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    • 专利摘要:
    There is disclosed a composition comprising at least one chromium compound, at least one aryloxy compound of an element M selected from the group consisting of magnesium, calcium, strontium, barium, of general formula [M (RO) 2- wherein R 1 is an aryloxy radical of a ROH derivative containing from 6 to 80 carbon atoms, X is a halogen or a hydrocarbyl radical containing from 1 to 30 carbon atoms, n is an integer which can take the integer values 0 or 1, and y is an integer between 1 and 10, and at least one additive selected from cyclic or non-cyclic ether compounds, introduced in an amount close to the stoichiometry with respect to the element M.
    公开号:FR3019064A1
    申请号:FR1452517
    申请日:2014-03-25
    公开日:2015-10-02
    发明作者:Lionel Magna；Sebastien Drochon；Helene Olivier-Bourbigou
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a novel composition comprising at least one chromium compound, at least one aryloxy compound of an element M and at least one additive selected from ether-type compounds and its method of preparation. The invention also relates to the use of said composition in a process for trimerization of ethylene to hexene-1. Another aspect of the invention relates to an intermediate composition comprising at least one aryloxy compound of an element M and at least one additive selected from ether-type compounds and its method of preparation.
    [0002] Hexene-1 plays a very important role as a reaction intermediate in the chemical and petrochemical industry. Its main use is the production of various grades of polyethylene in which it is engaged as a comonomer. This compound is today mainly obtained by oligomerization of ethylene. Systems capable of selectively trimerizing ethylene to hexene-1 are today essentially chromium-based (D. S. McGuinness, Chem Rev. 2011, 111, 2321). Among the systems known to lead to the selective production of hexene-1, mention may be made of the systems described, for example in US-A-5,198,563, US-A-5,288,823, US-A-5,382 738, EP-A-608,447, EP-A-611,743, EP-A-614,865. These catalysts are prepared from a chromium salt and a metal amide, in particular a pyrrolidine. Other catalysts involve an aluminoxane and a chromium complex in combination with phosphorus ligands as described for example in US-A-5 550 305.
    [0003] The patent FR-B-2 802 833 describes in particular a catalytic composition obtained by mixing at least one chromium compound with at least one aryloxy compound of an element M chosen from the group formed by magnesium, calcium and strontium. and barium, of the general formula M (R0) 2, X, wherein RO is an aryloxy radical containing from 6 to 80 carbon atoms, X is a halogen or a hydrocarbyl radical containing from 1 to 30 carbon atoms, and n is is an integer which can take the values from 0 to 2, and with at least one aluminum compound selected from the group consisting of tris (hydrocarbyl) aluminum and chlorinated or brominated hydrocarbylaluminum compounds, corresponding to the general formula Wherein R 'is a hydrocarbyl radical having 1 to 6 carbon atoms, Y is a chlorine or bromine atom and m is a number of 1 to 3, and aluminoxanes. In the industrial practice of a continuous mode petrochemical process, the catalytic solution is injected at the same time as the ethylene into a reactor stirred by conventional mechanical means or by external recirculation, and maintained at the desired temperature. The components of the catalyst can also be injected separately into the reaction medium, such as, for example, the product of interaction of the chromium compound with the aryloxy compound of the element M on the one hand, and the hydrocarbyl aluminum compound on the other go. In this case there is the problem of the stability of the components used in particular that of the aryloxy compound of the element M or that of the product of the interaction of the chromium compound with the aryloxy compound of the element M. It is necessary to take special care that these formulations do not degrade (precipitation, gel formation ...) before or during their use in the process.
    [0004] Surprisingly, it has now been found that a composition comprising at least one chromium compound, at least one aryloxy compound of an element M and at least one additive chosen from ether compounds introduced in a quantity close to stoichiometry. relative to the M element exhibited improved stability while maintaining good activity and good selectivity when used in the ethylene trimerization reaction. It has also been found that the intermediate composition comprising at least one aryloxy compound of an element M and at least one additive chosen from ether compounds introduced in a quantity close to the stoichiometry with respect to the element M has improved stability. .
    [0005] The invention relates to a composition comprising: at least one chromium compound, at least one aryloxy compound of an element M selected from the group consisting of magnesium, calcium, strontium and barium; preferably, magnesium, of the general formula [M (R0) 2_, Xdy wherein RO is an aryloxy radical of a ROH derivative containing from 6 to 80 carbon atoms, X is a halogen or a hydrocarbyl radical containing from 1 to 30 carbon atoms, n is an integer which can take the values of 0 or 1, and y is an integer from 1 to 10, preferably y is 1 or 2 or 3 or 4; and at least one additive chosen from cyclic and non-cyclic ether compounds introduced in a quantity close to the stoichiometry with respect to the element M. The invention also relates to an intermediate composition comprising: at least one aryloxy compound; an element M selected from the group consisting of magnesium, calcium, strontium and barium, preferably magnesium, of general formula [M (R0) 2_, Xdy wherein RO is an aryloxy radical of a ROH derivative containing 6 to 80 carbon atoms, X is a halogen or a hydrocarbyl radical containing 1 to 30 carbon atoms, n is an integer which can take the values of 0 or 1, and y is an integer of 1 and 10, preferably y is 1 or 2 or 3 or 4; and at least one additive chosen from ether-type compounds, cyclic or otherwise, introduced in a quantity close to the stoichiometry with respect to the element M.
    [0006] The composition according to the invention therefore comprises, in addition to the components of the intermediate composition, at least one chromium compound. For the sake of clarity, the term "composition" will be used hereinafter, the composition according to the invention comprising at least one chromium compound, as opposed to the "intermediate composition" which does not comprise a chromium compound.
    [0007] The invention also relates to the process for preparing said composition. In a first embodiment, said method for preparing said composition comprises the mixture of: at least one chromium compound, at least one MX2 compound of an element M selected from the group formed by magnesium, calcium , strontium, barium, X is a halogen or a hydrocarbyl radical containing from 1 to 30 carbon atoms, - at least one ROH derivative in which RO is an aryloxy radical of a ROH derivative containing from 6 to 80 carbon atoms and at least one additive chosen from cyclic or non-cyclic ether compounds introduced in a quantity close to the stoichiometry with respect to the element M. In a second embodiment, the composition according to the invention may also be advantageously prepared by adding at least one chromium compound to the intermediate composition as described above. In the case where the composition according to the invention further comprises an aluminum compound, the preparation method of the latter may comprise that it is for the first or the second embodiment described above, the addition at least an aluminum compound selected from the group consisting of tris (hydrocarbyl) aluminum and chlorinated or brominated hydrocarbylaluminum compounds, having the general formula AIR ',, Y3_, wherein R' is a hydrocarbyl radical having from 1 to 6 carbon atoms, Y is a chlorine or bromine atom and m is a number from 1 to 3, and aluminoxanes alone or in mixtures. The preparation process may optionally be carried out in the presence of a solvent.
    [0008] The invention also relates to the process for preparing said intermediate composition comprising the mixture of: at least one compound MX2 of an element M selected from the group formed by magnesium, calcium, strontium, barium, X is a halogen or a hydrocarbyl radical containing from 1 to 30 carbon atoms, - at least one ROH derivative in which RO is an aryloxy radical of a ROH derivative containing from 6 to 80 carbon atoms, and at least one an additive selected from the ether compounds, cyclic or not, introduced in an amount close to the stoichiometry with respect to the element M. The mixing order of the MX2 compound, the ROH derivative and the additive is not critical, this mixture can optionally be carried out in a solvent. Without wishing to be bound by any theory, the applicant considers that the interaction of a compound MX2 of an element M defined according to the invention and of at least one ROH derivative defined according to the invention results in the formation of at least one polymeric compound of general formula [M (R0) 2_, X, ly wherein M is selected from the group consisting of magnesium, calcium, strontium, barium, RO is an aryloxy radical of a ROH derivative containing 6 to 80 carbon atoms, X is a halogen or a hydrocarbyl radical containing 1 to 30 carbon atoms, n is an integer which can take the values of 0 or 1, and y is an integer of 1 and 10. The chromium compound present in the composition according to the invention may comprise one or more identical or different anions chosen from the group formed by halides, carboxylates, acetylacetonates, alkoxy and aryloxy anions. The chromium compound may be a chromium (II) or chromium (III) salt, but also a salt of a different oxidation state that may comprise one or more identical or different anions, such as, for example, halides, carboxylates, acetylacetonates, alkoxy or aryloxy anions. The chromium compounds preferably used in the invention are the chromium (III) compounds because they are more accessible, but a chromium (I) or chromium (II) compound may also be suitable.
    [0009] In the composition according to the invention and the intermediate composition according to the invention, X is advantageously a halogen (chlorine or bromine) or a hydrocarbyl radical containing from 1 to 30 carbon atoms, linear or branched, for example alkyl, cycloalkyl, alkenyl aryl, or aralkyl, aryl or substituted cycloalkyl, preferably a hydrocarbyl residue of 2 to 10 carbon atoms. In the composition according to the invention and the intermediate composition according to the invention, the aryloxy radical RO of the alcohol derivative ROH preferably has the general formula: in which R1, R2, R3, R4 and R5, which are identical or different, represent each a hydrogen atom, a halogen atom or a hydrocarbyl radical, for example alkyl, cycloalkyl, alkenyl, aryl, or aralkyl, aryl or substituted cycloalkyl, preferably comprising 1 to 16 carbon atoms, and more particularly 1 to 10 carbon atoms. By way of examples and without the list being limiting, R1, R2, R3, R4 and R5 may be methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, benzyl, phenyl, 2-methylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, or 2-methyl-2-phenylprop-1-yl.
    [0010] Among the preferred aryloxy radicals, mention may be made by way of non-limiting examples: 4-phenylphenoxy, 2-phenylphenoxy, 2,6-diphenylphenoxy, 2,4,6-triphenylphenoxy, 2,3,5, 6-tetraphenylphenoxy, 2-tert-butyl-6-phenylphenoxy, 2,4-ditertbutyl-6-phenylphenoxy, 2,6-diisopropylphenoxy, 2,6-dimethylphenoxy, 2,6-ditert-butylphenoxy, 4-methyl-2,6-ditert-butylphenoxy, 2,6-dichloro-4-tert-butylphenoxy and 2,6-dibromo-4-tert-butylphenoxy. The two aryloxy radicals may be carried by the same molecule, such as for example the biphenoxy radical, binaphthoxy or 1,8-naphthalene-dioxy, substituted or not by alkyl, aryl or halide radicals. Preferably, the aryloxy radical RO is 2,6-diphenylphenoxy, 2-tert-butyl-6-phenylphenoxy or 2,4-ditert-butyl-6-phenylphenoxy. The additive as described in the composition according to the invention and the intermediate composition according to the invention is chosen from ether compounds, cyclic or otherwise. It is preferably chosen from diethyl ether, dibutyl ether, diisopropyl ether, 2-methoxy-2-methylpropane, 2-methoxy-2-methylbutane, 2,5-dihydrofuran, tetrahydrofuran and 2-methoxytetrahydrofuran. , 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,3-dihydropyran, tetrahydropyran, 1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, dimethoxyethane, di (2-methoxyethyl) ) ether and benzofuran, alone or as a mixture. Preferably, the additive is dibutyl ether.
    [0011] In one embodiment, the composition according to the invention comprising the chromium compound may also comprise at least one aluminum compound (also called cocatalyst) chosen from the group formed by tris (hydrocarbyl) aluminum and the compounds chlorinated or brominated hydrocarbylaluminum compounds, having the general formula AIR ', Y3_, wherein R' is a hydrocarbyl radical having 1 to 6 carbon atoms, Y is a chlorine or bromine atom and m is a number of 1 to 3, and aluminoxanes, alone or as a mixture. When at least one chromium compound is present in the composition, the molar ratio between the aluminum compound and the chromium (Al / Cr) compound is advantageously between 1: 1 and 35: 1.
    [0012] The aluminum compounds used as co-catalyst are chosen from hydrocarbylaluminium-tris (hydrocarbyl) aluminum, chlorinated or brominated compounds of hydrocarbylaluminium and aluminoxanes. Tris (hydrocarbyl) alcohols and chlorinated or brominated hydrocarbylaluminum compounds are represented by the general formula AIR ', Y3_, wherein R' is a hydrocarbyl radical, preferably alkyl having 1 to 6 carbon atoms, Y is a chlorine or bromine atom, preferably a chlorine atom and m is a number from 1 to 3. Nonlimiting examples include: dichloroethylaluminium, ethylaluminium sesquichloride, chlorodiethylaluminum, chlorodiisobutylaluminium, triethylaluminum, tripropylaluminum, triisobutylaluminum, methylaluminoxane. The preferred hydrocarbyl aluminum compound is triethylaluminum. The composition according to the invention and the intermediate composition according to the invention may be in solution in a solvent consisting of a saturated hydrocarbon such as hexane, cyclohexane, heptane, butane or isobutane, with an unsaturated hydrocarbon such as a monoolefin or a diolefin containing for example 4 to 20 carbon atoms, or an aromatic hydrocarbon such as benzene, toluene, ortho-xylene, mesitylene, ethylbenzene, pure or in admixture. The concentration of chromium in the solution can vary from 1.10-8 to 2 mol / l, preferably from 1.10-7 to 1 mol / l.
    [0013] The compositions according to the invention comprising chromium have a molar ratio between the element M and chromium (M / Cr ratio) advantageously between 1: 1 and 30: 1, preferably between 1: 1 and 20: 1.
    [0014] According to the invention, the term "quantity close to the stoichiometry with respect to the element M" means a molar ratio between the ether additive and the element M (ether / M ratio) which can be between 1 and 200, of preferably between 1 and 100 and even more preferably between 1 and 60, or even between 1 and 40.
    [0015] Another subject of the invention relates to a process for the trimerization of ethylene using the composition according to the invention. During the implementation of the trimerization process, the various constituents of the composition according to the invention namely the chromium compound, the aryloxy compound of the element M and the additive as described in the invention, as well as Any co-catalyst may be injected into the reactor simultaneously or sequentially, separately or in admixture. The trimerization process of ethylene according to the invention can be carried out in continuous mode or in batch mode. In a particular embodiment, the ethylene trimerization process according to the invention is carried out batchwise according to the following steps: the composition according to the invention comprising at least one composition is introduced into a reactor under an ethylene atmosphere; a chromium compound, at least one aryloxy compound of an element M selected from the group consisting of magnesium, calcium, strontium and barium, of general formula [M (R0) 2_, X, ly in which RO is an aryloxy radical of a ROH derivative containing from 6 to 80 carbon atoms, X is a halogen or a hydrocarbyl radical containing from 1 to 30 carbon atoms, n is an integer which can take the values of 0 or 1, and y is an integer between 1 and 10, and at least one additive selected from cyclic or non-cyclic ether compounds introduced in an amount close to the stoichiometry with respect to the element M, ethylene is introduced at the desired pressure, - we have just the temperature to the desired value, and the previously described aluminum compound is added.
    [0016] The reactor used is advantageously equipped with the usual stirring, heating and cooling devices. Advantageously, the reactor is purged beforehand by empty / argon cycles. The trimerization reactor is advantageously maintained at constant pressure by introduction of ethylene until the total volume of liquid produced represents, for example, from 2 to 50 times the volume of the catalytic solution originally introduced. The catalyst is then destroyed by any usual means known to those skilled in the art, and the products of the reaction and the solvent are withdrawn and separated. In another particular embodiment, the trimerization process of the ethylene according to the invention is carried out continuously by simultaneous injection and separately: - constituents of the composition, that is to say: - at least one chromium compound, - at least one aryloxy compound an element M selected from the group consisting of magnesium, calcium, strontium and barium, of general formula [M (R0) 2, X, ly wherein RO is an aryloxy radical of a ROH derivative containing 6 to 80 carbon atoms, X is a halogen or a hydrocarbyl radical containing from 1 to 30 carbon atoms, n is an integer which can take the values of 0 or 1, and y is an integer of 1 to 10 at least one additive chosen from ether compounds, cyclic or otherwise, introduced it is in a quantity close to the stoichiometry with respect to the element M, of at least one aluminum compound as previously described; - and ethylene; in a reactor, the entire system being maintained at the desired temperature and pressure.
    [0017] The reactor used is advantageously stirred by conventional mechanical means or by an external recirculation. The ethylene is advantageously introduced into the reactor via a pressure-controlled inlet valve, which keeps it constant. The reaction mixture is withdrawn by means of a valve controlled at the liquid level so as to keep it constant. The catalyst is continuously 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. Ethylene which has not been converted can be recycled to the reactor. The trimerization reaction of ethylene can be carried out at a total pressure of 0.5 to 15 MPa, preferably 1 to 8 MPa, and at a temperature of 20 to 180 ° C, preferably 50 to 160 ° C.
    [0018] The following examples illustrate the invention without limiting its scope.
    [0019] Examples In the following examples, the "OPh" 2-terbutyl-6-phenylphenoxy radical is noted. The acronym "DBE" will be used for dibutyl ether. The formula "Cr (2- EH) 3" will describe chromium tris (2-ethylhexanoate).
    [0020] EXAMPLE 1 Non-compliant: S nthesis of a solution of M. OPh 2 at 0.3 mol / L in a cyclohexane / heptane mixture (Solution A) In a 200 ml Schlenk under argon, 12.2 g of 2- 6-tert-butyl phenol phenol (54 mmol) which is diluted in 47 ml of cyclohexane. 22.5 g (27 mmol, 30.9 ml) of a solution of butyl octyl magnesium at 20% by weight in n-heptane are then added. This solution is stirred under argon for approximately 1 hour. The solution obtained is initially homogeneous colorless. After only 12h at 3 ° C, there is the formation of a white precipitate which materializes the lack of physical stability of this formulation. Example 2 According to the synthesis of the intermediate composition "M. OPh 2 / DBE" (1/5 mol / mol) at 0.3 mol / L in a cyclohexane / heptane mixture (Solution III This solution is prepared according to the protocol described in Example 1. 12.2 g of 2-tert-butyl-6-phenyl phenol (54 mmol), 17.6 g of dibutyl ether (135 mmol, 23 ml), 24 ml of cyclohexane and 22.5 are brought into contact. g (27 mmol, 30.9 ml) of a solution of butyl octyl magnesium at 20% by weight in n-heptane and a homogeneous colorless solution which remains stable for more than 12 months at room temperature and at 3 ° C. the 3 compliant: S nthesis of the intermediate com.position "M. OPh DBE" (1/10 mol / mol) to 0.3 mol / L in a cyclohexane / heptane mixture (Solution 30 2 This solution is prepared according to the described protocol in Example 1. 12.2 g of 2-tert-butyl-6-phenyl phenol (54 mmol), 35.1 g of dibutyl ether (270 mmol, 46 ml) and 22.5 g (27 mmol, 30.9 ml) are brought into contact. a butyl solution 20 mg octyl magnesium in n-heptane, and a colorless homogeneous solution is obtained which remains stable for more than 12 months at room temperature as at 3 ° C. EXAMPLE (CONFORMER) - Synthesis of Corr (L) "M OPh 2 / DBE" (1/39 mol / mol) at 0.12 mol / L in a cyclohexane / heptane mixture (Solution D) This solution is prepared according to protocol described in Example 1. 4.7 g of 2-tert-butyl-6-phenyl phenol (20.7 mmol), 52.9 g of dibutyl ether (406 mmol, 69.2 ml) and 8.6 g (10.4 mmol, 11.8) were added. mL) of 20 wt% butyl octyl magnesium solution in n-heptane gives a colorless homogeneous solution which remains stable for more than 12 months at room temperature as at 3 ° C.
    [0021] EXAMPLE 5 Non-conforming solution of Cr 2 -EH 3 / M - OPh 0.3 mol / L in a cyclohexane / heptane mixture (Solution E) In a 200 ml Schlenk under argon, 13.6 g were introduced. of 2-tert-butyl-6-phenyl phenol (60 mmol) which is diluted in 33 ml of cyclohexane, 25 g (30 mmol, 34.3 ml) of a solution of butyloctylmagnesium at 20 wt. The solution is stirred under argon at room temperature for 1 h In a second 200 ml flask, 19.5 g of Cr (2-EH) 3 to 8% by weight of chromium (30 mmol, 19.3 ml) are introduced under argon. The previously prepared Mg (OPh) 2 solution is added to this compound.
    [0022] After stirring for 2 hours at room temperature, this solution is homogeneous in green color. However, after 12 hours at room temperature, the formation of a gel is observed which is deposited at the bottom of the preparation schlenk which materializes the absence of physical stability of this formulation.
    [0023] EXAMPLE 6 Conforming to: Composition of "Cr 2 -EH 3 / M.OPh 2 / DBE" (1/1/5 mol / mol / mol) at 0.3 mol / L in a cyclohexane / heptane mixture (Solution F) In a 200 mL Schlenk under argon, 12.2 g of 2-tert-butyl-6 phenylphenol (54 mmol), 17.6 g of dibutyl ether (135 mmol, 23 mL) and 6.5 mL of cyclohexane are introduced. 22.5 g (27 mmol, 30.9 ml) of a solution of butyl octyl magnesium at 20% by weight in n-heptane are then added. The solution is stirred under argon at room temperature for 1 h. In a second schlenk of 200 ml, 17.5 g of a solution of Cr (2-EH) 3 at 8% by weight of chromium (ie 27 mmol, 17.4 ml) are introduced under argon. This compound is added to the previously prepared solution of Mg (OPh) 2. A green colored homogeneous solution is thus obtained which remains stable for more than 12 months at room temperature and at 3 ° C. Examples 7-9: Evaluation of the Catalytic Performance of Solution F The ethylene trimerization tests presented in the table below were carried out in a stainless steel autoclave with a working volume of 250 ml, provided with a double jacket to regulate the temperature by circulation of oil. 43 ml of cyclohexane and 3.4 ml of a 0.03 mol solution of chromium prepared directly from the composition F (Solution F) and from the reaction medium are introduced into this reactor under an ethylene atmosphere at room temperature. cyclohexane. Once the temperature of the reactor has been raised to 140 ° C., 2.5 equivalents (relative to chromium) of triethylaluminium (previously diluted in cyclohexane) are introduced under ethylene pressure. The ethylene pressure is maintained at 3 MPa. After 1 hour of reaction, the introduction of ethylene is stopped and the reactor is cooled and degassed, then the gas and the liquid, which has been withdrawn by means of a syringe, are analyzed by gas chromatography. The composition of the products obtained is given in the table below: Ex. Molar ratio Aging - Activity Salt. C4 Salt. C6 Salt. C8 Salt. C10 (% wt) Salt. Waxes (% wt) Cr / Mg (OPh) 2 / DBE ment (g / gCr / h) (wt%) (wt%) (wt%) 7 1/1/5 Sol. F 6000 1 72 1 10 15 freshly prepared 8 1/1/5 Sol. F aged 4 months 6200 1 74 1 9 14 9 1/1/5 Sol. F aged 6400 1 72 1 9 15 14 months (sol = solution, salt = selectivity, pds = weight) These examples demonstrate the chemical stability of the formulations as described according to the invention. Examples 10-11: Evaluation of the Catalytic Performance of Compositions from an Intermediate Composition B The ethylene trimerization tests presented in the table below were carried out in a stainless steel autoclave with a useful volume of 250 mL, equipped with a double jacket to regulate the temperature by circulation of oil. 43 ml of cyclohexane and 3.4 ml of a 0.03 mol / l solution of chromium prepared directly from the intermediate composition B (solution B) are introduced into this reactor under an ethylene atmosphere at ambient temperature. ), a solution of Cr (-EH) 3 to 8% by weight of Cr, and cyclohexane. Once the temperature of the reactor has been raised to 140 ° C., 2.5 equivalents (relative to chromium) of triethylaluminium (previously diluted in cyclohexane) are introduced under ethylene pressure. The ethylene pressure is maintained at 3 MPa. After 1 hour of reaction, the introduction of ethylene is stopped and the reactor is cooled and degassed, then the gas and the liquid, which has been withdrawn by means of a syringe, are analyzed by gas chromatography. The composition of the products obtained is given in the table below: Ex. Molar ratio Aging-Activity Salt. C4 Salt. C6 Salt. C8 Salt. C10 (% wt) Salt. Wax (% wt) Cr / Mg (OPh) 2 / DBE ment (g / gCr / h) (wt%) (wt%) (wt%) 10 1/1/5 Sol. B 5100 1 74 0 10 13 freshly prepared 11 1/1/5 Sol. B aged 8000 1 69 1 12 16 16 months (sol = solution, salt = selectivity, weight = weight) These examples demonstrate the chemical stability of the intermediate formulations as described according to the invention.
    权利要求:
    Claims (17)
    [0001]
    CLAIMS1) Composition comprising: - at least one chromium compound, - at least one aryloxy compound of an element M selected from the group consisting of magnesium, calcium, strontium, barium, of general formula [M (R0) Wherein R1 is an aryloxy radical of a ROH derivative containing from 6 to 80 carbon atoms, X is a halogen or a hydrocarbyl radical containing from 1 to 30 carbon atoms, n is an integer which can take the values integers 0 or 1, and y is an integer from 1 to 10; at least one additive chosen from ether-type compounds, cyclic or otherwise, introduced in a quantity close to the stoichiometry with respect to the element M.
    [0002]
    2) Composition according to claim 1 wherein the molar ratio between the additive and the element M is between 1 and 200.
    [0003]
    3) Composition according to claim 1 or 2 wherein the molar ratio between the element M and chromium is between 1: 1 and 30: 1.
    [0004]
    4) Composition according to one of the preceding claims wherein the additive is selected from diethyl ether, dibutyl ether, diisopropyl ether, 2-methoxy-2-methylpropane, 2-methoxy-2-methylbutane, 2 5-dihydrofuran, tetrahydrofuran, 2-methoxytetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,3-dihydropyran, tetrahydropyran, 1,3-dioxolane, 1,3-dioxane, 1, 4-dioxane, dimethoxyethane, di (2-methoxyethyl) ether and benzofuran, alone or as a mixture.
    [0005]
    5) Composition according to one of the preceding claims wherein in the ROH derivative, the aryloxy radical RO has the general formula: in which R1, R2, R3, R4, R5, identical or different, represent a hydrogen, a halogen or a hydrocarbyl radical comprising from 1 to 16 carbon atoms.
    [0006]
    6) A composition according to claim 5 wherein the aryloxy radical RO is 2,6-diphenylphenoxy, 2-tert-butyl-6-phenylphenoxy or 2,4-ditert-butyl-6-phenylphenoxy.
    [0007]
    7) Composition according to one of the preceding claims in solution in a solvent consisting of a saturated hydrocarbon, unsaturated olefinic or diolefinic or aromatic.
    [0008]
    8) Composition according to one of the preceding claims further comprising at least one aluminum compound selected from the group consisting of tris (hydrocarbyl) aluminum and chlorinated or brominated compounds of hydrocarbylaluminium, corresponding to the general formula AIR ', , Y3_, wherein R 'is a hydrocarbyl radical having 1 to 6 carbon atoms, Y is a chlorine or bromine atom and m is a number of 1 to 3, and the aluminoxanes alone or in mixtures.
    [0009]
    9) Composition according to claim 8 wherein the hydrocarbylaluminum compound is selected from dichloroethylaluminium, sesquichlorure of ethylaluminium, chlorodiethylaluminium, chlorodiisobutyl-aluminum, triethylaluminium, tripropylaluminium, triisobutylaluminium, methylaluminoxane.
    [0010]
    10) Composition according to one of the preceding claims wherein the chromium compound is present with a molar ratio between the aluminum compound and the chromium compound of between 1: 1 and 35: 1.
    [0011]
    11) Intermediate composition comprising: at least one aryloxy compound of an element M selected from the group formed by magnesium, calcium, strontium, barium, of general formula [M (R0) 2, X, ly in which RO is an aryloxy radical of a ROH derivative containing from 6 to 80 carbon atoms, X is a halogen or a hydrocarbyl radical containing from 1 to 30 carbon atoms, n is an integer which can take the integer values 0 or 1 and y is an integer from 1 to 10; at least one additive chosen from ether-type compounds, cyclic or otherwise, introduced in a quantity close to the stoichiometry with respect to the element M.
    [0012]
    12) A process for preparing the intermediate composition according to claim 11 comprising the mixture of: at least one compound MX2 of an element M selected from the group consisting of magnesium, calcium, strontium, barium, X is a halogen or a hydrocarbyl radical containing from 1 to 30 carbon atoms, - at least one ROH derivative in which RO is an aryloxy radical of a ROH derivative containing from 6 to 80 carbon atoms, and at least one an additive chosen from ether compounds, cyclic or otherwise, introduced in an amount close to the stoichiometry with respect to the element M.
    [0013]
    13) Process for the preparation of the composition according to one of claims 1 to 10 comprising the mixture of: - at least one chromium compound, - at least one compound MX2 of an element M selected from the group formed by magnesium, calcium, strontium, barium, X is a halogen or a hydrocarbyl radical containing from 1 to 30 carbon atoms, - at least one ROH derivative in which RO is an aryloxy radical of a ROH derivative containing from 6 to 80 carbon atoms, at least one additive chosen from cyclic or non-cyclic ether compounds introduced in a quantity close to the stoichiometry with respect to the element M; optionally at least one aluminum compound selected from the group consisting of tris (hydrocarbyl) aluminum and chlorinated or brominated hydrocarbylaluminum compounds, corresponding to the general formula AIR ', Y3_, in which R' is a radical hydrocarbyl comprising 1 to 6 carbon atoms, Y is a chlorine or bromine atom and m is a number from 1 to 3, and aluminoxanes taken alone or in mixtures, - optionally at least one solvent. 10
    [0014]
    14) Use of the composition according to one of claims 1 to 10 in a method of trimerization of ethylene.
    [0015]
    15) Process for the trimerization of ethylene carried out in batch according to the following steps: the constituents of the composition according to one of Claims 1 to 7 are introduced into a reactor; ethylene is introduced under pressure; desired, the temperature is adjusted to the desired value, and at least one aluminum compound selected from the group consisting of tris (hydrocarbyl) aluminum and chlorinated or brominated hydrocarbylaluminum compounds, having the formula wherein R 'is a hydrocarbyl radical having from 1 to 6 carbon atoms, Y is a chlorine or bromine atom and m is a number from 1 to 3, and aluminoxanes taken alone or in mixtures.
    [0016]
    16) Process for the trimerization of ethylene carried out continuously, by the simultaneous injection and separately in a reactor, the constituents of the composition according to one of claims 8 to 10 and ethylene, the the entire system being maintained at the desired temperature and pressure.
    [0017]
    17) Method according to one of claims 15 or 16 wherein the trimerization reaction of ethylene is carried out under a total pressure of 0.5 to 15 MPa and at a temperature of 20 to 180 ° C.5
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    JP6484475B2|2019-03-13|
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    SG10201502172WA|2015-10-29|
    CN104941682B|2019-07-30|
    SA115360409B1|2017-02-16|
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    CA2886105A1|2015-09-25|
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    法律状态:
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    2017-03-27| PLFP| Fee payment|Year of fee payment: 4 |
    2018-03-28| PLFP| Fee payment|Year of fee payment: 5 |
    2019-03-27| PLFP| Fee payment|Year of fee payment: 6 |
    2020-03-26| PLFP| Fee payment|Year of fee payment: 7 |
    2021-03-26| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1452517A|FR3019064B1|2014-03-25|2014-03-25|NOVEL CATALYTIC COMPOSITION AND PROCESS FOR THE OLIGOMERIZATION OF ETHYLENE TO HEXENE-1|
    FR1452517|2014-03-25|FR1452517A| FR3019064B1|2014-03-25|2014-03-25|NOVEL CATALYTIC COMPOSITION AND PROCESS FOR THE OLIGOMERIZATION OF ETHYLENE TO HEXENE-1|
    ZA2015/01481A| ZA201501481B|2014-03-25|2015-03-04|Novel catalytic composition and process for oligomerizing ethylene into 1-hexene|
    RU2015109162A| RU2682334C2|2014-03-25|2015-03-16|New catalyst composition and ethylene oligomerisation method with production of hexene-1|
    KR1020150038962A| KR102342656B1|2014-03-25|2015-03-20|Novel catalytic composition and process for oligomerizing ethylene into 1-hexene|
    SG10201502172WA| SG10201502172WA|2014-03-25|2015-03-20|Novel Catalytic Composition and Process for Oligomerizing Ethylene into 1-Hexene|
    SA115360409A| SA115360409B1|2014-03-25|2015-03-22|Novel catalytic composition and process for oligomerizing ethylene into 1-hexene|
    JP2015059243A| JP6484475B2|2014-03-25|2015-03-23|Novel catalyst composition and process for oligomerization of ethylene to 1-hexene|
    CA2886105A| CA2886105A1|2014-03-25|2015-03-23|New catalytic composition and process for the oligomerization of ethylene into 1-hexene|
    TW104109442A| TWI645900B|2014-03-25|2015-03-24|Novel catalyst composition and method for oligomerizing ethylene into 1-hexene|
    CN201510132473.1A| CN104941682B|2014-03-25|2015-03-25|Catalyst composition and for making ethylene oligomerization at the method for 1- hexene|
    US14/668,132| US10150108B2|2014-03-25|2015-03-25|Catalytic composition and process for oligomerizing ethylene into 1-hexene|
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