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    • 专利摘要:
    The invention describes a new type of nickel complex and its method of preparation. The invention also relates to the use of said complex in an olefin transformation process.
    公开号:FR3020287A1
    申请号:FR1453818
    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 new family of nickel-based complexes, and their method of preparation. The invention also relates to the use of said complexes as catalysts for reactions of chemical transformations.
    [0002] PRIOR ART: It is known to prepare transition metal-based complexes for their application in various fields of chemistry, particularly in the field of catalytic transformations such as hydroformylation, hydrogenation, cross-coupling, oligomerization. Olefins ...
    [0003] The preparation of such complexes requires the choice of metal and suitable ligands. Among these ligands, bidentate ligands are an important class of ligands used in the preparation of transition metal catalysts for various types of catalytic chemical 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 family of nickel-based complexes and their method of preparation. It has been surprisingly found that such complexes exhibit interesting catalytic properties. In particular, these catalysts exhibit good activity in the oligomerization of olefins.
    [0005] An object of the invention is to provide a new family of nickel-based complexes. Another object of the invention is to propose a new catalytic system comprising said complexes for chemical transformation reactions, in particular for the oligomerization of olefins.
    [0006] DETAILED DESCRIPTION OF THE INVENTION Complexes of Nickel The complexes according to the invention are complexes based on nickel corresponding to formula (I) or (II) ARia AIRib N -------- 0 Ni 1 ## STR1 ## wherein: the P, N, S, O atoms are ligand fragment, - A and A ', identical or different, are independently 0, S, NR3, or a single bond between the phosphorus atom and a carbon atom, - the R3 group is either a hydrogen atom, either a cyclic or non-substituted or unsubstituted alkyl group and optionally containing heteroelements, or an aromatic group, substituted or unsubstituted and optionally containing heteroelements; - the groups R 1 represented on the formulas by R 1a and R 1b, with R 1a and Rb being identical or different from each other, whether or not linked to one another, are chosen from cyclic or non-cyclic alkyl groups, substituted or unsubstituted and optionally containing heteroel compounds. aromatic groups, substituted or unsubstituted and optionally containing heteroelements; - the group R2 is chosen from cyclic or non-cyclic alkyl groups, substituted or unsubstituted and optionally containing heteroelements, substituted or unsubstituted aromatic groups and containing or non-heteroelements, - L2 represents a Lewis base, - X1 is a hydrogen atom or a halogen or a carbon atom bonded to or part of at least one cyclic or non-cyclic alkyl group, unsaturated or unsaturated, substituted or no and containing or not containing heteroelements, a substituted or unsubstituted aromatic group and optionally containing heteroelements, - L2 and X1 are such that the degree of oxidation of nickel is respected. 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 and preferably from 1 to 10. Preferred alkyl groups are advantageously chosen from among methyl, ethyl and propyl, 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, 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.
    [0008] 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, that is to say that it comprises more than one ring nucleus, the ring nuclei 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 signify one or more of the limiting forms of the ligand corresponding to the formula la), 1 b) and / or 1 c): 0 IN A'R1 b (:) SI, PHA, R1 b 0T% N A'R '_ 0 AR1 to 0 AR 1 to OH Ria R2 H R2 R2 SI 1 1 1P / P 1 1 II A1' 1a) 1 b) 1c) in which - A and A ', identical or different, are independently O, S, NR3, or a single bond between the phosphorus atom and a carbon atom, - the R3 group is either a hydrogen atom or a cyclic or non-cyclic alkyl group, substituted or unsubstituted and containing or not containing heteroelements, or an aromatic group, substituted or unsubstituted and containing heteroelements or not, the groups R1, represented on the formula by Ria and R1b, with Ria and Rb being identical or different from each other, linked or not between them, are chosen from cyclic or non-cyclic alkyl groups, substituted or unsubstituted and optionally containing heteroelements, aromatic groups or Whether substituted or unsubstituted, 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. The two groups Ri (Ria and Rib) may be identical or different from each other. These two groups Ria and Rb can also be linked together. In such a case, the two groups R 1a and Rb 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 sulphonamide, for example para-n-butylphenylsulfonamide and a phosphine halide, such as Ph.sub.2 PCI, 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. L2 represents a 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 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 doublet of free or non-binding electrons, or a double bond 7 capable of forming with nickel a coordination type n2. The L 2 group of the complex of formula (I) or (II) according to the invention may represent a phosphine of P type (AiR'il (A, 1R, ibxic1 / 4'iR, ic) or a phosphinamine of type (RAi ) (R, ibA, i) p_NH (R, 2) or (Rp1 / 41) (RA, i) p-NH_s (O) 2 (-2,), in which: - Al, Ni and A "1 , identical or different from each other, are independently 0, 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 unsubstituted and optionally containing heteroelements, or an aromatic group, substituted or unsubstituted and optionally containing heteroelements, - the groups R'1, ie R'la '1 = ilb and R'ic being identical or different between they, linked 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 group R'2 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. X1 is a hydrogen atom or a halogen atom or a carbon atom bonded to or part of at least one cyclic or non-cyclic alkyl group, unsaturated or unsaturated, substituted or unsubstituted and optionally containing heteroelements, a substituted aromatic group or no and whether or not containing heteroelements. Advantageously, X 1 is a hydrogen atom, a cyclic or non-cyclic alkyl group, unsaturated or unsaturated, substituted or unsubstituted and optionally containing heteroelements or halogen. When the group X 1 is a halogen, the latter may be a bromine, chlorine, iodine or fluorine atom.
    [0009] According to the invention, the groups Ri, ie Ria and Rb, being identical or different, linked or not to each other, and the groups R'1, ie R'la 'R'lb and Filc, being identical or different, whether or not linked between they are independently selected from alkyl groups comprising 1 to 15 carbon atoms, aromatic groups comprising 5 to 20 carbon atoms; substituted or unsubstituted, containing heteroelements or not. Preferably, the groups Ri, ie Ria and Rb, being identical or different, linked or not to each other, and the groups R'1, ie R'la 'R'lb and R'ic, being identical or different, linked or otherwise 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 ; 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-di (trifluoromethyl) phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl, thiophenyl, substituted or unsubstituted, containing heteroelements or not. In the case where the groups Ria and Rib identical or different are bonded together, these groups may correspond to groups such as bis-phenyl, bis-naphthyl. In the case where the R'l groups, which are identical or different, are linked together, these groups may correspond to groups such as bis-phenyl or bis-naphthyl. 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. 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 unsubstituted, containing heteroelements or not.
    [0010] Preferably, the group R 3 is either a hydrogen atom or an alkyl group.
    [0011] The complexes according to the invention may be prepared by contacting at least one ligand comprising the ligand fragment consisting of the P, N, S and O atoms corresponding to formula (1a), (1b) or (1c ) as defined according to the invention, with at least one oxidation state nickel precursor (0), a precursor of the Xl group, and optionally a Lewis base. The presence of a Lewis base is, for example, optional. when a second equivalent of the ligand is implemented. In this case, the ligand according to the invention plays the role of a Lewis base. In a particular embodiment, the group X1 may come from the ligand itself.
    [0012] The complexes according to the invention may also be prepared by contacting at least one ligand comprising the ligand fragment consisting of the P, N, S and O atoms corresponding to formula (1a), (1b) or (1c) as defined according to the invention, with at least one oxidation state nickel precursor (+ II) in the presence of a reducing agent or a Brönsted base; and optionally a Lewis base. The presence of a Lewis base is, for example, optional when a second equivalent of the ligand is used. In this case, the ligand according to the invention plays the role of a Lewis base. In a particular embodiment, the X1 group can come from the oxidation state nickel precursor (+ II).
    [0013] In the case where a nickel precursor of oxidation state (+ II) is used in the presence of a reducing agent, any agent leading to the reduction of nickel known to those skilled in the art can be used. The reducing agent may be selected from NaBH4, LiAIH4, AlEt3, Na, K, KC8 and dihydrogen.
    [0014] In the case where an oxidation state nickel precursor (+ II) is used in the presence of a Brönsted base, any Brönsted base known to those skilled in the art can be used. By "Brönsted base" is meant any molecular entity or corresponding chemical species capable of accepting a proton, such as, for example, triethylamine.
    [0015] The preparation temperature of the complexes according to the invention can vary between -80 ° C. and 130 ° C. The preparation of the complexes according to the invention can be carried out in the presence or absence of solvent. Preferably, the preparation is carried out in the presence of a solvent. The preparation solvent may be 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. The complexes according to the invention comprise a nickel of degree of oxidation (+ I) or (+11), preferably a nickel of degree of oxidation (+11). The complexes according to the invention can also form multi-nuclear aggregates.
    [0016] 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. We present below some examples of complexes of formula (I) or (11) according to the invention as well as the operating conditions by means of which they were obtained. These examples are for illustrative purposes and are in no way limiting the scope of the invention. In Scheme 1, a complex according to the invention having formula (I) is illustrated. The addition of 2 equivalents of the ligand Li represented in limit form 1b) to one equivalent of NiBr 2 (DME) 2 and triethylamine in benzene leads after 16 hours at 60 ° C. to the complex Cl. In this complex, the phosphorus atoms are in the cis position and X1 corresponds to a bromine atom. The structure of the complex was characterized by X-ray diffraction (XRD). 30202 8 7 11 Diagram 1 0 0 Fi ........,) ,,, '....,> r ,,, ........... /. /' F3C N Li - NiBr2 (DME), NEt3 (2.2 eq) Yi. Benzene, 60 ° C., 16h Three complexes according to the invention corresponding to formula (II) are illustrated in Scheme 2. The addition of an equivalent of Li or L3 ligand represented in the form of limit 1 b) and one equivalent of tricyclohexylphosphine with one equivalent of nickel (O) bis (cycloocta-1,5-diene) in toluene leads to the C2 or C3 complexes after 3 hours and 16 hours respectively at 60 ° C. The addition of one equivalent of the L4 ligand represented as limit 1b) and one equivalent of tricyclohexylphosphine to one equivalent of nickel (O) bis (1,5-cycloocta-diene) (Ni (COD) 2) in toluene conducted after 3 hours at 90 ° C to the complex C4. In these complexes, the phosphorus atoms are in the trans position and X1 corresponds to a hydrogen atom. The complexes are characterized by 31P NMR by two double doublets with a large Jpp coupling constant of the order of 230 Hz and two smaller JpH coupling constants corresponding to the phosphorus hydride coupling in cis. Scheme 2 + PCy3 F3C N N1 = R. Neither H F3 - 0 PCy3 Ni (cod) 2 Toluene, 60 ° C, 3h Li C2 Cy + PCy3 N i (cod) 2 Cy 0 0 Cy Cy F I N Cy F3C> ^ 1 11 ' ## STR1 ## L4 C4 In Scheme 3, a complex according to the invention corresponding to formula (II) is illustrated.The bubbling of ethylene for 3 hours at atmospheric pressure in a mixture formed by an equivalent of Li ligand, PCy3 and an equivalent of Ni (COD) 2 leads to the formation of complex C5.15 Scheme 3 1) Ni (cod) 2, PCY3, toluene, 60 ° C, 3h - P F3C - if 0 0 PCy3 2) ethylene, 1 bar In a preferred manner, the complexes according to the invention correspond to the following formulas (I) or (II): ## STR2 ## ## STR2 ## / 0 / AoRcia NAll R1 b Al RO c AR1 \ AIRlb / AR1 a / AR ....-- H i ........ 'AciRcia / `AiRob lif LR' AR1 a RLb / N ----- P s N. iBr 0ii / 0 / _AniRla P R2 R2 0 SO II Br 'Aill Rila PI AiiRob AiRcic AR1 has Wing / N ----- P o I Ni / Br /..- it RI1 has R2 /, 0 / P iXAiRob HN R 'R2 0 II Br N; eNi Ail Rila PP' ARla / I R'2 XAll R11 b Al Ric N) eNi P ARla i A'Rlb / XAiRob A'Rlb HN R2 0 ## STR5 ## wherein R 1 is a compound of the formula ## STR1 ## wherein nickel is of oxidation state (+ II), and A, A ', A1, A, 1, A'1, Ria, Filb, Ria, Rib, R, 1c, R2 e1. - H, 2 meet the specifications of the invention. A non-exhaustive list of ligands that may be suitable for the preparation of the complexes according to the invention is shown below. The ligands are represented in their limiting forms 1 a) 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 Using the complexes of formula (I) or (II) in a chemical transformation reaction The nickel-based complexes of formula (1) or (II) according to the invention can be used as catalyst in a chemical transformation reaction, such as the reaction of hydrogenation, hydroformylation, cross-coupling or oligomerization of olefins. In particular, these complexes are used in a process for oligomerizing an olefin feed advantageously having 2 to 10 carbon atoms.
    [0017] The nickel complexes of formula (1) or (11) according to the invention may be used in the form of a catalytic composition, mixed with a compound known as 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 (AlEt3).
    [0018] 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.
    [0019] Preferably, said activating agent C 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.
    [0020] 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, the monoolefins or diolefins preferably comprising 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 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.
    [0021] 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.
    [0022] 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 complex 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 complex according to the invention is injected at the same time as the olefin in a reactor stirred by conventional mechanical means or by an 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.
    [0023] 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.
    [0024] The following examples illustrate the invention without limiting its scope. The notation Cy represents the cyclohexyl group. EXAMPLES EXAMPLE 1 Syntheses of Ligands and Complexes Synthesis of L1 Ligands L3 and L4. The synthesis of ligands Li, L3 and L4 was carried out according to the method described in the literature: F. G. Terrade, Eur. J. Inorg. Chem. 2014, 1826-1835. Synthesis of Cl Cl .Et3N The ligand Li F3C-SO2-N = P (iPr) 2H (82 mg, 0.31 mmol, 2.2 eq.), NiBr2 (DME) (43 mg, 0.14 mmol, 1 eq. ) and triethylamine (100 μL, 0.74 mmol, 5.3 eq) are suspended in a Schlenk with 2 mL of benzene and stirred for 10 minutes at room temperature. Then, the mixture is heated at 60 ° C for 16 hours (h) and the solvent is evaporated. The red powder obtained is washed with pentane. Crystals are obtained by diffusion of pentane into a solution of toluene.
    [0025] Fl. C 1 1 Synthesis of the complex C2 ------- (c F3 ---- s Ni% 0 C) PCy3 C2 The Li ligand (F3C-SO2-N = P (iPr) 2H, 796 mg, 3 mmol, 1 eq.), Ni (COD) 2 (825 mg, 3 mol, 1 eq.) and tricyclohexylphosphine (840 mg, 3 mmol, 1 eq.) are solubilized in 30 mL of toluene. The solution is stirred until the components are dissolved and then heated at 60 ° C. for 3 hours. The solvent is evaporated under reduced pressure to give a powder. After trituration and washing with pentane (3 x 10 mL), a yellow powder is obtained which is dried under vacuum corresponding to the isolated product: 694 mg, 38%. 31P NMR (C6D6): 36.5 (dd, 2Jpp = 232 Hz and 28.6 Hz); 103.0 (dd, 2Jpp = 233 Hz and JPH = 72.9 Hz) Synthesis of the complex C3 Cy Cy irP N1,. The ligand L3 (F3C-SO2-N = P (Cy) 2H, 205 mg, 0.5 mmol, 1 eq.), Ni (COD) 2 (412 mg, m.p. 1.5 mmol, 1 eq.) And tricyclohexylphosphine (420 mg, 1.5 mmol, 1 eq.) Are solubilized in 20 mL of toluene. The solution is stirred until the components dissolve and then heated at 60 ° C. for 16 hours. The solvent is evaporated under reduced pressure to give a powder. After trituration and washing with pentane (3 x 10 mL) a yellow powder (isolated: 465 mg, 45%) is obtained. 31P NMR (C6D6): 36.6 (dd, 2Jpp = 236 Hz and 67 Hz); 78.6 (dd, 2 Jpp = 237 Hz and LipH = 82 Hz). Synthesis of C4 C4 Complex The L4 ligand (F3C-SO2-N = P (tBu) 2H, 58mg, 0.2mmol, 1 eq.), Tricyclohexylphosphine (56mg, 0.2mmol, 1 eq.) And Ni (COD) 2 (55 mg, 0.2 mmol, 1 eq.) Are placed in a Schlenk in 5 mL of toluene. The mixture is heated and stirred at 90 ° C for 3h. The solvent is then evaporated to yield a solid. This solid is triturated and then washed with pentane (3x 5 mL) to yield a yellow solid. The product is characterized by 31 P NMR (C6D6): 40.4 ppm (dd, 2Jpp = 235 Hz and 2JpH = 69 Hz); 120.7 (2Jpp = 235 Hz and 2JpH = 68 Hz). Synthesis of the C5-complex ## STR1 ## The L3 ligand (F3C-SO2-N = P (iPr) 2H, 205 mg, 0.5 mmol, 1 eq.), Ni (COD) 2 (412 mg, 1.5 mmol, 1 eq.) and tricyclohexylphosphine (420 mg, 1.5 mmol, 1 eq.) are dissolved in 20 mL of toluene. The solution is stirred until the components are dissolved and then heated at 60 ° C. for 3 hours. A flow of ethylene is passed through this solution until the color becomes clear (10 minutes at room temperature, with stirring and 1 bar of ethylene). The complex C5 is then obtained. The product is characterized by 31P NMR (C6D6): 89.6 (d, 2 Jpp = 245 Hz); 18.7 (d, 2'ipp = 243 Hz). Example 2: Oligomerization of ethylene The oligomerization reaction of ethylene was evaluated with C2 and C3 complexes (10 μmol). 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). Once the internal temperature is stabilized, the complex is introduced (10 μmol in 5 ml of toluene). 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 and per hour.
    [0026] Table 1. Oligomerization of Ethylene with Various Com-Temp Complexes-Mass of Productivity Times Distribution of Butene-Hexene Oligomeric Oligomide Reaction Reaction G (g), 1-11 products (weight) ['1 Li) -1 (g) (min) C4 C6 Cs' C2 40 ° C 4.6 90 1040 38.9 26.6 34.5 98.8 99.1 C3 40 ° C 14.5 90 3300 19.5 21.4 59.1 99.9 99.0 a Determined by GO (percentage weight of cuts 04, 06 and C8 + with respect to all oligomers). Percent weight of butene-1 in section 04. The above examples demonstrate that the complexes according to the invention have a good activity for the oligomerization of ethylene.
    权利要求:
    Claims (15)
    [0001]
    REVENDICATIONS1. Nickel-based complex of the formula (I) or the formula (II) AR1a1b / AR / AR IIa II N- ## STR2 ## in which - the atoms P, N, S, O constitute a ligand fragment, - A and A ', which are identical or different, are independently 0 , 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 optionally containing hetero elements. , or an aromatic group, substituted or not and containing or not heteroelements, - the groups R1, represented on the formulas by Ria and R1b, with Ria and Rb being identical or different from each other, bound or not with each other, are chosen from the cyclic or non-cyclic alkyl groups, substituted or unsubstituted and optionally containing heteroelements, aromatic groups, substituted or unsubstituted and optionally containing heteroelements, the group R2 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, - L2 represents a Lewis base, - X1 is a hydrogen atom or a halogen atom or a carbon atom bonded to or part of at least one cyclic or non-cyclic alkyl group, unsaturated or unsaturated, substituted or unsubstituted and optionally containing heteroelements, a substituted or unsubstituted aromatic group and containing or not hetero elements, - L2 and X1 are such that the degree of oxidation of nickel is respected.
    [0002]
    2. Complex according to claim 1, in which L2 represents a phosphine of laxA, 1Rxicl / 4'1R, i lap1 / 41) (R, ibA, i) p_ P type (A1 R 'c) or a phosphinamine of type ( R 'NH (R'2) or) (Rp1 / 41) (RA, i) p -NH_s (O) 2 (-rt, 2s, in which: - A1, A'1 and A "1, identical or different between them, are independently 0, S, NR3, or a single bond between the phosphorus atom and a carbon atom, - the R3 group is either a hydrogen atom or a cyclic or non-cyclic alkyl group, substituted or unsubstituted and containing or not containing heteroelements, or an aromatic group, substituted or unsubstituted and containing heteroelements or not, the groups R'1, ie R'la, R'lb and R'lc 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 group R'2 is chosen from cyclic or non-substituted or unsubstituted or substituted alkyl groups containing or not containing heteroelements, substituted or unsubstituted aromatic groups containing or not containing heteroelements.
    [0003]
    3. Complex according to claim 1 or 2 wherein the groups R1, Ria and Rb being identical or different, bonded or not, and the groups R'1, Rla, R-up and rt -1c being identical or different, whether bound to each other or not, are independently selected from alkyl groups comprising 1 to 15 carbon atoms, aromatic groups comprising 5 to 20 carbon atoms; substituted or unsubstituted, containing heteroelements or not.
    [0004]
    4. Complex according to claim 3 wherein the groups R1, Ria and Rb being identical or different, bonded or not with each other, and R'1 groups, R'la, R'lb and Filc being identical or different, bound or not, 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 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-3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 4-chlorophenyl, 3,5-di (trifluoromethyl) phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl, thiophenyl, substituted or not, containing heteroelements or not. 10
    [0005]
    5. Complex according to one of claims 1 to 4 wherein the R2 groups and 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.
    [0006]
    6. Complex according to claim 5 wherein the R2 groups and the R'2 groups, identical or different, are independently selected from methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl groups. Tert-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.
    [0007]
    7. A process for preparing a complex according to one of claims 1 to 6 comprising contacting at least one ligand comprising said ligand fragment consisting of P, N, S and O atoms, with at least an oxidation state nickel precursor (0), a precursor of the X1 group, and optionally a Lewis base.
    [0008]
    8. The method of claim 7 wherein the nickel precursor is 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 (otolylphosphito) nickel (O) (ethylene), nickel (0) tetrakis (triphenylphosphite), nickel (0) tetrakis (triphenylphosphine), and nickel (0) bis (ethylene), alone or in admixture.
    [0009]
    9. Process for the preparation of a complex according to one of claims 1 to 6 comprising contacting at least one ligand comprising said ligand fragment consisting of P, N, S and O atoms, with at least one oxidation state nickel precursor (+11) in the presence of a reducing agent or a Briinsted base, and optionally a Lewis base.
    [0010]
    10. The process as claimed in claim 9, in which the nickel precursor is chosen from nickel chloride (11), nickel (II) chloride (dimethoxyethane), nickel bromide (11) and 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 (11), nickel trifluoroacetate (11), nickel triflate (11), nickel acetylacetonate (11), nickel hexafluoroacetylacetonate (11), allyl nickel chloride (11), bromide allylnickel (11), methallylnickel chloride dimer (11), allylnickel hexafluorophosphate (11), methallylnickel hexafluorophosphate (11), nickel biscyclopentadienyl (11), nickel bisallyl (11) and bismethallyl nickel (11); in their hydrated form or not, taken alone or in mixture.
    [0011]
    11. Use of a complex according to one of claims 1 to 6 or prepared according to one of claims 7 to 10 as a catalyst.
    [0012]
    12. A process for oligomerizing an olefin feedstock comprising bringing said feedstock into contact with a complex according to one of claims 1 to 6 or prepared according to claims 7 to 10, in the presence or absence of a solvent.
    [0013]
    13. The method of claim 12 wherein the complex is used in a mixture with a compound selected from the group consisting of tris (hydrocarbyl) aluminum compounds, chlorinated or brominated hydrocarbylaluminium compounds, aluminoxanes, organoboron compounds, organic compounds capable of giving or capturing a proton, alone or as a mixture.
    [0014]
    The process of claim 12 or 13 wherein the feedstock comprises olefins having a carbon number of from 2 to 10.
    [0015]
    15. Method according to one of claims 12 to 14 wherein the reaction is an oligomerization reaction of ethylene.
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    同族专利:
    公开号 | 公开日
    JP2015209429A|2015-11-24|
    CA2889601A1|2015-10-28|
    EP2939744A1|2015-11-04|
    FR3020287B1|2017-12-08|
    US9428531B2|2016-08-30|
    US20150307537A1|2015-10-29|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1453818A|FR3020287B1|2014-04-28|2014-04-28|NOVEL CYCLIC COMPLEXES BASED ON NICKEL AND THEIR USE IN PROCESS FOR PROCESSING OLEFINS|FR1453818A| FR3020287B1|2014-04-28|2014-04-28|NOVEL CYCLIC COMPLEXES BASED ON NICKEL AND THEIR USE IN PROCESS FOR PROCESSING OLEFINS|
    EP15305337.6A| EP2939744A1|2014-04-28|2015-03-04|Novel nickel-based cyclic complexes and use thereof in a method for transforming olefins|
    CA2889601A| CA2889601A1|2014-04-28|2015-04-23|New nickel-based cyclic compounds and their use in an olefin transformation process|
    JP2015090223A| JP2015209429A|2014-04-28|2015-04-27|Novel nickel-based complexes and use thereof in olefin transformation method|
    US14/698,500| US9428531B2|2014-04-28|2015-04-28|Cyclic nickel-based complexes and their use in a process for the transformation of olefins|
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