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  • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
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  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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  • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
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  • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
  • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
  • C07C2/08—Catalytic processes
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  • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
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  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/84—Metals of the iron group
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  • B01J2540/30—Non-coordinating groups comprising sulfur
  • B01J2540/32—Sulfonic acid groups or their salts
  • B01J2540/325—Sulfonic acid groups or their salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional groups
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  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0215—Sulfur-containing compounds
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  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
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  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
  • B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
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  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
  • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
  • B01J31/186—Mono- or diamide derivatives thereof
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  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
  • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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  • C07C2531/025—Sulfonic acids
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  • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • C07C2531/24—Phosphines
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/02—Ethene

Definitions

• the present invention relates to a novel nickel-based composition.
• the invention also relates to the use of said composition as a catalyst for chemical transformation reactions.
• EP 2 220 099 B1 indicates that the coordination complex system can be used as a catalyst for hydroformylation, hydrogenation, hydrogenation, polymerization, isoméhation ...
• This document does not describe a catalytic system based on nickel of degree of oxidation (+ II) and does not mention the use of specific activator according to the invention, in particular in a process for oligomerization of olefins.
• the applicant in his research has developed a new composition comprising a nickel precursor, a sulfonamido phosphine ligand or a mixture of sulfonamides with phosphine halides optionally in the presence of a Lewis base, and at least one specific activator.
• compositions exhibit interesting catalytic properties.
• these compositions exhibit good catalytic activity and good selectivity in the oligomerization of olefins, in particular in the dimerization of ethylene to butene-1.
• An object of the invention is to provide a new nickel-based composition (+11).
• 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.
• the catalytic composition according to the invention comprises: at least one oxidation state nickel precursor (+11),
• n takes a value from 1 to 2
• m is 1 to 3
• at least one mixture of a phosphine halide YP (AR 1a ) (A'R 1 b ) and a sulfonamide compound of formula R 2 SO 2 NH 2 optionally in the presence of a Lewis base denoted Z, in which
• a and A ' which are identical or different, are independently O, S, NR 3 , or a single bond between the phosphorus atom and a carbon atom
• the group R 3 is either a hydrogen atom, a cyclic or non-cyclic alkyl group, substituted or unsubstituted and optionally containing heteroelements, or an aromatic group, substituted or unsubstituted and optionally containing heteroelements
• the R groups; 1 represented by R 1a and R 1b , with R 1a and R 1b 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 hetero elements.
• 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 containing or not heteroelements,
• the catalytic composition according to the invention comprises:
• n at least one activator of formula [R3-mAIX m ] n , the group X being an alkoxy-OR group or a halogen, the R groups being identical to or different from one another and chosen from alkyl or aromatic groups, n takes a value from 1 to 2, m takes a value of 1 to 3,
• a and A ' which are identical or different, are independently O, S, NR 3 , or a single bond between the phosphorus atom and a carbon atom,
• the group R 3 is either a hydrogen atom, a cyclic or non-cyclic alkyl group, substituted or unsubstituted and optionally containing heteroelements, or a substituted or unsubstituted aromatic group containing or not containing heteroelements,
• R 1 represented in the formulas 1 a), 1 b) and 1 c) by R 1a and R 1 b , with R 1a and R 1b 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, and from aromatic groups, substituted or unsubstituted and optionally containing heteroelements,
• 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.
• 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, for example, advantageously chosen from methyl and ethyl groups.
• These alkyl groups may be substituted with heteroelements or groups containing heteroelements such as a halide, an alkoxy.
• alkoxy substituent means an alkyl-O- group in which the term alkyl has the meaning given above.
• Preferred examples of alkoxy substituents are methoxy or ethoxy.
• cyclic alkyl is meant a monocyclic hydrocarbon group having a number of carbon atoms greater than 3, preferably between 4 and 24, more preferably between 5 and 12, preferably a cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl, or polycyclic (bicyclic or tricyclic) having a number of carbon atoms greater than 3, preferably between 4 and 18, such as, for example, adamantyl or norbornyl groups.
• aromatic is meant an aromatic mono- or polycyclic group, preferably mono- or bicyclic, having a number of carbon atoms between 5 and 20.
• 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 in pairs by ⁇ bonds.
• the aromatic group according to the invention may contain heteroelements such as nitrogen, oxygen or sulfur.
• heteroelements are preferably selected from oxygen, nitrogen, sulfur or phosphorus.
• ligand according to the present invention is indifferently used to mean one or more of the tautomeric forms corresponding to the formula 1 a), 1 b), 1 c) used (s) to form the composition according to the invention.
• the groups R 1 , ie R 1a and R 1b are independently selected from cyclic or unsubstituted or unsubstituted alkyl groups and optionally containing heteroelements, from preferably from alkyl groups comprising 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms and optionally containing heteroelements; and from aromatic groups, substituted or unsubstituted and optionally containing heteroelements, preferably aromatic groups comprising 5 to 20 carbon atoms; substituted or unsubstituted, containing heteroelements or not.
• the two groups R 1 may be identical or different from each other. These two groups R 1a and R 1b can also be linked together. In in such a case, the two groups R 1a and R 1b may correspond to groups such as bis-phenyl or bis-naphthyl.
• the groups R 1 , ie R 1a and R 1b are independently selected from methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, cyclohexyl, adamantyl, substituted or unsubstituted, 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-3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 4-chloroph
• the groups R 1 , ie R 1a and R 1b are independently selected from 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 unsubstituted, containing heteroelements or not.
• the groups R 1 are independently selected from phenyl, o-tolyl, m
• the groups R 2 are chosen from cyclic or non-cyclic alkyl groups, substituted or unsubstituted and optionally containing heteroelements, preferably from alkyl groups comprising 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms. carbon atoms and whether or not containing heteroelements; and from substituted or unsubstituted aromatic groups containing or not containing heteroelements, preferably aromatic groups comprising 5 to 20 carbon atoms; substituted or unsubstituted, containing heteroelements or not.
• the groups R 2 are chosen from methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, cyclohexyl, adamantyl, substituted or unsubstituted, 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-ditert-butyl-4-methoxyphenyl, 4-chlorophenyl, 3,5-bis (trifluoromethyl) phenyl, benzyl, naphth
• the group R 3 is either a hydrogen atom, a cyclic or non-cyclic alkyl group, substituted or unsubstituted and optionally containing heteroelements, preferably an alkyl group comprising 1 to 15 carbon atoms, from preferably 1 to 10 carbon atoms and whether or not containing heteroelements; or an aromatic group, substituted or unsubstituted and optionally containing heteroelements, preferably an aromatic group comprising 5 to 20 carbon atoms; substituted or unsubstituted, containing heteroelements or not.
• the group R 3 is either a hydrogen atom or an alkyl group according to the invention.
• composition according to the invention comprises the mixture of the phosphine halide YP (AR 1a ) (A'R 1 b ) and the sulphonamide compound of formula R 2 SO 2 NH 2 , in the presence of a Lewis base denoted Z .
• composition according to the invention comprises an activator of formula [R3-mAIX m ] n , the group X being an alkoxy group -OR or a halogen, the groups R being identical or different from each other and selected from alkyl or aromatic groups, n takes a value from 1 to 2, m takes a value from 1 to 3.
• the indices m and n of the activator [R3-mAIX m ] n are integers.
• m is between 1 and 2.
• the activator is diethylaluminum chloride (Et 2 AlCl) and / or ethoxy diethylaluminum (Et 2 AlOEt).
• the activators of formula [R3-mAIX m ] n can be generated from the combination of trialkylaluminum AIR 3 and at least one alcohol of ROH type.
• the composition according to the invention may also comprise a Lewis base denoted Z.
• This Lewis Z base according to the invention may be an ether O (R 4 ) 2 or a tertiary amine N (R 4 ) 3 , the groups R 4 identical or different from each other, linked or not with each other, are independently chosen from cyclic or non-substituted or unsubstituted alkyl groups and containing or not containing heteroelements, preferably from alkyl groups comprising 1 to 15 carbon atoms, preferably 1 to 15 carbon atoms, preferably to 10 carbon atoms and whether or not containing heteroelements; and from aromatic groups, substituted or unsubstituted and optionally containing heteroelements, preferably aromatic groups comprising 5 to 20 carbon atoms; substituted or unsubstituted, containing heteroelements or not.
• the ether is preferably selected from diethyl ether, methyl tert-butyl ether, di / tert-butyl ether, tetrahydrofuran or dioxane, alone or as a mixture.
• the tertiary amine is preferably selected from triethylamine, pyridine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] undec-7-ene or N-methylmorpholine, taken alone or mixed.
• the composition according to the invention when the composition according to the invention comprises the Lewis base, it can form with the ligand of tautomeric forms 1 a), 1 b) and / or 1 c) an adduct 1 d) corresponding to the formula corresponding to 1 a ) .Z, 1b) .Z and / or 1c) .Z.
• the composition according to the invention comprises the Lewis Z base
• the composition may comprise in addition tautomeric forms 1 a), 1 b) and / or 1 c) at least one adduct 1 d) formed between said tautomeric forms and the Lewis Z base and having the formula 1 a) .Z, 1 b). Z and / or 1 c). Z.
• these adducts can coexist with the tautomeric forms 1 a), 1 b) and / or 1 c).
• the composition according to the invention comprises the mixture of a phosphine halide YP (AR 1a ) (A'R 1 b ) and a sulfonamide compound of formula R 2 S0 2 NH 2
• adduct 1 d) is likely to be formed in the presence of the Lewis base Z.
• the adduct 1 d) is the adduct formed with the tertiary amine of formula 1 a) .N (R 4) 3, R 4 match to the specifications according to the invention. More preferably, the adduct 1 d) is of formula 1 a) .NEt 3 .
• 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.
• the 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, orthoxylene, mesitylene, ethylbenzene, dichloromethane, chlorobenzene, methanol, ethanol, pure or in admixture, and ionic liquids.
• the solvent is an ionic liquid, it is advantageously chosen from the ionic liquids described in US Pat. Nos. 6,951, 831 B2 and FR 2,895,406 B1.
• the oxidation state (+ II) nickel precursor is chosen from nickel (II) chloride, nickel (II) chloride (dimethoxyethane), nickel bromide (II), nickel (II) bromide (dimethoxyethane), nickel (II) fluoride, nickel (II) iodide, nickel (II) sulfate, nickel (II) carbonate, nickel dimethylglyoxime (II) ), nickel (II) hydroxide, nickel (II) hydroxyacetate, nickel (II) oxalate, carboxylates of nickel (II) such as, for example, nickel (II) 2-ethylhexanoate, nickel (II) acetate, nickel (II) trifluoroacetate, nickel (II) triflate, nickel acetylacetonate (II) ), nickel hexafluoroacetylacetonate (II), nickel (II) phenates
• the molar ratio between the ligand of formula 1 a), 1 b), 1 c) and / or 1 d) and the nickel precursor is preferably between 0.05 and 10, preferably between 0. , 5 and 3.
• the molar ratio between the activator and the nickel precursor is preferably between 1 and 500, preferably between 1 and 100, preferably from 1 to 30, preferably between 2 and 15.
• ligands that may be suitable for the preparation of the compositions according to the invention are shown below.
• the ligands are represented in their limiting forms 1 a) and 1 b).
• composition according to the invention can be obtained by a mixture between the phosphine halide YP (AR 1a ) (A'R 1 b ) and the sulphonamide compound of formula R 2 S0 2 NH 2 , in the presence of the Lewis base.
• Z the oxidation state nickel precursor (+ II), the activator of formula [R3-mAIX m ] n -
• composition according to the invention can also be obtained by a mixture of the ligand corresponding to the tautomeric forms of formula 1 a), 1 b) and / or 1 c), the oxidation state (+11) nickel precursor and the the activator of formula [R 3 m AIX m ] n .
• compositions may further comprise at least adduct 1 d).
• compositions according to the invention can be used as a catalyst in a chemical transformation reaction, such as the reaction of hydrogenation, hydroformylation, cross-coupling or oligomerization of olefins.
• these compositions are used in a process for oligomerization of an olefin feed advantageously having 2 to 10 carbon atoms.
• the oligomerization process is a process for dimerizing ethylene to butene-1.
• 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.
• 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.
• reaction solvent is an ionic liquid
• it is advantageously chosen from the ionic liquids described in US Pat. Nos. 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 C p H 2p with 4 ⁇ p ⁇ 80, preferably with 4 ⁇ p ⁇ 50, most preferably with 4 ⁇ p ⁇ 26 and more preferably with 4 ⁇ p ⁇ 14.
• the olefins used in the oligomerization process are olefins having from 2 to 10 carbon atoms.
• said olefins are chosen from ethylene, propylene, n-butenes and n-pentenes, alone or as a mixture, pure or diluted.
• the olefin used in the oligomerization process is ethylene.
• 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.
• alkane s
• Said feed olefins can come from non-fossil resources such as biomass.
• the olefins used in the oligomerization process according to the invention can be produced from alcohols, and in particular by dehydration of alcohols.
• the concentration of nickel in the reactor is advantageously between 1 .10 "8 and 1 mol / L, and preferably between 1 .10" 6 and 1 .10 "2 mol / L.
• 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.
• the heat generated by the reaction can be removed by any means known to those skilled in the art.
• the oligomerization process according to the invention comprises a) a step of condensation of a phosphine halide YP (AR 1a ) (A'R 1 b ) and a sulfonamide compound of formula R 2 S0 2 NH 2 , optionally in the presence of the Lewis base according to the invention, b) optionally a separation step of the reaction product resulting from step a) to obtain the ligand corresponding to the tautomeric forms 1 a), 1 b and / or 1 c), and / or optionally the adduct 1 d), c) a step of bringing the charge into contact with the reaction product resulting from step a) or the ligand corresponding to the tautomeric forms 1 a ), 1 b) and / or 1 c), and / or optionally the adduct 1 d) from the separation step b), the nickel precursor and the activator.
• a phosphine halide YP AR 1a
• separation step is meant any step of purification of the reaction product of step a) for isolating impurities the ligand of formula 1 a), 1 b), 1 c) or 1 d) or their mixture.
• the separation step may be, for example, a filtration step.
• Step a) is preferably carried out at a temperature between -80 and 120 ° C, advantageously in an organic solvent.
• the Lewis base may be used in excess of the reactants of the condensation reaction of step a), for example between 1, 1 and 3 equivalents for one equivalent of reagent.
• the phosphine halide YP (AR 1a ) (A'R 1b ) and the sulfonamide compound of the formula R 2 SO 2 NH 2 are advantageously reacted in stoichiometric amounts.
• the phosphine halide YP (AR 1a ) (A'R 1b ) may be used relative to the sulfonamide compound of formula R 2 SO 2 NH 2 in a molar ratio of between 0.2 and 1.
• the oligomerization process can be carried out in a closed system, semi-open system or continuously with one or more reaction stages. Vigorous agitation is advantageously used to ensure good contact between the reagent (s) and the cata
• the oligomerization process is carried out by introducing a mixture of the nickel precursor and the ligand and / or optionally the adduct 1 d) resulting from the separation step b), or from a mixture of the nickel precursor and the reaction product resulting from step a) on the one hand, and the introduction of the activator on the other hand, into a reactor in the presence of the feed provided with the usual stirring devices , heating and cooling.
• the oligomerization process can be carried out batchwise.
• a selected volume of the solution comprising the composition according to the invention is introduced into a reactor equipped with the usual stirring, heating and cooling devices.
• the oligomerization process can also be carried out continuously.
• the solutions comprising the elements of the composition according to the invention are 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 catalytic 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 series reaction stages, the olefinic feedstock and / or the pre-conditioned catalytic composition being introduced continuously, either in the first floor, either in the first and any other floor.
• 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.
• 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.
• Trifluoromethanesulfonamide (2.4 g, 16 mmol, 1 eq.) And triethylamine Z (4.2 g, 40 mmol, 2.6 eq., 6 mL) are solubilized in 30 mL of tetrahydrofuran (THF). .
• di (o-tolyl) chlorophosphine is solubilized with 10 mL of THF.
• the chlorophosphine solution (4 g, 16 mmol, 1 eq) in 10 mL of THF is added dropwise to the sulfonamide solution to produce a white precipitate.
• the majority product SP2 corresponding to the tautomeric form 1 b) is characterized by 31 P ⁇ 1 H ⁇ NMR spectroscopy (C 6 D 6 ), 31 P NMR (C 6 D 6 ), 1 H NMR (C 6 D 6 ) and 13 C NMR (C 6 D 6 ).
• nickel precursor (II), ligand and activator nickel precursor (II), ligand and activator
• the test is stopped after 50 g of ethylene introduced or after the reaction time indicated in Table 1.
• the reactor is then depressurized and the gas phase quantified and qualified by gas chromatography.
• the liquid phase is weighed, neutralized and analyzed by gas chromatography.
• Ni 10 n ⁇ , 40 ° C, 30 bar ethylene, toluene (100 mL).
• % wt weight percentage relative to the products formed.
• b 1 -C 4 (%) butene-1 percentage in the C4 cut.
• the ratios Ligand / Ni and Ai / Ni are expressed in molar ratio
• the catalytic composition according to the invention (entry 1 to 7) has a good activity and a good selectivity for the dimerization of ethylene to butene-1 compared to the composition of the entry 8 not according to the invention comprising a ligand L.
• Sulfonamide S (amount see Table 2) and triethylamine are solubilized in 10 mL of anhydrous toluene.
• chlorophosphine P (2 mmol) is solubilized with 10 mL of anhydrous toluene, and then is added dropwise to the sulfonamide solution to produce a white precipitate.
• the mixture is filtered. It may contain a mixture of different ligands and / or adducts corresponding to formulas 1 a), 1 b), 1 c) and / or 1 d).
• a fraction of 20 ⁇ of phosphorus equivalent is then removed and added to a solution containing 10 ⁇ nickel catalytic precursor Ni (2-EH) 2 whose volume is adjusted to obtain a total volume of 5 mL.
• Toluene (94 mL) is introduced into the reactor which is heated to 40 ° C.
• the reaction medium is stirred for 15 minutes under approximately 2 bar of ethylene.
• the reactor is then degassed. 1 ml of solution containing the activator is then added.
• the reactor is rapidly pressurized (30 bar of ethylene).
• the reactor is then heated to 45 ° C.
• the test is stopped after 50 g of ethylene introduced or after the reaction time indicated in the table.
• the reactor is then depressurized and the gas phase quantified and qualified by gas chromatography.
• the liquid phase is weighed, neutralized and analyzed by gas chromatography.
• 2-EH 2-ethylhexanoate.
• a % wt weight percentage relative to the products formed.
• b 1 -C 4 (%) butene-1 percentage in the C4 cut.
• the ratio S / P / Ni is expressed in molar ratio
• the ratio NEt 3 / P is expressed in molar ratio.
• the catalytic composition according to the invention (entry 1 to 5) obtained from the mixture sulfonamide S and chlorophosphine P according to the invention has a good activity and a good selectivity for the dimerization of ethylene to butene-1.

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• 2015
  • 2015-10-30 FR FR1560432A patent/FR3042989A1/fr not_active Withdrawn
• 2016
  • 2016-10-20 CA CA3002161A patent/CA3002161A1/fr not_active Abandoned
  • 2016-10-20 WO PCT/EP2016/075288 patent/WO2017072026A1/fr active Application Filing
  • 2016-10-20 CN CN201680063092.5A patent/CN108472640A/zh active Pending
  • 2016-10-20 EP EP16785130.2A patent/EP3368217A1/de not_active Withdrawn
  • 2016-10-20 US US15/772,374 patent/US20180318819A1/en not_active Abandoned
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