CN109701662B - Catalyst composition and application thereof - Google Patents
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- CN109701662B CN109701662B CN201711011375.8A CN201711011375A CN109701662B CN 109701662 B CN109701662 B CN 109701662B CN 201711011375 A CN201711011375 A CN 201711011375A CN 109701662 B CN109701662 B CN 109701662B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 239000000203 mixture Substances 0.000 title claims abstract description 66
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 45
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000005977 Ethylene Substances 0.000 claims abstract description 39
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 27
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 26
- 239000003446 ligand Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 7
- 125000002950 monocyclic group Chemical group 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 69
- 238000006243 chemical reaction Methods 0.000 claims description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 35
- 238000010992 reflux Methods 0.000 claims description 35
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 26
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 25
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 13
- 239000001282 iso-butane Substances 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 238000005829 trimerization reaction Methods 0.000 claims description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 238000004817 gas chromatography Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001845 chromium compounds Chemical class 0.000 claims description 2
- KKQDIUNZFJXUNS-UHFFFAOYSA-L chromium(2+) oxolane dichloride Chemical compound [Cl-].[Cl-].[Cr++].C1CCOC1.C1CCOC1 KKQDIUNZFJXUNS-UHFFFAOYSA-L 0.000 claims description 2
- FRBFQWMZETVGKX-UHFFFAOYSA-K chromium(3+);6-methylheptanoate Chemical compound [Cr+3].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O FRBFQWMZETVGKX-UHFFFAOYSA-K 0.000 claims description 2
- CYOMBOLDXZUMBU-UHFFFAOYSA-K chromium(3+);oxolane;trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1.C1CCOC1.C1CCOC1 CYOMBOLDXZUMBU-UHFFFAOYSA-K 0.000 claims description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002506 iron compounds Chemical class 0.000 claims description 2
- 239000005078 molybdenum compound Substances 0.000 claims description 2
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002816 nickel compounds Chemical class 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000003609 titanium compounds Chemical class 0.000 claims description 2
- 150000003755 zirconium compounds Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- 239000003426 co-catalyst Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 9
- 239000003849 aromatic solvent Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 60
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 32
- 238000001816 cooling Methods 0.000 description 25
- 239000000047 product Substances 0.000 description 22
- 239000002904 solvent Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 13
- -1 Polyethylene Polymers 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000009616 inductively coupled plasma Methods 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000003367 polycyclic group Chemical group 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
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- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
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- 229920000098 polyolefin Polymers 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention relates to a catalyst composition for ethylene oligomerization, which comprises a ligand compound shown in a formula I, a transition metal compound and an alkane solution containing an aluminum cocatalyst;
Description
Technical Field
The present invention relates to a catalyst composition for oligomerization of ethylene. The invention also relates to an application of the catalyst composition in an ethylene oligomerization process.
Background
Ethylene oligomerization is one of the most important reactions in the olefin polymerization industry. Through oligomerization, cheap small-molecular olefins can be converted into products with high added value. The ethylene oligomerization product, linear alpha-olefin (LAO), is an important organic chemical raw material. For example, LAO C4-C8 is used as an important organic raw material and a chemical intermediate, and is mainly applied to the field of producing high-quality Polyethylene (PE). The Linear Low Density Polyethylene (LLDPE) produced by copolymerizing 1-hexene or 1-octene with ethylene can obviously improve various properties of PE, in particular can obviously improve the mechanical property, optical property, tear strength and impact strength of polyethylene, and the product is very suitable for the fields of packaging films, agricultural covering films for greenhouses, sheds and the like. LAO C10-C30 can be used as additives for preparing household cleaning agents, flotation agents, emulsifiers, lubricating components for refrigerators and lubricating components for drilling fluids, plasticizers, various additives, low-viscosity synthetic oils, polymers and copolymers, petroleum and petroleum product additives, higher alkylamines, higher organoaluminum compounds, higher alkylaryl hydrocarbons, higher fatty alcohols and fatty acids, epoxides, heat carriers, and the like. Adhesives, sealants and coatings can also be synthesized on the basis of LAO C20-C30. In recent years, with the continuous development of the polyolefin industry, the worldwide demand for α -olefins has rapidly increased. Wherein the majority of the alpha-olefin is prepared by ethylene oligomerization.
Since the last 70 s, the research on the polymerization and oligomerization of olefins catalyzed by transition metal complexes has been receiving the attention of scientists, and efforts have been made to research new catalysts and improve the existing catalysts, so as to improve the activity of the catalysts and the selectivity of catalytic products. Among the most developed and concentrated researches on the nickel-based cationic catalytic system were conducted in the earliest research, such as U.S. Pat. Nos. 3686351 and 3676523 reported earlier, and the Shell SHOP technology based on the technology of the above patents. The O-P bridging ligand is involved in the Shell company SHOP process, but the catalyst contains toxic organophosphorus groups, and the synthesis steps are complex and the stability is poor. Subsequently, many patents such as O-O, P-N, P-P and N-N type complex nickel catalysts have been developed, such as JP11060627, WO9923096, WO991550, CN1401666, CN1769270, etc. However, the catalysts obtained from the above patents suffer from the general disadvantage of relatively complicated preparation processes. Other catalysts are chromium, zirconium and aluminum, Brookhart groups (Brookhart, M et al, J.Am.chem.Soc.,1998,120, 7143-.
In the field of olefin polymerization, particularly metallocene catalysis, alkoxy aluminum such as Methyl Aluminoxane (MAO) or Modified Methyl Aluminoxane (MMAO) is generally used as a cocatalyst, and the price of MAO is dozens of times higher than that of other alkyl aluminum, so that the catalyst has long been a main bottleneck for restricting the industrialization of the field. In addition, MAO is very difficult to dissolve in alkane solvents, so commercially available MAO is generally an aromatic hydrocarbon solution such as toluene, which causes aromatic hydrocarbon residues in the reaction product, resulting in low catalyst activity and also seriously affecting product quality. While the use of co-polymer grade a-olefins in the preparation of polyethylene tends to severely limit their aromatic content.
There is no doubt that there is still a need for a novel catalyst with excellent comprehensive performance in the field of olefin oligomerization. Attention is paid to how to obtain a cocatalyst with lower cost and more excellent performance, so that an ethylene oligomerization catalyst with high activity and selectivity is developed, and the attention is paid to the industry.
Disclosure of Invention
The inventors of the present application have found a catalyst composition when studying an ethylene oligomerization catalyst. The catalyst composition is used for catalyzing ethylene oligomerization reaction, especially ethylene trimerization and tetramerization reaction, and has the advantages of high activity and high selectivity.
According to one aspect of the present invention, there is provided a catalyst composition comprising a ligand compound represented by formula I, a transition metal compound, and an alkane solution containing an aluminum cocatalyst;
in the formula I, R is selected from cycloalkyl, monocyclic aryl, polycyclic aryl and derivatives thereof; r 'and R' are independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, monocyclic and polycyclic aryl;
the preparation method of the alkane solution containing the aluminum cocatalyst comprises the following steps:
step a: reacting water with an aromatic hydrocarbon solution of aluminum alkyl; wherein the general formula of the alkyl aluminum is R1R2R3Al，R1、R2And R3Same or different, independently selected from C1-C20Alkyl groups of (a);
step b: reacting the solution obtained after the reaction in the step a with an aromatic hydrocarbon solution of aluminoxane; alkyl groups and R in said aluminoxanes1、R2And R3Different;
step c: and c, reacting the solution obtained after the reaction in the step b with water, removing aromatic hydrocarbon, and adding alkane to obtain an alkane solution containing the aluminum cocatalyst.
The catalyst composition has the advantages of simple preparation and low cost, can effectively catalyze ethylene oligomerization reaction, particularly ethylene trimerization and tetramerization reaction, and has high activity and high selectivity.
The catalyst composition according to the present invention, the preparation method thereof comprises: an alkane solution containing an aluminum promoter is first prepared by a process comprising the steps of:
step a: reacting water with an aromatic hydrocarbon solution of aluminum alkyl; wherein the general formula of the alkyl aluminum is R1R2R3Al，R1、R2And R3Same or different, independently selected from C1-C20Alkyl groups of (a);
step b: reacting the solution obtained after the reaction in the step a with an aromatic hydrocarbon solution of aluminoxane; alkyl groups and R in said aluminoxanes1、R2And R3Different;
step c: b, reacting the solution obtained after the reaction in the step b with water, removing aromatic hydrocarbon, and adding alkane to obtain an alkane solution containing the aluminum cocatalyst;
then mixing the prepared alkane solution containing the aluminum cocatalyst with the ligand compound shown in the formula I and the transition metal compound, or mixing the prepared alkane solution containing the aluminum cocatalyst with the ligand compound shown in the formula I and the transition metal compound when in use.
According to some preferred embodiments of the invention, in the general formula of the aluminum alkyl, R1、R2And R3Same or different, independently selected from C1-C10Alkyl group of (1). In some preferred embodiments, R1、R2And R3And the same is selected from one of methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, tert-butyl and n-pentyl.
According to some preferred embodiments of the present invention, the aluminoxane is selected from at least one of methylaluminoxane and ethylaluminoxane.
According to some preferred embodiments of the present invention, the step a comprises adding water to the triisobutylaluminum aromatic hydrocarbon solution at a low temperature, stirring the mixture for a certain time, heating the mixture to reflux, and then cooling the mixture to room temperature for standby. Preferably, step a comprises reacting the water with an aromatic hydrocarbon solution of an aluminum alkyl at-20 ℃ to 10 ℃, such as-20 ℃ to 0 ℃, such as-10 ℃ to 0 ℃ for 0.1h to 1h, and then heating under reflux for 0.1h to 1 h. In some preferred embodiments, the molar ratio of water to the aluminum alkyl in step a is (0.5-1): 1.
According to some preferred embodiments of the present invention, the step b comprises mixing the product of the step a with a methylaluminoxane aromatic hydrocarbon solution, heating the mixture to reflux for reaction, and cooling the mixture to room temperature for later use. Preferably, the solution obtained after the reaction of step a is mixed with an aromatic hydrocarbon solution of aluminoxane at 5 ℃ to 40 ℃, preferably at room temperature, and then heated under reflux for 0.1h to 1 h. In some preferred embodiments, the molar ratio of aluminoxane to aluminum alkyl in step b is (0.1-3):1, preferably (0.5-1): 1.
According to some preferred embodiments of the present invention, the step c comprises adding water to the aromatic hydrocarbon solution in the step b at a low temperature, stirring for a certain time, heating to reflux, and cooling to room temperature; preferably, the solution obtained after the reaction in step b is reacted with water at-20 ℃ to 10 ℃, preferably-10 ℃ to 0 ℃ for 0.1h to 1h, followed by heating under reflux for 0.1h to 1 h. In some preferred embodiments, the molar ratio of water to the aluminoxane in step c is (0.1-0.3): 1.
According to the invention, the reflux temperature is the boiling temperature of the aromatic hydrocarbon solvent.
In the present invention, the term "aromatic hydrocarbon" refers to hydrocarbon compounds having a benzene ring structure, such as benzene, toluene, xylene, naphthalene, and phenyl derivatives substituted with halogen, nitro or alkyl.
In the present invention, the term "alkane" refers to a saturated hydrocarbon such as at least one of pentane, hexane, heptane, cyclopentane, cyclohexane, methylcyclohexane, and the like.
According to some preferred embodiments of the invention, R is1-R3Likewise, for isobutyl, the isobutane content in the gaseous product, measured by gas chromatography after hydrolysis of said aluminium-containing cocatalyst, is higher than 75% by weight, preferably from 78% by weight to 94% by weight.
According to some preferred embodiments of the present invention, the method for preparing the aluminum-containing cocatalyst comprises:
a. adding water into the triisobutyl aluminum aromatic hydrocarbon solution at a low temperature, stirring and reacting for a certain time, heating and refluxing, and then cooling to room temperature for later use;
b. mixing the product obtained in the step a with methylaluminoxane aromatic hydrocarbon solution, heating for reflux reaction, and cooling to room temperature for later use;
c. and (c) adding water into the aromatic hydrocarbon solution in the step (b) at a low temperature, stirring and reacting for a certain time, heating and refluxing, cooling to room temperature, removing aromatic hydrocarbon from the mixture under reduced pressure, and adding alkane to obtain an alkane solution containing the aluminum cocatalyst. Triisobutyl aluminum is adopted in the step a, methylaluminoxane is adopted in the step b, and after the obtained aluminum-containing cocatalyst is hydrolyzed, the content of isobutane in a gas phase product is higher than 75 wt%, such as 78-94 wt%, and the balance is methane through gas chromatography detection.
In a preferred embodiment of the present invention, the transition metal compound is at least one selected from the group consisting of a chromium compound, a molybdenum compound, an iron compound, a titanium compound, a zirconium compound and a nickel compound, preferably at least one of chromium acetylacetonate, chromium isooctanoate, chromium tris (tetrahydrofuran) trichloride or chromium bis (tetrahydrofuran) dichloride.
According to a preferred embodiment of the present invention, the ligand compound represented by formula I may be selected from those commonly used in the art and conforming to the structure of formula I. Wherein alkyl includes straight or branched chain alkyl, such as C1-C20Straight chain alkyl or C1-C10Straight-chain alkyl of (2), C3-C20Branched alkyl or C3-C10A branched alkyl group of (a); cycloalkyl radicals such as C3-C20Cycloalkyl groups and the like; the monocyclic or polycyclic aryl group may be a substituted or unsubstituted monocyclic or polycyclic aryl group such as phenyl, substituted phenyl. Derivatives of cycloalkyl groups such as substituted cycloalkyl groups; derivatives of monocyclic or polycyclic aryl groups, such as substituted monocyclic or polycyclic sisters.
In a preferred embodiment of the invention, R is selected from C3-C10Cycloalkyl of, C6-C15Monocyclic aryl of (A) and C10-C20Preferably selected from the group consisting of cyclohexyl, phenyl and substituted phenyl.
In a preferred embodiment of the invention, said R 'and R' are independently selected from hydrogen, C1-C10Alkyl (linear or branched), C3-C10Cycloalkyl of, C6-C15Monocyclic aryl of (A) and C10-C20Preferably selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl.
According to some preferred embodiments of the catalyst composition of the present invention, the amount of the transition metal compound is 0.1 to 10 moles, preferably 0.25 to 2 moles, more preferably 0.5 to 2 moles, relative to 1 mole of the ligand compound; the amount of the aluminum-containing cocatalyst is 1 to 1000 moles, preferably 10 to 700 moles, more preferably 100 to 200 moles.
According to the invention, the cocatalyst has good solubility in alkane, and the catalyst composition formed by the cocatalyst, the ligand and the metal salt has high activity.
According to another aspect of the present invention, there is also provided a method for using the above catalyst composition, comprising carrying out an oligomerization reaction of ethylene in the presence of the above catalyst composition. In some preferred embodiments, the oligomerization of ethylene is carried out in an organic solvent, more preferably an alkane. In the ethylene oligomerization reaction, the reaction temperature is 0-200 ℃, and preferably 0-100 ℃; the ethylene pressure is from 0.1 to 20.0MPa, preferably from 0.5 to 5.0 MPa.
According to another aspect of the present invention, there is provided another method of using the above catalyst composition, comprising conducting ethylene trimerization and/or tetramerization in the presence of the above catalyst composition. In some preferred embodiments, the ethylene trimerization and/or tetramerization reaction is carried out in an organic solvent, preferably an alkane. The reaction conditions were as follows: the temperature is 0-200 ℃, preferably 0-100 ℃; the ethylene pressure is from 0.1 to 20.0MPa, preferably from 0.5 to 5.0 MPa.
According to the invention, when the catalyst composition is used, the components in the composition can be mixed and then added into a reactor, or the components in the composition can be added into the reactor respectively.
According to the invention, when the catalyst composition is reacted in alkane, an aromatic hydrocarbon solvent can be avoided, aromatic hydrocarbon residue is not left in the product, the product quality is high, and high-quality alpha-olefin monomers can be provided for the chemical industry.
When the catalyst composition containing the cocatalyst is reacted in an organic solvent, all the solvents are subjected to anhydrous treatment before use; the method for the anhydrous treatment of the organic solvent may employ a method commonly used in the art.
The catalyst composition containing the cocatalyst can effectively catalyze ethylene oligomerization reaction, particularly ethylene trimerization and/or tetramerization reaction, and the activity of the catalyst can reach 9 x 10 to the maximum6g/(gCr. h), the selectivity of 1-octene component can exceed 75% at most, and the selectivity of 1-hexene component is about 20%. The catalyst composition has the characteristics of high activity, high selectivity and the like. Therefore, the catalyst composition has better industrial application prospect and economic value.
Detailed Description
The following examples are merely illustrative of the present invention in detail, but it should be understood that the scope of the present invention is not limited to these examples.
In the present invention, the aluminum content test was performed by inductively coupled plasma emission spectroscopy (ICP Optima8300, PE corporation, usa).
In the present invention, the gas chromatography is performed using a Hewlett packard 5890 chromatograph. A chromatographic column: agilent HP-Al/KCL, the column length is 50m, and the inner diameter is 0.320 mm; column temperature: keeping the temperature at 100 ℃ for 10 minutes, heating the temperature to 160 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 10 minutes, keeping the temperature at a sample inlet of 250 ℃ and keeping the temperature at a detector of 250 ℃; carrier gas: nitrogen, FID detector.
Ligand references used in the present invention were made in house (ACS cat., 2013,3(10), 2311).
Example 1
Slowly adding 7mmol of water into 10mmol of triisobutylaluminum (1M toluene solution) in an ice bath under the protection of nitrogen, stirring for reaction for 0.5 hour, heating and refluxing for 1 hour, and then cooling to room temperature for later use; adding 10mmol of methylaluminoxane (1M toluene solution) into the solution, heating and refluxing for 1 hour, and cooling to room temperature; and slowly adding 2mmol of water into the mixed solution under ice bath, stirring for reaction for 0.5 hour, heating and refluxing for 1 hour, cooling to room temperature, removing the toluene solvent under reduced pressure, and adding the methylcyclohexane solvent to obtain the cocatalyst A (1M, methylcyclohexane solution) with the total volume of 20 mL.
And (3) product analysis: taking a quantitative cocatalyst A, slowly adding excessive water to decompose the cocatalyst A, and testing the content of aluminum in a liquid phase component to be 3.4 wt% by using ICP (inductively coupled plasma); gas phase composition test isobutane content 89 wt%, methane content 11 wt%.
Example 2
Slowly adding 5mmol of water into 10mmol of triisobutylaluminum (1M toluene solution) in an ice bath under the protection of nitrogen, stirring for reaction for 0.5 hour, heating and refluxing for 1 hour, and then cooling to room temperature for later use; adding 10mmol of methylaluminoxane (1M toluene solution) into the solution, heating and refluxing for 1 hour, and cooling to room temperature; and slowly adding 2mmol of water into the mixed solution under ice bath, stirring for reaction for 0.5 hour, heating and refluxing for 1 hour, cooling to room temperature, removing the toluene solvent under reduced pressure, and adding the methylcyclohexane solvent to obtain the cocatalyst B (1M, methylcyclohexane solution) with the total volume of 20 mL.
And (3) product analysis: taking a certain amount of cocatalyst B (same as example 1), slowly adding excessive water to decompose the cocatalyst B, wherein the content of aluminum in the liquid-phase component is 3.4 wt% by ICP test; gas phase composition test isobutane content 90 wt%, methane content 10 wt%.
Example 3
Slowly adding 10mmol of water into 10mmol of triisobutylaluminum (1M toluene solution) in an ice bath under the protection of nitrogen, stirring for reaction for 0.5 hour, heating and refluxing for 1 hour, and then cooling to room temperature for later use; adding 10mmol of methylaluminoxane (1M toluene solution) into the solution, heating and refluxing for 1 hour, and cooling to room temperature; and slowly adding 2mmol of water into the mixed solution under ice bath, stirring for reaction for 0.5 hour, heating and refluxing for 1 hour, cooling to room temperature, removing the toluene solvent under reduced pressure, and adding the methylcyclohexane solvent to obtain the cocatalyst C (1M, methylcyclohexane solution) with the total volume of 20 mL.
And (3) product analysis: taking a certain amount of cocatalyst C (same as example 1), slowly adding excessive water to decompose the cocatalyst C, wherein the content of aluminum in the liquid-phase component is 3.4 wt% by ICP test; gas phase composition test isobutane content 78 wt% and methane content 22 wt%.
Example 4
Slowly adding 7mmol of water into 10mmol of triisobutylaluminum (1M toluene solution) in an ice bath under the protection of nitrogen, stirring for reaction for 0.5 hour, heating and refluxing for 1 hour, and then cooling to room temperature for later use; adding 10mmol of methylaluminoxane (1M toluene solution) into the solution, heating and refluxing for 1 hour, and cooling to room temperature; and slowly adding 3mmol of water into the mixed solution under ice bath, stirring for reaction for 0.5 hour, heating and refluxing for 1 hour, cooling to room temperature, removing the toluene solvent under reduced pressure, and adding the methylcyclohexane solvent to obtain the cocatalyst D (1M, methylcyclohexane solution) with the total volume of 20 mL.
And (3) product analysis: taking a certain amount of cocatalyst D (same as example 1), slowly adding excessive water to decompose the cocatalyst D, wherein the content of aluminum in the liquid-phase component is 3.4 wt% by ICP test; gas phase composition test isobutane content 91 wt%, methane content 9 wt%.
Example 5
Slowly adding 7mmol of water into 10mmol of triisobutylaluminum (1M toluene solution) in an ice bath under the protection of nitrogen, stirring for reaction for 0.5 hour, heating and refluxing for 1 hour, and then cooling to room temperature for later use; adding 10mmol of methylaluminoxane (1M toluene solution) into the solution, heating and refluxing for 1 hour, and cooling to room temperature; slowly adding 1mmol of water into the mixed solution under ice bath, stirring for reaction for 0.5 hour, heating and refluxing for 1 hour, cooling to room temperature, removing the toluene solvent under reduced pressure, and adding the methylcyclohexane solvent to obtain the cocatalyst E (1M, methylcyclohexane solution) with the total volume of 20 mL.
And (3) product analysis: taking a certain amount of cocatalyst E (same as example 1), slowly adding excessive water to decompose the cocatalyst E, wherein the content of aluminum in the liquid-phase component is 3.4 wt% by ICP test; gas phase composition test isobutane content 87 wt% and methane content 13 wt%.
Example 6
Slowly adding 7mmol of water into 10mmol of triisobutylaluminum (1M toluene solution) in an ice bath under the protection of nitrogen, stirring for reaction for 0.5 hour, heating and refluxing for 1 hour, and then cooling to room temperature for later use; adding 5mmol of methylaluminoxane (1M toluene solution) into the solution, heating and refluxing for 1 hour, and cooling to room temperature; slowly adding 1mmol of water into the mixed solution under ice bath, stirring for reaction for 0.5 hour, heating and refluxing for 1 hour, cooling to room temperature, removing the toluene solvent under reduced pressure, and adding the methylcyclohexane solvent to obtain the cocatalyst F (1M, methylcyclohexane solution) with the total volume of 15 mL.
And (3) product analysis: taking a certain amount of cocatalyst F (same as example 1), slowly adding excessive water to decompose the cocatalyst F, wherein the content of aluminum in the liquid-phase component is 3.4 wt% by ICP test; gas phase composition test isobutane content 94 wt%, methane content 6 wt%.
Example 7 (polymerization example)
The ethylene oligomerization reaction adopts a stainless steel polymerization kettle. The autoclave is heated to 80 ℃, vacuumized, replaced by nitrogen for a plurality of times, cooled to room temperature, and then filled with ethylene for replacement for a plurality of times. Then methylcyclohexane was added at 40 ℃ while adding 2.5. mu. mol of chromium acetylacetonate and 5. mu. mol of ligand L1(formula I, R ═ Ph, R' ═ t-Bu, R ═ H), then cocatalyst a was added, the total volume of the mixture was 100mL, wherein the molar ratio of chromium, the ligating compound and the cocatalyst was 1: 2: 400, controlling the reaction pressure to be 4MPa, and introducing ethylene to carry out ethylene oligomerization.
And after the reaction is finished, cooling the system to room temperature, collecting the gas-phase product in a gas metering tank, collecting the liquid-phase product in a conical flask, and adding 1mL of ethanol as a terminator to terminate the ethylene oligomerization reaction. And (4) carrying out gas chromatographic analysis after the gas-liquid phase product is measured. The reaction results are shown in Table 1.
Example 8 (polymerization example)
The same as example 7 except that cocatalyst A was changed to cocatalyst B; the reaction results are shown in Table 1.
Example 9 (polymerization example)
The same as example 7 except that cocatalyst A was changed to cocatalyst C; the reaction results are shown in Table 1.
Example 10 (polymerization example)
The same as example 7 except that cocatalyst A was changed to cocatalyst D; the reaction results are shown in Table 1.
Example 11 (polymerization example)
The same as example 7 except that cocatalyst A was changed to cocatalyst E; the reaction results are shown in Table 1.
Example 12 (polymerization example)
The same as example 7 except that cocatalyst A was changed to cocatalyst F; the reaction results are shown in Table 1.
Example 13 (polymerization example)
The same as example 7, except that the reaction pressure was changed from 4MPa to 6 MPa; the reaction results are shown in Table 1.
Example 14 (polymerization example)
The same as example 7, except that the amount of chromium acetylacetonate was kept constant, the amount of cocatalyst A was reduced (wherein the molar ratio of chromium, ligand compound and cocatalyst was 1: 2: 200); the reaction results are shown in Table 1.
Example 15 (polymerization example)
The same as example 7, except that the ligand L1Instead of ligand L2(formula I, R ═ Ph, R' ═ Cy, R ═ H); the reaction results are shown in Table 1.
Example 16 (polymerization example)
The same as example 7, except that the ligand L1Instead of ligand L3(formula I, R ═ Ph, R' ═ Me, R ═ H); the reaction results are shown in Table 1.
Example 17 (polymerization example)
The same as example 7, except that the ligand L1Instead of ligand L4(formula I, R ═ Cy, R' ═ R ═ Me); the reaction results are shown in Table 1.
Example 18 (polymerization example)
The same as example 7, except that the ligand L1Instead of ligand L5(as in formula I, R ═ R' ═ R ═ Ph); the reaction results are shown in Table 1.
Comparative example 1 (polymerization example)
The same as example 7 except that the cocatalyst A was changed to methylaluminoxane (1.5M in toluene);
the reaction results are shown in Table 1.
Comparative example 2 (polymerization example)
The same as example 7 except that the solvent methylcyclohexane was changed to toluene, and the cocatalyst A was changed to methylaluminoxane (1.5M toluene solution);
the reaction results are shown in Table 1.
Comparative example 3 (polymerization example)
An equal amount (as in example 1) of methylaluminoxane (1.5M in toluene) was taken, the solvent was removed in vacuo, and the residue was a white powdery solid which was not dissolved by addition of methylcyclohexane. The resulting polymer was used in polymerization reaction under the same conditions as in example 7, and the reaction did not proceed normally.
Comparative example 4 (polymerization example)
The same as example 7 except that cocatalyst A was changed to modified methylaluminoxane (aluminum content 3.4% by weight, heptane solution, isobutane content 63% by weight, methane content 37% by weight). The modified methylaluminoxane is prepared by adding heptane into a commercially available MMAO-3A 7 wt% heptane solution and diluting. The reaction results are shown in Table 1.
TABLE 1
The selectivity refers to the mass percentage of the component in the product.
As can be seen from table 1: the cocatalyst can be completely dissolved in an alkane solvent, and has ultrahigh catalytic activity in the reaction; the commercially available methylaluminoxane can only be dissolved in an aromatic hydrocarbon solvent, and when the methylaluminoxane is used for oligomerization reaction, the catalytic activity is obviously reduced no matter the methylaluminoxane solvent is an alkane solvent or an aromatic hydrocarbon solvent; the commercially available methylaluminoxane can not be effectively used for the reaction because the white powder solid obtained by removing the solvent can not be dissolved in the alkane solvent; the commercially available modified methylaluminoxane has low catalytic activity and low product selectivity, such as low 1-octene content.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
In the present invention, Ph is a phenyl group, Me is a methyl group, Et is an ethyl group, t-Bu is a tert-butyl group, and Cy is a cyclohexyl group.
It should be noted that the above-mentioned embodiments are used for explaining the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to the exemplary embodiments illustrated above, but it is understood that all words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (33)
1. A catalyst composition comprises a ligand compound shown as a formula I, a transition metal compound and an alkane solution containing an aluminum cocatalyst;
in formula I, R is selected from cycloalkyl, monocyclic aryl, polycyclic aryl and derivatives; r 'and R' are independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, monocyclic and polycyclic aryl;
the preparation method of the alkane solution containing the aluminum cocatalyst comprises the following steps:
step a: reacting water with an aromatic hydrocarbon solution of aluminum alkyl; wherein the general formula of the alkyl aluminum is R1R2R3Al，R1、R2And R3Same or different, independently selected from C1-C20Alkyl groups of (a); the molar ratio of water to the aluminum alkyl in step a is (0.5-1): 1;
step b: heating and refluxing the solution obtained after the reaction in the step a and the aromatic hydrocarbon solution of the aluminoxane; alkyl groups and R in said aluminoxanes1、R2And R3Different;
step c: b, reacting the solution obtained after the reaction in the step b with water, removing aromatic hydrocarbon, and adding alkane to obtain an alkane solution containing the aluminum cocatalyst; the molar ratio of water to the aluminoxane in step c is (0.1-0.3): 1.
2. The catalyst composition of claim 1, wherein the aluminum alkyl has the formula wherein R1、R2And R3Same or different, independently selected from C1-C10Alkyl group of (1).
3. The catalyst composition of claim 2, wherein the aluminum alkyl has the formula wherein R1、R2And R3And the same is selected from one of methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, tert-butyl and n-pentyl.
4. The catalyst composition of any of claims 1-3, wherein the aluminoxane is selected from at least one of methylaluminoxane and ethylaluminoxane.
5. The catalyst composition of any one of claims 1-3, wherein step a comprises reacting the water with an aromatic hydrocarbon solution of an aluminum alkyl at-20 ℃ to 10 ℃ for 0.1h to 1h, followed by heating under reflux for 0.1h to 1 h.
6. The catalyst composition of claim 5, wherein step a comprises reacting the water with an aromatic hydrocarbon solution of an aluminum alkyl at-10 ℃ to 0 ℃ for 0.1h to 1h, followed by heating to reflux for 0.1h to 1 h.
7. The catalyst composition of any one of claims 1 to 3, wherein the step b comprises mixing the solution obtained after the reaction in the step a with an aromatic hydrocarbon solution of aluminoxane at a temperature of 5 ℃ to 40 ℃, followed by heating and refluxing for 0.1h to 1 h.
8. The catalyst composition of claim 7, wherein the step b comprises mixing the solution obtained after the reaction of the step a with an aromatic hydrocarbon solution of aluminoxane at room temperature, and then heating and refluxing for 0.1 to 1 hour.
9. The catalyst composition of any of claims 1-3, wherein the molar ratio of the aluminoxane to the aluminum alkyl in step b is (0.1-3): 1.
10. The catalyst composition of claim 9, wherein the molar ratio of the aluminoxane to the aluminum alkyl in step b is (0.5-1): 1.
11. The catalyst composition according to any one of claims 1 to 3, wherein the step c comprises reacting the solution obtained after the reaction in the step b with water at-20 ℃ to 10 ℃ for 0.1h to 1h, and then heating under reflux for 0.1h to 1 h.
12. The catalyst composition of claim 11, wherein the step c comprises reacting the solution obtained after the reaction in the step b with water at-10 ℃ to 0 ℃ for 0.1h to 1h, and then heating and refluxing for 0.1h to 1 h.
13. The catalyst composition of any one of claims 1-3, wherein R is1-R3And when the catalyst is isobutyl, the content of isobutane in the gas-phase product is higher than 75 wt% measured by gas chromatography after the aluminum-containing cocatalyst is hydrolyzed.
14. The catalyst composition of claim 13, wherein R is1-R3And when the catalyst is isobutyl, the content of the isobutane in the gas-phase product is 78-94 wt% measured by gas chromatography after the aluminum-containing cocatalyst is hydrolyzed.
15. The catalyst composition of any one of claims 1-3, wherein R is selected from C3-C10Cycloalkyl of, C6-C15Monocyclic aryl of (A) and C10-C20Polycyclic aryl groups of (a) and derivatives thereof; and/or R 'and R' are independently selected from hydrogen, C1-C10Alkyl of (C)3-C10Cycloalkyl of, C6-C15Monocyclic aryl of (A) and C10-C20The polycyclic aromatic group of (1).
16. The catalyst composition of claim 15, wherein R is selected from the group consisting of cyclohexyl, phenyl, and substituted phenyl; and/or R 'and R' are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
17. The catalyst composition of any of claims 1-3, wherein the transition metal compound is selected from at least one of a chromium compound, a molybdenum compound, an iron compound, a titanium compound, a zirconium compound, and a nickel compound.
18. The catalyst composition of claim 17, wherein the transition metal compound is selected from at least one of chromium acetylacetonate, chromium isooctanoate, chromium tris (tetrahydrofuran) trichloride, or chromium bis (tetrahydrofuran) dichloride.
19. The catalyst composition according to any one of claims 1 to 3, characterized in that the amount of the transition metal compound is 0.1 to 10 moles with respect to 1 mole of the ligand compound; the amount of the aluminum-containing cocatalyst is 1 to 1000 mol.
20. The catalyst composition according to claim 19, wherein the amount of the transition metal compound is 0.25 to 2 moles with respect to 1 mole of the ligand compound.
21. The catalyst composition according to claim 19, wherein the amount of the transition metal compound is 0.5 to 2 moles with respect to 1 mole of the ligand compound.
22. The catalyst composition of claim 19, wherein the amount of the aluminum-containing co-catalyst is 10 to 700 moles with respect to 1 mole of the ligand compound.
23. The catalyst composition according to claim 19, wherein the amount of the aluminum-containing cocatalyst is 100-200 moles with respect to 1 mole of the ligand compound.
24. A method of using a catalyst composition comprising carrying out an oligomerization of ethylene in the presence of the catalyst composition of any of claims 1-23.
25. Use according to claim 24, characterized in that the oligomerization of ethylene is carried out in an organic solvent.
26. Use according to claim 24, characterized in that the oligomerization of ethylene is carried out in an alkane.
27. The use according to any one of claims 24 to 26, wherein in the ethylene oligomerization reaction, the reaction temperature is 0 to 200 ℃; the ethylene pressure is 0.1-20.0 MPa.
28. The use method of claim 27, wherein in the ethylene oligomerization reaction, the reaction temperature is 0-100 ℃; the ethylene pressure is 0.5-5.0 MPa.
29. A method of using a catalyst composition comprising conducting an ethylene trimerization and/or tetramerization reaction in the presence of the catalyst composition of any one of claims 1-23.
30. Use according to claim 29, characterized in that the ethylene trimerization and/or tetramerization reaction is carried out in an organic solvent.
31. Use according to claim 29, wherein ethylene trimerization and/or tetramerization reactions are carried out in alkanes.
32. Use according to any one of claims 29 to 31, wherein the reaction conditions are as follows: the temperature is 0-200 ℃; the ethylene pressure is 0.1-20.0 MPa.
33. Use according to claim 32, wherein the reaction conditions are as follows: the temperature is 0-100 ℃; the ethylene pressure is 0.5-5.0 MPa.
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