorure de tétrabutylphosphonium, le chlorure de N-butylpyridinium, le bromure d'éthylpyridinium, le chlorure de butyl-3-méthyl-l-imidazolium, le chlorure de diéthylpyrazolium, le chlorhydrate de pyridinium, le chlorure de triméthylphénylammonium et le chlorure de butylméthylpyrrolidinium. In the case where the solvent is an ionic liquid, it is advantageously chosen from N-butyl-pyridinium hexafluorophosphate, N-ethyl-pyridinium tetrafluoroborate, pyridinium fluorosulfonate and butyl-3-methyl-1 tetrafluoroborate. imidazolium, butyl-3-methyl-1-imidazolium bis-trifluoromethanesulfonyl amide, triethylsulfonium bis-trifluoromethanesulfonyl amide, butyl-3-methyl-1-imidazolium hexafluoro-antimonate , butyl-3-methyl-1-imidazolium hexafluorophosphate, butyl-3-methyl-1-imidazolium trifluoroacetate, butyl-3-methyl-1-imidazolium trifluoromethylsulfonate, trimethylphenylammonium hexafluorophosphate and tetrabutylphosphonium tetrafluoroborate, tetrabutylphosphonium chloride, N-butylpyridinium chloride, ethylpyridinium bromide, butyl-3-methyl-1-imidazolium chloride, diethylpyrazolium chloride, pyridinium hydrochloride, slaved thylphenylammonium and butylmethylpyrrolidinium chloride.
Mise en œuyre de la composition dans un procédé d'oligomérisation des oléfines Embodiment of the composition in an olefin oligomerization process
Un autre objet de l'invention concerne la mise en œuvre de la composition catalytique selon l'invention dans un procédé d'oligomérisation d'oléfines et en particulier de dimérisation de l’éthylène en but-l-ène. Another object of the invention relates to the implementation of the catalyst composition according to the invention in a process for oligomerization of olefins and in particular dimerization of ethylene to but-1-ene.
L’oligomérisation est définie comme la transformation d’une unité monomère en un composé ou mélange de composés insaturés de formule générale CpH2p dans lequel p est compris entre 4 et 80, de préférence entre 4 et 50, de manière préférée entre 4 et 26 et de manière plus préférée entre 4 et 14. Les oléfines mises en œuvre dans le procédé d'oligomérisation sont des oléfines comportant entre 2 et 10 atomes de carbone. De préférence, lesdites oléfines sont choisies parmi l'éthylène, le propylène, les n-butènes et les n-pentènes, seules ou en mélange, pures ou diluées. Oligomerization is defined as the conversion of a monomeric unit into a compound or mixture of unsaturated compounds of general formula C p H 2p in which p is between 4 and 80, preferably between 4 and 50, preferably between 4 and 50. and 26 and more preferably between 4 and 14. The olefins used in the oligomerization process are olefins having between 2 and 10 carbon atoms. Preferably, said olefins are chosen from ethylene, propylene, n-butenes and n-pentenes, alone or as a mixture, pure or diluted.
Dans le cas où lesdites oléfines sont diluées, lesdites oléfines sont diluées par un ou plusieurs alcane(s) ou toute autre coupe pétrolière, tels qu'on les trouve dans des « coupes » issues des procédés de raffinage du pétrole ou de la pétrochimie, comme le craquage catalytique ou le craquage à la vapeur. In the case where said olefins are diluted, said olefins are diluted with one or more alkane (s) or any other petroleum fraction, such as they are found in "cuts" from petroleum refining or petrochemical processes, such as catalytic cracking or steam cracking.
Lesdites oléfines peuvent venir de ressources non fossiles telles que la biomasse. Par exemple, les oléfines utilisées dans le procédé d'oligomérisation selon l'invention peuvent être produites à partir d'alcools et en particulier par déshydratation des alcools. Said olefins can come from non-fossil resources such as biomass. For example, the olefins used in the oligomerization process according to the invention can be produced from alcohols and in particular by dehydration of alcohols.
De manière préférée, l'oléfine utilisée dans le procédé d'oligomérisation est l'éthylène. Preferably, the olefin used in the oligomerization process is ethylene.
La concentration en nickel mise en œuvre dans le procédé d'oligomérisation est comprise entre 1012 et 1 mol/L, et de préférence entre 109 et 0.4 mol/L. The nickel concentration used in the oligomerization process is between 10 12 and 1 mol / L, and preferably between 10 9 and 0.4 mol / L.
Le procédé d'oligomérisation peut avantageusement être mis en œuvre en présence d'un solvant tel que décrit précédemment. The oligomerization process may advantageously be carried out in the presence of a solvent as described above.
Le procédé d'oligomérisation opère avantageusement à une pression totale comprise entre 0,1 et 20,0 MPa, de préférence entre 0,1 et 15,0 MPa, et de manière préférée entre 0,5 et 8,0 MPa, et à une température comprise entre -40 et 250°C, de préférence entre -20°C et 150°C, de préférence entre 20°C et 100°C, et de manière préférée entre 30 à 80°C. The oligomerization process advantageously operates at a total pressure of between 0.1 and 20.0 MPa, preferably between 0.1 and 15.0 MPa, and preferably between 0.5 and 8.0 MPa, and a temperature between -40 and 250 ° C, preferably between -20 ° C and 150 ° C, preferably between 20 ° C and 100 ° C, and preferably between 30 to 80 ° C.
La chaleur engendrée par la réaction peut être éliminée par tous les moyens connus de l'homme du métier. The heat generated by the reaction can be removed by any means known to those skilled in the art.
De façon préférée, le procédé d'oligomérisation et en particulier de dimérisation de l'éthylène en but-l-ène peut être mis en œuvre en continu. Dans un cas, les constituants de la composition catalytique selon l’invention sont injectés dans un réacteur agité par les moyens mécaniques classiques ou par une recirculation extérieure, dans lequel réagit l'oléfine, de préférence avec un contrôle de la température. Dans un autre cas, les solutions comprenant le mélange précatalytique et le composé à base d'aluminium sont injectées dans un réacteur agité par les moyens mécaniques classiques ou par une recirculation extérieure, dans lequel réagit l'oléfine, de préférence avec un contrôle de la température. Preferably, the oligomerization process and in particular the dimerization of ethylene to but-1-ene can be carried out continuously. In one case, the constituents of the catalytic composition according to the invention are injected into a stirred reactor by conventional mechanical means or by an external recirculation, in which the olefin reacts, preferably with a control of the temperature. In another case, the solutions comprising the precatalytic mixture and the aluminum compound are injected into a stirred reactor by mechanical means. conventional or by external recirculation, in which the olefin reacts, preferably with a temperature control.
La composition catalytique peut être neutralisée en fin de procédé par tout moyen connu par l’homme du métier. Les exemples suivants illustrent l’invention sans en limiter la portée. The catalytic composition may be neutralized at the end of the process by any means known to those skilled in the art. The following examples illustrate the invention without limiting its scope.
EXEMPLES : EXAMPLES
Dans les exemples ci-après, les réactifs mis en oeuvre sont commerciaux et utilisés sans purification supplémentaire. In the examples below, the reagents used are commercial and used without additional purification.
Le précurseur de nickel(ll) utilisé est le 2-éthylhexanoate de nickel, noté Ni(2-EH)2. Le composé phosphoré utilisé est choisi parmi la tricyclohexylphosphine, notée PCy3, la triphénylphosphine, notée PPh3, et la tributylphosphine, notée Pn-Bu3. The nickel precursor (II) used is nickel 2-ethylhexanoate, denoted Ni (2-EH) 2 . The phosphorus compound used is chosen from tricyclohexylphosphine, denoted PCy 3 , triphenylphosphine, denoted PPh 3 , and tributylphosphine, denoted Pn-Bu 3.
L'acide sulfonique utilisé est l'acide trifluorométhanesulfonique, noté CF3S03H. The sulphonic acid used is trifluoromethanesulphonic acid, denoted CF 3 SO 3 H.
L'acide carboxylique utilisé est l'acide trifluoroacétique, noté CF3C02H. The carboxylic acid used is trifluoroacetic acid, denoted CF 3 CO 2 H.
Le composé à base d'aluminium utilisé est choisi parmi le triéthylaluminium, noté AIEt3, le triisobutylaluminium, noté Al/Bu3, et le diéthyléthoxyaluminium, noté AIEt2(OEt). The aluminum-based compound used is chosen from triethylaluminium, noted AIEt 3 , triisobutylaluminium, noted Al / Bu 3 , and diethylethoxyaluminium, noted AIEt 2 (OEt).
L'activité du système catalytique (kg/(gNi.h)) est exprimée en masse d'éthylène consommé (en kilogramme) par gramme de nickel mis en oeuvre et par heure. The activity of the catalyst system (kg / (g Ni .h)) is expressed by weight of ethylene consumed (in kg) per gram of nickel implemented per hour.
Protocole général de mise en œuyre du système catalytique General Protocol for Implementation of the Catalytic System
Dans un réacteur préalablement séché sous vide et mis sous atmosphère d'éthylène, est ajouté le composé à base d'aluminium en solution dans un solvant. Après quelques minutes d'agitation sous atmosphère d'éthylène, une solution du mélange précatalytique (précurseur de Ni(ll), composé phosphoré et acide) dans un solvant de dilution de volume (Vd) est introduite dans le réacteur. Le volume total de solvant est de 100 mL. Le réacteur est mis sous une pression de 3,0 MPa d'éthylène à 45°C et à une agitation de 1000 tr/min. Après le temps de réaction défini, le mélange est refroidi à 30 °C, le réacteur est dépressurisé. La phase liquide obtenue est pesée, neutralisée et analysée en GC. La phase gaz est comptabilisée et analysée en GC. In a reactor previously dried under vacuum and placed under an ethylene atmosphere, is added the aluminum-based compound in solution in a solvent. After stirring for a few minutes under an ethylene atmosphere, a solution of the precatalytic mixture (precursor of Ni (II), phosphorus compound and acid) in a volume dilution solvent (V d ) is introduced into the reactor. The total volume of solvent is 100 mL. The reactor is pressurized with 3.0 MPa of ethylene at 45 ° C. and at a stirring of 1000 rpm. After the defined reaction time, the mixture is cooled to 30 ° C, the reactor is depressurized. The liquid phase obtained is weighed, neutralized and analyzed in GC. The gas phase is accounted for and analyzed in GC.
Exemple 1 selon invention : Le composé à base d'aluminium utilisé est le Al Et3, l'acide est le CF3S03H, le composé phosphoré est la PCy3 et le solvant est le toluène, Vd = 5,0 mL. Example 1 according to the invention: The aluminum compound used is Al Et 3 , the acid is CF 3 SO 3 H, the phosphorus compound is PCy 3 and the solvent is toluene, V d = 5.0 mL.
La composition catalytique est mise en oeuvre avec des rapports molaires P/Ni égal à 2,0, RS03H/P égal à 1,0, et Al/Ni égal à 2,5, selon le protocole général, durant 65 minutes. The catalyst composition is carried out with molar ratios P / Ni equal to 2.0, RS0 3 H / P equal to 1.0, and Al / Ni equal to 2.5, according to the general protocol, for 65 minutes.
L'activité du système catalytique s'élève à 9,3 kg/(gNi.h). Exemple 2 selon invention : The activity of the catalyst system was 9.3 kg / (g Ni .h). Example 2 according to the invention
Le composé à base d'aluminium utilisé est le Al Et3, l'acide est le CF3S03H, le composé phosphoré est la PCy3 et le solvant est le toluène, Vd = 5,0 mL. The aluminum-based compound used is Al Et 3 , the acid is CF 3 SO 3 H, the phosphorus compound is PCy 3 and the solvent is toluene, V d = 5.0 mL.
La composition catalytique est mise en oeuvre avec des rapports molaires P/Ni égal à 3,0, RS03H/P égal à 1,0 et Al/Ni égal à 2,5, selon le protocole général, durant 97 minutes. L'activité du système catalytique s'élève à 6,1 kg/(gNi.h). The catalyst composition is carried out with P / Ni molar ratios equal to 3.0, RS0 3 H / P equal to 1.0 and Al / Ni equal to 2.5, according to the general protocol, for 97 minutes. The activity of the catalyst system amounted to 6.1 kg / (g Ni .h).
Exemple 3 selon invention : Example 3 according to the invention
Le composé à base d'aluminium utilisé est le Al Et3, l'acide est le CF3S03H, le composé phosphoré est la PCy3 et le solvant est le toluène, Vd = 5,0 mL. The aluminum-based compound used is Al Et 3 , the acid is CF 3 SO 3 H, the phosphorus compound is PCy 3 and the solvent is toluene, V d = 5.0 mL.
La composition catalytique est mise en oeuvre avec des rapports molaires P/Ni égal à 2,0, RS03H/P égal à 0,5 et Al/Ni égal à 2,5, selon le protocole général, durant 90 minutes. The catalyst composition is carried out with molar ratios P / Ni equal to 2.0, RS0 3 H / P equal to 0.5 and Al / Ni equal to 2.5, according to the general protocol, for 90 minutes.
L'activité du système catalytique s'élève à 4,8 kg/(gNi.h). The activity of the catalyst system was 4.8 kg / (g Ni .h).
Exemple 4 comparatif : Comparative Example 4:
Le composé à base d'aluminium utilisé est le AIEt3, l'acide est CF3C02H, le composé phosphoré est la PCy3 et le solvant est le toluène, Vd = 5,0 mL. La composition catalytique est mise en oeuvre avec des rapports molaires P/Ni égal à 2,0, RC02H/P égal à 1,0 et Al/Ni égal à 2,5, selon le protocole général, durant 60 minutes. The aluminum compound used is AIEt 3 , the acid is CF 3 CO 2 H, the phosphorus compound is PCy 3 and the solvent is toluene, V d = 5.0 mL. The catalyst composition is carried out with molar ratios P / Ni equal to 2.0, RC0 2 H / P equal to 1.0 and Al / Ni equal to 2.5, according to the general protocol, for 60 minutes.
L'activité du système catalytique n'a pas pu être déterminée du fait de la trop faible activité du système catalytique. Exemple 5 selon invention : The activity of the catalytic system could not be determined due to the weak activity of the catalytic system. Example 5 according to the invention
Le composé à base d'aluminium utilisé est le AIEt2(OEt), l'acide est le CF3S03H, le composé phosphoré est la PCy3 et le solvant est le chlorobenzène, Vd = 0,7 mL. The aluminum-based compound used is AIEt 2 (OEt), the acid is CF 3 SO 3 H, the phosphorus compound is PCy 3 and the solvent is chlorobenzene, V d = 0.7 mL.
La composition catalytique est mise en oeuvre avec des rapports molaires P/Ni égal à 2,0, RS03H/P égal à 1,0 et Al/Ni égal à 2,5, selon le protocole général, durant 120 minutes. L'activité du système catalytique s'élève à 14,1 kg/(gNi.h). The catalyst composition is carried out with molar ratios P / Ni equal to 2.0, RS0 3 H / P equal to 1.0 and Al / Ni equal to 2.5, according to the general protocol, for 120 minutes. The activity of the catalyst system was 14.1 kg / (g Ni .h).
Exemple 6 selon invention : Example 6 according to the invention
Le composé à base d'aluminium utilisé est le Al/Bu3, l'acide est le CF3S03H, le composé phosphoré est la PCy3 et le solvant est le chlorobenzène, Vd = 1,0 mL. The aluminum-based compound used is Al / Bu 3 , the acid is CF 3 SO 3 H, the phosphorus compound is PCy 3 and the solvent is chlorobenzene, V d = 1.0 mL.
La composition catalytique est mise en oeuvre avec des rapports molaires P/Ni égal à 2,0, RS03H/P égal à 1,0 et Al/Ni égal à 2,5, selon le protocole général, durant 90 minutes. The catalyst composition is carried out with molar ratios P / Ni equal to 2.0, RS0 3 H / P equal to 1.0 and Al / Ni equal to 2.5, according to the general protocol, for 90 minutes.
L'activité du système catalytique s'élève à 21,4 kg/(gNi.h). The activity of the catalyst system amounted to 21.4 kg / (g Ni .h).
Exemple 7 selon invention : Example 7 according to the invention
Le composé à base d'aluminium utilisé est le AIEt2(OEt), l'acide est le CF3S03H, le composé phosphoré est la PCy3 et le solvant est le chlorobenzène, Vd = 0,7 mL. La composition catalytique est mise en oeuvre avec des rapports molaires P/Ni égal à 2,0, RS03H/P égal à 1,0 et Al/Ni égal à 5,0, selon le protocole général, durant 90 minutes. The aluminum-based compound used is AIEt 2 (OEt), the acid is CF 3 SO 3 H, the phosphorus compound is PCy 3 and the solvent is chlorobenzene, V d = 0.7 mL. The catalyst composition is carried out with molar ratios P / Ni equal to 2.0, RS0 3 H / P equal to 1.0 and Al / Ni equal to 5.0, according to the general protocol, for 90 minutes.
L'activité du système catalytique s'élève à 24,9 kg/(gNi.h). 8 selon invention : The activity of the catalyst system amounted to 24.9 kg / (g Ni .h). 8 according to the invention:
Le composé à base d'aluminium utilisé est le AIEt2(OEt), l'acide est le CF3S03H, le composé phosphoré est la PCy3 et le solvant est le dichlorobenzène, Vd = 0,7 mL. The aluminum compound used is AIEt 2 (OEt), the acid is CF 3 SO 3 H, the phosphorus compound is PCy 3 and the solvent is dichlorobenzene, V d = 0.7 mL.
La composition catalytique est mise en oeuvre avec des rapports molaires P/Ni égal à 2,0, RS03H/P égal à 1,0 et Al/Ni égal à 5,0, selon le protocole général, durant 50 minutes. The catalyst composition is carried out with molar ratios P / Ni equal to 2.0, RS0 3 H / P equal to 1.0 and Al / Ni equal to 5.0, according to the general protocol, for 50 minutes.
L'activité du système catalytique s'élève à 47,6 kg/(gNi.h). The activity of the catalyst system amounted to 47.6 kg / (g Ni .h).
Exemple 9 comparatif : Comparative Example 9:
Le composé à base d'aluminium utilisé est le Al Et3, l'acide est le CF3S03H et le solvant est le toluène, Vd = 1.0 mL. The aluminum compound used is Al Et 3 , the acid is CF 3 SO 3 H and the solvent is toluene, V d = 1.0 mL.
La composition catalytique est mise en oeuvre avec des rapports molaire P/Ni égal à 0, RS03H/Ni égale à 2,5 et Al/Ni égal à 2,5, selon le protocole général, durant 60 minutes. The catalyst composition is carried out with molar ratios P / Ni equal to 0, RS0 3 H / Ni equal to 2.5 and Al / Ni equal to 2.5, according to the general protocol, for 60 minutes.
L'activité du système catalytique est de 28,0 kg/(gNi.h). The activity of the catalyst system is 28.0 kg / (g Ni .h).
Exemple 10 selon invention Example 10 according to invention
Le composé à base d'aluminium utilisé est le Al Et3, l'acide est le CF3S03H et le solvant est le toluène, Vd =1,0 mL. The aluminum compound used is Al Et 3 , the acid is CF 3 SO 3 H and the solvent is toluene, V d = 1.0 mL.
La composition catalytique est mise en oeuvre avec des rapports molaire P/Ni égal à 1,0, RS03H/P égale à 1,0 et Al/Ni égal à 2,5, selon le protocole général, durant 60 minutes. The catalyst composition is carried out with molar ratios P / Ni equal to 1.0, RS0 3 H / P equal to 1.0 and Al / Ni equal to 2.5, according to the general protocol, for 60 minutes.
L'activité du système catalytique est de 18,2 kg/(gNi.h). The activity of the catalyst system was 18.2 kg / (g Ni .h).
Exemple 11 comparatif : Comparative Example 11:
Le composé à base d'aluminium utilisé est le AIEt3, le composé phosphoré est la PCy3 et le solvant est le toluène, Vd = 1,0 mL. The aluminum compound used is AIEt 3 , the phosphorus compound is PCy 3 and the solvent is toluene, V d = 1.0 mL.
La composition catalytique est mise en oeuvre avec des rapports molaire P/Ni égal à 1,0, RS03H/Ni égal à 0 et Al/Ni égal à 2,5, selon le protocole général, durant 30 minutes. The catalyst composition is carried out with molar ratios P / Ni equal to 1.0, RS0 3 H / Ni equal to 0 and Al / Ni equal to 2.5, according to the general protocol, for 30 minutes.
L'activité du système catalytique est nulle et il n'est pas constaté de formation d'oléfines et en particulier de but-l-ène. Tableau récapitulatif des exemples selon l'invention : The activity of the catalytic system is zero and there is no evidence of formation of olefins and in particular of but-1-ene. SUMMARY TABLE OF EXAMPLES ACCORDING TO THE INVENTION
Les sélectivités, décrites dans le tableau ci-dessous, sont exprimées en pourcentage poids. La sélectivité en butènes (notée C4), en hexènes (noté C6) et en octènes (notée C8) correspond à la quantité d'oligomère en C4, C6 et C8, respectivement, par rapport aux autres produits formés lors de la réaction. La sélectivité en but-l-ène (notée 1-C4) correspond à la quantité de but-l-ène par rapport aux oligomères en C4. The selectivities, described in the table below, are expressed as weight percentages. The selectivity to butenes (denoted C4), hexenes (denoted C6) and octenes (denoted C8) corresponds to the amount of oligomer C4, C6 and C8, respectively, relative to the other products formed during the reaction. The selectivity to but-1-ene (denoted 1-C4) corresponds to the amount of but-1-ene relative to the C4 oligomers.
Figure imgf000017_0001
Figure imgf000017_0001
* Exemples comparatifs. Masse C2H4 cons. signifie masse d'éthylène consommé en gramme. Il apparaît clairement au vu des résultats contenus dans le tableau ci-dessus que les compositions catalytique selon la présente invention correspondant aux exemples 1-3, 5-8 et 10 permettent d'obtenir de très bonne activité pour la dimérisation de l'éthylène et de très bonne sélectivité en faveur du but-l-ène comparés aux résultats obtenus avec les compositions des exemples comparatifs (correspondant aux exemples 4, 9, 11). * Comparative examples. Mass C 2 H 4 cons. means mass of ethylene consumed in grams. It is clear from the results in the table above that the catalyst compositions according to the present invention corresponding to Examples 1-3, 5-8 and 10 make it possible to obtain very good activity for the dimerization of ethylene and very good selectivity in favor of but-1-ene compared to the results obtained with the compositions of the comparative examples (corresponding to Examples 4, 9, 11).

Claims

REVENDICATIONS
1. Composition catalytique comprenant: A catalyst composition comprising:
• au moins un composé à base d'aluminium de formule générale AIR1R2R3 dans lequel les groupements R1, R2 et R3, identiques ou différents, linéaires ou ramifiés, sont choisis indépendamment parmi un hydrogène, les groupements alkyles en Ci-C2o, alkoxy en Ci-C2o et aryloxy en C5-C3o, At least one aluminum-based compound of general formula AIR 1 R 2 R 3 in which the groups R 1 , R 2 and R 3 , which are identical or different, linear or branched, are chosen independently from a hydrogen, the alkyl groups Ci-C 2 o alkoxy, Ci-C 2 o aryloxy and C 5 -C 3 o,
• au moins un précurseur de nickel de degré d'oxydation +11, At least one nickel precursor of oxidation state +11,
• au moins un composé phosphoré de formule générale P(A1R4)(A2R5)(A3R6) dans lequel o A1, A2 et A3, identiques ou différents, sont choisis indépendamment parmi S, NR7 ou une liaison covalente entre l'atome de phosphore et un atome de carbone ou un atome d'hydrogène, o les groupements R4, R5 et R6, identiques ou différents, liés ou non entre eux, sont choisis indépendamment parmi un hydrogène, un groupement alkyle en Ci-C2o, hétéroalkyle en Ci-C2o, aryle en C5-C3o et hétéroaryle en C4-C30, o le groupement R7 est choisi indépendamment parmi un hydrogène, un groupement alkyle en Ci-C2o, hétéroalkyle en Ci-C2o, aryle en C5-C30 et hétéroaryle en C4-C30, et At least one phosphorus compound of general formula P (A 1 R 4 ) (A 2 R 5 ) (A 3 R 6 ) in which o A 1 , A 2 and A 3 , which are identical or different, are chosen independently from S, NR 7 or a covalent bond between the phosphorus atom and a carbon atom or a hydrogen atom, o the R 4 , R 5 and R 6 groups , which are identical or different, whether or not they are linked together, are chosen independently from among hydrogen, an alkyl group Ci-C 2 o, heteroalkyl, Ci-C 2 o aryl, C 5 -C 3 o and heteroaryl, C 4 -C 30, where the R 7 group is independently selected from hydrogen, -alkyl, Ci-C 2 o, heteroalkyl, Ci-C 2 o aryl, C 5 -C 30 heteroaryl and C 4 -C 30, and
• au moins un acide sulfonique de formule générale R8S03H, dans lequel R8 est choisi parmi un groupement alkyle en C C20, hétéroalkyle en Ci-C20, aryle en C5-C30 et hétéroaryle en C4-C30. • at least one sulfonic acid of the general formula R 8 S0 3 H, wherein R 8 is selected from alkyl DC 20, heteroalkyl, Ci-C 20 aryl, C 5 -C 30 heteroaryl and C 4 -C 30 .
2. Composition selon la revendication 1 dans laquelle un mélange précatalytique est préalablement formé, ledit mélange précatalytique comprenant le ou les précurseurs de nickel (II), le ou les composés phosphorés et le ou les acides sulfoniques. 2. Composition according to claim 1 wherein a precatalytic mixture is previously formed, said precatalytic mixture comprising the precursor (s) of nickel (II), the phosphorus compound (s) and the sulphonic acid (s).
3. Composition selon l'une quelconque des revendications précédentes dans laquelle les groupements R1, R2, et R3 sont choisis parmi un hydrogène, les groupements alkyles en Ci-Cis, alkoxy en Ci-Cis et aryloxy en C5-C2o. 3. Composition according to any one of the preceding claims wherein the groups R 1 , R 2 and R 3 are chosen from hydrogen, C 1 -C 18 alkyl, C 1 -C 18 alkoxy and C 5 -C aryloxy groups. 2 o.
4. Composition selon l'une quelconque des revendications précédentes dans laquelle le rapport molaire du composé à base d'aluminium sur le précurseur de nickel, noté Al/Ni, est compris entre 0,5 et 100. 4. Composition according to any one of the preceding claims wherein the molar ratio of the aluminum-based compound on the nickel precursor, denoted Al / Ni, is between 0.5 and 100.
5. Composition selon l'une quelconque des revendications précédentes dans laquelle les groupements A1, A2 et A3 sont choisis indépendamment parmi NR7 et une liaison covalente entre l'atome de phosphore et un atome de carbone ou un atome d'hydrogène et le groupement R7 est choisi indépendamment parmi un hydrogène, un groupement alkyle en Ci-C2o, hétéroalkyle en Ci-C2o, aryle en C5-C3o et hétéroaryle en C4-C30. 5. Composition according to any one of the preceding claims wherein the groups A 1 , A 2 and A 3 are independently selected from NR 7 and a covalent bond between the phosphorus atom and a carbon atom or a hydrogen atom. and the group R 7 is independently selected from hydrogen, alkyl Ci-C 2 o, heteroalkyl, Ci-C 2 o aryl, C 5 -C 3 o and heteroaryl, C 4 -C 30.
6. Composition selon l'une quelconque des revendications précédentes dans laquelle les groupements R4, R5, et R6 sont choisis parmi un hydrogène, un groupement alkyle en C1-C15, hétéroalkyle en C1-C15, aryle en C5-C2o et hétéroaryle en C4-C2o· 6. A composition according to any preceding claim in which the groups R 4, R 5, and R 6 is selected from hydrogen, alkyl C 1 -C 15 heteroalkyl, C 1 -C 15 aryl, C 5 -C 2 O and C 4 -C 2 heteroaryl
7. Composition selon l'une quelconque des revendications précédentes dans laquelle R8 est choisi parmi un groupement alkyle en C1-C15, hétéroalkyle en C1-C15, aryle en C5 _C20 et hétéroaryle en C -C20. 7. A composition according to any preceding claim wherein R 8 is selected from alkyl C 1 -C 15 heteroalkyl, C 1 -C 15 aryl, C 5 _ -C 20 heteroaryl and C 20 -C .
8. Composition selon la revendication précédente dans laquelle R8 comprend au moins un atome de fluor. 8. Composition according to the preceding claim wherein R 8 comprises at least one fluorine atom.
9. Composition selon l'une quelconque des revendications précédentes dans laquelle le rapport molaire de l'acide sulfonique sur le composé phosphoré est compris entre 0,1 et 20. 9. Composition according to any one of the preceding claims wherein the molar ratio of the sulfonic acid to the phosphorus compound is between 0.1 and 20.
10. Composition selon l'une quelconque des revendications précédentes dans laquelle le rapport molaire entre le composé phosphoré et le précurseur de nickel, noté P/Ni, est compris entre 0,1 et 20,0. 10. Composition according to any one of the preceding claims wherein the molar ratio between the phosphorus compound and the nickel precursor, denoted P / Ni, is between 0.1 and 20.0.
11. Composition selon l'une quelconque des revendications précédentes dans laquelle le précurseur de nickel(ll) est choisi parmi le chlorure de nickel(ll), le chlorure de nickel(ll)(diméthoxyéthane), le bromure de nickel(ll), le bromure de nickel(ll)(diméthoxyéthane), le fluorure de nickel(ll), l’iodure de nickel(ll), le sulfate de nickel(ll), le carbonate de nickel(ll), le diméthylglyoxime de nickel(ll), l’hydroxyde de nickel(ll), l’hydroxyacétate de nickel(ll), l’oxalate de nickel(ll), les carboxylates de nickel(ll) tels que par exemple le 2-éthylhexanoate de nickel(ll), les alcoolates de nickel(ll) tel que par exemple le Ni(0CH2CH20CH2CH20CH3)2, les alcoolates de nickel(ll) chlorés tel que par exemple le Ni(OCH3)CI, les alcoolates carboxylates de nickel(ll) tel que par exemple le Ni(OEt)(OOCCH3), les phénates de nickel(ll), les naphténates de nickel(ll), l’acétate de nickel(ll), le trifluoroacétate de nickel(ll), le triflate de nickel(ll), le stéarate de nickel(ll), le formate de nickel(ll), l’acétylacétonate de nickel(ll), l’hexafluoroacétylacétonate de nickel(ll), le chlorure de p- allylnickel(ll), le bromure de Tt-allylnickel(ll), le dimère du chlorure de méthallylnickel(ll), l’hexafluorophosphate de q3-allylnickel(ll), l’hexafluorophosphate de q3-méthallylnickel(ll), le 1,5-cyclooctadiényle de nickel(ll), le Ni(cyclopentadiényl)2, le (cyclopentadiényl)NiCI, le NiCI2(sulfolane), le NiCI2(POBu3)2, le NiCI2(PBu3)2, le NiCI2(PPh3)2, le NiCI2(PCy3)2, le11. Composition according to any one of the preceding claims, in which the nickel precursor (II) is chosen from nickel (II) chloride, nickel (II) chloride (dimethoxyethane), nickel bromide (II), nickel (II) bromide (dimethoxyethane), nickel (II) fluoride, nickel (II) iodide, nickel (II) sulfate, nickel (II) carbonate, nickel dimethylglyoxime (II) ), nickel (II) hydroxide, nickel (II) hydroxyacetate, nickel (II) oxalate, nickel (II) carboxylates such as, for example, nickel (II) 2-ethylhexanoate, nickel (II) alkoxides, such as, for example, Ni (OCH 2 CH 2 OCH 2 CH 2 OCH 3) 2, chlorinated nickel (II) alkoxides such as, for example, Ni (OCH 3 ) CI, nickel (II) alcoholates carboxylates; such as, for example, Ni (OEt) (OOCCH 3 ), nickel (II) phenates, nickel (II) naphthenates, nickel (II) acetate, nickel trifluoroacetate (II), triflate of nickel (ll), nick stearate el (II), nickel (II) formate, nickel (II) acetylacetonate, nickel (II) hexafluoroacetylacetonate, p-allyl nickel (II) chloride, tert-allyl nickel bromide (II) , dimer of methallylnickel chloride (II), hex 3 -allylnickel (II) hexafluorophosphate, q 3 -methallyl nickel (11) hexafluorophosphate, nickel (II) 1,5-cyclooctadienyl, Ni ( cyclopentadienyl) 2 , (cyclopentadienyl) NiCl, NiCl 2 (sulfolane), NiCl 2 (POBu 3 ) 2 , NiCl 2 (PBu 3 ) 2 , NiCl 2 (PPh 3 ) 2 , NiCl 2 (PCy 3 ) 2 , the
Ni(SCN)2(PBu3)2, le Ni(SCN)2(PPh3)2, le NiCI2(TMEDA), le NiCI2(pyridine)2, les xanthates de nickel(ll) et les dicarbamates de nickel(ll) sous leur forme hydratée ou non, pris seul ou en mélange. Ni (SCN) 2 (PBu 3 ) 2 , Ni (SCN) 2 (PPh 3 ) 2 , NiCI 2 (TMEDA), NiCI 2 (pyridine) 2 , nickel xanthates (II) and nickel dicarbamates (ll) in their hydrated form or not, taken alone or as a mixture.
12. Composition selon l'une quelconque des revendications précédentes comprenant au moins un solvant. 12. Composition according to any one of the preceding claims comprising at least one solvent.
13. Composition selon la revendication 12 dans laquelle le ou les solvants sont choisis parmi : 13. The composition of claim 12 wherein the one or more solvents are chosen from:
• les éthers, les alcools, les solvants halogénés et les hydrocarbures, saturés ou insaturés, cycliques ou non, aromatiques ou non, comprenant entre 1 et 20 atomes de carbone, de préférence entre 1 et 15 atomes de carbone et de préférence entre 4 et 15 atomes de carbone, • les liquides ioniques choisi parmi l’hexafluorophosphate de N-butyl-pyridinium, le tétrafluoroborate de N-éthyl-pyridinium, le fluorosulfonate de pyridinium, le tétrafluoroborate de butyl-3-méthyl-l-imidazolium, l'amidure de bis-trifluorométhane- sulfonyle de butyl-3-méthyl-l-imidazolium, l'amidure de bis-trifluorométhane-sulfonyle de triéthylsulfonium, l’hexafluoro-antimonate de butyl-3-méthyl-l-imidazolium, l’hexa- fluorophosphate de butyl-3-méthyl-l-imidazolium, le trifluoroacétate de butyl-3-méthyl-l- imidazolium, le trifluorométhylsulfonate de butyl-3-méthyl-l-imidazolium, l’hexafluorophosphate de triméthyl-phénylammonium et le tétrafluoroborate de tétrabutyl- phosphonium, le chlorure de tétrabutylphosphonium, le chlorure de N-butylpyridinium, le bromure d'éthylpyridinium, le chlorure de butyl-3-méthyl-l-imidazolium, le chlorure de diéthylpyrazolium, le chlorhydrate de pyridinium, le chlorure de triméthylphénylammonium et le chlorure de butylméthylpyrrolidinium. Saturated or unsaturated, cyclic or non-cyclic, aromatic or non-aromatic ethers, alcohols, halogenated solvents and hydrocarbons comprising between 1 and 20 carbon atoms, preferably between 1 and 15 carbon atoms and preferably between 4 and 15 carbon atoms, The ionic liquids chosen from N-butyl-pyridinium hexafluorophosphate, N-ethyl-pyridinium tetrafluoroborate, pyridinium fluorosulfonate, butyl-3-methyl-1-imidazolium tetrafluoroborate or bis-trifluoromethane amide; butyl-3-methyl-1-imidazolium sulfonyl, triethylsulfonium bis-trifluoromethanesulfonyl amide, butyl-3-methyl-1-imidazolium hexafluoro-antimonate, butyl-3 hexafluorophosphate 1-methyl-1-imidazolium, butyl-3-methyl-1-imidazolium trifluoroacetate, butyl-3-methyl-1-imidazolium trifluoromethylsulfonate, trimethylphenylammonium hexafluorophosphate and tetrabutylphosphonium tetrafluoroborate, chloride tetrabutylphosphonium chloride, N-butylpyridinium chloride, ethylpyridinium bromide, butyl-3-methyl-1-imidazolium chloride, diethylpyrazolium chloride, pyridinium hydrochloride, trimethylphenylammonium chloride and butylmethylpyrr chloride olidinium.
14. Procédé de dimérisation de l'éthylène mettant en oeuvre la composition catalytique selon l'une des revendications 1 à 13. 14. Process for the dimerization of ethylene using the catalytic composition according to one of claims 1 to 13.
15. Utilisation de la composition catalytique selon l'une des revendications 1 à 13 dans un procédé de dimérisation de l'éthylène selon la revendication 14. 15. Use of the catalytic composition according to one of claims 1 to 13 in an ethylene dimerization process according to claim 14.
PCT/EP2018/082220 2017-11-30 2018-11-22 New catalytic composition based on nickel, a phosphorus compound and a sulfonic acid, and use thereof for the oligomerization of olefins WO2019105843A1 (en)

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