CN116020558A - Pyrrole bridged ethylene oligomerization catalyst composition and application - Google Patents
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Abstract
The invention discloses a pyrrole bridged ethylene oligomerization catalyst composition and application thereof. The ethylene oligomerization catalyst composition comprises a catalyst ligand shown in a formula (I), a transition metal compound and an aluminum-containing cocatalyst, or comprises a catalyst complex shown in a formula (II) and an aluminum-containing cocatalyst. The catalyst composition has the characteristics of high catalytic activity, high selectivity and the like, and has better industrial application prospect and economic value.
Description
Technical Field
The invention relates to the field of ethylene oligomerization, in particular to the field of ethylene trimerization or ethylene tetramerization, and more particularly relates to a pyrrole bridged ethylene oligomerization catalyst composition and application of the composition in ethylene oligomerization or ethylene trimerization or ethylene tetramerization.
Background
Alpha-olefins are important organic raw materials and chemical intermediates, and are mainly applied to the fields of producing high-quality Polyethylene (PE), lubricating oil base oil, plasticizer, detergent and the like. The linear low-density polyethylene (LLDPE) produced by copolymerizing 1-hexene or 1-octene and ethylene can obviously improve various properties of PE, in particular can obviously improve mechanical properties, optical properties, tear strength and impact strength of the PE, and the product is very suitable for the fields of packaging films, agricultural covering films such as greenhouse, greenhouse and the like. Polyolefin plastomers and polyolefin elastomers produced by copolymerizing 1-octene with ethylene are currently in great commercial consumption and demand. With the continued development of the polyolefin industry, the worldwide demand for alpha-olefins has grown rapidly.
Ethylene oligomerization is one of the most important reactions in the olefin polymerization industry, by which inexpensive small molecule ethylene can be converted into products with high added value, i.e., different long chain alpha-olefins. Since the 70 s of the last century, research on the polymerization and oligomerization of olefins catalyzed by transition metal complexes has been increasingly receiving attention from scientists, and efforts have been made to develop new catalysts and to improve existing catalysts, to increase the activity of the catalysts and the selectivity of the catalytic products. Among the many studies that have been carried out the earliest and most rapidly, the more concentrated are nickel-based cationic catalytic systems, as reported earlier in U.S. Pat. nos. 3686351a and 3676523a, and the shell corporation SHOP process based on this patent technology. O-P bridged ligand is involved in shell company SHOP process, but the catalyst contains toxic organic phosphorus group, and has complex synthesis steps and poor stability. A number of patents such as JP11060627, WO9923096A1, CN1401666A, CN1769270A and the like have been developed for O-O, P-N, P-P and N-N type complex nickel catalysts. However, the catalysts obtained from the above patents have the disadvantage of being relatively complex in terms of the preparation process.
Patent WO2004056478A1 by Sasol discloses a PNP framework catalyst having a C8 component selectivity of about 66wt% and a C6 component selectivity of about 21wt% in ethylene tetramerization, wherein the content of 1-hexene in the C6 component is only 82%, and the total selectivity of 1-hexene and 1-octene is about 84%. In US20100137669A1 patent, a symmetrical framework type catalyst for PCCP is disclosed, which is more stable than PNP system in ethylene tetramerization reaction, and the total selectivity of 1-hexene and 1-octene is not more than 85%
In these reaction systems, the byproducts such as cycloolefin and cyclized product present in the C6 product can be removed by separation and purification, but the economy of the whole process is disadvantageous.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a novel pyrrole bridged ethylene oligomerization catalyst composition, which has the characteristics of high catalytic activity, high selectivity and the like, and has better industrial application prospect and economic value.
In view of the above-mentioned shortcomings of the prior art, the present inventors have conducted intensive studies on this type of phosphorus-containing catalyst, and have found a pyrrole bridged ethylene oligomerization catalyst composition comprising a catalyst ligand represented by formula (I), a transition metal compound and an aluminum-containing cocatalyst, or a catalyst complex represented by formula (II) and an aluminum-containing cocatalyst. The catalyst ligand or the complex is of a pyrrole bridged biphosphine structure, and the aromatic ring contains an ortho halogen substituent, so that the catalyst ligand or the complex is novel in structure, simple to prepare and low in cost. The catalyst composition of the invention can effectively catalyze ethylene oligomerization, especially ethylene trimerization and tetramerization, and catalyzeThe activity exceeds 0.8X10 8 g·mol(Cr) -1 ·h -1 Up to 3.0X10 8 g·mol(Cr) -1 ·h -1 Under different conditions, the total selectivity of 1-hexene and 1-octene is more than 93wt% and can be up to 97wt%. Compared with the catalyst of the comparative example, the catalyst composition provided by the invention has obviously improved catalyst activity, especially greatly improved content of 1-hexene in C6, and obviously reduced byproducts such as cycloolefin, cyclized product and the like. Therefore, the catalyst composition provided by the invention has the characteristics of high catalytic activity, high selectivity and the like, and has good industrial application prospect and economic value.
The first aspect of the invention provides a pyrrole bridged ethylene oligomerization catalyst composition, which comprises a catalyst ligand shown in a formula (I), a transition metal compound and an aluminum-containing cocatalyst, or comprises a catalyst complex shown in a formula (II) and an aluminum-containing cocatalyst,
in the formula (I), R 1 、R 2 、R 3 、R 4 The same or different, each independently selected from hydrogen or fluorine atoms;
in the formula (II), R 1 ’、R 2 ’、R 3 ’、R 4 'same or different', each independently selected from hydrogen or fluorine atoms, M is a transition metal, X is selected from halogen, and n is an integer of 1 to 3.
According to some embodiments of the invention, M in formula (II) is selected from at least one of chromium, molybdenum, iron, titanium, zirconium and nickel.
According to some embodiments of the invention, the aluminum-containing cocatalyst is an organoaluminum compound, preferably at least one from the group consisting of an alkylaluminum compound, an alkylaluminum compound and an alkylaluminum chloride compound, more preferably at least one from the group consisting of methylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, ethylaluminoxane and modified methylaluminoxane, more preferably at least one from the group consisting of modified methylaluminoxane, methylaluminoxane and triethylaluminum. In the present invention, the modified methylaluminoxane may be an alkyl modified methylaluminoxane, such as alkyl modified methylaluminoxane MMAO which is conventional in the art.
According to some embodiments of the invention, the transition metal compound is selected from at least one of chromium, molybdenum, iron, titanium, zirconium and nickel compounds; preferably, the transition metal compound is selected from at least one of chromium acetylacetonate, chromium isooctanoate, chromium tri (tetrahydrofuran) trichloride, and chromium di (tetrahydrofuran) dichloride.
According to some embodiments of the present invention, the molar ratio of the transition metal compound, the catalyst ligand of formula (I) and the aluminum-containing cocatalyst, calculated as metal elements, is 1:0.1-10:1-1000, preferably 1:0.25-2:10-700, more preferably 1:0.5-2:100-500.
According to some embodiments of the present invention, the molar ratio of the catalyst complex of formula (II) to the aluminum-containing cocatalyst is from 1:1 to 1000, preferably from 1:10 to 700, more preferably from 1:100 to 500.
According to some embodiments of the invention, the organic solvent may be an organic solvent commonly used for polymerization, preferably at least one selected from methylcyclohexane, heptane, cyclohexane, toluene and xylene.
According to one embodiment of the present invention, a pyrrole bridged ethylene oligomerization catalyst composition comprises: a catalyst ligand represented by formula (I), a transition metal compound and an aluminum-containing cocatalyst;
in the formula (I), R 1 、R 2 、R 3 、R 4 The same or different are each independently selected from hydrogen or fluorine atoms.
According to another embodiment of the present invention, a pyrrole bridged ethylene oligomerization catalyst composition comprises: a catalyst complex represented by the formula (II) and an aluminum-containing cocatalyst,
in the formula (II), R 1 ’、R 2 ’、R 3 ’、R 4 'same or different', each independently selected from hydrogen or fluorine atoms, M is a transition metal, X is selected from halogen, n is an integer from 1 to 3, preferably M is selected from at least one of chromium, molybdenum, iron, titanium, zirconium and nickel.
In a second aspect, the invention provides a process for the oligomerization of ethylene comprising: the ethylene oligomerization reaction is carried out in an organic solvent in the presence of the catalyst composition according to the above.
According to some embodiments of the invention, the concentration of the catalyst composition is 0.1 to 10. Mu. Mol/L on a metal basis, calculated on the volume of the organic solvent. For example, when the transition metal is Cr, the catalyst composition has a concentration of 0.1 to 10. Mu. Mol/L in terms of Cr.
According to some embodiments of the invention, the reaction conditions may be those commonly used in the art. Preferably, the reaction temperature of the ethylene oligomerization is from 0 to 200 ℃, preferably from 0 to 100 ℃, more preferably from 30 to 100 ℃.
According to some embodiments of the invention, the reaction conditions may be those commonly used in the art. Preferably, the ethylene oligomerization reaction has an ethylene pressure of 0.1 to 20.0MPa, preferably 0.5 to 5.0MPa, more preferably 2.0 to 5.0MPa.
According to some embodiments of the present invention, any two of the catalyst ligand, the transition metal compound and the aluminum-containing cocatalyst in the catalyst composition may be premixed and then added to the reaction system together with the other in the above-mentioned ethylene oligomerization process; or directly adding the three components of the catalyst ligand, the transition metal compound and the aluminum-containing cocatalyst into a reaction system for in-situ synthesis; or premixing the catalyst ligand, the transition metal compound and the aluminum-containing cocatalyst, and directly adding the mixture into a reaction system.
According to some embodiments of the present invention, in the above-mentioned ethylene oligomerization process, the catalyst complex and the aluminum-containing cocatalyst in the catalyst composition may be pre-mixed and then added together to the reaction system, or both components of the catalyst complex and the aluminum-containing cocatalyst may be directly added to the reaction system.
In a third aspect the invention provides a process for trimerising or tetramerising ethylene comprising: ethylene trimerization or ethylene tetramerization is carried out in an organic solvent in the presence of a catalyst composition according to the above.
According to some embodiments of the invention, the concentration of the catalyst composition is 0.1 to 10. Mu. Mol/L on a metal basis, calculated on the volume of the organic solvent. For example, when the transition metal is Cr, the catalyst composition has a concentration of 0.1 to 10. Mu. Mol/L in terms of Cr.
According to some embodiments of the invention, the reaction conditions may be those commonly used in the art. Preferably, the reaction temperature of the ethylene oligomerization is from 0 to 200 ℃, preferably from 0 to 100 ℃, more preferably from 30 to 100 ℃.
According to some embodiments of the invention, the reaction conditions may be those commonly used in the art. Preferably, the ethylene oligomerization reaction has an ethylene pressure of 0.1 to 20.0MPa, preferably 0.5 to 5.0MPa, more preferably 2.0 to 5.0MPa.
According to some embodiments of the present invention, any two of the catalyst ligand, the transition metal compound and the aluminum-containing cocatalyst in the catalyst composition may be premixed and then added to the reaction system together with the other in the above-mentioned ethylene oligomerization process; or directly adding the three components of the catalyst ligand, the transition metal compound and the aluminum-containing cocatalyst into a reaction system for in-situ synthesis; or premixing the catalyst ligand, the transition metal compound and the aluminum-containing cocatalyst, and directly adding the mixture into a reaction system.
According to some embodiments of the present invention, in the above-mentioned ethylene oligomerization process, the catalyst complex and the aluminum-containing cocatalyst in the catalyst composition may be pre-mixed and then added together to the reaction system, or both components of the catalyst complex and the aluminum-containing cocatalyst may be directly added to the reaction system.
The invention has the beneficial effects that:
(1) The catalyst ligand or the complex in the pyrrole bridged ethylene oligomerization catalyst composition is of a pyrrole bridged biphosphine structure, and the preparation is simple and the cost is low.
(2) The pyrrole bridged ethylene oligomerization catalyst composition can effectively catalyze ethylene oligomerization reactions, especially ethylene trimerization and tetramerization reactions, and has high catalyst activity and good product selectivity; and the byproducts such as cycloolefin, cyclized product and the like in the C6 product are obviously reduced.
(3) The catalyst composition provided by the invention has the characteristics of high catalytic activity, high selectivity and the like, and has good industrial application prospect and economic value.
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples, which are given by way of illustration only and are not limiting of the scope of application of the invention.
The test method and the equipment used in the test are as follows:
(1) In the embodiment of the invention, nuclear magnetic resonance is detected by using a Bruker AV400 type nuclear magnetic resonance apparatus, wherein the detection conditions of nuclear magnetic resonance are as follows: deuterated chloroform is used as solvent.
(2) The room temperature test gas chromatograph adopts an Agilent 7890 chromatograph to detect, wherein the detection conditions of the gas chromatograph are as follows: a chromatographic column SE-54, a high-purity nitrogen carrier gas and a FID detector; the column temperature adopts two-stage temperature programming.
[ PREPARATION EXAMPLE 1 ]
Preparation of catalyst ligand I 1 (R 1 ＝R 2 ＝R 3 ＝R 4 ＝F)
N-Boc-2, 5-dibromopyrrole (15 mmol) and tetrahydrofuran (200 mL) are added into a three-neck flask under the protection of nitrogen, cooled to-78 ℃, N-butyllithium (30 mmol) is added dropwise, stirred for 1 hour, and di- (2-bromophenyl) phosphorus chloride is added dropwise30 mmol) was added and the reaction was allowed to proceed to room temperature for 18 hours, and after completion of the reaction, the solvent was removed under reduced pressure. The residue is dissolved in toluene (50 mL) under the protection of nitrogen, heated to 155 ℃ for 18 hours, the solvent is removed in vacuum after the reaction is completed, yellow solid is obtained, and toluene is used for recrystallization to obtain white solid product, namely the catalyst ligand I 1 。
1 H-NMR(δ，ppm，CDCl 3 ，TMS)：6.9～7.2(m，16H，Ar-H)，5.9(s，2H，CH)，4.9(s，1H，NH)。
[ PREPARATION EXAMPLE 2 ]
Preparation of catalyst ligand I 2 (R 1 ＝R 2 ＝H，R 3 ＝R 4 ＝F)
N-Boc-2, 5-dibromopyrrole (15 mmol) and tetrahydrofuran (200 mL) were added to a three-necked flask under the protection of nitrogen, cooled to-78 ℃, N-butyllithium (30 mmol) was added dropwise, stirred for 1 hour, bis- (2-bromophenyl) phosphorus chloride (15 mmol) was added first, after half an hour, diphenyl phosphorus chloride (15 mmol) was added, the mixture was transferred to room temperature to react for 18 hours after the completion of the reaction, and the solvent was removed under reduced pressure. Separating the residue by column chromatography, dissolving in toluene (50 mL) under nitrogen protection, heating to 155 deg.C for 18 hr, vacuum removing solvent after reaction, and recrystallizing the residue with toluene to obtain white solid product (catalyst ligand I) 2 。
1 H-NMR(δ，ppm，CDCl 3 ，TMS)：7.0～7.3(m，18H，Ar-H)，6.0(s，2H，CH)，5.1(s，1H，NH)。
[ PREPARATION EXAMPLE 3 ]
Preparation of catalyst Complex II 1 (R 1 ＝R 2 ＝H，R 3 ＝R 4 =f, M is Cr, X is Cl, n is 2
5mmol of catalyst ligand I under nitrogen 2 And 5mmol CrCl 3 (THF) 3 Transfer to Schlenk tube, add 50mL toluene solution, then warm to 80 ℃ and stir for 8 hours. Cooling the reaction liquid to room temperature, carrying out suction filtration, washing the obtained solid with toluene and normal hexane respectively, and carrying out vacuum drying to obtain the corresponding biphosphine chromium complexNamely catalyst complex II 1 。
1 H-NMR(δ，ppm，CDCl 3 TMS): 7.0 to 7.3 (m, 18H, ar-H), 6.0 (s, 2H, CH), 5.1 (s, 1H, NH). Elemental analysis test C 28 H 21 Cl 2 CrF 2 NP 2 (calcd)：C,56.50(56.59)；H,3.88(3.56)；N,2.29(2.36)。
[ example 1 ]
A300 mL stainless steel polymerizer was used. The autoclave was heated to 80 ℃, evacuated, replaced several times with nitrogen, then replaced by ethylene and cooled to the set temperature. Then methylcyclohexane was added at 40℃with 0.5. Mu. Mol of chromium acetylacetonate and catalyst ligand I 1 (obtained in preparation example 1) and cocatalyst-Modified Methylaluminoxane (MMAO), the total volume of the mixture was 100mL, in which the molar ratio of chromium acetylacetonate (calculated as chromium), ligand and cocatalyst was 1:2:500, ligand I 1 The addition amount is 1.0 mu mol/L, MMAO calculated by Cr, the addition amount is 250 mu mol, the reaction pressure is controlled to be 3MPa, the temperature is controlled to be 40 ℃, ethylene is introduced, and the ethylene oligomerization reaction is carried out.
After half an hour, the reaction was completed, the system was cooled to room temperature, the gas phase product was collected in a gas metering tank, the liquid phase product was collected in a conical flask, and 1mL of ethanol was added as a terminator to terminate the reaction. The gas-liquid phase product was measured and analyzed by gas chromatography (chromatograph is Hewlett-packard 5890). The data results are shown in Table 1.
[ example 2 ]
The same as in example 1, except that the catalyst ligand I 1 Replacement with catalyst ligand I 2 . The data results are shown in Table 1.
[ example 3 ]
A300 mL stainless steel polymerizer was used. The autoclave was heated to 80 ℃, evacuated, replaced several times with nitrogen, then replaced by ethylene and cooled to the set temperature. Then methylcyclohexane was added at 40℃followed by 0.5. Mu. Mol of catalyst complex II 1 (R 1 ＝R 2 ＝H，R 3 ＝R 4 ＝F,M＝Cr,X n ＝Cl 2 ) Finally adding cocatalyst to modify methyl aluminum100. Mu. Mol of an oxygen alkane (MMAO) and 100mL of a total volume of the mixture, wherein the molar ratio of the catalyst complex to the cocatalyst is 1:500. controlling the reaction pressure to 3MPa and the temperature to 40 ℃, introducing ethylene, and carrying out ethylene oligomerization.
After half an hour, the reaction was completed, the system was cooled to room temperature, the gas phase product was collected in a gas metering tank, the liquid phase product was collected in a conical flask, and 1mL of ethanol was added as a terminator to terminate the reaction. The gas-liquid phase product was measured and analyzed by gas chromatography (chromatograph is Hewlett-packard 5890). The data results are shown in Table 1.
[ example 4 ]
The procedure is as in example 1, except that the modified methylaluminoxane is replaced by triethylaluminum. The data results are shown in Table 1.
[ example 5 ]
The procedure of example 1 was repeated except that the reaction temperature was changed from 40℃to 30 ℃. The data results are shown in Table 1.
[ example 6 ]
The procedure of example 1 was repeated except that the reaction temperature was changed from 40℃to 60 ℃. The data results are shown in Table 1.
[ example 7 ]
The procedure of example 1 was repeated except that the reaction temperature was changed from 40℃to 100 ℃. The data results are shown in Table 1.
[ example 8 ]
The same as in example 3 was found to be different in that the reaction pressure was replaced with 5MPa from 3 MPa. The data results are shown in Table 1.
[ example 9 ]
The procedure is as in example 1, except that the molar ratio of chromium acetylacetonate (calculated as chromium), ligand and cocatalyst is replaced by 1:0.5:100 with a 1:2:500 molar ratio. The data results are shown in Table 1.
[ example 10 ]
The procedure is as in example 1, except that the molar ratio of chromium acetylacetonate (calculated as chromium), ligand and cocatalyst is replaced by 1:2:700 with a 1:2:500 ratio. The data results are shown in Table 1.
[ example 11 ]
The procedure is as in example 1, except that the molar ratio of chromium acetylacetonate (calculated as chromium), ligand and cocatalyst is replaced by 1:10:1000 with a 1:2:500 molar ratio. The data results are shown in Table 1.
[ example 12 ]
The difference from example 3 is that the molar ratio of catalyst complex to cocatalyst is 1:500 instead of 1:100. The data results are shown in Table 1.
[ example 13 ]
The difference from example 3 is that the molar ratio of catalyst complex to cocatalyst is 1:500 instead of 1:700. The data results are shown in Table 1.
[ example 14 ]
The difference from example 3 is that the molar ratio of catalyst complex to cocatalyst is 1:500 instead of 1:1000. The data results are shown in Table 1.
Comparative example 1
The compound bis [ (S, S) - (phenyl) is adopted 2 PCH (Me) CH (Me) P (phenyl) 2 Dichloro (mu-chloro) chromium]Ethylene oligomerization is carried out.
The method of implementation was as described in comparative example 2 in CN104169003 a. The data results are shown in Table 1.
Comparative example 2
Using the compound bis [ (S, S) - (o-fluoro-phenyl) 2 PCH (Me) CH (Me) P (o-fluoro-phenyl) 2 Dichloro (mu-chloro) chromium]Ethylene oligomerization is carried out.
The procedure was as described in example 4 of CN104169003 a. The data results are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the pyrrole bridged biphosphine type catalyst provided by the invention has the catalytic activity exceeding 0.8X10 8 g·mol(Cr) -1 ·h -1 Up to 3.0X10 8 g·mol(Cr) -1 ·h -1 Under different conditions, the total selectivity of 1-hexene and 1-octene is more than 93wt% and can be up to 97wt%. Compared with comparative example 1Compared with the catalyst, the catalyst activity of the catalyst composition provided by the invention is obviously improved, especially the content of 1-hexene in C6 is greatly improved, and byproducts such as cycloolefin, cyclized product and the like are obviously reduced; the catalyst composition provided by the invention has significantly improved catalyst activity compared with the catalyst of the comparative example, indicating that the catalyst described in the invention has better performance. The change of the structure of the catalyst ligand or the complex influences the coordination capacity and the electronic effect of the ligand or the complex, so that the effect on the catalytic performance is obvious.
The catalyst composition can effectively catalyze ethylene trimerization and tetramerization reactions, and has the advantages of rapid initiation, stable operation, good repeatability, strong practicability and wide industrialization prospect.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent modifications and improvements will occur to those skilled in the art, and are intended to be within the scope of the present invention, as a matter of common general knowledge in the art, in light of the technical teaching provided by the present invention.
Claims (10)
1. A pyrrole bridged ethylene oligomerization catalyst composition comprises a catalyst ligand shown in a formula (I), a transition metal compound and an aluminum-containing cocatalyst, or comprises a catalyst complex shown in a formula (II) and an aluminum-containing cocatalyst,
in the formula (I), R 1 、R 2 、R 3 、R 4 The same or different, each independently selected from hydrogen or fluorine atoms;
in the formula (II), R 1 ’、R 2 ’、R 3 ’、R 4 'same or different', each independently selected from hydrogen or fluorine atoms, M is a transition metal, X is selected from halogen, and n is an integer of 1 to 3.
2. The composition of claim 1, wherein in formula (II), M is selected from at least one of chromium, molybdenum, iron, titanium, zirconium, and nickel.
3. The composition according to claim 1 or 2, wherein the aluminium-containing cocatalyst is an organoaluminium compound, preferably at least one from the group consisting of alkylaluminium compounds, alkoxyaluminium compounds and alkylaluminium chloride compounds, more preferably at least one from the group consisting of methylaluminoxane, trimethylaluminium, triethylaluminium, triisobutylaluminium, tri-n-hexylaluminium, tri-n-octylaluminium, diethylaluminium monochloride, diethylaluminium dichloride, ethylaluminium oxide and modified methylaluminium oxide, more preferably at least one from the group consisting of modified methylaluminium oxide, methylaluminium oxide and triethylaluminium.
4. A composition according to any one of claims 1 to 3, wherein the transition metal compound is selected from at least one of chromium, molybdenum, iron, titanium, zirconium and nickel compounds; preferably, the transition metal compound is selected from at least one of chromium acetylacetonate, chromium isooctanoate, chromium tri (tetrahydrofuran) trichloride, and chromium di (tetrahydrofuran) dichloride.
5. Composition according to any one of claims 1 to 4, characterized in that the molar ratio of transition metal compound, catalyst ligand of formula (I) and aluminium-containing cocatalyst, calculated as metal element, is 1:0.1 to 10:1 to 1000, preferably 1:0.25 to 2:10 to 700, more preferably 1:0.5 to 2:100 to 500.
6. The composition according to any of claims 1 to 4, wherein the molar ratio of the catalyst complex of formula (II) to the aluminium-containing cocatalyst is from 1:1 to 1000, preferably from 1:10 to 700, more preferably from 1:100 to 500.
7. A process for oligomerization of ethylene comprising: the oligomerization of ethylene in an organic solvent in the presence of the pyrrole bridged ethylene oligomerization catalyst composition according to any one of claims 1-6.
8. The method according to claim 7, wherein the concentration of the catalyst composition is 0.1 to 10. Mu. Mol/L on a metal basis, calculated on the volume of the organic solvent.
9. The process according to claim 7 or 8, characterized in that the reaction temperature of the ethylene oligomerization reaction is 0-200 ℃, preferably 0-100 ℃, more preferably 30-100 ℃; and/or the number of the groups of groups,
the ethylene oligomerization reaction has an ethylene pressure of 0.1 to 20.0MPa, preferably 0.5 to 5.0MPa, more preferably 2.0 to 5.0MPa.
10. A process for trimerization or tetramerization of ethylene comprising: ethylene trimerization or ethylene tetramerization in an organic solvent in the presence of the pyrrole bridged ethylene oligomerization catalyst composition according to any one of claims 1-6.
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