FR3087773A1 - NEW ALUMINUM-BASED COMPOUND - Google Patents

Abstract

The object of the present invention relates to an aluminum-based compound corresponding to the general formulas (I), (II) and / or (III): and their use in a catalytic composition in the presence of nickel of degree of oxidation (+ II).

Description

Description Title of the invention: New aluminum-based compound Technical field

The present invention relates to a new compound based on aluminum and its preparation process.

Another subject of the invention also relates to a catalytic composition comprising a compound containing an aluminum base and nickel with a degree of oxidation (+11), and its use in catalytic reactions, in particular in oligomerization reactions. an olefinic feed and more particularly ethylene.

Prior art

In the field of catalytic processes such as metathesis, hydrogenation, cross coupling, oligomerization of olefins, it is common to use catalytic systems using a metal such as Ni, Pd, Fe, Cr, Ti, W, Mo in the presence of a ligand and an activating agent.

[0003] For example, application WO2017072026 describes a composition comprising a nickel (11), an activating agent with an aluminum base and a ligand of the sulfonamidophosphine type.

The use of a composition comprising 3 compounds requires precise control during the introduction of said compounds and may be accompanied by a degradation of the catalytic performance of the process.

Another drawback which results from this complexity of implementation is the difficulty of reproducibility of the performances of the catalytic process.

[0004] There is therefore still a need to develop new compounds for their use in catalytic compositions in order to overcome these drawbacks.

Surprisingly, the Applicant has discovered a new stable compound with an aluminum base which can advantageously be isolated and stored.

Advantageously, the use of said compound containing aluminum in a process for oligomerization of ethylene, in particular in a catalytic composition comprising nickel (+11) makes it possible to obtain very good yield of butene with excellent selectivity in but-l-ene.

Another advantage of the aluminum-based compound according to the invention is to make it possible to limit the number and the quantity of reagents necessary to obtain a yield and a selectivity which are equivalent in particular in oligomerization of ethylene to what is obtained with the compositions of the prior art Thus, the present invention makes it possible to simplify the use of said compound in a catalytic composition while retaining good performance and in particular good yields.

Another advantage of the aluminum-based compound according to the invention is, without being bound by any theory, of simultaneously fulfilling the functions of ligand and activator when used in catalytic compositions.

Summary of the invention

The object of the present invention therefore relates to a new aluminum-based compound corresponding to the general formulas (I), (II) and / or (III): [Chem.1-1 A1R1 A2R2 \ Al \ O R4 A1R1 -A2R2 (M)

In which: A 'and A2, identical or different, are independently chosen from S, O, NR6 or a covalent bond between the phosphorus atom and a carbon atom, the groups R' and122, identical or different, linked or not to each other, are independently selected from a C1-Co alkyl, C1-C20 heteroalkyl, C5-C30 aryl and C4-C30 heteroaryl group, 123 and R4, identical or different, linked or not to each other, are independently selected from an alkyl group in C1-C20, heteroalkyl in Cre, o, aryl in C, -CO and heteroaryl in C4-C30, the group R, is independently selected from an alkyl group in C1-C20, heteroalkyl in C1 -C20, C5-C30 aryl and C.4-C30 heteroaryl, the R6 group is independently selected from hydrogen, C1-C20 alkyl, C1-C20 heteroalkyl, C5-C30 aryl and Ca heteroaryl -Cm.

Another object of the invention relates to the process for preparing the compound containing aluminum of general formula (1), (II) or (III).

Another subject of the invention relates to a catalytic composition comprising, preferably consisting of: - a compound containing an aluminum base of general formula (I), (II) or (III) as defined previously, and - a nickel compound with an oxidation state (+11).

An advantage of the compound of formula (I), (II) or (III) according to the invention is to be stable and therefore to be able to be isolated and stored. 3

Another advantage of the compound containing an aluminum base according to the invention is to limit the number and the quantity of reagents necessary to obtain a yield and a selectivity which are equivalent in particular in oligomerization of ethylene to what is obtained with the compositions of the prior art.

Thus, the present invention makes it possible to simplify the use of said compound in said catalytic composition while retaining good performance and in particular good yields.

[0015] Definitions and Abbreviations

It is specified that, throughout this description, the expressions "included between ... and ..." "including between ... and ..." must be understood as including the limits cited.

[0017] The term “oligomerization” means any transformation of an olefinic monomer unit into a compound or a mixture of unsaturated compounds of general formula C '1-1,' where n is between 4 and 80.

For example, the dimerization of ethylene is defined as an oligomerization reaction leading to the selective formation of butenes, preferably of but-1-ene.

By heteroatom is meant an atom other than carbon and hydrogen.

A heteroatom can be chosen from oxygen, sulfur, nitrogen, phosphorus, silicon and halogens such as fluorine, chlorine, bromine or iodine.

The term “hydrocarbon” is understood to mean an organic compound consisting exclusively of carbon (C) and hydrogen (H) atoms of the crude formula C, '1-11 ,, with m and p natural integers.

The term “alkyl group” is understood to mean a hydrocarbon chain comprising between 1 and 20 carbon atoms, denoted C1-C20 alkyl, saturated or not, linear or branched, non-cyclic, cyclic or polycyclic, substituted or not.

For example, by C1-C6 alkyl is meant an alkyl chosen from methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, sec-butyl, pentyl, iso-pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.

The term “alkoxy group” is understood to mean a monovalent radical consisting of an alkyl group bonded to an oxygen atom such as the groups CI-L0-, C115.0-, C'1170-.

The term “aryl group” is understood to mean an aromatic group, mono or polycyclic, fused or not, substituted or not, comprising between 5 and 30 carbon atoms, denoted C5.-C′0 aryl.

The term “heteroalkyl group” means an alkyl group comprising between 1 and 20 carbon atoms and substituted by at least one heteroatom, denoted C 1-Cno heteroalkyl.

Preferably the heteroatom is chosen from a fluorine, chlorine, bromine, iodine atom, nitrogen, oxygen, phosphorus, silicon and sulfur.

The term “heteroaryl group” means an aromatic group comprising between 4 and 30 carbon atoms and at least within at least one aromatic nucleus, a heteroatom chosen from oxygen (0), sulfur (S ), nitrogen (N) and silicon (Si), Iluor (F), chlorine (Cl), bromine (Br), iodine (1), phosphorus (P) noted C4- heteroaryl C30.

Detailed description of the invention

In the sense of the present invention, the various embodiments presented can be used alone or in combination with each other, without limitation of combinations.

Aluminum-based compound

The present invention therefore relates to compounds based on aluminum.

Without being bound by any theory, said compounds advantageously make it possible to simultaneously fulfill the functions of ligand and of activator when they are used in a catalytic composition.

Lcs compounds according to the invention have the advantage of simplifying the implementation of a catalytic process such as the oligomerization of olefin using a composition containing said compounds based

Another advantage of the compounds according to the invention is to limit the reactants in catalytic processes while maintaining good catalytic performance.

According to the invention, the compounds containing aluminum correspond to the general formulas (1), (II) and / or (III): [Chem.2] Al A / RI 1AiR -2 N., A2R2 P - MP --- 1 \\ N ËS to ---- ', Pd "' R5 'R5- ,,, IO R4 (III)

In which: A 'and A2, identical or different, are independently chosen from S, O, NR6 or a covalent bond between the phosphorus atom and a carbon atom, the groups R1 and R =, identical or different , linked or not to each other, are independently chosen from a C 1 -C 20 alkyl, C 1 -C 20 heteroalkyl, G-Cm aryl and C4-Coe, R3 and R4 heteroaryl group, which are identical or different, whether or not linked to each other , are independently selected, QR1 1 2 2 .--- AR from a C1-C20 alkyl, C1-Coo heteroalkyl, C5-C3o aryl and C4-C30 heteroaryl group, the R5 group is independently selected from a group C 1 -C 6 alkyl, C 1 -C, D heteroalkyl, C5-C30 aryl and C4-C3u heteroaryl, the R6 group is independently selected from hydrogen, a C1-C2D alkyl group, C1-C20 heteroalkyl, C5-Cm aryl and C4-C30 heteroaryl.

Preferably, the Al and A2 groups, which are identical or different, are chosen from O and a covalent bond between the phosphorus atom and a carbon atony, and preferably are a covalent bond between the phosphorus atony and a carhone atom.

Preferably, the R6 group is chosen from alkyl and heteroalkyl groups comprising between 1 and 15 carbon atoms, preferably between 1 and 10 carbon atonies and preferably between 1 and 6 carbon atonies.

When at least one of the groups 12,, R2 and R5 is chosen from alkyl and heteroalkyl groups, said groups preferably comprise between 1 and 15 carbon atoms, more preferably between 1 and 10 carhone and carbon atoms. preferably between 1 and 6 carbon atoms.

Preferably, the R ′ and R4 groups are chosen independently from alkyl and heteroalkyl groups, which are identical or different, comprising between 1 and 15 carbon atoms, more preferably between 1 and 10 carhone atoms and preferably between 1 and 6 carbon atoms.

Very preferably, the W and R4 groups are independently chosen from methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, sec-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cyclooctyl.

When at least one of the groups R ', R2, and W is chosen from aryls, said group comprises between 5 and 20 carbon atoms, preferably between 5 and 15 carbon atoms and preferably between 5 and 10 carbon atoms.

When at least one of the R ', R2 and West groups chosen from heteroaryls, said group comprises between 4 and 20 carbon atoms, preferably between 4 and 15 carbon atoms and preferably between 4 and 10 carbon atoms. carbon.

Preferably, at least one of the groups R ', R2 and W is chosen independently from methyl, trifluoromethyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, adamantyl, norbornyl, phenyl, benzyl, otolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-n-butylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-isopropoxyphenyl, 4-methoxy-3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 4-chlorophenyl, 4-bromophenyl, 3,5-di (tritluoromethyl) phenyl, benzyl, naphthyl, bisnaphthyl, 6 pyridylc, bisphenylc, furanylc, thiophenylc.

Preferably, the R5 group is chosen methyl, trifluoromethyl, ethyl, propyl, isopropyl, cyclopropyl, n-hutyl, isobutylc, / en-butyl, pentyl, hexyl, heptyl, octylc, cyclopentyle, cyclohexylc, cyclooctylc, cyclododécyle, adamantylc, norbornylc, phenyl, benzyl, o-tolylc, m-tolylc, p-tolylc, mesityl, 3,5-dimethylphenyl, 4-n-butylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-isopropoxyphenyl, 4-rnethoxy-3,5-dimethylphenyl, 3,5-ditert-buty1-4-rnethoxyphenyl, 4-chlorophenyl, 4-bromophenyl, 3,5-di (trifluoromethyl) phenyl, benzyl, naphthylc, bisnaphthylc, pyridylc, bisphenylc, furanylc, thiophenylc.

Process for preparing the compound with an aluminum base

Another object of the invention relates to the process for preparing the compound containing an aluminum base, as described above.

In particular, the process for preparing said aluminum-containing compounds of general formula (1), (II) or (111) comprises, preferably consists of,

A step of bringing into contact - a sulfonamidophosphine compound of general formula (IVa, IVb, or IVc) [Chem.3] IVa IVb - and an aluminum-based compound of general formula A1R3R4R7, 100451 in which the groups A ′, N2, R ′, R2, R3, R4 and R5 are as defined above, the group R7 is chosen from a C 1 -C 0 alkyl group, preferably comprising between 1 and 15 atoms of carbon, more preferably between 1 and 10 carbon atoms and more preferably between 1 and 6 carbon atoms.

Very preferably, the R7 group is chosen from methyl, ethyl, propyl, iso-propyl, n-hutyl, iso-hutyl, tert-hutyl, sec-butyl, pentyl, iso-pentyl, hexyl, heptyl, octyl groups. , cyclopentylc, cyclohexyl, cyclooctylc,

Of a step of recovering the compound containing aluminum of general formula (1), (II) or (III).

It is understood that the sulfonamidophosphine compounds of general formula (IVa, IVb, or IVc) used for the preparation of the compounds with an aluminum base according to the invention can be, in an equivalent manner, in any one of the forms tautomers IVa, IVb, and / or IVc.

In particular, the contacting step can be carried out in the presence of a solvent chosen from ethers, halogenated solvents and hydrocarbons, saturated or unsaturated, cyclic or not, aromatic or not, comprising between 1 and 20 carhone atoms, preferably between 4 and 15 carbon atoms, preferentially between 4 and 12 carbon atoms and even more preferably between 4 and 8 carhone atoms.

Preferably, the solvent is chosen from pentanc, hexane, cyclohexane, rne-thylcyclohexanc, heptane, cycloocta-1,5-diene, benzene, toluene, ortho-xylene , mesitylene, ethyllienzene, diethyl ether, tetrahydrofuran, 1,4-dioxane, dichloromethane, dichloroethanc, tetrachloroethanc, r hexachloroethanc, chlorobenzene, dichlorobenzene, pure or as a mixture.

Preferably, step a) of bringing into contact is carried out under an inert atmosphere, preferably under a nitrogen atmosphere or under an argon atmosphere, at a temperature between -20 and 100 ° C, preferably between -10 and 80 ° C, preferably between 0 and 60 ° C, and more preferably between 15 and 50 ° C.

Step h) of recovering the aluminum-based compound can be carried out by any means known to those skilled in the art.

Preferably the recovery step is a filtration step, optionally rinsing and / or a drying step, for example by vacuum evaporation of the solvent.

Advantageously, step h) is carried out under an inert atmosphere, preferably under a nitrogen atmosphere or under an argon atmosphere.

Preferably, during step a) of bringing into contact the molar ratio between the aluminum-based compound of general formula A112124127 and the sulfonamidophosphine compound of formula (IVa, IVb, or IVc) is between 0, 8 and 2.0, preferably between 0.9 and 1.5.

Preferably, the mixture of the sulfonamidophosphine compound of formula (IVa, IVb, or IVc) and of the aluminum-based compound is stoichiometric.

[0054] Catalytic composition

Another subject of the invention relates to a catalytic composition comprising, preferably consisting of: - an aluminum-based compound of general formula (I), (II) or (III) as defined previously, and - a nickel compound of oxidation degree (+ II).

An advantage of the present invention is to limit the number and the quantity of reagents necessary to obtain a yield and a selectivity which are equivalent in particular in oligomerization of ethylene to what is obtained with the usual catalytic compositions.

Thus, the present invention makes it possible to simplify the use of said compound 8 in said catalytic composition while retaining good performance and in particular good yields.

In addition, the implementation of said catalytic composition according to the invention makes it possible to obtain very good yield of butenes with excellent selectivity of but1-ene.

Advantageously, the compositions according to the invention do not comprise any additional compound based on aluminum such as tri methylaluminum, triethylaluminum, tripropylaluminum, tri-n-hutylaluminum, triisohutylaluminum, tri-tort-butylaluminum , trihexylaluminum, trioctylaluminum, diethylethoxyaluminum, di methylethoxyaluminum, methylaluminoxanc, modified or not.

Nickel (II)

The catalytic composition according to the invention comprises Ni (II), preferably chosen from nickelai chloride), nickel (Ti) chloride (dimethoxyethanc), nickelal bromide), nickel bromide (11 ) (dimethoxyethanc), nickelai fluoride), nickelai iodide), nickelai sulfate), nickelai carbonate), nickelai dimethylglyoxime), nickel hydroxide (Ti), nickelai hydroxyacetate ), nickelal oxalate), nickel carboxylates (Ii) such as for example nickel 2-ethylhexanoate), nickelal alcoholates) such as for example Ni (OCH, CH2OCH2CHLOCK0z, chlorinated nickel alcoholates) such as for example Ni (00-11) CI, alcoholates carboxylates of nickelai) such as for example Ni (OEt) (00CCH3), phenates of nickelai), naphthenates of nickel (II), acetate of nickel (II), nickel trifluoroacetate (Ii), nickel triflate (II), nickel stearate), nickel formate (II), nickel acetylacetonate (II), nickel (II) hexafluoroacetylacetonate, ir-allylnickel (II) chloride, ir-allylnickel (II) bromide, methallylnickel (II) chloride dimer, ri3-allylnickel (II) hexafluorophosphate, i3-methallylnickel (II) hexafluorophosphate, nickel (II) 1,5-cyclooctadienyl, Ni (cyclopentadienyl) 2, (cyclopentadienyl) NiC1, NiC12 (sulfolane), NiC12 (P0Bu3) 2, NiC12 ( P13113) 2, NiC12 (PP1-02, NiC12 (PCy3) 2 Ni (SCN) 2 (P13102, Ni (SCN) 2 (PP1-02, NiC12 (TMEDA) (TMEDA = N, N, N ', N'-tetramethylethylenediamine), NiC12 (pyridine) 2, nickel (II) xanthates and nickelai dicarbarnates) in their hydrated form or not, taken alone or as a mixture.

Preferably, the composition according to the invention has a molar ratio between the aluminum-based compound (I), (II) or (HI) and the nickel compound of oxidation degree (+ II), noted AllNi, between 0.1 and 50.0, preferably between 0.2 and 30.0, preferably between 0.3 and 15.0, preferably between 0.5 and 10.0, preferably between 0.8 and 6.0 and very preferably between 0.9 and 5.5.

[0063] Solvent 9

The catalytic composition according to the invention can also comprise a solvent or a mixture of solvents.

Advantageously, the catalytic composition consists of an aluminum base compound according to the invention, a Ni (11) compound and a solvent or a mixture of solvents.

Preferably, each constituent of the catalytic composition can be used in a solvent or a mixture of solvents, which are identical or different.

The solvent (s) are advantageously chosen from ethers, alcohols, halogenated solvents and hydrocarbons, saturated or unsaturated, cyclic or not, aromatic or not, comprising between 1 and 20 carbon atoms, preferably between 4 and 15 carbon atoms, preferably between 4 and 12 carbon atoms and even more preferably between 4 and 8 carbon atoms.

Preferably, the solvent is chosen from pentanc, hexane, cyclohexanc, rne-thylcyclohexanc, heptane, butane or isobutanc, cycloocta-1,5-diene, benzene, toluene, ortho-xylene, rnesitylene, ethylbenzene, diethyl ether, tetrahydrofuranc, 1,4-dioxane, dichloromethane, dichloroethanc, tetrachloroethane, r hexachloroethanc, chlorobenzene, dichlorobenzene and methanol ethanol, pure or as a mixture.

Preferably, the solvent can be advantageously chosen from the products of the catalytic reaction, more preferably, the catalytic reaction is an oligomerization reaction.

Olefin oligomerization process

Another subject of the invention relates to an oligomerization process using the catalytic composition according to the invention, said process comprising bringing said catalytic composition into contact with an olefinic charge chosen from a compound or mixture of compounds. unsaturated of general formula CnEL, 'in which n is between 4 and 80, preferably between 4 and 50, preferably between 4 and 26, and preferably between 4 and 14, and more preferably between 4 and 8.

Preferably, the process using the composition according to the invention is a process for dimerizing ethylene to but-1-ene.

The oligomerization process comprises bringing said catalyst composition according to the invention into contact with an olefinic feedstock.

The olefins used in the oligomerization process are olefins comprising between 2 and 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) or any other petroleum cut, such as they are found in “cuts” resulting from petroleum refining processes or from petrochemicals, like catalytic cracking or steam cracking.

100741 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 alcohols.

Preferably, the olefin used in the oligomerization process is ethylene.

In the implementation of the catalytic composition in an oligomerization process, the nickel (II) concentration in the oligomerization process is between 1.0.10-12 and 1.0 mol / L, preferably between 1.0.10-9 and 0.4 mol / L, more preferably between 1.0.10-8 and 0.1 mol / L and more preferably between 1.0.10-7 and 1.0.10-2 mol / L.

The oligomerization process can advantageously be carried out in the presence of a solvent as described above.

The oligomerization process advantageously operates at a total pressure of between 0.1 and 20.0 MPa, preferably between 0.1 and 15.0 MPa, and preferably between 0.5 and 8.0 MPa , and at a temperature between -40 and 250 ° C, preferably between -20 ° C and 150 ° C, preferably between 20 ° C and 100 ° C, and preferably between 30 to 80 ° C.

Preferably, the oligomerization process and in particular, the process for dimerization of ethylene to but-1-ene, can be carried out continuously.

In one case, the constituents of the catalytic composition according to the invention are injected into a reactor stirred by conventional mechanical means or by external recirculation, in which the olefin reacts, preferably with temperature control.

The heat generated by the reaction can be removed by any means known to those skilled in the art.

The catalytic composition can be neutralized at the end of the process by any means known to those skilled in the art.

The following examples illustrate the invention without limiting its scope.

Examples

In the examples below, the reagents used are commercial and used without additional purification.

The nickel (1i) used is nickel 2-ethylhexanoatc denoted [Ni (2-EI-1) 2].

Synthesis of the aluminum-based compound according to the invention

The trifluoromethanesulfonamido (bis (o-tolyl) phosphine corresponding to the compound of formula IVa is obtained by evaporation of the triethylamine contained in the adduct trifluoromethanesulfonamido (bis (o-tolyl) phosphine.NEt "synthesized according to the protocol described in the literature: Organoînetallics 2015, 34, 1139-1142.

Said trifluoromethanesulfonamido (bis (o-tolyl) phosphine (0.42 g, 1.16 mmol) is introduced into a Schlenk under an inert atmosphere, then with stirring is added 6.3 mL of a solution of triethylaluminum at a concentration of 0.186mo1 / L in toluene.

Gas evolution is observed and a clear colorless solution is obtained.

The solvent is then evaporated off in vacuo.

A viscous oil is obtained (m = 0.38 g) with a yield of 74%.

The aluminum-based compound thus obtained is characterized by NMR 3.13 NMR (in CA,): 38 ppm.

Said aluminum-based compound corresponds to the following formula: [Chem. 4] 100851 Use of the compound with an aluminum base in a catalytic composition 100861 A 250 ml reactor is dried beforehand under vacuum at 100 ° C. for 2 h then placed under 0.5 MPa of ethylene pressure.

The reactor is then cooled to room temperature. 94 mL toluene are introduced and the reactor is heated to 45 ° C.

Then 5 mL of a solution containing 5 pmol of 1Ni (2-EH),] in toluene are introduced.

The reaction medium is stirred for 15 minutes under approximately 0.2 MPa of ethylene.

The reactor is then degassed. 1 ml of a solution containing the compound containing aluminum (at n = 5 or 10 pmol) in toluene is then added.

100871 The reactor is placed under a pressure of 3.0 MPa and under stirring at a temperature of 45 ° C.

After 40 or 60 minutes of reaction time, the ethylene feed is cut off, stirring stopped and the gas phase discharged.

The liquid phase is collected and neutralized with an aqueous solution of sulfuric acid H2SO4 (10% vol.).

After extraction, the organic phase is dried over magnesium sulfate MgSO4 and analyzed by gas chromatography (CC Agilent 6850 Series II with a PONA column).

Table 1 shows the results obtained during the oligomerization reaction by the use of compositions according to the invention.

12 [Tablesl] Input n ,,, Activity Time Ratio (10 'C4 (% C6 (% C8' (% 1-C4 ((prnol) Al / Ni (minutes) g / (gNi.h)) wt) wt ) wt)%) 1 10 2 60 69 84.6 13.6 1.8 99.0 2 5 1 40 42 88.1 10.7 1.2 99.3

In the table above, the activ'té corresponds to the mass of ethylene transformed into oligomerization products per gram of nickel and per hour.

The term C4 (% by weight) corresponds to the percentage by weight of butenes relative to the products formed.

The term C6 (% by weight) corresponds to the percentage by weight of hexenes relative to the products formed.

The term C8 + (% by weight) corresponds to the percentage by weight of olefins having 8 or more carbon atoms relative to the products formed.

The term 1-C4 (% by weight) corresponds to the percentage of but-1-ene in the C4 cut.

It clearly emerges from the results of Table 1 that the catalytic compositions comprising compounds based on aluminum according to the invention exhibit very good yields of butenes with excellent selectivities for but-1-ene.

It is important to note that the aluminum-based compounds according to the invention make it possible to dispense with the use of additional aluminum-based compound. 13

Claims (4)

CLAIMS [Claim 1] Compound corresponding to the general formulas (1), (II) or (III): [Chem.5] AiR1 [Claim 2] [Claim 3] in which: A 'and A2, identical or different, are chosen independently from S, O. NR6 or a covalent bond between the phosphorus atom and a carbon atom, the groups R ′ and R2, which are identical or different, linked or not to each other, are independently chosen from a C1- alkyl group. C20, C1-C20 heteroalkyl, C5-C30 aryl and C4-Cm heteroaryl, R3 and R4, identical or different, linked or not to each other, are independently chosen from an alkyl group in C1-C20, heteroalkyl in C1- C20, C5-Cm aryl and C4-C31 heteroaryl), the R5 group is independently selected from a C 1 -C20 alkyl group, C 1 -C 20 heteroalkyl, C5-C30 aryl and C4-Cm heteroaryl, the group R6 is independently selected from hydrogen, C1-C20 alkyl, C5-C, 0 aryl heteroalkyl and heteroary the in C4-C30. Compound according to Claim 1, in which the groups A 'and A2, which may be identical or different, are chosen from O and a covalent bond between the phosphorus atom and a carbon atom, and preferably are a covalent bond between the atom of phosphorus and a carbon atom. Compound according to one of the preceding claims in which the groups R3 and R4 are chosen independently from an alkyl or heteroalkyl group, identical or different, comprising between 1 and 15 carbon atoms, more preferably between 1 and 10 carbon atoms and preferably between 1 and 6 atoms of 14 [Claim 4] [Claim 5] [Claim 6] [Claim 7] [Claim 8] carhone. Compound according to one of the preceding claims in which at least one of the groups RI, R2, and R5 is chosen from aryls, said group comprises between 5 and 20 carbon atoms, preferably between 5 and 15 carbon atoms and in such a manner preferred between 5 and 10 atoms of carhone. Compound according to one of the preceding claims in which at least one of the groups RI, R2 and R5 is chosen from heteroaryls, said group comprises between 4 and 20 carhone atoms, preferably between 4 and 15 carbon atoms and preferably between 4 and 10 atoms of carhone. Compound according to one of the preceding claims in which at least one of the groups RI, R2 and R5 is chosen from alkyl and heteroalkyl groups, said groups preferably comprise between 1 and 15 carbon atoms, more preferably between 1 and 10 atoms of carbon and preferably between 1 and 6 atoms of carhone. Compound according to one of the preceding claims in which the R 'and R4 groups are independently chosen from methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, sec-butyl, pentyl, iso-pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cyclooctyl, and at least one of the groups R ', R' and Rs is chosen independently from the groups methyl, trifluoromethyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, adamantyl, norbornyl, phenyl, benzyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-n-butylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl '2-isopropoxyphenyl, 4-methoxy-3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 4-chlorophenyl, 3,5-di (titluoromethyl) phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl, thiophenyl. Process for preparing a compound of general formula (I), (II) or (III) according to one of claims 1 to 7 comprising a step of bringing a sulfonamidophosphine compound of general formula (IVa, IVb, or IVc) 15 [Chcm.6] 1Vb [Claim 9] and an aluminum-based compound of general formula A1WR4R7, in which A 'and A', identical or different, are independently selected from S. O, NR6 or a covalent bond between the phosphorus atom and a carbon atom, the groups R 'and 122, identical or different, linked or not to each other, are independently chosen from an alkyl group in Ci-C20, heteroalkyl in Ci-C , 0, C5-C39 aryl and C4-C30 heteroaryl, R5 and R4, identical or different, linked or not to each other, are independently selected from a C1-C20 alkyl, C1-C20 heteroalkyl, aryl group in C5-C30 and heteroaryl in C4-C30, the group W is independently selected from an alkyl group in C1-C, 0, heteroalkyl in C1-C, 9, aryl e C5-C30 and C4-050 heteroaryl, the R6 group is independently selected from hydrogen, C1-C20 alkyl, C1-C20 heteroalkyl, C5-C39 aryl and C4-C30 heteroaryl. the R7 group is chosen from a C1-C20 alkyl group, preferably comprising between 1 and 15 carbon atoms, more preferably between 1 and 10 carbon atoms and preferably between 1 and 6 carbon atoms, of a step recovery of said compound of general formula (1), (11) or (III). Preparation process according to Claim 8, in which step a) of bringing into contact is carried out in the presence of a solvent chosen from ethers, halogenated solvents and hydrocarbons, saturated or unsaturated, cyclic or not, aromatic or no, comprising between 1 and 20 carbon atoms, preferably between 4 and 15 carbon atoms, preferably between 4 and 12 carbon atoms and even more preferably between 4 and. 8 carbon atoms, under an inert atmosphere, at a temperature between -20 and 100 ° C, preferably between -10 and 80 ° C, preferably between 0 and 60 ° C, and preferably between 15 and 1650 ° vs. [Claim 10] The preparation process according to claims 8 and 9, wherein the molar ratio between the general aluminum base compound AIR3R4R7 and the compound of formula (IVa, IVb or I-Nrc) is between 0.8 and 2.0, preferably between 0.9 and 1.5. [Claim 11] Catalytic composition comprising a compound dc of formula (1), (II) or (III) according to claims 1 to 7 or prepared according to claims 8 to 10, and nickel of oxidation degree (+ II). [Claim 12] A composition according to claim 11 comprising a solvent or mixture of solvents chosen from ethers, alcohols, halogenated solvents and hydrocarbons, saturated or unsaturated, cyclic or not, aromatic or not, comprising between 1 and 20 atoms of carbon, preferably between 4 and 15 carbon atoms, preferably between 4 and 12 carbon atoms and even more preferably between 4 and 8 carbon atoms. [Claim 13] A composition according to claims 11 and 12 in which the molar ratio between the compound of formula (I), (II), or (III) and the nickel is between 0.1 and 50.0, preferably between 0.2 and 30.0, preferably between 0.3 and 15.0, preferably between 0.5 and 10.0, preferably between 0.8 and 6.0 and very preferably between 0, 9 and 5.5. [Claim 14] An oligomerization process using the catalytic composition according to claims 11 to 13, said process comprising bringing said composition into contact with an olefinic charge chosen from a compound or mixture of unsaturated compounds of general formula CnI-1 2n, in which n is between 4 and 80, preferably between 4 and 50, preferably between 4 and 26, and more preferably between 4 and 14, and more preferably between 4 and 8. [Claim 15] Method according to Claim 14, carried out at a total pressure of between 0.1 and 20.0 MPa, preferably between 0.1 and 15.0 MPa, and preferably between 0.5 and 8.0 MPa, and at a temperature between -40 and 250 ° C, preferably between -20 ° C and 150 ° C, preferably between 20 ° C and 100 ° C, and preferably between 30 to 80 ° C.