Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
  • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
  • B01J31/0255—Phosphorus containing compounds
  • B01J31/0264—Phosphorus acid amides
  • B01J31/0265—Phosphazenes, oligomers thereof or the corresponding phosphazenium salts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
  • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—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
  • B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
  • B01J31/188—Amide derivatives thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—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
  • B01J31/189—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 containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
  • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
  • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
  • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
  • C07C2/08—Catalytic processes
  • C07C2/26—Catalytic processes with hydrides or organic compounds
  • C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/20—Olefin oligomerisation or telomerisation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/84—Metals of the iron group
  • B01J2531/847—Nickel
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • C07C2531/24—Phosphines

Definitions

• the present invention relates to a new catalyst composition based on nickel.
• the invention also relates to the use of said catalyst composition as a catalyst for chemical transformation reactions.
• nickel-based catalytic compositions for their application in various fields of chemistry, especially in the field of catalytic transformations such as hydroformylation, hydrogenation, cross-coupling, oligomerization of olefins. .
• 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. Inorg. Chem, 2009, 3016-3024, Organometallics, 2001, 20, 4769-4771).
• patent application WO01 / 10876 discloses nickel diphosphinamine complexes, the symmetrical ligands described being substituted, on phosphorus, solely by aromatic groups and used for the polymerization of ethylene.
• the Applicant has found a novel nickel-based catalytic composition prepared from diphosphinamine or iminobisphosphine ligands unsymmetrical, in which one of the phosphorus atoms carries at least one nonaromatic group and the other phosphorus atom carries 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.
• a first subject of the invention concerns a new catalytic composition comprising:
• R 3 is chosen from hydrogen, halogens, aliphatic hydrocarbon groups, cyclic or not, whether or not containing heteroelements, aromatic groups containing or not heteroelements, substituted or unsubstituted,
• the groups R 1 and R ' 1 are chosen from non-aromatic groups and not containing silicon.
• R 1 and R ' 1 are identical.
• the groups R 1 and R ' 1 are chosen from methyl, ethyl, isopropyl, n-butyl, / sobutyl, tert-butyl, pentyl and cyclohexyl groups, which may or may not be substituted.
• the groups R 2 and R ' 2 are chosen from phenyl, otolyl, 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.
• R 2 and R ' 2 are identical.
• R 3 is chosen from hydrogen, alkoxy, aryloxy, sulphide, sulphonamino, sulphonamido, nitro, carbonyl, amino or amido groups, whether or not comprising aliphatic, cyclic or aromatic groups, whether or not containing substituted or unsubstituted heteroelements. .
• the nickel precursor A can be chosen from nickel (II) chloride, nickel (II) chloride (dimethoxyethane), nickel (II) bromide, nickel (II) (dimethoxyethane) bromide, nickel (II), nickel iodide (II), nickel (II) sulfate, nickel (II) carbonate, nickel (II) dimethylglyoxime, nickel (II) hydroxide, hydroxyacetate nickel (II), nickel oxalate (II), nickel (II) carboxylates such as, for example, 2-ethylhexanoate, nickel (II) phenates, nickel (II) acetate, trifluoroacetate nickel (II), nickel triflate (II), nickel (II) acetylacetonate, nickel (II) hexafluoroacetylacetonate, nickel (O) bis (cycloocta-1,5-diene), nickel (O) bis
• 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 CI-P (R1) (R'1 and 1 equivalent of chlorophosphine CI-P (R2) (R'2) with a primary or aromatic amine R3-NH2 in the presence of triethylamine.
• the iminobisphosphine ligands B2 of formula (R3) N P (R1) (R'1) -P (R2) (R'2) can be prepared and isolated by reacting a primary or aromatic amine R3-NH2 and 1 equivalent of chlorophosphine CI-P (R1) (R'1) and 1 equivalent of chlorophosphine CI-P (R2) (R'2) introduced successively in the presence of triethylamine.
• the iminobisphosphine ligands B'2 of formula (R3) N P (R2) (R'2) -P (R1) (R'1) can be prepared and isolated by reacting a primary or aromatic amine R3-NH2 and 1 equivalent of chlorophosphine CI-P (R2) (R'2) and 1 equivalent of chlorophosphine CI-P (R1) (R'1) introduced successively in the presence of triethylamine.
• the catalyst composition according to the invention can be used in a chemical transformation reaction, such as the hydrogenation reaction, hydroformylation, cross-coupling or oligomerization of olefins.
• 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.
• the tris (hydrocarbyl) aluminum, the chlorinated or brominated hydrocarbylaluminum compounds and the aluminum halides preferably correspond to the general formula Al x R y W z in which R represents a monovalent hydrocarbon radical containing, for example, up to 12 atoms of carbon 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 0 to 3.
• Examples of such compounds include ethyl aluminum sesquichloride (Et 3 Al 2 Cl 3 ), methylaluminum dichloride (MeAlCl 2 ), ethylaluminum dichloride (EtAlCl 2 ), isobutylaluminum dichloride (iBuAICI 2 ), diethylaluminum chloride (Et 2 AlCl), trimethylaluminum, tributylaluminum, tri-n-octylaluminum and triethylaluminum (AIEta).
• Et 3 Al 2 Cl 3 ethyl aluminum sesquichloride
• MeAlCl 2 methylaluminum dichloride
• EtAlCl 2 ethylaluminum dichloride
• iBuAICI 2 isobutylaluminum dichloride
• Et 2 AlCl diethylaluminum chloride
• AIEta trimethylaluminum, tributylalum
• said activating agent is chosen from aluminoxanes
• said activating agent is advantageously chosen from methylaluminoxane (MAO), ethylaluminoxane and modified methylaluminoxanes (MMAO).
• MAO methylaluminoxane
• MMAO modified methylaluminoxanes
• said activating agent C is chosen from dichloroethylaluminum (EtAlCl 2 ) and methylaluminoxane (MAO).
• 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, ⁇ , ⁇ -diethylanilinium tetrakis (3,5-bis (trifluor
• 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.
• 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.
• 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 monomer unit into a compound or mixture of compounds of the general formula CpH2p 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 or dimerization 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.
• 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.
• the olefin used in the oligomerization or dimerization process is ethylene or propylene.
• Said olefins can come from non-fossil resources such as biomass.
• 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 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 or B'2 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 nickel precursor is advantageously between 1/1 and 10,000/1, preferably between 1/1 and 1000/1 for the aluminoxanes and preferably between 1/1 and 100/1. for other aluminum derivatives and other Lewis acids.
• 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 between -40 and +250 ° C, preferably between -20 ° C and 150 ⁇ 0.
• the structures of the four ligands are shown below.
• N-diphenylphosphino-4-butylbenzenesulfonamide 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%).
• 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%).
• 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%).
• composition 9 is a reference composition comprising tricyclohexylphosphine and NiCl 2 .
• 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.
• the reactor is cooled to room temperature and depressurized with stirring.
• the liquid phase is neutralized with aqueous H 2 SO 4 and analyzed by GC.
• compositions 5 and 6 activated by MAO (300 eq.) are considered inactive, ethylene consumption is negligible.
• GC analyzes confirm that the products formed are mainly butenes and hexenes. The results are shown in Table 1.
• Table 1 Oxygenization of Ethylene Catalysed by 5, 6, 7, T and 8 '. at
• 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).
• EADC ethylaluminum dichloride
• MAO methylaluminoxane
• 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 activator EADC ethylaluminum dichloride, 0.075 M in toluene, 15 eq, 2 ml
• the catalyst 0.1 mmol in 5 ml of chlorobenzene. 12 g of propylene are then introduced.
• 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.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Inorganic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Catalysts (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Applications Claiming Priority (3)

Publications (1)

Family

ID=51300779

Family Applications (1)

Country Status (5)

Families Citing this family (2)

Family Cites Families (6)

• 2014
  • 2014-06-26 JP JP2016522707A patent/JP6379190B2/ja not_active Expired - Fee Related
  • 2014-06-26 CA CA2915734A patent/CA2915734A1/fr not_active Abandoned
  • 2014-06-26 WO PCT/FR2014/051626 patent/WO2014207394A1/fr active Application Filing
  • 2014-06-26 EP EP14749889.3A patent/EP3013474A1/fr not_active Withdrawn
  • 2014-06-26 US US14/901,495 patent/US10421066B2/en not_active Expired - Fee Related

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events