FR3007674A1 - NOVEL NICKEL CATALYTIC COMPOSITION AND USE THEREOF IN OLEFIN OLIGOMERIZATION PROCESS - Google Patents

Abstract

The invention describes a new catalytic composition comprising at least one nickel precursor A with at least one diphosphinamine B1 ligand of formula (R1) (R'1) PN (R3) -P (R2) (R'2) or a ligand iminobisphosphine B2 of formula (R3) N = P (R1) (R'1) -P (R2) (R'2). The invention also describes the use of said catalyst composition in an olefin oligomerization process.

Description

The present invention relates to a new catalyst composition based on nickel. The invention also relates to the use of said catalyst composition as a catalyst for chemical transformation reactions.

PRIOR ART It is known to prepare nickel-based catalytic compositions for their application in various fields of chemistry, particularly in the field of catalytic transformations such as hydroformylation, hydrogenation, cross-coupling, oligomerization of olefins ...

By way of example, reference may be made to article C.R. Acad. Sci. 1967, C103-106 and J. Mol. Catal. A 2001, 169, 19-25 in which nickel complexes are described in the presence of monophosphine.

The nickel-diphosphinamine complexes described in the prior art are symmetrical and prepared by means of diphosphinamine ligands in which the two phosphorus atoms carry identical groups of aromatic nature (Eur J. J. Inorg Chem, 2009, 3016-3024 , Organometallics, 2001, 20, 47694771). For example, patent application W001 / 10876 discloses nickel diphosphinamine complexes, the symmetrical ligands described being substituted, on phosphorus, only by aromatic groups and used for the polymerization of ethylene. These catalyst systems are not very active in oligomerization of ethylene and are generally used for the polymerization of ethylene. The Applicant has found a novel nickel-based catalytic composition, prepared from asymmetric diphosphinamine or iminobisphosphine ligands, in which one of the phosphorus atoms carries at least one nonaromatic group and the other phosphorus atom bears at least one aromatic group. . It has been found that the compositions, in the presence of a solvent or not, exhibit improved activity and selectivity for catalytic conversion reactions, especially for the catalysis of the olefin oligomerization or dimerization reaction.

Detailed Description of the Invention Catalytic Composition A first subject of the invention relates to a new catalytic composition comprising: at least one nickel A precursor, with at least one diphosphinamine B1 ligand of formula (R1) (R'1) PN (R3) -P (R2) (R'2), or an iminobisphosphine ligand B2 of formula (R3) N = P (R1) (R'1) -P (R2) (R'2), in which The groups R 1 and R '1, which are identical or different, whether or not they are linked to one another, are chosen from nonaromatic groups; the groups R 2 and R' 2, which are identical or different, whether or not linked to one another, are chosen from the aromatic groups, R3 is chosen from hydrogen, halogens, aliphatic hydrocarbon groups, cyclic or otherwise, containing or not heteroelements, aromatic groups containing or not heteroelements, substituted or not, preferably groups; R1 and R'1 are selected from non-aromatic groups and not containing sil ICIUM. Preferably R1 and R'1 are identical. Preferably, the groups R 1 and R '1 are chosen from methyl, ethyl, isopropyl, n-butyl, iso-butyl, tert-butyl, pentyl and cyclohexyl groups, which may or may not be substituted. Preferably, the groups R 2 and R '2 are chosen from the groups phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 2-isopropoxyphenyl, 4-methoxy-3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 3,5-bis (trifluoromethyl) phenyl, benzyl, naphthyl, pyridyl, substituted or unsubstituted, containing heteroelements or not. Preferably R2 and R'2 are identical.

Advantageously, R 3 is chosen from hydrogen, alkoxy, aryloxy, sulphide, sulphonamino, sulphonamido, nitro, carbonyl, amino or amido groups, which may or may not contain aliphatic, cyclic or aromatic groups, whether or not containing substituted or unsubstituted heteroelements.

The nickel precursor A may be chosen from nickel chloride (11), nickel chloride (11) (dimethoxyethane), nickel bromide (11), nickel bromide (11) (dimethoxyethane), fluoride from nickel (11), nickel iodide (11), nickel sulphate (11), nickel carbonate (11), nickel dimethylglyoxime (11), nickel hydroxide (11), hydroxyacetate nickel (11), nickel oxalate (11), nickel carboxylates (11) such as, for example, 2-ethylhexanoate, nickel phenates (11), nickel acetate (11), trifluoroacetate nickel (11), nickel triflate (11), nickel acetylacetonate (11), nickel hexafluoroacetylacetonate (11), 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-tolylphosphite) nickel (0) (ethylene), nickel (0) tetrakis (triphenylphosphite), nickel (0) tetrakis (triphenylphosphine), nickel bis (ethylene), tr-allylnickel chloride (11), tr-allylnickel bromide (11), methallylnickel chloride dimer (11), n3-allylnickel hexafluorophosphate (11), hexafluorophosphate n3-methallylnickel (11) and 1,5-cyclooctadienyl nickel (11), in their hydrated form or not, taken alone or in mixture. Said nickel precursors may optionally be complexed with Lewis bases. The preparation of diphosphinamine ligands B1 of formula (R1) (R'1) PN (R3) -P (R2) (R'2), or iminobisphosphines B2 of formula (R3) N = P (R1) (R'1) -P (R2) (R'2) is carried out according to the known methods of the literature (Inorg Chem 2003, 2125-2130). The diphosphinamine ligands B1 of formula (R1) (R'1) PN (R3) -P (R2) (R'2) can be prepared and isolated by reacting 1 equivalent of chlorophosphine ClP (R1) (R'1) and 1 equivalent of chlorophosphine Cl-P (R2) (R'2) with a primary or aromatic amine R-NH2 in the presence of triethylamine. The iminobisphosphine ligands B2 of formula (R3) N = p (R1) (R1) p (R2, e-, 2t) can be prepared and isolated by reacting a primary or aromatic amine R3-NH2 and 1 equivalent of chlorophosphine Cl_p (Ri) (R, 1) and 1 equivalent of chlorophosphine Cl-P (R2) (R'2) introduced successively in the presence of triethylamine. Use of the Catalytic Composition in a Chemical Transformation Reaction The catalyst composition according to the invention can be used in a chemical transformation reaction, such as the hydrogenation, hydroformylation, cross-coupling or oligomerization reaction of olefins. In particular, the catalytic composition according to the invention is used in an oligomerization process of olefins advantageously comprising 2 to 10 carbon atoms; preferably in a dimerization process of ethylene or propylene. The catalytic composition according to the invention may be used in admixture with a compound C called 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 (MeA1C12), ethylaluminum dichloride (EtA1C12), isobutylaluminum dichloride (iBuAlC12), diethylaluminum chloride (Et2AlCl), trimethylaluminum, tributylaluminum, tri-n-octylaluminum and triethylaluminum (Al Et3).

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.

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 tris (aryl) borane type Lewis acids 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. In the case where said activating agent is chosen from organic compounds which may give 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 Bronsted bases.

The catalytic composition according to the invention is advantageously used in a process for oligomerization or dimerization of olefins, preferably in a dimerization process of ethylene or propylene.

The solvent of the oligomerization or dimerization process may be chosen from organic solvents and preferably from ethers, alcohols, chlorinated solvents and saturated, unsaturated, aromatic or non-aromatic hydrocarbons, 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. The catalytic compositions according to the invention can be prepared in situ in the reaction section or not.

Oligomerization is defined as the conversion of a monomeric unit into a compound or mixture of compounds of the general formula CpH2p with 4 p 80, preferably with 4 p 50, preferably with 4 p 26 and more preferably with 4 p. p 14.

The olefins used in the oligomerization or dimerization 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 alkane (s), as found in "cuts" from petroleum refining processes, such as catalytic cracking or cracking at the same time. steam. Preferably, the olefin used in the oligomerization or dimerization process is ethylene or propylene. Said olefins can come from non-fossil resources such as biomass. For example, the olefins used in the oligomerization process according to the invention may advantageously be produced from alcohols, and in particular by dehydration of alcohols. The concentration of the nickel in the catalytic solution is advantageously between 1 × 10 -8 and 1 mol / L, and preferably between 1 × 10 -6 and 1 × 10 -2 mol / L. The molar ratio between the ligand B1 or B2 and the nickel precursor A is advantageously between 0.05 and 10, preferably between 0.5 and 2 and preferably 1. The molar ratio between the activating agent C and the precursor nickel is advantageously between 1/1 and 10000/1, preferably between 1/1 and 1000/1 for the aluminoxanes and preferably between 1/1 and 100/1 for the other aluminum derivatives and the other acids of Lewis. The oligomerization or dimerization process according to the invention advantageously operates at a total pressure of between atmospheric pressure and 20 MPa, preferably between 0.5 and 8 MPa, and at a temperature of between -40 and + 250 ° C. C, preferably between -20 ° C and 150 ° C. The following examples illustrate the invention without limiting its scope. The notation Cy represents the tricyclohexyl group.

Example 1 Synthesis of Ligands Iminobisphosphine ligands R'-SO2-N = P (R1) (R'1) -P (R2) (R'2) are prepared and isolated by reacting a sulfonamide and 2 equivalents of chlorophosphine ( identical or different) in the presence of triethylamine. Ligands 1 and 2 in which R 1 = R '1 = R 2 = R' 2 (comparative examples) and ligands 3 and 4 in which R 1 = R '1 and R 2 = R' 2 and R 1 are different from R 2 are exemplified. The structures of the four ligands are shown below. Synthesis of ligand 1: (4-bromo-N- (1,1,2,2-tetraphenyldiphosphanylidene) benzenesulfonamide) To a solution of 4-bromobenzenesulfonamide (500 mg, 2.12 mmol, 1 eq.) and triethylamine (1.6 mL) 11.2 mmol, 5.3 eq.) In THF (10 mL) is added dropwise at room temperature and with vigorous stirring the chlorodiphenylphosphine (0.760 mL, 4.24 mmol, 2 eq.) Freshly distilled. After the addition is complete, the mixture is stirred for 5 minutes and then the suspension is filtered under a nitrogen atmosphere on a sintered material. Evaporation of the solvent and volatiles leads to the formation of a solid. This solid is dissolved in a minimum of dichloromethane and then pentane (20 mL) is added. By evaporating this solution, a precipitate appears. The supernatant is removed using a syringe and the solid is washed with pentane (2 x 10 mL) and dried under vacuum to give the ligand 1 as a white powder (isolated yield: 68%). H NMR (300 MHz, CD2Cl2): δ 7.82 - 6.89 (m, 24H). 31P NMR (121 MHz, CD2Cl2) 19.72 (d, J = 281.1 Hz), -18.74 (d, J = 281.1 Hz). 31 P {1 HI NMR (121 MHz, CD2Cl2): 19.72 (d, J = 279.9 Hz), -18.74 (d, J = 281.2 Hz). MS (FAB ±): m / z calc. for C30H25NO2P2BrS ([MH] +): 606.0248; obs .: 606,0255.

Synthesis of ligand 2: (4-butyl-N- (1,1,2,2-tetraphenyldiphosphanylidene) benzenesulfonamide) To a solution of 4-butylbenzenesulfonamide (500 mg, 2.34 mmol, 1 eq) and triethylamine (1 mL, 7.17 mmol, 3 eq.) In THF (20 mL) is added dropwise, at room temperature and with vigorous stirring, the freshly distilled chlorodiphenylphosphine (0.840 mL, 4.68 mmol, 2 eq.). After the addition is complete, the mixture is stirred for 5 minutes and then the suspension is filtered under a nitrogen atmosphere on a sintered material. Evaporation of the solvent and volatiles leads to the formation of an oil. This oil is solubilized in diethyl ether (10 mL) and the solution is evaporated. This step is repeated 4 times until the product precipitates. The solid is then dried under vacuum to obtain the ligand 2 in the form of a white powder (isolated yield: 79%). 1H NMR (300 MHz, CD2Cl2): δ 7.91-6.33 (m, -CHAT, 24H), 2.59 (t, CH3-CH2-CH2-CH2-CAr, J = 7.7 Hz, 2H), 1.57 (m, CH3- CH2-CH2-CH2-CAr, 2H), 1.33 (m, CH3-CH2-CH2-CH2-Car, 2H), 0.93 (t, CH3-CH2-CH2-CH2-Car, J = 7.3 Hz, 3H). 31P NMR (121 MHz, CD2Cl2): δ 19.47 (d, J = 277.9 Hz), -17.90 (d, J = 278.0 Hz). MS (FAB +): m / z calc. for C34H3402NP2S ([M + H] +): 582.1786; Obs .: 582.1790 Synthesis of N-diphenylphosphino-4-butylbenzenesulfonamide To a solution of 4-butylbenzene-1-sulfonamide (9.38 mmol, 1 eq.) and triethylamine (25 mmol) in THF (20 mL) is added dropwise. dropwise, at room temperature and with vigorous stirring, the freshly distilled chlorodiphenylphosphine (9.38 mmol, 1 eq.). The suspension is left stirring overnight at room temperature. Evaporation of the solvent and volatiles leads to the formation of a solid. This solid is dissolved in 10 ml of dichloromethane, then pentane (40 ml) is added, a precipitate appears. The supernatant is removed with a syringe and the solid is washed with pentane (2 × 20 mL) and dried in vacuo to give N-diphenylphosphino-4-butylbenzenesulfonamide as a white powder. This compound can be isolated and purified or used directly for another synthesis step (isolated yield: 74%).

Synthesis of the ligand 3. 4-Butyl-N- (1,1-diisopropyl-2,2-diphenyl-diphosphanylidene) benzenesulfonamide To a solution of N-diphenylphosphino-4-butylbenzenesulfonamide (1.86 g, 4.68 mmol, 1 eq.) And triethylamine (1.30 mL, 9.36 g. mmol, 2 eq.) in THF (20 mL) is added dropwise, at room temperature and with vigorous stirring, diisopropylchlorophosphine (0.746 mL, 4.68 mmol, 1 eq.). Once the addition is complete, the mixture is stirred for 10 minutes and then the suspension is filtered under a nitrogen atmosphere on a sintered material. Evaporation of the solvent and volatiles leads to the formation of an oil. Pentane (20 mL) is added to this oil, and after trituration the pentane is removed using a syringe. The oil is then suspended in pentane (10 mL) and the solution evaporated under vacuum. This step is repeated once with pentane and then twice with diethyl ether (10 mL) which allows the formation of a solid. The solid is washed with pentane (2 × 10 mL) and then dried under vacuum to give the ligand 3 as a white solid (isolated yield: 34%). 1 H (300 MHz, CD 2 Cl 2): δ: 7.98 - 7.83 (m, 4H, -PPh 2), 7.76 - 7.64 (m, 2H, -CH 2 -Ar-SO 2), 7.60-7.35 (m, 6H, -PPh 2) , 7.23 - 7.12 (m, 2H, -CH2-Ar-SO2), 2.69 - 2.57 (t, 2H, J = 7.4 Hz, CH3-CH2-CH2-CH2-Ar), 2.44 (m, 2H, CH3-CH). -CH3), 1.69-1.48 (m, 2H, CH3-CH2-CH2-CH2-Ar), 1.35 (m, 2H, CH3-CH2-CH2-CH2-Ar), 1.18- 0.99 (m, 12H, CH3- CH 3 CH 3), 0.93 (t, J = 7.3 Hz, 3H, CH 3 -CH 2 -CH 2 -CH 2 -Ar). 31P (121MHz, CD2Cl2) δ: 20.13 (d, J = 311.6Hz); 2.80 (d, J = 311.6 Hz).

Synthesis of 4,4-butyl-N- (1,1-dicyclohexyl-2,2-diphenyl-diphosphanylidene) benzenesulfonamide ligand To a solution of -diphenylphosphino-4-butylbenzenesulfonamide (0.361 g, 0.91 mmol, 1 eq.) And triethylamine (0.126 g. mL, 1.82 mmol, 2 eq.) in THF (10 mL) is added dropwise, at room temperature and with vigorous stirring, dicyclohexylylphosphine (0.200 mL, 0.91 mmol, 1 eq.). After the addition is complete, the mixture is stirred for 5 minutes and then the suspension is filtered under a nitrogen atmosphere on a sintered material. Evaporation of the solvent and volatiles leads to the formation of an oil. Pentane (10 mL) is added to this oil, then after trituration, it is evaporated under vacuum. This step is repeated once with pentane and then twice with diethyl ether (10 mL) which allows the formation of a solid. The solid is dried under vacuum to give the ligand 4 as a white solid (isolated yield: 51%). 1 H NMR (300 MHz, CD 2 Cl 2): δ 7.90 (dd, J = 12.5, 7.6 Hz, 4H, PPh 2), 7.78-7.67 (dd, J = 8.4, 2.0 Hz, 2H, Ar-SO 2), 7.61-7.40 ( m, 6H, PPh 2), 7.18 (dd, J = 8.4, 2.0 Hz, 2H, Ar-SO 2), 2.63 (t, J = 7.6 Hz, 2H, -CH 2 -Ar), 2.30 - 2.01 (m, 2H, Cy), 1.81 (m, 2H, Cy), 1.73 - 1.49 (m, 8H, Cy), 1.73 - 1.49 (m, 2H, -CH 2 -CH 2 -Ar) 1.33 (dt, J = 16.3, 7.3 Hz, 2H). , -CH2-CH2-CH2-Ar), 1.17 (m, 10H, Cy), 0.93 (t, J = 7.3 Hz, 3H, H3C-CH2-CH2). 31P NMR (121 MHz, CD2Cl2): δ 20.44 (d, J = 314.9 Hz), -4.98 (d, J = 314.4 Hz).

MS (FAB +): m / z calcd. For C34H3402NP2S ([M + H] +): 594.2725; obsd .: 594.2732. Preparation of the compositions The ligands 1, 2, 3 and 4 are mixed with NiBr 2 (dme) to give the compositions 5, 6, 7 and 8. The composition 9 is a reference composition comprising tricyclohexylphosphine and NiCl2. Preparation of Composition (Comparative) 4-Bromo-N- (1,1,2,2-tetraphenyldiphosphanylidene) benzenesulfonamide 1 (200 mg, 0.331 mmol, 1.01 eq) and nickel bromide (11) dimethoxyethane (101 mg 0.327 mmol, 1 eq) are suspended in toluene (3 mL). The solution is then evaporated and diluted in the reaction solvent. Preparation of Composition 6 (Comparative) 4-Butyl-N- (1,1,2,2-tetraphenyldiphosphanylidene) benzenesulfonamide 2 (200 mg, 0.344 mmol, 1 eq) and nickel bromide (11) dimethoxyethane (106 mg 0.344 mmol, 1 eq) are suspended in toluene (3 mL). Preparation of Composition 7 4-Butyl-N- (1,1-diisopropyl-2,2-diphenyl-diphosphanylidene) benzenesulfonamide 3 (400 mg, 0.786 mmol, 1 eq) and nickel bromide (11) dimethoxyethane (266 mg, 0.864 mmol, 1.1 eq) are suspended in dichloromethane (5 mL). Preparation of Composition 8 4-Butyl-N- (1,1-dicyclohexyl-2,2-diphenyl-diphosphanylidene) benzenesulfonamide 4 (98 mg, 0.165 mmol, 1.02 eq) and nickel bromide (11) dimethoxyethane (50 mg, 0.162 mmol, 1 eq) are suspended in dichloromethane (3 mL). Example 2 Oligomerization of Ethylene The oligomerization reaction of ethylene was evaluated with compositions 5 and 6 and 7 in the presence of methylaluminoxane (MAO) at 45 ° C. and 30 bar of ethylene (1 bar = 0.1 MPa).

Operating Conditions: The 100 mL reactor is dried under vacuum at 100 ° C. for 2 hours and pressurized with ethylene. The catalyst is introduced (0.1 mmol in 8 ml of toluene) followed by methylaluminoxane (2 ml, 10% in toluene, 300 eq.). The temperature and pressure are set at 45 ° C and 35 bar. Stirring is started (t = 0). After the defined reaction time, the reactor is cooled to room temperature and depressurized with stirring. The liquid phase is neutralized with aqueous H 2 SO 4 and is analyzed by GC.

Compositions 5 and 6 activated by MAO (300 eq.) Are considered inactive, ethylene consumption is negligible. The MAO-activated composition 7 is very active in the oligomerization of ethylene (> 107 gc 2 H 4 / (molm · h)) and no polymer is formed. GC analyzes confirm that the products formed are mainly butenes and hexenes. The results are shown in Table 1. Table 1.0 Ethylene oligomerization catalyzed by 5, 6, 7a Compound Input (min.) Conso. C2H4 (g) Activityb Distribution in oligomers [% wt] sition C4c C6c C8 ± c 1-C4d 2-C4d on 5 22 ndf - - - - - - 2e 6 20 ndf - - - - - - 3 7 14 31,5 14. 106 60.3 25.7 14.0 6.6 93.4 a Reaction conditions: n = 10 mol, cocatalyst: MAO (300 eq.), 30 bar C2H4, 45 ° C, solvent: toluene (10 mL). b gC2H4 / (MOINi.h). c Determined by GC,% w / all oligomers. d% w / other C4 cut products. e Comparative examples. f not determined: negligible ethylene consumption, activities observed <0.7. 106.

The composition 7 comprising the dissymmetrical ligand 3 leads to a much higher performance in terms of activity compared to the compositions 5 or 6 comprising the symmetrical ligands 1 and 2. EXAMPLE 3 Oligomerization of propylene The oligomerization of propylene was carried out with two different activators: EADC (ethylaluminum dichloride) and MAO (methylaluminoxane). The tests carried out with the 9 NiCl 2 (PCy 3) 2 composition are reference tests.

Tests with EADC Operating Conditions: The 250 mL reactor is dried under vacuum at 100 ° C. for 2 hours, cooled to 10 ° C. and then filled with propylene (pressure of 1.4 bar). 33 mL of chlorobenzene and 10 mL of n-heptane (accurately weighed internal standard) are then introduced, followed by 8 g of propylene. Under stirring, the reactor is cooled to -10 ° C. The EADC activator (ethylaluminium dichloride, 0.075 M in toluene, 15 eq, 2 mL) is then injected, followed by the catalyst (0.1 mmol in 5 mL of chlorobenzene). 12 g of propylene are then introduced. The agitation is then started (t = 0). The temperature is maintained at -10 ° C for 10 min and then gently brought to 10 ° C. The consumption of propylene is followed by the decrease of the pressure. The liquid phase is then removed and neutralized with aqueous NaOH. The organic phase is weighed and analyzed by GC equipped with a cryostat. The results are shown in Table 2.

Compositions 7, 8 and 9 after activation with the EADC activator are very active for the oligomerization of propylene at 10 ° C. The C6 selectivity of the compositions 7 and 8 is greater than the reference composition 9. The selectivity to 1-dimethylbutene and 2-dimethylbutene is about 25% for the compositions 7 and 8 activated. Table 2: Oligomerization of propylene with different compositions activated by the activator EADC.a Entry Composition Time (min.), Distribution in oligomers [% wt] c Activity C6 C9 C12 C15 + 1d 6 54 inactive 2 7 30 4 96.8 2 , 9 0.2 0.1 3 8 5 24 97.1 2.3 0.2 0.4 4d 9 42 2.9 86.4 12.1 1.3 0.2 a Reaction concilions: nn = 10 mol, cocatalyst: EADC (15 eq), 20g C3H6, 10 ° C, solvent: chlorobenzene (50 mL). b 106 goligaMOINi-b.h-1. c Determined by GC with n-heptane as internal standard. d Comparative example.

The selectivity in dimers obtained with the compositions 7, 8 and 9 activated with the EADC activator is reported in Table 3.

Table 3: Dimer selectivity Entry Composition 4M1P 1-DMB 4M2P 2M1P 2M2P Hex 2-DMB 2 7 1,2 23,7 35,5 13 13,4 11,4 1,8 3 8 1,1 17,3 43, 3 12.4 11 13.6 1.3 4a 9 6.6 62.2 10.9 17.2 0.5 2.4 0.2 Dimer selectivity in% wt. Determined by GC. 4M1P: 4-methylpentene-1,1-DMB: 2,3-dimethylbutene-1,4M2P: 4-methylpentene-2,2M1P: 2-methylpentene-1,2,2-methyl-2-pentene-2-hexylhexenes, 2-DMB: 2,3-dimethylbutene-2. a Comparative Examples.

The above examples demonstrate that the catalyst compositions used in the process according to the invention exhibit improved activity and selectivity for the oligomerization of olefins preferably comprising 2 to 10 carbon atoms, more particularly for the dimerization of olefins comprising 2 to 10 carbon atoms.

Claims (11)

REVENDICATIONS1. Catalytic composition comprising: at least one nickel A precursor, with at least one diphosphinamine B1 ligand of formula (R1) (R'1) PN (R3) -P (R2) (R'2), or a ligand iminobisphosphine B2 of formula (R3) N = P (R1) (R'1) -P (R2) (R'2), in which - the groups R1 and R'1, identical or different, linked or not to each other, are selected from non-aromatic groups, - the groups R 2 and R '2, identical or different, linked or not to each other, are chosen from aromatic groups, - R 3 is chosen from hydrogen, halogens, aliphatic hydrocarbon groups cyclic or non-cyclic, whether or not containing heteroelements, aromatic groups containing or not substituted or unsubstituted heteroelements. 2. Composition according to claim 1 wherein the groups R1 and R'1 are chosen from non-aromatic groups and not containing silicon. 20 3. Composition according to claim 1 or 2 wherein the groups R1 and R'1 are selected from methyl, ethyl, isopropyl, n-butyl, iso-butyl, tert-butyl, pentyl, cyclohexyl, substituted or unsubstituted. 4. Composition according to one of the preceding claims wherein the R2 and R'2 groups are chosen from phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-methoxyphenyl groups. , 2-methoxyphenyl, 2-isopropoxyphenyl, 4-methoxy-3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 3,5-bis (trifluoromethyl) phenyl, benzyl, naphthyl, pyridyl, substituted or unsubstituted , containing heteroelements or not. 30 5. Composition according to one of the preceding claims further comprising a compound C 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. 6. Process for oligomerization of an olefin feedstock comprising bringing said feedstock into contact with the composition according to one of claims 1 to 5, in the presence or absence of a solvent. 7. Process according to claim 6, in which the olefins are chosen from ethylene, propylene, n-butenes and n-pentenes, alone or as a mixture, pure or diluted. 8. Method according to one of claims 6 to 7 wherein the nickel is present in a concentration between 1.10-8 and 1 mol / L. 9. Method according to one of claims 6 to 8 wherein one operates at a total pressure between atmospheric pressure and 20 MPa and at a temperature between -40 and + 250 ° C. 10. Process according to one of claims 6 to 9 wherein the reaction is a dimerization reaction. 25 The process of claim 10 wherein the reaction is a dimerization reaction of ethylene or propylene.