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    • 专利摘要:
    The invention describes a nickel-based composition. The invention also relates to the use of said composition as a catalyst composition in an olefin oligomerization process.
    公开号:FR3020285A1
    申请号:FR1453816
    申请日:2014-04-28
    公开日:2015-10-30
    发明作者:Pierre Boulens；Pierre-Alain Breuil；Joost Reek；Helene Olivier-Bourbigou
    申请人:IFP Energies Nouvelles IFPEN；Universiteit Van Amsterdam ；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a novel nickel-based composition. The invention also relates to the use of said composition as a catalyst for chemical transformation reactions.
    [0002] PRIOR ART It is known to prepare catalytic compositions based on transition metals for their application in various fields of chemistry, especially in the field of catalytic transformations such as hydroformylation, hydrogenation, cross-coupling, oligomerization of olefins ...
    [0003] The preparation of such catalytic compositions requires the choice of metal and suitable ligands. Of these ligands, bidentate ligands are an important class of ligands used in the preparation of transition metal catalyst compositions for various types of catalytic transformations.
    [0004] EP 2 220 099 B1 discloses a coordination complex system comprising multidentate ligands having the formula: Ri-SO2-NH-P (XR2) 2; or R1-SO2-N = PH (XR2) 2, or R1-SO (OH) = NP (XR2) 2, wherein X is independently 0, S, NH, or a bond; wherein R1 and R2 are independently selected from a substituted or unsubstituted alkyl group and an aryl group, wherein at least one equivalent of ligand is complexed to one equivalent of a metal selected from rhodium, iridium, platinum, palladium and lanthanides. EP 2 220 099 B1 indicates that the coordination complex system can be used as a catalyst for hydroformylation, hydrogenation, hydrogenation, polymerization, isomerization, etc. The Applicant in his research has point a new composition based on nickel. It has surprisingly been found that such compositions exhibit interesting catalytic properties. In particular, these compositions have a good catalytic activity in the oligomerization of olefins, more specifically in the dimerization of ethylene to butene-1.
    [0005] An object of the invention is to provide a novel nickel-based composition. Another object of the invention is to provide a novel catalyst system comprising said composition for chemical transformation reactions, in particular for the oligomerization of olefins.
    [0006] Detailed Description of the Invention Composition According to the Invention The catalytic composition according to the invention comprises: at least one oxidation state (0) or (+ II) nickel precursor, at least one ligand corresponding to the formula la), 1b) or 1c) 0 IN A'R1 b (:) SI, PHA, R1 b 0T% N A'R '_ 0 AR1 to 0 AR 1 a OH Ria R2 H R2 R2 SI 1 1 1P / P Embedded image in which - A and A ', which may be identical or different, are independently O, S, NR 3, or a single bond between the phosphorus atom and a carbon atom, - the grouping R3 is either a hydrogen atom, or a cyclic or non-substituted or unsubstituted cyclic alkyl group and optionally containing heteroelements, or an aromatic group, substituted or unsubstituted and optionally containing heteroelements, - the groups R 1, represented on the formula by R1a and R1b, with R1a and Rb being the same or different from each other, linked or not with each other, are chosen from cyclic or non-cyclic alkyl groups, whether or not containing and not containing heteroelements, aromatic groups, substituted or unsubstituted and containing heteroelements or not, 1a) - the group R2 is chosen from cyclic or non-substituted or unsubstituted or substituted alkyl groups and optionally containing heteroelements, substituted or unsubstituted aromatic groups and optionally containing heteroelements, with the proviso that when an oxidation state nickel precursor (+11) is used in the composition, it is used in the presence of an agent reducer or in the presence of a Briinsted base. For the purposes of the present invention, the term "alkyl" is understood to mean a linear or branched hydrocarbon-based chain containing from 1 to 15 carbon atoms, preferably from 1 to 10. Preferred alkyl groups are advantageously chosen from methyl, ethyl and propyl groups. isopropyl, butyl, isobutyl and tert-butyl. These alkyl groups may be substituted with heteroelements or groups containing heteroelements such as a halide, an alkoxy. By an "alkoxy" substituent is meant an alkyl-O- group in which the term alkyl has the meaning given above. Preferred examples of alkoxy substituents are methoxy or ethoxy. By "cyclic alkyl" is meant a monocyclic hydrocarbon group having a carbon number greater than 3, preferably between 4 and 24, more preferably between 6 and 12, preferably a cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl group. or polycyclic (bi- or tricyclic) having a carbon number greater than 3, preferably between 4 and 18, such as for example the adamantyl or norbornyl groups.
    [0007] By "linear unsaturated alkyl" or "cyclic unsaturated alkyl" is meant a linear or cyclic alkyl having at least one unsaturation, the term alkyl and cyclic alkyl having the meaning given above. By "aromatic" is meant an aromatic mono- or polycyclic group, preferably mono- or bicyclic, having a number of carbon atoms between 5 and 20. When the group is polycyclic, i.e. it comprises more than one ring nucleus, the ring rings can advantageously be condensed two by two or attached two by two by links a. The aromatic group according to the invention may contain a heteroelement such as nitrogen, oxygen or sulfur. The term ligand according to the present invention is indifferently used to mean one or more of the limiting forms corresponding to formula la), lb) or 1c) used (s) to form the composition according to the invention. The two groups Ri (Ria and Rib) may be identical or different from each other. These two groups Ria and Rib can also be linked together. In such a case, the two groups Ria and Rib may correspond to groups such as bis-phenyl or bis-naphthyl. The ligands according to the invention may be prepared by a condensation reaction of a sulfonamide, for example para-n-butylphenylsulfonamide and a phosphine halide, such as Ph2PCI, in the presence of a Briinsted base. such as triethylamine for example, in a solvent. In solution, these ligands can (co) exist in the three forms 1a), 1b) or 1c) described above. The composition according to the invention may also comprise an additional Lewis base. For the purposes of the present invention, the term "Lewis base" means any chemical entity of which one constituent has a doublet or more of free or non-binding electrons. The Lewis bases according to the invention correspond in particular to any ligand comprising an oxygen, nitrogen or phosphorus atom having a pair of free or non-binding electrons, or a double bond 7 capable of forming with nickel. n2 type coordination. The additional Lewis base of the composition according to the invention may be a phosphine of P type (A 1 R, 11 (A, 1 R, 1 R, 1 R, 1 C), or a phosphinamine of the type (RA 1) (R, ibA , i) p_NH (R, 2) or (Rp1 / 41) (RA, i) p -NH_s (O) 2 (-2,), rt in which: - Al, A'l and A "1, identical or different from each other, are independently O, S, NR 3, or a single bond between the phosphorus atom and a carbon atom, - the R 3 group is either a hydrogen atom, a cyclic alkyl group or not, substituted or not and containing or not containing heteroelements, or an aromatic group, substituted or unsubstituted and containing heteroelements or not, the groups R'1, R'ia, R'lb and Filc being identical or different from each other, bound or not between them, are chosen from cyclic or non-cyclic alkyl groups, substituted or unsubstituted and optionally containing heteroelements, aromatic groups, substituted or unsubstituted and optionally containing heteroelements, - the R'2 grouping is chosen from cyclic or non-cyclic alkyl groups, substituted or unsubstituted and optionally containing heteroelements, substituted or unsubstituted aromatic groups and optionally containing heteroelements. According to the invention, the groups R 1, R 1 and R 1, which are identical or different, whether or not they are linked to each other, and the groups R 1, R 1a, R-up and -1c, which are identical or different, whether or not they are linked to each other are independently selected from alkyl groups having 1 to 15 carbon atoms, the aromatic groups comprising 5 to 20 carbon atoms; substituted or unsubstituted, containing heteroelements or not. Preferably, the groups R 1, R 1 and R 1, which are identical or different, whether or not they are linked to one another, and the groups R 1, R 1, R 1 and R 1, which are identical or different, whether or not they are linked. between them, are independently selected from methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, cyclohexyl, adamantyl, substituted or unsubstituted, containing or not containing hetero elements ; phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-n-butylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-isopropoxyphenyl groups; , 4-methoxy-3,5-dimethylphenyl, 3,5-ditertbutyl-4-methoxyphenyl, 4-chlorophenyl, 3,5-di (trifluoromethyl) phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl, thiophenyl, substituted or not, containing heteroelements or not. In the case where the groups Ri is Ria and Rb identical or different, are linked together, these groups may correspond to groups such as bis-phenyl, bis-naphthyl. In the case where the identical or different R'1 groups are bonded together, these groups may correspond to groups such as bis-phenyl, bis-naphthyl.
    [0008] According to the invention, the groups R2 and the groups R'2, which are identical or different, are independently chosen from alkyl groups comprising 1 to 15 carbon atoms, the aromatic groups comprising 5 to 20 carbon atoms; substituted or unsubstituted, containing heteroelements or not.
    [0009] Preferably, the groups R 2 and the groups R '2, which are identical or different, are independently chosen from methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl and pentyl groups. substituted or unsubstituted cyclohexyl, adamantyl, containing heteroelements or not; phenyl, 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-ditertbutyl-4-methoxyphenyl, 4-chlorophenyl, 3,5-bis (trifluoromethyl) phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl, thiophenyl, substituted or no, containing heteroelements or not.
    [0010] Preferably, the group R 3 is either a hydrogen atom or an alkyl group. The compositions according to the invention may be in the presence or absence of a solvent. It is possible to use a solvent chosen from organic solvents and in particular from ethers, alcohols, chlorinated solvents and saturated, unsaturated, aromatic or non-aromatic hydrocarbons, cyclic or otherwise. Preferably, the solvent is chosen from hexane, cyclohexane, methylcyclohexane, heptane, butane or isobutane, the monoolefins or diolefins preferably containing 4 to 20 carbon atoms, cycloocta-1,5- diene, benzene, toluene, ortho-xylene, mesitylene, ethylbenzene, dichloromethane, chlorobenzene, methanol, ethanol, pure or in admixture, and ionic liquids. In the case where the solvent is an ionic liquid, it is advantageously chosen from the ionic liquids described in US Pat. No. 6,951,831 B2 and FR No. 2,895,406 B1. When the nickel precursor has a degree of oxidation (0), the latter may be chosen from nickel (0) bis (cycloocta-1,5-diene), nickel (0) bis (cycloocta-1,3- diene), nickel (0) bis (cyclooctatetraene), nickel (0) bis (cycloocta-1,3,7-triene), bis (otolylphosphito) nickel (0) (ethylene), nickel (0) tetrakis (triphenylphosphite), nickel (0) tetrakis (triphenylphosphine), and nickel (0) bis (ethylene), alone or in admixture. Said nickel precursors may optionally be complexed with Lewis bases. When the nickel precursor is of oxidation state (+11), the latter can be chosen from nickel chloride (11), nickel (II) chloride (dimethoxyethane), nickel bromide (11), nickel (II) bromide (dimethoxyethane), nickel fluoride (11), nickel iodide (11), nickel sulphate (11), nickel carbonate (11), nickel dimethylglyoxime (11) , nickel hydroxide (11), nickel hydroxyacetate (11), nickel oxalate (11), nickel carboxylates (11) such as, for example, 2-ethylhexanoate, nickel phenates (11), ), nickel acetate (11), nickel trifluoroacetate (11), nickel triflate (11), nickel acetylacetonate (11), nickel hexafluoroacetylacetonate (11), allyl nickel chloride (11), 11), allyl nickel bromide (11), methallylnickel chloride dimer (11), allyl nickel hexafluorophosphate (11), methallyl nickel hexafluorophosphate (11), nickel biscyclopentadienyl (11), bisallyl nickel (11) and bismethallyl nickel (11); in their hydrated form or not, taken alone or in mixture. Said nickel precursors may optionally be complexed with Lewis bases. When an oxidation state nickel precursor (+11) is used in the composition, it is used in the presence of a reducing agent or in the presence of a Briinsted base. leading to the reduction of nickel known to those skilled in the art. The reducing agent may be selected from NaBH4, LiAlH4, AlEt3, Na, K, KC8 and dihydrogen.
    [0011] Any Briinsted base known to those skilled in the art can be used. The term "Briinsted base" will be understood to mean any corresponding molecular entity or chemical species capable of accepting a proton, such as, for example, triethylamine. According to the invention, the molar ratio between the ligand (s) corresponding to formula la), 1 b) or 1c) and the nickel precursor is advantageously between 0.05 and 10, preferably between 0.5 and According to the invention, the molar ratio between the Lewis base and the nickel precursor is advantageously between 0.05 and 10, preferably between 0.5 and 3.
    [0012] A non-exhaustive list of ligands that may be suitable for the preparation of the compositions according to the invention is shown below. The ligands are represented in their limiting forms la) and 1b). 0% 2) ## STR2 ## ^, S F3C " N = --- PHPh2 H N 0 S /% 0% S 0 0 N = - PHPh2, -0 0% 2) N, --- PHPh2 0% 0 N = PHEt2 0% 0 e HN-PEt2 0% 0 N = PHPh2 0% 20 HN-PPh2 0% 20, S F3C " HN-PPr2 0% 2) HN-PPr2 0 O 20, S F3C" ## EQU1 ## PEt2 0% S-HN-PCY2 0% (## STR2 ## % 0 S N = - PHBu2 0 0 0 0% 0% 0% 0% 0, S, S F30 S, S F30 F30 N = - PHCy2 F30, N = PHBu2 HN-PCY2 HN- PBu2 0% 0 e, Ph HN-P Bu 0% 0 S, Ph HN-F ' Bu 0% 2) S ph F3C NP H / Bu 0% 2) S hp /. .. N = PH Bu 0% 20 S / Ph N = PH Bu 0% 2) S ph N = PH Bu 0% 2; ^ S ph / 1 11 N = -PH Bu, Ph The compositions according to the invention can be used as a catalyst in a chemical transformation reaction, such as the hydrogenation, hydroformylation, cross-coupling or oligomerization of olefins. In particular, these compositions are used in a process for oligomerizing an olefin feed advantageously having 2 to 10 carbon atoms. Preferably, the oligomerization process is a process for dimerizing ethylene to butene-1. The compositions according to the invention may further comprise a compound called an activating agent. Said activating agent is advantageously chosen from the group formed by tris (hydrocarbyl) aluminum compounds, chlorinated or brominated hydrocarbylaluminium compounds, aluminum halides, aluminoxanes, organoboron compounds, organic compounds capable of giving or to capture a proton, taken alone or mixed. Tris (hydrocarbyl) aluminum, chlorinated or brominated hydrocarbylaluminum compounds and aluminum halides preferably correspond to the general formula AlxRyW, in which R represents a monovalent hydrocarbon radical containing, for example, up to 12 carbon atoms, such as alkyl, aryl, aralkyl, alkaryl or cycloalkyl, W represents a halogen atom chosen for example from chlorine and bromine, W being preferably a chlorine atom, x is 1 to 2, y and z are value of 0 to 3. Examples of such compounds include ethyl aluminum sesquichloride (Et3Al2C13), methylaluminum dichloride (MeAIC12), ethylaluminum dichloride (EtAIC12), isobutylaluminum dichloride (iBuAlC12), diethylaluminum chloride (Et2AlCl), trimethylaluminum, tributylaluminum, tri-n-octylaluminum and triethylaluminum (Al Et3).
    [0013] In the case where said activating agent is chosen from aluminoxanes, said activating agent is advantageously chosen from methylaluminoxane (MAO), ethylaluminoxane and modified methylaluminoxanes (MMAO). These activating agents can be used alone or as a mixture.
    [0014] Preferably, said activating agent is chosen from dichloroethylaluminum (EtAIC12) and methylaluminoxane (MAO). In the case where said activating agent is chosen from organoboron compounds, said activating agent is preferably chosen from Lewis acids of tris (aryl) borane type such as tris (perfluorophenyl) borane, tris (3,5-bis (trifluoromethyl) phenyl) borane, tris (2,3,4,6-tetrafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluobiphenyl) borane and their derivatives and (aryl) borates associated with a triphenylcarbenium cation or a trisubstituted ammonium cation such as triphenylcarbenium tetrakis (perfluorophenyl) borate, N, N-dimethylanilinium tetrakis (perfluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate.
    [0015] In the case where said activating agent is chosen from organic compounds capable of giving a proton, said activating agent is preferably chosen from the acids of formula HY in which Y represents an anion. In the case where said activating agent is chosen from organic compounds capable of capturing a proton, said activating agent is preferably chosen from Briinsted bases. The solvent of the oligomerization process may be chosen from organic solvents and preferably from ethers, alcohols, chlorinated solvents and saturated or unsaturated hydrocarbons, aromatic or otherwise, cyclic or otherwise. In particular, said solvent is chosen from hexane, cyclohexane, methylcyclohexane, heptane, butane or isobutane, monoolefins or diolefins preferably comprising 4 to 20 carbon atoms, benzene, toluene, toluene or toluene. ortho-xylene, mesitylene, ethylbenzene, dichloromethane, chlorobenzene, methanol, ethanol, pure or in admixture, and ionic liquids. In the case where said reaction solvent is an ionic liquid, it is advantageously chosen from the ionic liquids described in US Pat. No. 6,951,831 B2 and FR 2,895,406 B1. Oligomerization is defined as the conversion of a monomer unit into a compound or mixture of compounds of the general formula CpH2p with 4 p 80, preferably with 4 p 50, more preferably with 4 p 26 and more preferably with The olefins used in the oligomerization process are olefins having from 2 to 10 carbon atoms. Preferably, said olefins are chosen from ethylene, propylene, n-butenes and n-pentenes, alone or as a mixture, pure or diluted. In the case where said olefins are diluted, said olefins are diluted with one or more alkanes, as found in "slices" from petroleum refining processes, such as catalytic cracking or cracking. steam. Preferably, the olefin used in the oligomerization process is ethylene. 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 the alcohols. The concentration of nickel in the catalyst solution is advantageously between 1 × 10-8 and 1 mol / L, and preferably between 1 × 10 -6 and 1 × 10 -2 mol / L.
    [0016] The oligomerization process advantageously operates at a total pressure of between atmospheric pressure and 20 MPa, preferably between 0.1 and 8 MPa, and at a temperature between -40 and + 250 ° C., preferably between -20 ° C. C and 150 ° C.
    [0017] The heat generated by the reaction can be removed by any means known to those skilled in the art. The oligomerization process can be carried out in a closed system, in a semi-open system or continuously, with one or more reaction stages. Sturdy stirring is advantageously carried out to ensure good contact between the reagent (s) and the catalyst system. The oligomerization process may be carried out batchwise. In this case, a selected volume of the solution comprising the composition according to the invention is introduced into a reactor provided with the usual stirring, heating and cooling devices. The oligomerization process can also be carried out continuously. In this case, the solution comprising the composition according to the invention is injected at the same time as the olefin into a reactor stirred by conventional mechanical means or by external recirculation, and maintained at the desired temperature. The catalyst composition is destroyed by any usual means known to those skilled in the art, then the reaction products and the solvent are separated, for example by distillation. The olefin that has not been transformed can be recycled to the reactor. The process according to the invention can be carried out in a reactor with one or more reaction stages in series, the olefinic feedstock and / or the pre-conditioned catalytic composition being introduced continuously, or in the first stage, either in the first and any other floor. At the outlet of the reactor, the catalytic composition can be deactivated, for example by injection of ammonia and / or an aqueous solution of sodium hydroxide and / or an aqueous solution of sulfuric acid. Unconverted olefins and alkanes optionally present in the feed are then separated from the oligomers by distillation.
    [0018] The products of the present process can find application as, for example, automotive fuel components, fillers in a hydroformylation process for the synthesis of aldehydes and alcohols, as components for the chemical, pharmaceutical or perfume industry and or as fillers in a metathesis process for the synthesis of propylene for example.
    [0019] The following examples illustrate the invention without limiting its scope.
    [0020] Example 1 Synthesis of Li Ligand The synthesis of Li ligand was carried out according to the method described in the literature: F. G. Terrade, Eur. J. Inorg. Chem. 2014, 1826-1835. Preparation of the compositions according to the invention Preparation of the composition C1 Li ligand (4-nBu-C6H4-802-NH-PPh2, 22 mg, 40 μmol, 1 eq), trimethylphosphine (1M solution in toluene, 88 μL 40 mol, 1 eq) and Ni (COD) 2 (31.8 mg, 40 μmol, 1 eq) are suspended in 10 ml of toluene and stirred for 30 minutes. Then, 5 ml of this solution (ie 20 μmol of Ni) are taken and injected into the reactor.
    [0021] Preparation of composition C2 The Li ligand (4-nBu-C6H4-802-NH-PPh2, 31.8 mg, 80 μmol, 2 eq.) And Ni (COD) 2 (11 mg, 40 μmol, 1 eq. ) are dissolved in toluene (10 mL) and the mixture is stirred for 30 min. Two experiments are conducted in parallel with two solutions of different concentrations of said composition C2, a 20 mol solution of Ni and another 100 mol of Ni are evaluated in a reactor. Example 2: Oligomerization of ethylene The oligomerization reaction of ethylene was evaluated with compositions C1 and C2. The results obtained are reported in Table 1. The 250 ml reactor is dried under vacuum at 130 ° C. for 2 hours and then pressurized with 0.5 MPa of ethylene. The temperature is lowered to 20 ° C, then the ethylene overpressure is removed to reach 0.1 MPa. The solvent is added (45 mL of toluene), and the internal temperature set point is set (40 ° C or 80 ° C). Once the internal temperature has stabilized, a part of the catalytic composition C1 or the catalytic composition C2 is introduced (20 μmol of Ni or 100 μmol of Ni). Then the reactor is pressurized with ethylene at 3 MPa. Stirring (1000 rpm) is started (t = 0). After the defined reaction time, the mixture is cooled to 30 ° C with stirring, the reactor is depressurized and the liquid and gas phases are analyzed by gas chromatography (GC). The productivity (goligAgNi.h) is expressed as the mass of oligomers produced (in grams) per nickel mass used per hour.
    [0022] Table 1. Oligomerization of ethylene with compositions C1 and C2. Compo Temp Quantity Quantity Tenos Productivity Distribution of 104 [h1 sition -rature of dbligomers', products (weight) 14 (° C) catalyst (g) reaction g'lig ° / (gNi.hl (k.tmol) (min) C4 C6 C8 + Cl 80 20 3.9 120 1657 91.2 7.9 0.9 95.2 C2 40 20 7.1 90 4035 93.0 6.5 0.5 99.6 C2 40 100 22.5 90 2551 93.7 5.9 0.4 99.2 a Percentage weight determined by GO (percentage of cuts 04, 06 and Ce compared to all oligomers) b Percent weight of butene-1 in section 04. The above examples demonstrate that the compositions according to the invention exhibit good activity for the oligomerization of ethylene.
    权利要求:
    Claims (15)
    [0001]
    REVENDICATIONS1. Composition comprising: at least one oxidation state (0) or (+11) nickel precursor, at least one ligand corresponding to the formula la), 1b) or 1c) 0 ARla 0 ARla OH ARla Il 1 1 In which - A and A ', which may be identical or different, have the same or different properties, are independently O, S, NR 3, or a single bond between the phosphorus atom and a carbon atom, - the R 3 group is either a hydrogen atom or a cyclic or non-cyclic alkyl group, substituted or unsubstituted and containing or no heteroelements, or an aromatic group, substituted or unsubstituted and containing or not heteroelements, - the groups R1, represented on the formula by Ria and R1b, with Rla and Rb being identical or different from each other, linked or not with each other, are chosen from cyclic or non-cyclic alkyl groups, substituted or unsubstituted and optionally containing heteroelements, aromatic groups, substituted or unsubstituted, and whether or not containing heteroelements, the group R2 is chosen from cyclic or non-substituted or unsubstituted or substituted alkyl groups and optionally containing heteroelements, substituted or unsubstituted aromatic groups and optionally containing heteroelements, with the proviso that when An oxidation state (+11) nickel precursor is used in the composition, which is used in the presence of a reducing agent or in the presence of a Briinsted base.
    [0002]
    2. The composition of claim 1 comprising an additional Lewis base.
    [0003]
    3. A composition according to claim 2 wherein the additional Lewis base is a P-type phosphine (A 1 R 11 (A 1 R, ibxicl / 4'I R), or a phosphinamine of the type (R 1 -IAA-1). (R, -ibA, i) p_NH (R, 2) or (R, -iaA-1) (R, -ibA, i) p_NH_s (O) 2 (-2, it) in which: - Al, A 1 and A "1, which are identical or different from each other, are independently O, S, NR 3, or a single bond between the phosphorus atom and a carbon atom; the R 3 group is either a hydrogen atom or a cyclic or non-substituted or unsubstituted alkyl group and optionally containing heteroelements, or a substituted or unsubstituted aromatic group containing or not containing heteroelements, the R'1 groups, namely R'la, R'lb and R '; lc being identical or different from each other, whether or not they are linked to each other, are chosen from cyclic or non-substituted or unsubstituted or cyclic alkyl groups and containing heteroelements, aromatic groups, substituted or unsubstituted, and optionally containing hetero elements. - The R'2 group is chosen from cyclic or non-cyclic alkyl groups, substituted or unsubstituted and optionally containing heteroelements, substituted or unsubstituted aromatic groups and optionally containing heteroelements.
    [0004]
    4. Composition according to one of claims 1 to 3 wherein the groups R1, Ria and Rb being identical or different, or not connected to each other, and the groups R'1, R'la, R'lb and R 1c being identical or different, bonded or not with each other, are independently chosen from alkyl groups comprising 1 to 15 carbon atoms, the aromatic groups comprising 5 to 20 carbon atoms; substituted or unsubstituted, containing heteroelements or not.
    [0005]
    5. Composition according to one of claims 1 to 4 wherein, the groups R1, Ria and Rb being identical or different, bonded or not with each other, and the groups R'1, R'la, R'lb and R'lc being identical or different, whether linked together or not, are independently selected from methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, cyclohexyl, substituted or unsubstituted adamantyl, whether or not containing heteroelements; phenyl, 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 groups; 3,5,5-dimethylphenyl, 3,5-ditertbutyl-4-methoxyphenyl, 4-chlorophenyl, 3,5-di (trifluoromethyl) phenyl, benzyl, naphthyl, bis-naphthyl, pyridyl, bisphenyl, furanyl, thiophenyl, substituted or unsubstituted, containing heteroelements or not.
    [0006]
    6. Composition according to one of claims 1 to 5 wherein the R2 groups and the R'2 groups, identical or different, are independently selected from alkyl groups comprising 1 to 15 carbon atoms, the aromatic groups comprising 5 to 20 carbon atoms; substituted or unsubstituted, containing heteroelements or not.
    [0007]
    7. Composition according to one of claims 1 to 6 wherein the R2 groups and R'2 groups, identical or different, are independently selected from methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl, t-butyl, pentyl, cyclohexyl, adamantyl, substituted or unsubstituted, containing heteroelements or not; the phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-n-butylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl and 2-isopropoxyphenyl groups, 4-methoxy-3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 4-chlorophenyl, 3,5-bis (trifluoromethyl) phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl, thiophenyl, substituted or unsubstituted, containing heteroelements or not.
    [0008]
    8. Composition according to one of claims 1 to 7 wherein when the nickel precursor is oxidation degree (0), the latter can be selected from nickel (0) bis (cycloocta-1,5-diene) , nickel (0) bis (cycloocta-1,3-diene), nickel (0) bis (cyclooctatetraene), nickel (0) bis (cycloocta-1,3,7-triene), bis (o- tolylphosphito) nickel (0) (ethylene), nickel (0) tetrakis (triphenylphosphite), nickel (0) tetrakis (triphenylphosphine), and nickel (0) bis (ethylene), alone or in admixture.
    [0009]
    9. Composition according to one of claims 1 to 7 wherein the oxidation state nickel precursor (+11) is selected from nickel chloride (11), nickel chloride (II) (dimethoxyethane), nickel bromide (11), nickel (II) bromide (dimethoxyethane), nickel fluoride (11), nickel iodide (11), nickel sulphate (11), nickel carbonate (11) , nickel dimethylglyoxime (11), nickel hydroxide (11), nickel hydroxyacetate (11), nickel oxalate (11), nickel carboxylates (11) such as for example 2- ethylhexanoate, nickel phenates (11), nickel acetate (11), nickel trifluoroacetate (11), nickel triflate (11), nickel acetylacetonate (11), nickel hexafluoroacetylacetonate ( 11), allyl nickel chloride (11), allyl nickel bromide (11), methallyl nickel chloride dimer (11), allyl nickel hexafluorophosphate (11), methallyl nickel hexafluorophosphate (11), biscyclopentadienyl nickel (11), nickel bisallyl (11) and bismethallyl nickel (11); in their hydrated form or not, taken alone or in mixture.
    [0010]
    10. Composition according to one of the preceding claims further comprising an activating agent selected from the group consisting of tris (hydrocarbyl) aluminum compounds, chlorinated or brominated hydrocarbylaluminium compounds, aluminoxanes, organoboron compounds, compounds organic compounds capable of giving or capturing a proton, taken alone or as a mixture.
    [0011]
    11. Composition according to one of the preceding claims wherein the molar ratio between the ligand and the nickel precursor is between 0.05 and 10.
    [0012]
    12. Use of a composition according to one of claims 1 to 11 as a catalyst.
    [0013]
    13. A process for oligomerizing an olefin feedstock comprising bringing said feedstock into contact with a composition according to one of claims 1 to 11.
    [0014]
    The process of claim 13 wherein the feedstock comprises olefins having a carbon number of from 2 to 10.
    [0015]
    15. The process of claim 13 or 14 wherein the reaction is an oligomerization reaction of ethylene.
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    同族专利:
    公开号 | 公开日
    US9283554B2|2016-03-15|
    US20150306588A1|2015-10-29|
    JP2015214540A|2015-12-03|
    EP2939742A1|2015-11-04|
    FR3020285B1|2017-12-08|
    JP6574599B2|2019-09-11|
    CA2889602A1|2015-10-28|
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    FR3042989A1|2015-10-30|2017-05-05|Ifp Energies Now|NOVEL NICKEL CATALYTIC COMPOSITION IN THE PRESENCE OF A SPECIFIC ACTIVATOR AND USE THEREOF IN A METHOD OF OLIGOMERIZING OLEFINS|
    FR3045414B1|2015-12-18|2019-12-27|IFP Energies Nouvelles|NOVEL CATALYTIC COMPOSITION BASED ON NICKEL AND LIGAND PHOSPHINE TYPE AND A LEWIS BASE AND ITS USE IN A PROCESS OF OLEFIN OLIGOMERIZATION|
    KR102028614B1|2017-10-16|2019-10-04|고려대학교 산학협력단|Synthesis of Ni-loaded Porous Organic Polymers and its Application to Heterogeneous Catalyst for Ethylene Dimerization|
    CN108607613B|2018-04-16|2020-11-24|天津科技大学|Catalyst system for ethylene selective oligomerization, preparation method and ethylene oligomerization reaction method|
    SG11202108215PA|2019-04-01|2021-10-28|Exxonmobil Res & Eng Co|Processes for polymerizing alpha-olefins, internal olefins and compositions thereof|
    FR3109741A1|2020-04-29|2021-11-05|IFP Energies Nouvelles|NEW CATALYTIC COMPOSITION BASED ON NICKEL, A CATIONIC COMPLEX OF YTTRIUM AND ITS USE FOR THE OLIGOMERIZATION OF OLEFINS|
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    2021-01-15| ST| Notification of lapse|Effective date: 20201214 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1453816A|FR3020285B1|2014-04-28|2014-04-28|NOVEL NICKEL CATALYTIC COMPOSITION AND USE THEREOF IN OLEFIN OLIGOMERIZATION PROCESS|FR1453816A| FR3020285B1|2014-04-28|2014-04-28|NOVEL NICKEL CATALYTIC COMPOSITION AND USE THEREOF IN OLEFIN OLIGOMERIZATION PROCESS|
    EP15305334.3A| EP2939742A1|2014-04-28|2015-03-04|Novel nickel-based catalytic composition and use thereof in a method for oligomerising olefins|
    US14/694,052| US9283554B2|2014-04-28|2015-04-23|Nickel-based catalytic composition, and its use in a process for the oligomerization of olefins|
    CA2889602A| CA2889602A1|2014-04-28|2015-04-23|New nickel-based cyclic compound and its use in an olefin oligomerization process|
    JP2015090217A| JP6574599B2|2014-04-28|2015-04-27|Novel nickel-based composition and use of the composition for olefin oligomerization|
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