CATALYTIC COMPOSITION BASED ON CHROMIUM AND A LIGAND BASED ON PHOSPHINE AND ITS USE IN A METHOD FOR PRODUCING OCTENES

Abstract

The invention pertains to a composition that comprises at least one chromium precursor, at least one heteroatomic ligand, and, optionally, at least one activator. The invention also pertains to the method for preparation of the composition in accordance with the invention and the use of said composition in a method for oligomerization of olefins.

Claims

1. Composition comprising: at least one chromium precursor, at least one heteroatomic ligand described by the general formula (I)
(R.sup.1).sub.2PO(CH.sub.2).sub.nN[P(R.sup.2).sub.2].sub.2 in which the groups R.sup.1 and R.sup.2, identical or not, bonded together or not, are selected from among the cyclic alkyl groups or not and the aromatic groups, and n is an integer greater than or equal to 1; and, optionally, at least one activator.

2. Composition in accordance with claim 1, in which the whole number n of the fragment (CH.sub.2)n- of the ligand is between 1 and 15.

3. Composition in accordance with claim 1, in which the molar ratio between the ligand and the chromium precursor is between 0.01 and 100.

4. Composition in accordance with claim 1, in which the molar ratio between the activator and the chromium precursor is between 1 and 10,000.

5. Composition in accordance with claim 1, in which the chromium precursor is selected from among CrCl.sub.3, CrCl.sub.3(tetrahydrofuran).sub.3, Cr(acetylacetonate).sub.3, Cr(naphthenate).sub.3, Cr(2-ethylhexanoate).sub.3, and Cr(acetate).sub.3.

6. Composition in accordance with claim 1, in which the activator agent is selected from among the tris(hydrocarbyl)aluminum compounds, the chlorinated or brominated compounds of hydrocarbylaluminum, aluminum halides, aluminoxanes, the organoboronated compounds, and the organic compounds that are capable of providing a proton, taken individually or in a mixture.

7. Method for preparing the composition according to claim 1, involving bringing the following into contact: at least one chromium precursor; with at least one heteroatomic ligand that is described by the general formula (I)
(R.sup.1).sub.2PO(CH.sub.2).sub.nN[P(R.sup.2).sub.2].sub.2 in which the groups R.sup.1, R.sup.2 and n correspond to the definition in accordance with one of the preceding claims, and, optionally, with at least one activator that corresponds to the definition in accordance with one of the preceding claims.

8. Preparation method in accordance with claim 7, in which the components of the composition are mixed at a temperature of between 40 and +150 C.

9. (canceled)

10. Method for oligomerization of an olefinic feedstock that involves bringing said feedstock that comprises olefins having between 2 and 10 carbon atoms into contact with a composition in accordance with claim 1, where said method is run at a total pressure of between atmospheric pressure and 20 MPa and at a temperature of between 40 and +250 C.

11. Method in accordance with claim 10, in which the method is a method for tetramerization of ethylene into octene-1.

Description

DETAILED DESCRIPTION OF THE INVENTION

Compositions According to the Invention

[0029] This invention pertains to a composition that comprises:

[0030] at least one chromium precursor,

[0031] with at least one heteroatomic ligand described by the general formula (I)

(R.sup.1).sub.2PO(CH.sub.2).sub.nN[P(R.sup.2).sub.2].sub.2

in which the groups R.sup.1 and R.sup.2, identical or not, bonded together or not, are selected from among the cyclic alkyl groups or not and the aromatic groups, and n is an integer greater than or equal to 1;

[0032] and, optionally, at least one activator.

The Chromium Precursor

[0033] The chromium precursor in accordance with the invention can be selected from among the chromium compounds used in the methods for oligomerization of olefins.

[0034] The chromium precursor that is present in the composition in accordance with the invention may comprise one or more identical or different anions that are selected from among the group made up of halides, carboxylates, acetylacetonates, and the alkoxy and aryloxy anions. The chromium compound can be a salt of chromium(II) or chromium(III), but also a salt with a different degree of oxidation that can comprise one or more identical or different anions, such as, for example, halides, carboxylates, acetylacetonates, and alkoxy or aryloxy anions. The chromium precursors used preferably in the invention are compounds of chromium(III) because they are more accessible, but a compound of chromium(I) or chromium(II) may also be suitable.

[0035] Preferably, according to the invention, the chromium precursor is selected from among CrCl.sub.3, CrCl.sub.3(tetrahydrofuran).sub.3, Cr(acetylacetonate).sub.3, Cr(naphthenate).sub.3, Cr(2-ethylhexanoate).sub.3, Cr(acetate).sub.3.

The Heteroatomic Ligand

[0036] The ligand of the catalytic composition according to the invention is described by the general formula (I)

(R.sup.1).sub.2P.O(CH.sub.2).sub.nN[P(R.sup.2).sub.2].sub.2

in which the groups R.sup.1 and R.sup.2, identical or not, bonded together or not, are selected from among the cyclic alkyl groups or not and the aromatic groups, and n is an integer greater than or equal to 1.

[0037] The whole number n of the fragment (CH.sub.2).sub.n of the ligand according to the invention is preferably between 1 and 15, in a more preferred manner between 2 and 15, in an even more preferred manner between 2 and 10, and even more preferably between 3 and 6.

[0038] According to the invention, the groups R.sup.1 and R.sup.2, identical or not, bonded together or not, are selected from among a cyclic alkyl group or not having 1-15 carbon atoms, preferably 1-10 carbon atoms, or an aromatic group having a number of carbons of greater than 3, preferably between 4 and 24, and in an even more preferred manner between 5 and 18.

[0039] Preferably, the groups R.sup.1 and R.sup.2, identical or not, bonded together or not, are selected from among the groups methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, adamantyl, substituted or not, that may or may not contain heteroelements; the groups phenyl, o-tolyl, 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-di-tert-butyl-4-methoxyphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-trifluoromethylphenyl, 3,5-di(trifluoromethyl)phenyl, benzyl, naphthyl, bis-naphthyl, pyridyl, bis-phenyl, furanyl, thiophenyl, substituted or not, may or may not contain heteroelements.

[0040] In one particular implementation, the groups R.sup.1 and R.sup.2, identical or not, bonded together or not, are selected from among the groups methyl, ethyl, i-propyl, n-butyl, i-butyl, t-butyl, cyclopentyl, and cyclohexyl.

[0041] In one particular implementation, the groups R.sup.1 and R.sup.2, identical or not, bonded together or not, are selected from among the groups phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl.

The Activator Agent

[0042] The composition according to the invention can include an activator agent. The activator agent can be selected from among the compounds known to one skilled in the art. Mixtures of activator agents may also be used.

[0043] Advantageously, the activator agents according to the invention are selected from among the tris(hydrocarbyl)aluminum compounds, the chlorinated or brominated hydrocarbylaluminum compounds, aluminum halides, aluminoxanes, organoboronated compounds, and organic compounds that are capable of providing a proton, taken individually or in a mixture.

[0044] Among the derivatives of aluminum, the following can be cited: the alkylaluminum halides, such as dimethylaluminum chloride, diethylaluminum chloride, ethylaluminum dichloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, methylaluminum dichloride, isobutylaluminum dichloride, aluminum trichloride; and aluminoxanes, used individually or in a mixture.

[0045] The aluminoxanes are well known to one skilled in the art as oligomeric compounds that can be prepared by the controlled addition of water to an alkylaluminum, for example trimethylaluminum. Such compounds may be linear, cyclic, or mixtures of these compounds. They are generally represented by the formula [RAIO]a, where R is a hydrocarbon group and a is a number from 2 to 50. Preferably, the aluminoxane is selected from among methylaluminoxane (MAO) and/or ethylaluminoxane (EAO) and/or from among the modified aluminoxanes such as the modified methylaluminoxane (MMAO).

[0046] In the case where said activator agent is selected from among the organoboronated compounds, said activator agent is preferably selected from among the Lewis acids of the 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(perfluorobiphenyl)borane and derivatives thereof, and the (aryl)borates associated with a triphenylcarbenium cation or with a trisubstituted ammonium cation, such as triphenylcarbenium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and triphenylcarbenium tetrakis(3, 5-bis(trifluoromethyl)phenyl)borate.

[0047] In the case where said activator agent is selected from among the organic compounds that are capable of providing a proton, said activator agent is preferably selected from among the acids of formula HY, in which Y represents an anion, such as HBF.sub.4 or F.sub.3CSO.sub.3H.

Preparation of the Compositions According to the Invention

[0048] Another object of the invention pertains to the method for preparing compositions according to the invention.

[0049] The compositions according to the invention are preferably prepared by bringing the following into contact:

[0050] at least one chromium precursor,

[0051] with at least one heteroatomic ligand described by the general formula (I)

(R.sup.1).sub.2PO(CH.sub.2).sub.nN[P(R.sup.2).sub.2].sub.2

in which the groups R.sup.1 and R.sup.2, identical or not, bonded together or not, are selected from among the cyclic alkyl groups or not and the aromatic groups, and n is an integer greater than or equal to 1,

[0052] and, optionally, with at least one activator.

[0053] In one particular embodiment, the molar ratio between the ligand and the chromium precursor is between 0.01 and 100, and preferably between 0.5 and 5, in particular between 0.8 and 3.

[0054] When the activator is present in the composition, the molar ratio between the activator and the chromium precursor is between 1 and 10,000, preferably between 100 and 5,000, and in an even more preferred manner between 200 and 3,500.

[0055] During the preparation method, the components of the composition can be added simultaneously or in sequence, in any order. The composition according to the invention can be prepared in situ with the feedstock, particularly ethylene, being either present or absent.

[0056] The compositions according to the invention can be in the presence of a solvent or not. It is possible to use a solvent that is advantageously selected from among the solvents that are capable of dissolving the reagents. To do this, the use of organic solvents is preferred. These include the aliphatic hydrocarbon solvents that are saturated or not, such as pentane, hexane, cyclohexane, methyl cyclohexane, or heptane, cyclohexene, cyclooctene, or cyclooctadiene. Aromatic solvents that can be mentioned include benzene, toluene, or xylenes. Oxidized solvents that can be mentioned include diethyl ether or tetrahydrofuran and chlorinated solvents such as dichloromethane or chlorobenzene. These solvents can be used by themselves or in a mixture.

[0057] The temperature at which the components of the composition according to the invention are mixed is advantageously between 40 and +150 C. and preferably between 0 and +80 C., for example at a temperature close to room temperature (15-30 C.). The mixture can be made under an atmosphere of ethylene or inert gas.

Use of the Compositions According to the Invention

[0058] Another object of the invention pertains to using compositions according to the invention as catalysts.

[0059] The compositions according to the invention can be used as catalysts in a chemical transformation reaction, in particular in an oligomerization method that involves bringing said feedstock comprising olefins having between 2 and 10 carbon atoms into contact with the composition according to the invention, where said method is advantageously run at a total pressure of between atmospheric pressure and 20 MPa and at a temperature of between 40 and +250 C.

[0060] The composition according to the invention is advantageously employed in a method for tetramerization of olefins, in particular in a method for tetramerization of ethylene into octene-1.

[0061] The solvent of the oligomerization method can be selected from among organic solvents and preferably from among ethers, alcohols, chlorinated solvents, and saturated or unsaturated hydrocarbons, aromatic or not, cyclic or not. In particular, said solvent is selected from among hexane, cyclohexane, methylcyclohexane, heptane, butane, or isobutane, where the monoolefins or diolefins preferably comprise 4-20 carbon atoms, benzene, toluene, orthoxylene, mesitylene, ethylbenzene, dichloromethane, chlorobenzene, methanol, ethanol, in pure form or in a mixture, and the ionic liquids. In the case where said reaction solvent is an ionic liquid, it is advantageously selected from among the ionic liquids described in the patents U.S. Pat. No. 6,951,831 B2 and FR 2895406 B1.

[0062] Oligomerization is defined as the transformation of a monomer unit into a compound or a mixture of compounds having the general formula C.sub.pH.sub.2p with 4p80, preferably with 4p50, in a preferred manner with 4p26, and in a more preferred manner with 4p14.

[0063] The olefins used in the method of oligomerization are olefins that comprise 2-10 carbon atoms. Preferably, said olefins are selected from among ethylene, propylene, n-butenes, and n-pentenes, by themselves or in a mixture, pure or dilute.

[0064] In the case where said olefins are dilute, said olefins are diluted with one or more alkane(s), such as those found in fractions resulting from petroleum refining methods, such as catalytic cracking or steam cracking.

[0065] In a preferred manner, the olefin used in the oligomerization method and, in particular, in the tetramerization method according to the invention is ethylene.

[0066] Said olefins can come from non-fossil resources such as biomass. For example, the olefins used in the oligomerization method according to the invention and, in particular, in the tetramerization method according to the invention can be produced from alcohols, and in particular by the dehydration of alcohols.

[0067] The oligomerization method, in particular the tetramerization method according to the invention, advantageously operates at a total pressure of between atmospheric pressure and 20 MPa, preferably between 0.1 and 8 MPa, and at a temperature of between 40 and +250 C., preferably between 0 and 150 C., preferably between 20 and 135 C., preferably between 45 and 100 C., preferably between 75 and 100 C., and preferably between 80 and 100 C.

[0068] The heat that is generated by the reaction can be eliminated by any means known to one skilled in the art.

[0069] The oligomerization method, in particular the tetramerization method according to the invention, can be carried out in a closed system, a semi-open system, or continuously, with one or more reaction stages. Vigorous stirring is advantageously employed to ensure good contact between the reagent(s) and the catalytic system.

[0070] The products obtained from this method can be used, for example, as components in plastics and more particularly polyethylene, fuels for motor vehicles, as feedstocks in a hydroformylation method for synthesizing aldehydes and alcohols, as components for the chemical industry, pharmaceutical industry, perfume-making and/or as feedstocks in a metathesis method for the synthesis of, for example, propylene.

[0071] The following examples illustrate the invention without limiting its scope.

EXAMPLES

Synthesis of Ligands

Ligand L1

[0072] ##STR00001##

[0073] 30 mL of dichloromethane (CH.sub.2Cl.sub.2), 6 mL of triethylamine (44.4 mmol), and 2.71 g (12.3 mmol) of Ph.sub.2PCl are introduced into a 100-mL Schlenk. At 0 C., 0.256 g (3.4 mmol) of 3-aminopropanol is added. The mixture is allowed to stir for 2 hours at room temperature. The solvent is evaporated. The product is extracted with pentane, and the pentane is then evaporated under a vacuum. The product is purified on an alumina column with a mixture of dichloromethane/pentane at a ratio of 30/70 (volume/volume). 0.4 g of a very viscous, whitish oil is obtained, i.e., a yield of approximately 19%. [0074] NMR .sup.1H (300.1 MHz, CD.sub.2Cl.sub.2); (ppm): 7.55-7.12 (m, 30H); 3.48 (m, 2H); 3.41 (m, 2H); 1.55-1.40 (m, 2H); NMR .sup.31P (121.5 MHz, CD.sub.2Cl.sub.2); (ppm): 111.4; 63.4; NMR .sup.13C (75.5 MHz, CD.sub.2Cl.sub.2); (ppm): 142.6; 140.0; 133.1; 130.4; 129.6; 129.2; 128.6; 128.5; 68.2; 50.7; 33.6.

Ligand L2

[0075] ##STR00002##

[0076] 60 mL of CH.sub.2Cl.sub.2, 3.0 g (29.6 mmol) of triethylamine, and 4.37 g (19.8 mmol) of Ph.sub.2PCl are introduced into a 100-mL Schlenk. At 0 C., 0.54 g (6.0 mmol) of 4-aminobutanol is added. The mixture is allowed to stir for one night at room temperature. The solvent is filtered and then evaporated. The triethylamine is eliminated by co-evaporation with toluene. Purification is then done by recrystallization in ethanol. Approximately 1 g of a very viscous oil is obtained, i.e., a yield of approximately 26%. [0077] NMR .sup.1H (300.1 MHz, CD.sub.2Cl.sub.2); (ppm): 7.55-7.27 (m, 30H); 3.54 (m, 2H); 3.31 (dt, 2H); 1.44-1.27 (m, 2H); 1.27-1.13 (m, 2H); NMR .sup.13C (75.5 MHz, CD.sub.2Cl.sub.2); (ppm): 142.8; 140.1; 133.1; 130.4; 129.5; 129.1; 128.6; 128.5; 70.0; 53.1; 29.1; 28.5; NMR .sup.31P (121.5 MHz, CD.sub.2Cl.sub.2); (ppm): 110.4; 62.6.

Ligand L3

[0078] ##STR00003##

[0079] 0.436 g (3.72 mmol) of 6-aminohexanol is weighed into a Schlenk. 6 mL (44.45 mmol) of triethylamine and 30 mL of dichloromethane (CH.sub.2Cl.sub.2) are added. At 0 C., 1.81 g (8.20 mmol) of Ph.sub.2PCl is added drop by drop. The mixture is allowed to stir for 2 hours at room temperature. The volatile products are filtered and then evaporated. Extraction is done with 6 times 7 mL of pentane. The solvent is eliminated under vacuum. 1.2 g of a yellowish, very viscous oil is obtained, i.e., a yield of approximately 66%. [0080] NMR .sup.1H (300.1 MHz, CD.sub.2Cl.sub.2); (ppm): 7.53-7.22 (m, 30H); 3.71 (m, 2H); 3.23 (m, 2H); 1.44 (m, 2H); 1.06 (m, 4H); 0.91 (m, 2H). NMR .sup.31P (121.5 MHz, CD.sub.2Cl.sub.2); (ppm): 110.6; 62.5; NMR .sup.13C (75.5 MHz, CD.sub.2Cl.sub.2); (ppm): 143.0; 140.2; 133.1; 130.4; 129.5; 129.1; 128.7; 128.4; 70.4; 53.4; 31.7; 31.6; 26.7; 25.7.

Catalytic Tests

[0081] The ligands L1, L2, and L3 are evaluated in the presence of Cr(acac).sub.3 (acac=acetylacetonate) for the ethylene tetramerization reaction. The molar ratio between the ligand and chromium is 2. The activator agent used is methylaluminoxane (MAO) at a molar ratio of MAO to the precursor Cr(acac).sub.3 of 600. The reaction is run under 4.5 MPa of ethylene. The ligands are evaluated at three different temperatures, i.e., 45 C., 80 C., and 100 C.

[0082] The ligand Ref below is used for comparison and is evaluated under the same conditions as the ligands L1, L2, and L3.

##STR00004##

[0083] Operating Conditions: A 100-mL reactor is placed under ethylene pressure. The reaction solvent is introduced into the reactor as well as the MAO (10% by weight in toluene). The reactor is then put under 0.5 MPa of ethylene and is stirred for 5 minutes. After depressurization, the solution that is formed by the chromium precursor Cr(acac).sub.3 and the ligand is then introduced into the reactor. The reactor is then placed under 2 MPa of ethylene pressure and is heated to the test temperature. The pressure is finished off at 4.5 MPa, and stirring at 1,000 RPM is initiated. The system is then monitored for pressure.

[0084] At the end of the test, the ethylene feed is cut off, and the reactor is cooled. Once the reactor has been degassed, the liquid phase and the polymer that is optionally formed are recovered and weighed. The polymer is weighed after drying at 100 C. for one night. The liquid phase is then neutralized with a 10% by weight sulfuric acid solution. The analysis of the liquid phase is done by gas phase chromatography with a GC HP 685 that is equipped with a column of the PONA brand.

[0085] The results of the experiments are presented in the table below. The ethylene consumption described in the table corresponds to the quantity (in grams) of ethylene that is transformed during the catalytic test into reaction products. The activity described in g/(g.sub.Cr.h) in the table corresponds to the quantity of ethylene (in grams) that is transformed by 1 g of chromium obtained from the catalytic composition relative to one hour of reaction.

[0086] FIG. 1 depicts the changes in C8 productivity as a function of the reaction temperature. The C8 productivity described in FIG. 1 corresponds to the quantity of octenes (in grams) that is transformed by 1 g of chromium obtained from the catalytic composition relative to one hour of reaction. Said productivity is calculated by multiplying the activity by the percentage of C8 that is the weight percentage of C8 with respect to the products formed.

TABLE-US-00001 Temp. Tps Consumption Activity C.sub.6 C.sub.8 PE Ligand ( C.) (min) of C.sub.2H.sub.4 (g) (g/(g.sub.Cr-h) % C.sub.6.sup.a % 1-C.sub.6.sup.b % C.sub.8.sup.a % 1-C.sub.8.sup.c %.sup.a (mg) Ref* 45 8 21.5 621 21.2 76.0 62.6 98.8 1.0 210 Ref* 80 30 18.1 140 33.2 88.6 55.8 99.1 1.6 283 Ref* 100 30 16.2 125 46.1 93.9 39.6 98.9 3.7 569 L1 45 8 17.3 494 14.7 31.5 42.3 93.7 14.0 2,259 L1 80 15 18.2 278 27.9 66.3 57.4 97.4 1.3 228 L1 100 30 16.6 127 38.6 84.3 44.3 97.9 4.0 628 L2 45 15 21.1 321 16.7 35.6 50.0 94.4 8.3 1,615 L2 80 10 16.7 380 27.4 66.6 58.4 97.5 2.2 334 L2 100 15 19.5 296 38.3 82.8 45.7 97.8 3.0 562 L3 45 8 10.0 288 14.7 32.9 53.1 95.2 5.2 497 L3 80 15 7.8 274 27.3 68.4 60.1 97.8 1.5 260 L3 100 30 19.9 153 36.0 83.5 43.8 97.9 7.8 1,437 Reaction conditions: Cr(acac).sub.3, n.sub.Cr = 5 mol; Ligand/Cr = 2, (MAO/Cr = 600); Solvent = Cyclohexane (50 mL), Pressure = 4.5 MPa of C.sub.2H.sub.4. *= Comparison example. .sup.a% = Percent by weight relative to products formed. .sup.b% 1-C.sub.6: Percentage of hexene-1 in the C.sub.6 fraction. .sup.c%1-C.sub.8: Percentage of octene-1 in the C.sub.8 fraction. PE = Polyethylene, Temp. = Temperature, Tps = Time.

[0087] We observe that the compositions according to the invention make it possible to increase significantly the proportion of C8 (% C8) relative to the other products that are formed when the temperature is raised from 45 C. to 80 C. In particular, at 80 C., it can be noted that the C8 productivity observed with the compositions (with L1, L2, and L3) according to the invention is thus considerably superior to that observed with the composition used as a comparison example (Ref).