RU2802018C2 - Halogen-containing compound and its use as ligand in ethylene oligomerization catalyst - Google Patents

Abstract

FIELD: chemical technology.

SUBSTANCE: halogenated compound represented by formula II, where R⁵ in formula II represents C₁-C₁₂ alkyl, C₃-C₁₂ cycloalkyl, or C₆-C₂₀ aryl. Also proposed are the use of the said halogen-containing compound as a ligand in an ethylene oligomerization catalyst composition, an ethylene oligomerization catalyst composition containing said halogen-containing compound, and methods for ethylene oligomerization, trimerization and tetramerization using the said catalyst.

EFFECT: improved catalytic properties of the catalyst system, especially the catalytic properties in the reaction of ethylene trimerization and ethylene tetramerization, significantly improved activity and selectivity, and significantly reduced formation of by-products such as cycloolefin and cyclization product.

31 cl, 1 tbl, 31 ex

Description

Technical field

The present invention relates to a halogenated compound, and also relates to the use of this halogenated compound as a ligand in a catalyst for ethylene oligomerization. The present invention also relates to an ethylene oligomerization catalyst composition and an ethylene oligomerization method, an ethylene trimerization method, and an ethylene tetramerization method using the catalyst composition.

State of the art

Ethylene oligomerization is one of the most important reactions in the olefin polymerization industry. An inexpensive low molecular weight olefin can be converted to high value added products such as 1-octene and 1-hexene through oligomerization. 1-octene and 1-hexene, as important organic raw materials and chemical intermediates, are mainly used in the field of high-quality polyethylene (PE) production. Linear low density polyethylene (LLDPE), obtained by copolymerizing 1-hexene or 1-octene with ethylene, can greatly improve various properties of PE, especially mechanical properties, optical properties, and tear and impact resistance of polyethylene. The resulting product is very suitable for the manufacture of packaging films and covering films for agriculture, for example, for use in greenhouses and barns.

Recently, due to the constant development of the polyolefin industry, the demand for α-olefins is growing rapidly all over the world. Most α-olefins are obtained by ethylene oligomerization.

Since the 1970s, the study of polymerization and oligomerization of olefins catalyzed by transition metal complexes has gradually attracted the attention of scientists. Researchers have begun to study new catalysts and improve existing catalysts to improve catalyst activity and selectivity of catalytic products.

Among studies, the nickel-based cation exchange catalyst system represents the earliest, fastest developing and relatively concentrated catalyst system as described in US 3686351 and US 3676523 and Shell's SHOP process based on proprietary technology. The Shell's SHOP process uses an O-P bridged ligand, however the catalyst contains a toxic organophosphorus group and has complex synthetic steps and poor stability.

Subsequently, researchers have also developed O-O, P-N, P-P and N-N coordinated nickel catalysts as described in JP 11060627, WO 9923096, WO 991550, CN 1401666 and CN 1769270. However, the catalysts produced in the above patents generally have the disadvantage is that they are obtained in a relatively complex way.

The PNP backbone catalyst is disclosed in WO 04056478 by Sasol. In the ethylene tetramerization reaction, the selectivity of the C8 component is about 66% (mass) and the selectivity of the C6 component is about 21% (mass), while 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%.

A catalyst with a symmetrical PCCP backbone is disclosed in US 20100137669. In the ethylene tetramerization reaction, this catalyst is more stable than the PNP system, but the overall selectivity of 1-hexene and 1-octene does not exceed 85%.

In the reaction systems described above, although by-products such as cycloolefin and cyclization product occurring in the C6 product can be removed by separation and purification or the like, this is unfavorable to the economics of the process as a whole.

The essence of the invention

In light of the above disadvantage of the prior art, the inventor of the present invention conducted an in-depth study of phosphorus-containing catalysts for ethylene oligomerization, and found that the introduction of an asymmetric bisphosphine skeleton ligand with a halogen substituent into the catalyst system can effectively improve the catalytic properties of the catalyst system, especially the catalytic properties in ethylene trimerization reaction and ethylene tetramerization reaction, exhibits greatly improved activity and selectivity, and greatly reduces the formation of by-products such as cycloolefin and cyclization product.

According to a first aspect, the present invention provides a halogenated compound represented by formula I:

where in the formula IR ¹ , R ² , R ³ and R ⁴ are the same or different, each independently represents a halogen; each R ⁵ , R ⁶ , R ⁷ and R ⁸ independently represents hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl, and R ⁵ and R ⁶ are different or R ⁷ and R ⁸ are different.

According to a second aspect, the present invention provides the use of a halogen-containing compound according to the first aspect of the present invention as a ligand in an ethylene oligomerization catalyst.

According to a third aspect, the present invention provides a catalyst composition for ethylene oligomerization comprising one halogen-containing compound of the first aspect of the present invention, one transition metal compound, and one co catalyst.

According to a fourth aspect, the present invention provides an ethylene oligomerization process which includes the step of contacting ethylene with a catalyst composition according to the third aspect of the present invention.

According to a fifth aspect, the present invention provides an ethylene trimerization process which includes the step of contacting ethylene with a catalyst composition according to the third aspect of the present invention at a temperature of 60° C. or higher.

According to a sixth aspect, the present invention provides an ethylene tetramerization process which includes the step of contacting ethylene with a catalyst composition according to the third aspect of the present invention at a temperature below 60°C.

The halogen-containing compound of the present invention as a catalyst ligand for ethylene oligomerization can effectively improve the catalytic properties of the catalyst system, especially by showing greatly improved catalytic properties in the ethylene oligomerization reaction. The catalyst activity is above 0.8×10 ⁸ g⋅mol(Cr) ^-1 ⋅h ^-1 and the maximum catalytic activity exceeds 92% (mass), while the content of 1-hexene in the C6 product can reach about 97%, and the content of 1-octene in the C8 product can be as high as 98% or higher.

In addition, when the catalyst composition of the present invention is used for ethylene oligomerization, a high initiation rate is achieved, and ethylene absorption can reach a maximum value in a short time (within 5 minutes) and be maintained for a long time (0.5 hour or longer). This shows that the catalyst composition of the present invention initiates quickly and has high stability during the polymerization reaction.

Thus, the catalyst composition of the present invention has the properties of high catalytic activity and high selectivity, and has good prospects for industrial application and economic value.

DETAILED DESCRIPTION OF EMBODIMENTS The endpoints and any values of the ranges disclosed herein are not limited to exact ranges or values, and these ranges or values are to be understood to include values close to those ranges or values. For numerical ranges, the end point values of each range, the end point values and the individual point value in each range, and the individual point values in each range may be combined with each other to produce one or more new numerical ranges, which should be considered as specifically disclosed in this application. .

In the present invention, the term "C ₁ -C ₁₂ alkyl" includes C ₁ -C ₁₂ linear alkyl and C ₃ -C ₁₂ branched alkyl. Specific examples thereof may include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2- dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2,3-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 2-methylhexyl, 3- methylhexyl, 4-methylhexyl, 5-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2.4-dimethylpentyl, 3,3-dimethylpentyl, 3,4-dimethylpentyl, 4,4-dimethylpentyl, 2-ethylpentyl, 3- ethylpentyl, n-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2,2-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2.5-dimethylhexyl, 3, 3-dimethylhexyl, 3,4-dimethylhexyl, 3,5-dimethylhexyl, 4,4-dimethylhexyl, 4,5-dimethylhexyl, 5,5-dimethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-n- propylpentyl, 2-isopropylpentyl, octyl (including various isomers of octyl), decyl (including various isomers of decyl), undecyl (including various isomers of undecyl), and dodecyl (including various isomers of dodecyl).

In the present invention, the term "C ₃ -C ₁₂ cycloalkyl" includes substituted or unsubstituted cycloalkyl. Substituted cycloalkyl refers to a group in which at least one hydrogen atom bonded to a carbon atom in the ring is substituted with a substituent which may be C ₁ -C ₆ alkyl, where specific examples of this substituent may include, but are not limited to: methyl , ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, mpem-butyl, n-pentyl, isopentyl, mpem-pentyl, neopentyl and hexyl (including various isomers of hexyl). Specific examples of C ₃ -C ₁₂ cycloalkyl may include, but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, and butylcyclohexyl.

In the present invention, the term "C ₆ -C ₂₀ aryl" includes substituted or unsubstituted aryl. Substituted aryl refers to a group in which at least one hydrogen atom on an aromatic ring has been replaced by a substituent which may be a C ₁ -C ₆ alkyl group and/or halogen, where specific examples of this substituent may include, but are not limited to: methyl , ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, t-pentyl, neopentyl, hexyl (including various hexyl isomers), chlorine, bromine, and iodine. Specific examples of C ₆ -C ₂₀ aryl may include, but are not limited to: phenyl, naphthyl, tolyl, ethylphenyl, chlorophenyl, or naphthyl.

According to a first aspect, the present invention provides a halogenated compound represented by formula I:

where in the formula IR ¹ , R ² , R ³ and R ⁴ may be the same or different, each independently represents a halogen; each R ⁵ , R ⁶ , R ⁷ and R ⁸ independently represents hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl, and R ⁵ and R ⁶ are different or R ⁷ and R ⁸ are different.

In formula I, Ρ represents phosphorus.

In the formula, IR ¹ , R ² , R ³ and R ⁴ may be the same or different, each independently representing a halogen such as fluorine, chlorine, bromine or iodine. Preferably R ¹ , R ² , R ³ and R ⁴ may be the same or different, each independently representing chlorine or fluorine. More preferably, all of R ¹ , R ² , R ³ and R ⁴ are fluoro.

In formula I, at least one of R ¹ , R ² , R ³ , and R ⁴ is an ortho substituent. Preferably, all of R ¹ , R ² , R ³ and R ⁴ are ortho substituents.

Preferably in formula I, each R ⁵ , R ⁶ , R ⁷ and R ⁸ is independently hydrogen, C ₁ -C ₈ alkyl, C ₃ -C ₈ cycloalkyl or C ₆ -C ₁₆ aryl, and R ⁵ and R ⁶ are different or R ⁷ and R ⁸ are different.

More preferably, in formula I, each R ⁵ , R ⁶ , R ⁷ and R ⁸ is independently hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, or C ₆ -C ₁₂ aryl, and R ⁵ and R ⁶ are different or R ⁷ and R ⁸ are different.

Also preferably in formula I, each R ⁵ , R ⁶ , R ⁷ and R ⁸ independently represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, n-pentyl, isopentyl, t- pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl, ethylphenyl, chlorophenyl or naphthyl, and R ⁵ and R ⁶ are different or R ⁷ and R ⁸ are different.

Even more preferably in formula I, each R ⁵ , R ⁶ , R ⁷ and R ⁸ is independently hydrogen, t-butyl, cyclohexyl, phenyl, isopropyl or ethyl and R ⁵ and R ⁶ are different or R ⁷ and R ⁸ are different.

Particularly preferably in formula I, each R ⁵ , R ⁶ , R ⁷ and R ⁸ is independently hydrogen, t-butyl, cyclohexyl or phenyl, and R ⁵ and R ⁶ are different or R ⁷ and R ⁸ are different.

In formula I, one, two or three of R ⁵ , R ⁶ , R ⁷ and R ⁸ are preferably hydrogen.

In a preferred example, in the formula IR ⁵ is C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl, and R ⁶ , R ⁷ and R ⁸ are hydrogen. Preferably in the formula IR ⁵ is C ₁ -C ₈ alkyl, C ₃ -C ₈ cycloalkyl or C ₆ -C ₁₆ aryl, and R ⁶ , R ⁷ and R ⁸ are hydrogen. More preferably in the formula IR ⁵ is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl or C ₆ -C ₁₂ aryl, and R ⁶ , R ⁷ and R ⁸ are hydrogen. Also preferably in the formula IR ⁵ is methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, mpem-pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl, ethylphenyl, chlorophenyl or naphthyl, and R ⁶ , R ⁷ and R ⁸ are hydrogen. Even more preferably in the formula IR ⁵ is tert-butyl, cyclohexyl, phenyl, isopropyl or ethyl, and R ⁶ , R ⁷ and R ⁸ are hydrogen. Particularly preferably in the formula IR ⁵ is tert-butyl, cyclohexyl or phenyl and R ⁶ , R ⁷ and R ⁸ are hydrogen.

According to the first aspect of the present invention, in a preferred embodiment, the halogenated compound is a compound represented by formula II:

where in the formula II R ⁵ represents C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl.

Preferably in formula II R ⁵ is C ₁ -C ₈ alkyl, C ₃ -C ₈ cycloalkyl or C ₆ -C ₁₆ aryl. More preferably in formula II, R ⁵ is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, or C ₆ -C ₁₂ aryl. Also preferably in formula II R ⁵ is methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, mpem-pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl , ethylphenyl, chlorophenyl or naphthyl. Even more preferably in formula II R ⁵ is tert-butyl, cyclohexyl, phenyl, isopropyl or ethyl. Particularly preferably in formula II, R ⁵ is tert-butyl, cyclohexyl or phenyl.

The halogen-containing compound of the present invention can be produced with reference to the method disclosed in ACS Catalysis, 2013, 3, 2311-2317. In particular, the halogen-containing compound can be obtained by a method comprising the following steps: methylsulfonyl chloride is first contacted with an alkylethylene glycol represented by formula III to obtain a compound represented by formula IV; the compound represented by formula IV is subjected to a second contact with LiP(2-F-Ph) ₂ ; and the mixture obtained in the second contact is separated to obtain a halogen-containing compound represented by formula I.

In formulas III and IV, R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same as defined for R ⁵ , R ⁶ , R ⁷ and R ⁸ in formula I and will not be described in detail here. In formula IV, Ms is the abbreviation for methylsulfonyl, which refers to CH ₃ SO _2- .

The first contact is carried out in a halogenated alkane as solvent, and the halogenated alkane may be, for example, dichloromethane. Methylsulfonyl chloride is mixed with a solvent, then the mixture is mixed with an alkylethylene glycol represented by formula III, and a reaction is carried out. Alkylethylene glycol is preferably added dropwise to a solution containing methylsulfonyl chloride. The first contact can be made at -10°C to 30°C. Preferably, the first contact is carried out sequentially at temperatures from -5°C to 5°C and from 15°C to 30°C, while the reaction can be carried out at a temperature from -5°C to 5°C for 0.5-2 hours and at a temperature of 15°C to 30°C for 1-3 hours.

After completion of the first contact, an acid may be added to the reaction mixture obtained from the first contact. The reaction mixture is then separated into an aqueous phase and an organic phase, the aqueous phase is extracted with a halogenated alkane (preferably dichloromethane) and the organic phases are mixed. The mixed organic phase is neutralized and then washed and dried, the solvent is removed, and the resulting residue is a compound represented by formula IV. The molar ratio of LiP(2-F-Ph) ₂ to the compound represented by formula IV may be 2-3:1. The second contact can be carried out at a temperature of 15-30°C. The second contact may be carried out in an oxygen-containing heterocyclic compound, preferably in tetrahydrofuran.

The halogen-containing compound represented by formula I can be separated from the reaction mixture obtained by the second contact using conventional methods.

For example, the solvent is removed from the reaction mixture obtained by the second contact, and then water precipitation is carried out. The precipitate is collected and subjected to column separation to obtain a halogen-containing compound represented by formula I.

The reaction mechanism for producing a halogen-containing compound represented by formula II is shown by way of example as follows:

The halogenated compound of the present invention is particularly suitable as a catalyst ligand for ethylene oligomerization. When the catalyst ligand contains a halogen-containing compound, the catalytic efficiency of the catalyst is greatly improved.

According to a second aspect, the present invention provides the use of a halogen-containing compound according to the first aspect of the present invention as a ligand in an ethylene oligomerization catalyst.

The halogen-containing compound of the present invention can be used in combination with a transition metal compound and a co-catalyst commonly used in ethylene oligomerization.

In one preferred embodiment, the catalyst composition contains a transition metal compound, a co-catalyst, and a halogenated compound.

The transition metal element in the transition metal compound may be chromium, molybdenum, iron, titanium, zirconium, or nickel. Accordingly, the transition metal compound may be 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. The transition metal compound may be at least one selected from the group consisting of a transition metal acetylacetonate, a transition metal carboxylate, and a transition metal tetrahydrofuran complex. The transition metal compound is preferably at least one selected from the group consisting of chromium acetylacetonate, chromium isooctanate, tris(tetrahydrofuran)chromium trichloride and bis(tetrahydrofuran)chromium dichloride. The transition metal compound is more preferably chromium acetylacetonate.

The molar ratio of halogen-containing compound to transition metal compound may be 1:0.1-10, for example: 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1, 4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1: 2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3, 1:3.1, 1:3.2, 1:3.3, 1:3.4, 1:3.5, 1:3.6, 1:3.7, 1:3.8, 1:3.9, 1: 4, 1:4.1, 1:4.2, 1:4.3, 1:4.4, 1:4.5, 1:4.6, 1:4.7, 1:4.8, 1:4.9, 1:5, 1:5.1, 1:5.2, 1:5.3, 1:5.4, 1:5.5, 1:5.6, 1:5, 7, 1:5.8, 1:5.9, 1:6, 1:6.1, 1:6.2, 1:6.3, 1:6.4, 1:6.5, 1: 6.6, 1:6.7, 1:6.8, 1:6.9, 1:7, 1:7.1, 1:7.2, 1:7.3, 1:7.4, 1:7.5, 1:7.6, 1:7.7, 1:7.8, 1:7.9, 1:8, 1:8.1, 1:8.2, 1:8, 3, 1:8.4, 1:8.5, 1:8.6, 1:8.7, 1:8.8, 1:8.9, 1:9, 1:9.1, 1: 9.2, 1:9.3, 1:9.4, 1:9.5, 1:9.6, 1:9.7, 1:9.8, 1:9.9 or 1:10.

Preferably, the molar ratio of halogenated compound to transition metal compound is 1:0.25-2. More preferably, the molar ratio of halogenated compound to transition metal compound is 1:0.5-2. Also preferably, the molar ratio of halogen-containing compound to transition metal compound is 1:0.5-1. Even more preferably, the molar ratio of halogenated compound to transition metal compound is 1:0.5-0.8.

The cocatalyst may be a cocatalyst containing aluminum. Preferably, the cocatalyst is an organoaluminum compound. More preferably, the cocatalyst is at least one selected from the group consisting of aluminum alkyl, aluminum alkoxy, and aluminum alkyl halide. Also preferably, the cocatalyst is at least one selected from the group consisting of methylalumoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, ethylalumoxane, and modified methylalumoxane. Even more preferably, the cocatalyst is at least one selected from the group consisting of modified methylalumoxane, methylalumoxane and triethylaluminum. Particularly preferably, the cocatalyst is a modified methylalumoxane. In the present invention, "modified methylalumoxane" means methylalumoxane that is modified with an alkyl group, for example, methylalumoxane modified with a butyl group. The modified methylalumoxane may be modified methylalumoxane purchased from Akzo Nobel.

The molar ratio of the halogenated compound to the cocatalyst may be 1:1-1000. Preferably, the molar ratio of halogenated compound to cocatalyst is 1:10-700. More preferably, the molar ratio of halogenated compound to cocatalyst is 1:100-500, for example: 1:100, 1:105, 1:110, 1:115, 1:120, 1:125, 1:130, 1:135, 1 :140, 1:145, 1:150, 1:155, 1:160, 1:165, 1:170, 1:175, 1:180, 1:185, 1:190, 1:195, 1:200 , 1:205, 1:210, 1:215, 1:220, 1:225, 1:230, 1:235, 1:240, 1:245, 1:250, 1:255, 1:260, 1 :265, 1:270, 1:275, 1:280, 1:285, 1:290, 1:295, 1:300, 1:305, 1:310, 1:315, 1:320, 1:325 , 1:330, 1:335, 1:340, 1:345, 1:350, 1:355, 1:360, 1:365, 1:370, 1:375, 1:380, 1:385, 1 :390, 1:395, 1:400, 1:405, 1:410, 1:415, 1:420, 1:425, 1:430, 1:435, 1:440, 1:445, 1:450 , 1:455, 1:460, 1:465, 1:470, 1:475, 1:480, 1:485, 1:490, 1:495 or 1:500.

Also preferably, the molar ratio of the halogenated compound to the cocatalyst is 1:150-300. Even more preferably, the molar ratio of halogenated compound to cocatalyst is 1:200-280.

In a third aspect, the present invention provides a catalyst composition for ethylene oligomerization. The composition contains one halogen-containing compound represented by formula I, a transition metal compound, and a co-catalyst. The halogen-containing compound and the method for producing the same have been described above and will not be described in detail here.

The transition metal element in the transition metal compound may be chromium, molybdenum, iron, titanium, zirconium, or nickel. Accordingly, the transition metal compound may be 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.

The transition metal compound may be at least one selected from the group consisting of a transition metal acetylacetonate, a transition metal carboxylate, and a transition metal tetrahydrofuran complex.

The transition metal compound is preferably at least one selected from the group consisting of chromium acetylacetonate, chromium isooctanate, tris(tetrahydrofuran)chromium trichloride and bis(tetrahydrofuran)chromium dichloride. The transition metal compound is more preferably chromium acetylacetonate.

The molar ratio of halogen-containing compound to transition metal compound may be 1:0.1-10, for example: 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1, 4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1: 2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3, 1:3.1, 1:3.2, 1:3.3, 1:3.4, 1:3.5, 1:3.6, 1:3.7, 1:3.8, 1:3.9, 1: 4, 1:4.1, 1:4.2, 1:4.3, 1:4.4, 1:4.5, 1:4.6, 1:4.7, 1:4.8, 1:4.9, 1:5, 1:5.1, 1:5.2, 1:5.3, 1:5.4, 1:5.5, 1:5.6, 1:5, 7, 1:5.8, 1:5.9, 1:6, 1:6.1, 1:6.2, 1:6.3, 1:6.4, 1:6.5, 1: 6.6, 1:6.7, 1:6.8, 1:6.9, 1:7, 1:7.1, 1:7.2, 1:7.3, 1:7.4, 1:7.5, 1:7.6, 1:7.7, 1:7.8, 1:7.9, 1:8, 1:8.1, 1:8.2, 1:8, 3, 1:8.4, 1:8.5, 1:8.6, 1:8.7, 1:8.8, 1:8.9, 1:9, 1:9.1, 1: 9.2, 1:9.3, 1:9.4, 1:9.5, 1:9.6, 1:9.7, 1:9.8, 1:9.9 or 1:10.

Preferably, the molar ratio of halogenated compound to transition metal compound is 1:0.25-2. More preferably, the molar ratio of halogenated compound to transition metal compound is 1:0.5-2. Also preferably, the molar ratio of halogen-containing compound to transition metal compound is 1:0.5-1. Even more preferably, the molar ratio of halogenated compound to transition metal compound is 1:0.5-0.8.

The cocatalyst may be a cocatalyst containing aluminum. Preferably, the cocatalyst is an organoaluminum compound. More preferably, the cocatalyst is at least one selected from the group consisting of aluminum alkyl, aluminum alkoxy, and aluminum alkyl halide. Also preferably, the cocatalyst is at least one selected from the group consisting of methylalumoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, ethylalumoxane, and modified methylalumoxane. Even more preferably, the cocatalyst is at least one selected from the group consisting of modified methylalumoxane, methylalumoxane and triethylaluminum. Particularly preferably, the cocatalyst is a modified methylalumoxane.

The molar ratio of the halogenated compound to the cocatalyst may be 1:1-1000. Preferably, the molar ratio of halogenated compound to cocatalyst is 1:10-700. More preferably, the molar ratio of halogenated compound to cocatalyst is 1:100-500, for example: 1:100, 1:105, 1:110, 1:115, 1:120, 1:125, 1:130, 1:135, 1 :140, 1:145, 1:150, 1:155, 1:160, 1:165, 1:170, 1:175, 1:180, 1:185, 1:190, 1:195, 1:200 , 1:205, 1:210, 1:215, 1:220, 1:225, 1:230, 1:235, 1:240, 1:245, 1:250, 1:255, 1:260, 1 :265, 1:270, 1:275, 1:280, 1:285, 1:290, 1:295, 1:300, 1:305, 1:310, 1:315, 1:320, 1:325 , 1:330, 1:335, 1:340, 1:345, 1:350, 1:355, 1:360, 1:365, 1:370, 1:375, 1:380, 1:385, 1 :390, 1:395, 1:400, 1:405, 1:410, 1:415, 1:420, 1:425, 1:430, 1:435, 1:440, 1:445, 1:450 , 1:455, 1:460, 1:465, 1:470, 1:475, 1:480, 1:485, 1:490, 1:495 or 1:500.

Also preferably, the molar ratio of the halogenated compound to the cocatalyst is 1:150-300. Even more preferably, the molar ratio of halogenated compound to cocatalyst is 1:200-280.

According to a fourth aspect, the present invention provides a process for the oligomerization of ethylene. The method includes the step of contacting ethylene with a catalyst composition according to the third aspect of the present invention.

According to the ethylene oligomerization process of the present invention, the contacting is preferably carried out in at least one organic solvent. The organic solvent is a solvent capable of dissolving the oligomerization product and may be at least one selected from the group consisting of an alkane, a cycloalkane and an aromatic hydrocarbon, preferably at least one selected from the group consisting of C ₆ -C ₁₂ alkane, C ₆ -C ₁₂ cycloalkane and C ₆ -C ₁₂ aromatic hydrocarbon. Specific examples of the organic solvent may include, but are not limited to: hexane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, cyclohexane, methylcyclopentane, heptane, 2-methylhexane, 3-methylhexane, methylcyclohexane, 2-ethylpentane, 3-ethylpentane , 2,3-dimethylpentane, 2,4-dimethylpentane, octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3-ethylhexane, 2 ,2,3-trimethylpentane, 2,3,3-trimethylpentane, 2,4,4-trimethylpentane, 2-methyl-3-ethylpentane, nonane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 2,3-dimethylheptane , 2,4-dimethylheptane, 3-ethylheptane, 4-ethylheptane, 2,3,4-trimethylhexane, 2,3,5-trimethylhexane, 2,4,5-trimethylhexane, 2,2,3-trimethylhexane, 2,2 ,4-trimethylhexane, 2,2,5-trimethylhexane, 2,3,3-trimethylhexane, 2,4,4-trimethylhexane, 2-methyl-3-ethylhexane, 2-methyl-4-ethylhexane, 3-methyl-3 -ethylhexane, 3-methyl-4-ethylhexane, 3,3-diethylpentane, 1-methyl-2-ethylcyclohexane, 1-methyl-3-ethylcyclohexane, 1-methyl-4-ethylcyclohexane, n-propylcyclohexane, isopropylcyclohexane, trimethylcyclohexane (including various trimethylcyclohexane isomers such as 1,2,3-trimethylcyclohexane, 1,2,4-trimethylcyclohexane, 1,2,5-trimethylcyclohexane, 1,3,5-trimethylcyclohexane), decane, 2-methylnonane, 3-methylnonane, 4 -methylnonane, 5-methylnonane, 2,3-dimethyloctane, 2,4-dimethyloctane, 3-ethyloctane, 4-ethyloctane, 2,3,4-trimethylheptane, 2,3,5-trimethylheptane, 2,3,6-trimethylheptane , 2,4,5-trimethylheptane, 2,4,6-trimethylheptane, 2,2,3-trimethylheptane, 2,2,4-trimethylheptane, 2,2,5-trimethylheptane, 2,2,6-trimethylheptane, 2 ,3,3-trimethylheptane, 2,4,4-trimethylheptane, 2-methyl-3-ethylheptane, 2-methyl-4-ethylheptane, 2-methyl-5-ethylheptane, 3-methyl-3-ethylheptane, 4-methyl -3-ethylheptane, 5-methyl-3-ethylheptane, 4-methyl-4-ethylheptane, 4-propylheptane, 3,3-diethylhexane, 3,4-diethylhexane, 2-methyl-3,3-diethylpentane, 1,2 -diethylcyclohexane, 1,3-diethylcyclohexane, 1,4-diethylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, tert-butylcyclohexane, tetramethylcyclohexane (including various isomers of tetramethylcyclohexane such as 1,2,3,4-tetramethylcyclohexane, 1,2,4, 5-tetramethylcyclohexane, 1,2,3,5-tetramethylcyclohexane), toluene, ethylbenzene and xylene (including o-xylene, m-xylene and p-xylene). The organic solvent is more preferably at least one selected from the group consisting of methylcyclohexane, heptane, cyclohexane, toluene and xylene.

In the present invention, the amount of the organic solvent is not particularly limited, and may be selected in a conventional manner. Typically, the organic solvent is used in such an amount that the concentration of the catalyst composition in terms of the transition metal element in the transition metal compound is 1-20 µmol/L. In particular, the organic solvent is used in such an amount that the concentration of the catalyst composition in terms of the transition metal element in the transition metal compound is 1 µmol/L, 2 µmol/L, 3 µmol/L, 4 µmol/L, 5 µmol/L, 6 µmol/l, 7 µmol/l, 8 µmol/l, 9 µmol/l, 10 µmol/l, 11 µmol/l, 12 µmol/l, 13 µmol/l, 14 µmol/l, 15 µmol/l, 16 µmol/L, 17 µmol/L, 18 µmol/L, 19 µmol/L or 20 µmol/L. Preferably, the organic solvent is used in such an amount that the concentration of the catalyst composition in terms of the transition metal element in the transition metal compound is 5-10 µmol/l.

According to the ethylene oligomerization method of the present invention, the contacting can be carried out at a temperature of 0-200°C, for example: 0°C, 1°C, 2°C, 3°C, 4°C, 5°C, 6°C , 7°С, 8°С, 9°С, 10°С, 11°С, 12°С, 13°С, 14°С, 15°С, 16°С, 17°С, 18°С, 19 °С, 20°С, 21°С, 22°С, 23°С, 24°С, 25°С, 26°С, 27°С, 28°С, 29°С, 30°С, 31°С , 32°С, 33°С, 34°С, 35°С, 36°С, 37°С, 38°С, 39°С, 40°С, 41°С, 42°С, 43°С, 44 °С, 45°С, 46°С, 47°С, 48°С, 49°С, 50°С, 51°С, 52°С, 53°С, 54°С, 55°С, 56°С , 57°С, 58°С, 59°С, 60°С, 61°С, 62°С, 63°С, 64°С, 65°С, 66°С, 67°С, 68°С, 69 °С, 70°С, 71°С, 72°С, 73°С, 74°С, 75°С, 76°С, 77°С, 78°С, 79°С, 80°С, 81°С , 82°С, 83°С, 84°С, 85°С, 86°С, 87°С, 88°С, 89°С, 90°С, 91°С, 92°С, 93°С, 94 °С, 95°С, 96°С, 97°С, 98°С, 99°С, 100°С, 101°С, 102°С, 103°С, 104°С, 105°С, 106°С , 107°С, 108°С, 109°С, 110°С, 111°С, 112°С, 113°С, 114°С, 115°С, 116°С, 117°С, 118°С, 119 °С, 120°С, 121°С, 122°С, 123°С, 124°С, 125°С, 126°С, 127°С, 128°С, 129°С, 130°С, 131°С , 132°С, 133°С, 134°С, 135°С, 136°С, 137°С, 138°С, 139°С, 140°С, 141°С, 142°С, 143°С, 144 °С, 145°С, 146°С, 147°С, 148°С, 149°С, 150°С, 151°С, 152°С, 153°С, 154°С, 155°С, 156°С , 157°С, 158°С, 159°С, 160°С, 161°С, 162°С, 163°С, 164°С, 165°С, 166°С, 167°С, 168°С, 169 °С, 170°С, 171°С, 172°С, 173°С, 174°С, 175°С, 176°С, 177°С, 178°С, 179°С, 180°С, 181°С , 182°С, 183°С, 184°С, 185°С, 186°С, 187°С, 188°С, 189°С, 190°С, 191°С, 192°С, 193°С, 194 °C, 195°C, 196°C, 197°C, 198°C, 199°C or 200°C.

Preferably bringing into contact is carried out at a temperature of 0-100°C. More preferably bringing into contact is carried out at a temperature of 30-90°C.

According to the ethylene oligomerization method of the present invention, the ethylene pressure can be 0.1-20 MPa, for example: 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, 1 MPa, 1.1 MPa, 1.2 MPa, 1.3 MPa, 1.4 MPa, 1.5 MPa, 1.6 MPa, 1, 7 MPa, 1.8 MPa, 1.9 MPa, 2 MPa, 2.1 MPa, 2.2 MPa, 2.3 MPa, 2.4 MPa, 2.5 MPa, 2.6 MPa, 2.7 MPa , 2.8 MPa, 2.9 MPa, 3 MPa, 3.1 MPa, 3.2 MPa, 3.3 MPa, 3.4 MPa, 3.5 MPa, 3.6 MPa, 3.7 MPa, 3 .8 MPa, 3.9 MPa, 4 MPa, 4.1 MPa, 4.2 MPa, 4.3 MPa, 4.4 MPa, 4.5 MPa, 4.6 MPa, 4.7 MPa, 4.8 MPa, 4.9 MPa, 5 MPa, 5.1 MPa, 5.2 MPa, 5.3 MPa, 5.4 MPa, 5.5 MPa, 5.6 MPa, 5.7 MPa, 5.8 MPa, 5.9 MPa, 6 MPa, 6.1 MPa, 6.2 MPa, 6.3 MPa, 6.4 MPa, 6.5 MPa, 6.6 MPa, 6.7 MPa, 6.8 MPa, 6, 9 MPa, 7 MPa, 7.1 MPa, 7.2 MPa, 7.3 MPa, 7.4 MPa, 7.5 MPa, 7.6 MPa, 7.7 MPa, 7.8 MPa, 7.9 MPa , 8 MPa, 8.1 MPa, 8.2 MPa, 8.3 MPa, 8.4 MPa, 8.5 MPa, 8.6 MPa, 8.7 MPa, 8.8 MPa, 8.9 MPa, 9 MPa, 9.1 MPa, 9.2 MPa, 9.3 MPa, 9.4 MPa, 9.5 MPa, 9.6 MPa, 9.7 MPa, 9.8 MPa, 9.9 MPa, 10 MPa, 10.1 MPa, 10.2 MPa, 10.3 MPa, 10.4 MPa, 10.5 MPa, 10.6 MPa, 10.7 MPa, 10.8 MPa, 10.9 MPa, 11 MPa, 11, 1 MPa, 11.2 MPa, 11.3 MPa, 11.4 MPa, 11.5 MPa, 11.6 MPa, 11.7 MPa, 11.8 MPa, 11.9 MPa, 12 MPa, 12.1 MPa , 12.2 MPa, 12.3 MPa, 12.4 MPa, 12.5 MPa, 12.6 MPa, 12.7 MPa, 12.8 MPa, 12.9 MPa, 13 MPa, 13.1 MPa, 13.2 MPa, 13.3 MPa, 13.4 MPa, 13.5 MPa, 13.6 MPa, 13.7 MPa, 13.8 MPa, 13.9 MPa, 14 MPa, 14.1 MPa, 14.2 MPa, 14.3 MPa, 14.4 MPa, 14.5 MPa, 14.6 MPa, 14.7 MPa, 14.8 MPa, 14.9 MPa, 15 MPa, 15.1 MPa, 15.2 MPa, 15.3 MPa , 15.4 MPa, 15.5 MPa, 15.6 MPa, 15.7 MPa, 15.8 MPa, 15.9 MPa, 16 MPa, 16.1 MPa, 16.2 MPa, 16.3 MPa, 16 .4 MPa, 16.5 MPa, 16.6 MPa, 16.7 MPa, 16.8 MPa, 16.9 MPa, 17 MPa, 17.1 MPa, 17.2 MPa, 17.3 MPa, 17.4 MPa, 17.5 MPa, 17.6 MPa, 17.7 MPa, 17.8 MPa, 17.9 MPa, 18 MPa, 18.1 MPa, 18.2 MPa, 18.3 MPa, 18.4 MPa, 18, 5 MPa, 18.6 MPa, 18.7 MPa, 18.8 MPa, 18.9 MPa, 19 MPa, 19.1 MPa, 19.2 MPa, 19.3 MPa, 19.4 MPa, 19.5 MPa, 19 .6 MPa, 19.7 MPa, 19.8 MPa, 19.9 MPa or 20 MPa.

Preferably, the ethylene pressure is 0.5-10 MPa. More preferably, the ethylene pressure is 2-8 MPa.

According to the ethylene oligomerization method of the present invention, this can be carried out by a conventional method. In one embodiment, the halogenated compound, transition metal compound, and cocatalyst may be mixed and then the mixture is added to a reactor and contacted with ethylene in the presence of an optional organic solvent to undergo an oligomerization reaction. In another embodiment, a halogenated compound, a transition metal compound, and a cocatalyst may be added to the reactor, respectively, and contacted with ethylene in the presence of an optional organic solvent to undergo an oligomerization reaction.

According to a fifth aspect, the present invention provides a method for trimerizing ethylene. The method includes the step of bringing ethylene into contact with the catalyst composition according to the third aspect of the present invention at a temperature of 60° C. or higher. In the present invention, "ethylene trimerization" means that the product formed by trimerization of ethylene is mainly a C6 olefin (i.e., hexene), and the C6 olefin content may be 50% (mass) or more, preferably 60% (mass). ) or more.

According to the ethylene trimerization method of the present invention, the contacting temperature is preferably 60-90°C, and may be, for example, 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78° C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C or 90°C. More preferably, the contacting temperature is 70-90°C.

According to the ethylene trimerization process of the present invention, the contacting is preferably carried out in at least one organic solvent. The organic solvent is a solvent capable of dissolving the oligomerization product and may be at least one selected from the group consisting of an alkane, a cycloalkane and an aromatic hydrocarbon, preferably at least one selected from the group consisting of C ₆ -C ₁₂ alkane, C ₆ -C ₁₂ cycloalkane and C ₆ -C ₁₂ aromatic hydrocarbon. Specific examples of the organic solvent may include, but are not limited to: hexane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, cyclohexane, methylcyclopentane, heptane, 2-methylhexane, 3-methylhexane, methylcyclohexane, 2-ethylpentane, 3-ethylpentane , 2,3-dimethylpentane, 2,4-dimethylpentane, octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3-ethylhexane, 2 ,2,3-trimethylpentane, 2,3,3-trimethylpentane, 2,4,4-trimethylpentane, 2-methyl-3-ethylpentane, nonane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 2,3-dimethylheptane , 2,4-dimethylheptane, 3-ethylheptane, 4-ethylheptane, 2,3,4-trimethylhexane, 2,3,5-trimethylhexane, 2,4,5-trimethylhexane, 2,2,3-trimethylhexane, 2,2 ,4-trimethylhexane, 2,2,5-trimethylhexane, 2.3.3-trimethylhexane, 2,4,4-trimethylhexane, 2-methyl-3-ethylhexane, 2-methyl-4-ethylhexane, 3-methyl-3-ethylhexane , 3-methyl-4-ethylhexane, 3,3-diethylpentane, 1-methyl-2-ethylcyclohexane, 1-methyl-3-ethylcyclohexane, 1-methyl-4-ethylcyclohexane, n-propylcyclohexane, isopropylcyclohexane, trimethylcyclohexane (including various isomers trimethylcyclohexane such as 1,2,3-trimethylcyclohexane, 1,2,4-trimethylcyclohexane, 1,2,5-trimethylcyclohexane, 1,3,5-trimethylcyclohexane), decane, 2-methylnonane, 3-methylnonane, 4-methylnonane , 5-methylnonane, 2,3-dimethyloctane, 2,4-dimethyloctane, 3-ethyloctane, 4-ethyloctane, 2,3,4-trimethylheptane, 2,3,5-trimethylheptane, 2,3,6-trimethylheptane, 2 ,4,5-trimethylheptane, 2,4,6-trimethylheptane, 2,2,3-trimethylheptane, 2,2,4-trimethylheptane, 2,2,5-trimethylheptane, 2,2,6-trimethylheptane, 2,3 ,3-trimethylheptane, 2,4,4-trimethylheptane, 2-methyl-3-ethylheptane, 2-methyl-4-ethylheptane, 2-methyl-5-ethylheptane, 3-methyl-3-ethylheptane, 4-methyl-3 -ethylheptane, 5-methyl-3-ethylheptane, 4-methyl-4-ethylheptane, 4-propylheptane, 3,3-diethylhexane, 3,4-diethylhexane, 2-methyl-3,3-diethylpentane, 1,2-diethylcyclohexane , 1,3-diethylcyclohexane, 1,4-diethylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, tert-butylcyclohexane, tetramethylcyclohexane (including various tetramethylcyclohexane isomers such as 1,2,3,4-tetramethyl cycle ore xane, 1,2,4 ,5-tetramethyl ring ore xane, 1,2,3,5-tetramethylcyclohexane), toluene, ethylbenzene and xylene (including o-xylene, m-xylene and p-xylene). The organic solvent is more preferably at least one selected from the group consisting of methylcyclohexane, heptane, cyclohexane, toluene and xylene.

In the present invention, the amount of the organic solvent is not particularly limited, and may be selected in a conventional manner. Typically, the organic solvent is used in such an amount that the concentration of the catalyst composition in terms of the transition metal element in the transition metal compound is 1-20 µmol/L. In particular, the organic solvent is used in such an amount that the concentration of the catalyst composition in terms of the transition metal element in the transition metal compound is 1 µmol/L, 2 µmol/L, 3 µmol/L, 4 µmol/L, 5 µmol/L, 6 µmol/l, 7 µmol/l, 8 µmol/l, 9 µmol/l, 10 µmol/l, 11 µmol/l, 12 µmol/l, 13 µmol/l, 14 µmol/l, 15 µmol/l, 16 µmol/L, 17 µmol/L, 18 µmol/L, 19 µmol/L or 20 µmol/L. Preferably, the organic solvent is used in such an amount that the concentration of the catalyst composition in terms of the transition metal element in the transition metal compound is 5-10 µmol/l.

According to the ethylene trimerization method of the present invention, the ethylene pressure can be 0.1-20 MPa, for example: 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa, 0.5 MPa, 0.6 MPa , 0.7 MPa, 0.8 MPa, 0.9 MPa, 1 MPa, 1.1 MPa, 1.2 MPa, 1.3 MPa, 1.4 MPa, 1.5 MPa, 1.6 MPa, 1 .7 MPa, 1.8 MPa, 1.9 MPa, 2 MPa, 2.1 MPa, 2.2 MPa, 2.3 MPa, 2.4 MPa, 2.5 MPa, 2.6 MPa, 2.7 MPa, 2.8 MPa, 2.9 MPa, 3 MPa, 3.1 MPa, 3.2 MPa, 3.3 MPa, 3.4 MPa, 3.5 MPa, 3.6 MPa, 3.7 MPa, 3.8 MPa, 3.9 MPa, 4 MPa, 4.1 MPa, 4.2 MPa, 4.3 MPa, 4.4 MPa, 4.5 MPa, 4.6 MPa, 4.7 MPa, 4, 8 MPa, 4.9 MPa, 5 MPa, 5.1 MPa, 5.2 MPa, 5.3 MPa, 5.4 MPa, 5.5 MPa, 5.6 MPa, 5.7 MPa, 5.8 MPa , 5.9 MPa, 6 MPa, 6.1 MPa, 6.2 MPa, 6.3 MPa, 6.4 MPa, 6.5 MPa, 6.6 MPa, 6.7 MPa, 6.8 MPa, 6 .9 MPa, 7 MPa, 7.1 MPa, 7.2 MPa, 7.3 MPa, 7.4 MPa, 7.5 MPa, 7.6 MPa, 7.7 MPa, 7.8 MPa, 7.9 MPa, 8 MPa, 8.1 MPa, 8.2 MPa, 8.3 MPa, 8.4 MPa, 8.5 MPa, 8.6 MPa, 8.7 MPa, 8.8 MPa, 8.9 MPa, 9 MPa, 9.1 MPa, 9.2 MPa, 9.3 MPa, 9.4 MPa, 9.5 MPa, 9.6 MPa, 9.7 MPa, 9.8 MPa, 9.9 MPa, 10 MPa , 10.1 MPa, 10.2 MPa, 10.3 MPa, 10.4 MPa, 10.5 MPa, 10.6 MPa, 10.7 MPa, 10.8 MPa, 10.9 MPa, 11 MPa, 11 .1 MPa, 11.2 MPa, 11.3 MPa, 11.4 MPa, 11.5 MPa, 11.6 MPa, 11.7 MPa, 11.8 MPa, 11.9 MPa, 12 MPa, 12.1 MPa, 12.2 MPa, 12.3 MPa, 12.4 MPa, 12.5 MPa, 12.6 MPa, 12.7 MPa, 12.8 MPa, 12.9 MPa, 13 MPa, 13.1 MPa, 13.2 MPa, 13.3 MPa, 13.4 MPa, 13.5 MPa, 13.6 MPa, 13.7 MPa, 13.8 MPa, 13.9 MPa, 14 MPa, 14.1 MPa, 14, 2 MPa, 14.3 MPa, 14.4 MPa, 14.5 MPa, 14.6 MPa, 14.7 MPa, 14.8 MPa, 14.9 MPa, 15 MPa, 15.1 MPa, 15.2 MPa , 15.3 MPa, 15.4 MPa, 15.5 MPa, 15.6 MPa, 15.7 MPa, 15.8 MPa, 15.9 MPa, 16 MPa, 16.1 MPa, 16.2 MPa, 16 .3 MPa, 16.4 MPa, 16.5 MPa, 16.6 MPa, 16.7 MPa, 16.8 MPa, 16.9 MPa, 17 MPa, 17.1 MPa, 17.2 MPa, 17.3 MPa, 17.4 MPa, 17.5 MPa, 17.6 MPa, 17.7 MPa, 17.8 MPa, 17.9 MPa, 18 MPa, 18.1 MPa, 18.2 MPa, 18.3 MPa, 18.4 MPa, 18.5 MPa, 18.6 MPa, 18.7 MPa, 18.8 MPa, 18.9 MPa, 19 MPa, 19.1 MPa, 19.2 MPa, 19.3 MPa, 19, 4 MPa, 19.5 MPa, 19.6 MPa, 19.7 MPa, 19.8 MPa, 19.9 MPa or 20 MPa.

Preferably, the ethylene pressure is 0.5-5 MPa. More preferably, the ethylene pressure is 1-4 MPa. Also preferably, the ethylene pressure is 2-3 MPa.

According to the present invention, the ethylene trimerization method can be carried out by a conventional method. In one embodiment, the halogenated compound, transition metal compound, and cocatalyst may be mixed and then the mixture is added to a reactor and contacted with ethylene in the presence of an optional organic solvent to undergo an oligomerization reaction. In another embodiment, a halogenated compound, a transition metal compound, and a cocatalyst may be added to the reactor, respectively, and contacted with ethylene in the presence of an optional organic solvent to undergo an oligomerization reaction.

According to a sixth aspect, the present invention provides a process for tetramerization of ethylene. The method includes the step of bringing ethylene into contact with the catalyst composition according to the third aspect of the present invention at a temperature lower than 60°C. In the present invention, "ethylene tetramerization" means that the product formed by ethylene tetramerization is mainly C8 olefin (i.e., octene), and the content of C8 olefin may be 50% (mass) or more, preferably 55% (mass). ) or more.

According to the ethylene tetramerization process of the present invention, the reaction temperature is preferably 30-50°C, and may be, for example, 30°C, 31°C, 32°C, 33°C, 34°C, 35°C, 36°C, 37°C, 38°C, 39°C, 40°C, 41°C, 42°C, 43°C, 44°C, 45°C, 46°C, 47°C, 48°C, 49° C or 50°C.

According to the ethylene tetramerization method of the present invention, the contacting temperature is preferably 30-50°C, and may be, for example, 30°C, 31°C, 32°C, 33°C, 34°C, 35°C, 36° С, 37°С, 38°С, 39°С, 40°С, 41°С, 42°С, 43°С, 44°С, 45°С, 46°С, 47°С, 48°С, 49°C or 50°C.

According to the ethylene tetramerization process of the present invention, the contacting is preferably carried out in at least one organic solvent. The organic solvent is a solvent capable of dissolving the tetramerization product and may be at least one selected from the group consisting of an alkane, a cycloalkane and an aromatic hydrocarbon, preferably at least one selected from the group consisting of a C ₆ -C ₁₂ alkane , C ₆ -C ₁₂ cycloalkane and C ₆ -C ₁₂ aromatic hydrocarbon. Specific examples of the organic solvent may include, but are not limited to: hexane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, cyclohexane, methylcyclopentane, heptane, 2-methylhexane, 3-methylhexane, methylcyclohexane, 2-ethylpentane, 3-ethylpentane , 2,3-dimethylpentane, 2,4-dimethylpentane, octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3-ethylhexane, 2 ,2,3-trimethylpentane, 2,3,3-trimethylpentane, 2,4,4-trimethylpentane, 2-methyl-3-ethylpentane, nonane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 2,3-dimethylheptane , 2,4-dimethylheptane, 3-ethylheptane, 4-ethylheptane, 2,3,4-trimethylhexane, 2,3,5-trimethylhexane, 2,4,5-trimethylhexane, 2,2,3-trimethylhexane, 2,2 ,4-trimethylhexane, 2,2,5-trimethylhexane, 2,3,3-trimethylhexane, 2,4,4-trimethylhexane, 2-methyl-3-ethylhexane, 2-methyl-4-ethylhexane, 3-methyl-3 -ethylhexane, 3-methyl-4-ethylhexane, 3,3-diethylpentane, 1-methyl-2-ethylcyclohexane, 1-methyl-3-ethylcyclohexane, 1-methyl-4-ethylcyclohexane, n-propylcyclohexane, isopropylcyclohexane, trimethylcyclohexane (including various trimethylcyclohexane isomers such as 1,2,3-trimethylcyclohexane, 1,2,4-trimethylcyclohexane, 1,2,5-trimethylcyclohexane, 1,3,5-trimethylcyclohexane), decane, 2-methylnonane, 3-methylnonane, 4 -methylnonane, 5-methylnonane, 2,3-dimethyloctane, 2,4-dimethyloctane, 3-ethyloctane, 4-ethyloctane, 2,3,4-trimethylheptane, 2,3,5-trimethylheptane, 2,3,6-trimethylheptane , 2,4,5-trimethylheptane, 2,4,6-trimethylheptane, 2,2,3-trimethylheptane, 2,2,4-trimethylheptane, 2,2,5-trimethylheptane, 2,2,6-trimethylheptane, 2 ,3,3-trimethylheptane, 2,4,4-trimethylheptane, 2-methyl-3-ethylheptane, 2-methyl-4-ethylheptane, 2-methyl-5-ethylheptane, 3-methyl-3-ethylheptane, 4-methyl -3-ethylheptane, 5-methyl-3-ethylheptane, 4-methyl-4-ethylheptane, 4-propylheptane, 3,3-diethylhexane, 3,4-diethylhexane, 2-methyl-3,3-diethylpentane, 1,2 -diethylcyclohexane, 1,3-diethylcyclohexane, 1,4-diethylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, tert-butylcyclohexane, tetramethylcyclohexane (including various isomers of tetramethylcyclohexane such as 1,2,3,4-tetramethylcyclohexane, 1,2,4, 5-tetramethylcyclohexane, 1,2,3,5-tetramethylcyclohexane), toluene, ethylbenzene and xylene (including o-xylene, m-xylene and p-xylene). The organic solvent is more preferably at least one selected from the group consisting of methylcyclohexane, heptane, cyclohexane, toluene and xylene.

In the present invention, the amount of the organic solvent is not particularly limited, and may be selected in a conventional manner. Typically, the organic solvent is used in such an amount that the concentration of the catalyst composition in terms of the transition metal element in the transition metal compound is 1-20 µmol/l. In particular, the organic solvent is used in such an amount that the concentration of the catalyst composition in terms of the transition metal element in the transition metal compound is 1 µmol/L, 2 µmol/L, 3 µmol/L, 4 µmol/L, 5 µmol/L, 6 µmol/l, 7 µmol/l, 8 µmol/l, 9 µmol/l, 10 µmol/l, 11 µmol/l, 12 µmol/l, 13 µmol/l, 14 µmol/l, 15 µmol/l, 16 µmol/L, 17 µmol/L, 18 µmol/L, 19 µmol/L or 20 µmol/L. Preferably, the organic solvent is used in such an amount that the concentration of the catalyst composition in terms of the transition metal element in the transition metal compound is 5-10 µmol/l.

According to the ethylene tetramerization method of the present invention, the ethylene pressure can be 0.1-20 MPa, for example: 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa, 0.5 MPa, 0.6 MPa , 0.7 MPa, 0.8 MPa, 0.9 MPa, 1 MPa, 1.1 MPa, 1.2 MPa, 1.3 MPa, 1.4 MPa, 1.5 MPa, 1.6 MPa, 1 .7 MPa, 1.8 MPa, 1.9 MPa, 2 MPa, 2.1 MPa, 2.2 MPa, 2.3 MPa, 2.4 MPa, 2.5 MPa, 2.6 MPa, 2.7 MPa, 2.8 MPa, 2.9 MPa, 3 MPa, 3.1 MPa, 3.2 MPa, 3.3 MPa, 3.4 MPa, 3.5 MPa, 3.6 MPa, 3.7 MPa, 3.8 MPa, 3.9 MPa, 4 MPa, 4.1 MPa, 4.2 MPa, 4.3 MPa, 4.4 MPa, 4.5 MPa, 4.6 MPa, 4.7 MPa, 4, 8 MPa, 4.9 MPa, 5 MPa, 5.1 MPa, 5.2 MPa, 5.3 MPa, 5.4 MPa, 5.5 MPa, 5.6 MPa, 5.7 MPa, 5.8 MPa , 5.9 MPa, 6 MPa, 6.1 MPa, 6.2 MPa, 6.3 MPa, 6.4 MPa, 6.5 MPa, 6.6 MPa, 6.7 MPa, 6.8 MPa, 6 .9 MPa, 7 MPa, 7.1 MPa, 7.2 MPa, 7.3 MPa, 7.4 MPa, 7.5 MPa, 7.6 MPa, 7.7 MPa, 7.8 MPa, 7.9 MPa, 8 MPa, 8.1 MPa, 8.2 MPa, 8.3 MPa, 8.4 MPa, 8.5 MPa, 8.6 MPa, 8.7 MPa, 8.8 MPa, 8.9 MPa, 9 MPa, 9.1 MPa, 9.2 MPa, 9.3 MPa, 9.4 MPa, 9.5 MPa, 9.6 MPa, 9.7 MPa, 9.8 MPa, 9.9 MPa, 10 MPa , 10.1 MPa, 10.2 MPa, 10.3 MPa, 10.4 MPa, 10.5 MPa, 10.6 MPa, 10.7 MPa, 10.8 MPa, 10.9 MPa, 11 MPa, 11 .1 MPa, 11.2 MPa, 11.3 MPa, 11.4 MPa, 11.5 MPa, 11.6 MPa, 11.7 MPa, 11.8 MPa, 11.9 MPa, 12 MPa, 12.1 MPa, 12.2 MPa, 12.3 MPa, 12.4 MPa, 12.5 MPa, 12.6 MPa, 12.7 MPa, 12.8 MPa, 12.9 MPa, 13 MPa, 13.1 MPa, 13.2 MPa, 13.3 MPa, 13.4 MPa, 13.5 MPa, 13.6 MPa, 13.7 MPa, 13.8 MPa, 13.9 MPa, 14 MPa, 14.1 MPa, 14, 2 MPa, 14.3 MPa, 14.4 MPa, 14.5 MPa, 14.6 MPa, 14.7 MPa, 14.8 MPa, 14.9 MPa, 15 MPa, 15.1 MPa, 15.2 MPa , 15.3 MPa, 15.4 MPa, 15.5 MPa, 15.6 MPa, 15.7 MPa, 15.8 MPa, 15.9 MPa, 16 MPa, 16.1 MPa, 16.2 MPa, 16 .3 MPa, 16.4 MPa, 16.5 MPa, 16.6 MPa, 16.7 MPa, 16.8 MPa, 16.9 MPa, 17 MPa, 17.1 MPa, 17.2 MPa, 17.3 MPa, 17.4 MPa, 17.5 MPa, 17.6 MPa, 17.7 MPa, 17.8 MPa, 17.9 MPa, 18 MPa, 18.1 MPa, 18.2 MPa, 18.3 MPa, 18.4 MPa, 18.5 MPa, 18.6 MPa, 18.7 MPa, 18.8 MPa, 18.9 MPa, 19 MPa, 19.1 MPa, 19.2 MPa, 19.3 MPa, 19, 4 MPa, 19.5 MPa, 19.6 MPa, 19.7 MPa, 19.8 MPa, 19.9 MPa or 20 MPa.

Preferably, the ethylene pressure is 0.5-8 MPa. More preferably, the ethylene pressure is 3-6 MPa. Also preferably, the ethylene pressure is 4-5 MPa.

According to the present invention, the ethylene tetramerization process can be carried out by a conventional method. In one embodiment, the halogenated compound, transition metal compound, and cocatalyst may be mixed and then the mixture is added to a reactor and contacted with ethylene in the presence of an optional organic solvent to undergo an oligomerization reaction. In another embodiment, a halogenated compound, a transition metal compound, and a cocatalyst may be added to the reactor, respectively, and contacted with ethylene in the presence of an optional organic solvent to undergo an oligomerization reaction.

The present invention will be illustrated in detail below with reference to examples, without thereby limiting the scope of the present invention.

In the following examples and comparative examples, analysis by nuclear magnetic resonance spectroscopy was carried out on a Bruker AV400 NMR spectrometer, where the detection conditions for the nuclear magnetic resonance method were as follows: deuterated chloroform was used as a solvent, and tests were carried out at room temperature. Gas chromatographic analysis was carried out on an HP 5890 chromatograph, and the detection conditions for the gas chromatography method were as follows: the chromatographic column was an SE-54 chromatographic column, high purity nitrogen was used as a carrier gas, and a FID detector was used; the column temperature was raised in two steps, in particular: the initial temperature was 40°C, maintained for 5 minutes, then the temperature was raised to 300°C at a rate of 30°C/min, maintained for 15 minutes.

In the following examples and comparative examples, the activity of the catalyst was defined as the mass of the polymerization product obtained with a unit mass of catalyst during a unit of polymerization time, the catalyst was determined in terms of the metal element in the transition metal compound (in mol), the polymerization time was measured in hours and the product polymerization was measured in grams. Selectivity=(weight of target product in polymerization reaction product/total weight of polymerization reaction product)×100%.

The meanings of the abbreviations used in the following examples and comparative examples are as follows:

^t Bu is tert-butyl; ⁱ Pr is isopropyl; Su is cyclohexyl; Ph is phenyl; Et is ethyl; THF stands for tetrahydrofuran; acac is acetylacetone and Me is methyl.

Preparation Examples 1-8 are used to prepare the halogen-containing compounds of the present invention. Receiving Example 1

Preparation Example 1 was used to prepare a halogen-containing compound I ¹ .

The production method of the halogen-containing compound I ¹ refers to the above reaction formula, and the specific steps are as follows.

Methylsulfonyl chloride (2.15 ml, 55.2 mmol) was dissolved in 5 ml dichloromethane and the resulting solution was added dropwise to tert-butylethylene glycol (26.3 mmol) in dichloromethane at 0°C. After reaction for 1 h, the reaction mixture was heated to room temperature (25°C, then the same) and continued to stir for 2 hours After completion of the reaction, 1M aqueous hydrochloric acid was added, and then the reaction mixture was separated into an aqueous phase and an organic phase. The aqueous phase was extracted three times with dichloromethane and the organic phases were mixed. The organic phase was washed successively with saturated aqueous NaHCO ₃ and saturated aqueous brine, and then dried over anhydrous magnesium sulfate, followed by rotary evaporation to remove the solvent. The residue was dissolved in 5 ml of tetrahydrofuran (THF) and then 5 ml of LiP(2-F-Ph) ₂ (10 mmol) in THF was added dropwise. After completion of the addition over 10 minutes, the reaction mixture was warmed to room temperature and continued to react for 10 hours. After completion of the reaction, the solvent was evaporated and water was added to the residue to form more precipitate, which must be filtered off. The precipitate was passed through a silica gel column (petroleum ether (PE)/ethyl acetate (EA)=20:1) to give the halogenated compound I ¹ .

The resulting compound was subjected to nuclear magnetic resonance analysis, and it can be demonstrated that the resulting compound was a compound represented by formula II, where R ⁵ is ^t Bu.

¹ H NMR (400 MHz, CDCl ₃ ): δ=7.25-6.80 (m, 16H), 3.85 (m, 1H), 2.87-2.65 (m, 2H), 1, 20(s, 9H).

Receiving example 2

Preparation Example 2 was used to prepare the halogen-containing compound I ² .

In this Production Example, a halogen-containing compound was obtained in the same manner as in Production Example 1, except that t-butylethylene glycol was replaced with cyclohexylethylene glycol. The resulting compound was subjected to nuclear magnetic resonance analysis, and it can be demonstrated that the resulting compound was a compound represented by formula II, where R ⁵ is Cy.

¹ H NMR (400 MHz, CDCl ₃ ): δ=7.30-6.83 (m, 16H), 3.16 (m, 1H), 2.95 (m, 1H), 2.68 (m, 1H), 1.80 (m, 1H), 1.25-1.55 (m, 10H).

Receiving Example 3

Production Example 3 was used to prepare the halogen-containing compound I ³ .

In this Production Example, a halogen-containing compound was obtained in the same manner as in Production Example 1, except that t-butylethylene glycol was replaced with phenylethylene glycol. The resulting compound was subjected to nuclear magnetic resonance analysis, and it can be demonstrated that the resulting compound was a compound represented by formula II, wherein R ⁵ is Ph.

¹ H NMR (400 MHz, CDCl ₃ ): δ=7.45-7.29 (m, 4H), 7.24-6.80 (m, 16H), 6.77-6.69 (m, 1H ), 3.94-3.81 (m, 1H), 2.87-2.75 (m, 1H), 2.74-2.65 (m, 1H).

Receiving Example 4

Production Example 4 was used to prepare the halogen-containing compound I ⁴ .

In this Production Example, a halogen-containing compound was obtained in the same manner as in Production Example 1, except that t-butylethylene glycol was replaced with isopropylethylene glycol. The resulting compound was subjected to nuclear magnetic resonance analysis, and it can be demonstrated that the resulting compound was a compound represented by formula II, where R ⁵ is ⁱ Pr.

¹ H NMR (400 MHz, CDCl ₃ ): δ=7.20-6.90 (m, 16H), 3.50 (m, 1H), 3.00 (m, 1H), 2.70 (m, 1H), 2.33 (m, 1H), 1.05-1.16 (m, 6H).

Receiving Example 5

Preparation Example 5 was used to prepare the halogen-containing compound I ⁵ .

In this Production Example, a halogen-containing compound was obtained in the same manner as in Production Example 1, except that t-butylethylene glycol was replaced with ethylene glycol. The resulting compound was subjected to nuclear magnetic resonance analysis, and it can be demonstrated that the resulting compound was a compound represented by formula II, where R ⁵ is Et.

¹ H NMR (400 MHz, CDCl ₃ ): δ=7.25-6.88 (m, 16H), 3.62 (m, 1H), 2.93 (m, 1H), 2.67 (m, 1H), 1.77(m, 2H), 1.04(m, 3H).

Receiving example 6

Production Example 6 was used to prepare the halogen-containing compound I ⁶ .

In this Production Example, a halogen-containing compound was obtained in the same manner as in Production Example 1, except that t-butylethylene glycol was replaced with methyl ethylene glycol. The resulting compound was subjected to nuclear magnetic resonance analysis, and it can be demonstrated that the resulting compound was a compound represented by formula II, where R ⁵ is Me.

¹ H NMR (400 MHz, CDCl ₃ ): δ=7.30-6.92 (m, 16H), 3.70 (m, 1H), 2.96 (m, 1H), 2.65 (m, 1H), 1.09 (m, 3H).

Receiving Example 7

Production Example 7 was used to prepare the halogen-containing compound I ⁷ .

In this Production Example, a halogen-containing compound was obtained in the same manner as in Production Example 1, except that difluorophenylphosphine chloride was replaced with dichlorophenylphosphine chloride. The resulting compound was subjected to nuclear magnetic resonance analysis, and it can be demonstrated that the resulting compound was a compound represented by formula I in which substituents on the benzene ring are chlorine (that is, in the formula IR ¹ , R ² , R ³ and R ⁴ are ortho substituents and are all chlorine), R ⁵ is ^t Bu, and all of R ⁶ , R ⁷ and R ⁸ are hydrogen.

¹ H NMR (400 MHz, CDCl ₃ ): δ=7.30-6.95 (m, 16H), 3.79 (m, 1H), 2.79-2.60 (m, 2H), 1, 15(s, 9H).

Receiving Example 8

Production Example 8 was used to prepare the halogen-containing compound I ⁸ .

In this Production Example, a halogen-containing compound was obtained in the same manner as in Production Example 1, except that t-butylethylene glycol was replaced by 1-cyclohexyl-2-t-butylethylene glycol. The resulting compound was subjected to nuclear magnetic resonance analysis, and it can be demonstrated that the resulting compound was a compound represented by formula I in which R ¹ , R ² , R ³ and R ⁴ are ortho substituents and all of them are fluorine, R ⁵ is ^t Bu, R ⁶ is Cy, and both R ⁷ and R ⁸ are hydrogen.

¹ H NMR (400 MHz, CDCl ₃ ): δ=7.30-6.90 (m, 16H), 3.60-3.50 (m, 2H), 2.93 (m, 1H), 1, 53-1.26 (m, 11H), 1.20 (s, 9H).

Examples 1-18 were used to illustrate the present invention.

Example 1

A 300 ml stainless steel polymerization autoclave was heated to 80° C. and evacuated, then substituted with nitrogen and then replaced with ethylene. Then the temperature in the autoclave was lowered to 40°C. Methylcyclohexane (purchased from J&K chemicals, Beijing), 0.5 µmol chromium acetylacetonate (purchased from J&K chemicals, Beijing), halogenated compound I ¹ as ligand (i.e., in formula II, R ⁵ is ^t Bu) and modified methylalumoxane (MMAO , purchased from Akzo Nobel) as a co-catalyst was added to the autoclave and evenly stirred, the total volume of the mixed solution was 100 ml, and the molar ratio of chromium acetylacetonate to the halogen-containing compound and to the co-catalyst was 1:2:400, that is, the amount of added halogen-containing compound I ¹ was 1 µmol and the amount of MMAO added was 200 µmol. Ethylene was introduced, the pressure of ethylene was adjusted to be 3 MPa, and ethylene was oligomerized at a temperature of 40°C. After 30 minutes, 1 ml of ethanol was added as a terminating agent to complete the reaction. The temperature in the autoclave was lowered to room temperature (25° C.) and the gas phase products were collected in a gas volumetric vessel and the liquid phase products were collected in an Erlenmeyer flask. Gaseous and liquid products, respectively, were measured and analyzed by gas chromatography to calculate the catalyst activity and product composition, and the results are shown in Table 1.

Example 2

Ethylene oligomerization was carried out using the same method as in Example 1, except that the halogen-containing compound as a ligand was changed to the halogen-containing compound I ² (i.e., in formula II, R ⁵ is Cy), and the results of the experiment were listed in the table 1.

Example 3

Ethylene oligomerization was carried out using the same method as in Example 1, except that the halogen-containing compound as the ligand was changed to the halogen-containing compound I ³ (i.e., in formula II, R ⁵ is Ph), and the results of the experiment were listed in the table 1.

Example 4

Ethylene oligomerization was carried out using the same method as in Example 1, except that the halogen-containing compound as a ligand was changed to the halogen-containing compound I ⁴ (i.e., in formula II, R ⁵ is ⁱ Pr), and the results of the experiment were listed in table 1.

Example 5

Ethylene oligomerization was carried out using the same method as in Example 1, except that the halogen-containing compound as a ligand was changed to the halogen-containing compound I ⁵ (i.e., in formula II, R ⁵ is Et), and the results of the experiment were listed in the table 1.

Example 6

Ethylene oligomerization was carried out using the same method as in Example 1, except that the modified methylalumoxane as a cocatalyst was replaced with triethylaluminum (purchased from J&K chemicals, Beijing). The results of the experiment are listed in Table 1.

Example 7

Ethylene oligomerization was carried out using the same method as in Example 1, except that chromium acetylacetonate was replaced by tris(tetrahydrofuran)chromium trichloride (purchased from J&K chemicals, Beijing). The results of the experiment were listed in Table 1.

Example 8

The ethylene oligomerization was carried out using the same method as in example 1, except that the ethylene oligomerization was carried out at a temperature of 50°C. The results of the experiment were listed in Table 1.

Example 9

The ethylene oligomerization was carried out using the same method as in example 1, except that the ethylene oligomerization was carried out at a temperature of 60°C. The results of the experiment were listed in Table 1.

Example 10

The ethylene oligomerization was carried out using the same method as in example 1, except that the ethylene oligomerization was carried out at a temperature of 70°C. The results of the experiment were listed in Table 1.

Example 11

The ethylene oligomerization was carried out using the same method as in example 1, except that the ethylene oligomerization was carried out at a temperature of 90°C. The results of the experiment were listed in Table 1.

Example 12

The ethylene oligomerization was carried out using the same method as in example 1, except that the ethylene oligomerization was carried out at a temperature of 30°C. The results of the experiment were listed in Table 1.

Example 13

Ethylene oligomerization was carried out using the same method as in Example 1, except that the reaction pressure was adjusted to be 5 MPa, and the experimental results were listed in Table 1.

Example 14

Ethylene oligomerization was carried out using the same method as in Example 1, except that the halogen-containing compound as a ligand was replaced by the halogen-containing compound I ⁶ (ie, in formula II, R ⁵ is Me). The results of the experiment were listed in Table 1.

Example 15

Ethylene oligomerization was carried out using the same method as in Example 1, except that the halogen-containing compound as a ligand was replaced with a halogen-containing compound I ⁷ (i.e., in the formula IR ¹ , R ² , R ³ , and R ⁴ are ortho -substituents and all of them are chlorine, R ⁵ is ^t Bu, and all of R ⁶ , R ⁷ and R ⁸ are hydrogen), and the results of the experiment were listed in Table 1.

Comparative Example 1

Ethylene oligomerization was carried out using the same method as in Example 1, except that the halogen-containing compound was replaced by (S,S)-(phenyl) ₂ PCH(Me)CH(Me)P(phenyl) ₂ (denoted D1) , and the results of the experiment were listed in Table 1.

Comparative Example 2

Ethylene oligomerization was carried out using the same method as in Example 1, except that the halogen-containing compound was replaced by (S,S)-(ofluorophenyl) ₂ PCH(Me)CH(Me)P(ofluorophenyl) ₂ (denoted D2) , and the results of the experiment were listed in Table 1.

Comparative Example 3

Ethylene oligomerization was carried out using the same method as in Example 1, except that the halogen-containing compound was replaced by (in which R is ^t Bu, denoted D3) and the results of the experiment were listed in Table 1.

Comparative Example 4

Ethylene oligomerization was carried out using the same method as in Example 1, except that the halogen-containing compound was replaced by (designated D4), and the results of the experiment were listed in Table 1.

Example 16

A 300 ml stainless steel polymerization autoclave was heated to 80° C. and evacuated, then substituted with nitrogen and then replaced with ethylene. Then the temperature in the autoclave was lowered to 50°C. Heptane (purchased from J&K chemicals, Beijing), 0.5 µmol chromium acetylacetonate, halogen compound I ² as ligand (i.e., R ⁵ is Cy in formula II) and modified methylalumoxane (MMAO, purchased from Akzo Nobel) as cocatalyst a was added to the autoclave and evenly stirred, while the total volume of the mixed solution was 100 ml, and the molar ratio of chromium acetylacetonate to the halogen-containing compound and to the cocatalyst was 1:2:500. That is, the amount of added halogenated compound Ϋ was 1 µmol and the amount of MMAO added was 250 µmol. Ethylene was introduced, the ethylene pressure was adjusted so that it was 4 MPa, and ethylene oligomerization was carried out at a temperature of 50°C. After 60 minutes, 1 ml of ethanol was added as a terminator to complete the reaction. The temperature in the autoclave was lowered to room temperature (25°C). The gas phase products were collected in a gas measuring vessel and the liquid phase products were collected in an Erlenmeyer flask, and the gaseous and liquid products were respectively measured and analyzed by gas chromatography to calculate the catalyst activity and product composition, and the results are shown in Table 1.

Example 17

A 300 ml stainless steel polymerization autoclave was heated to 80° C. and evacuated, then substituted with nitrogen and then replaced with ethylene. Toluene (purchased from J&K chemicals, Beijing), 1.0 µmol chromium acetylacetonate, halogen compound I ¹ as ligand (i.e., in formula II R ⁵ is ^t Bu) and methylalumoxane (MAO, purchased from Akzo Nobel) as cocatalyst was added was added to the autoclave and evenly stirred, while the total volume of the mixed solution was 100 ml, and the molar ratio of chromium acetylacetonate to the halogen-containing compound and to the co-catalyst was 1:1.5:300, that is, the amount of added halogen-containing compound I ¹ is 1.5 µmol and the amount of added MAO is 300 µmol. Ethylene was introduced, the ethylene pressure was adjusted so that it was 2 MPa, and ethylene oligomerization was carried out at a temperature of 80°C. After 30 minutes, 1 ml of ethanol was added as a terminating agent to complete the reaction. The temperature in the autoclave was lowered to room temperature (25°C). The gas phase products were collected in a gas measuring vessel and the liquid phase products were collected in an Erlenmeyer flask, and the gas and liquid products were respectively measured and analyzed by gas chromatography to calculate the catalyst activity and product composition, and the results are shown in Table 1.

Comparative Example 5

Ethylene oligomerization was carried out using the same method as in Example 12, except that the halogen-containing compound was replaced by (S,S)-(ofluoro-phenyl) ₂ PCH(Me)CH(Me)P(o-fluoro-phenyl ) ₂ (labeled D2), and the results of the experiment were listed in Table 1.

Example 18

The oligomerization of ethylene was carried out using the same method as in example 1, except that the halogen-containing compound was replaced by the halogen-containing compound I ⁸ (that is, in the formula IR ¹ , R ² , R ³ , and R ⁴ are ortho substituents and all of them are fluorine, R ⁵ is ^t Bu, R ⁶ is Cy, and both R ⁷ and R ⁸ are hydrogen), and the results of the experiment were listed in Table 1.

As can be seen from the data in Table 1, the catalyst composition of the present invention has outstanding efficiency in ethylene oligomerization with a catalytic activity of 0.8×10 ⁸ g⋅mol(Cr) ^-1 ⋅h ^-1 or higher, up to 4×10 ⁸ g ⋅mol(Cr) ^-1 ⋅h ^-1 or higher, while the total selectivity of 1-hexene and 1-octene is under different conditions 92% (wt.) or higher, and up to more than 95% (wt.).

The data in Table 1 show that changing the structure of the ligand in the catalyst has a significant effect on the catalytic properties. Compared with the catalysts in Comparative Examples 1 to 4, the catalyst composition of the present invention has significantly improved catalytic activity, which can create a good balance of catalytic activity and product selectivity and reduce the formation of by-products such as cycloolefins and cyclization products, demonstrating that the halogenated compound according to the present invention has a better performance as a ligand.

In addition, the catalytic system of the catalyst composition of the present invention quickly initiates a polymerization reaction that proceeds smoothly and can more effectively catalyze the trimerization and tetramerization of ethylene. Meanwhile, the catalyst composition of the present invention can maximize ethylene absorption in just a few minutes (within 5 minutes) for half an hour or more. This shows that the catalyst composition of the present invention has a high practical value and broad prospects for industrial applications.

Preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Many simple variations can be made in the technical solutions of the present invention within the technical concept of the present invention, including combinations of individual technical characteristics in any other suitable way, and these simple changes and combinations should also be considered as a disclosure of the present invention and within the protection scope of the present invention.

Claims (48)

1. Halogen-containing compound represented by formula II: , in which in formula II R ⁵ represents C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₂₀ aryl. 2. Halogenated compound according to claim 1, in which in the formula II R ⁵ represents C ₁ -C ₈ alkyl, C ₃ -C ₈ cycloalkyl or C ₆ -C ₁₆ aryl; more preferably in formula II R ⁵ is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl or C ₆ -C ₁₂ aryl; also preferably in formula II R ⁵ is methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, n-pentyl, isopentyl, t-pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl , ethylphenyl, chlorophenyl or naphthyl; even more preferably in formula II R ⁵ is tert-butyl, cyclohexyl, phenyl, isopropyl or ethyl; particularly preferably in formula II R ⁵ is tert-butyl, cyclohexyl or phenyl. 3. The use of a halogen-containing compound according to any one of paragraphs. 1, 2 as a ligand in the composition of the catalyst for ethylene oligomerization. 4. Use according to claim 3, wherein the catalyst composition contains a transition metal compound, a cocatalyst, and a halogenated compound. 5. Use according to claim 4, wherein the molar ratio of halogenated compound to transition metal compound is 1:0.1-10, preferably 1:0.25-2, more preferably 1:0.5-2. 6. Use according to claim 4 or 5, wherein the molar ratio of halogenated compound to cocatalyst is 1:1-1000, preferably 1:10-700, more preferably 1:100-500. 7. Application according to any one of paragraphs. 4-6, wherein 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 selected from the group, consisting of chromium acetylacetonate, chromium isooctanate, tris(tetrahydrofuran)chromium trichloride and bis(tetrahydrofuran)chromium dichloride. 8. Application according to any one of paragraphs. 4-7, wherein the cocatalyst is an aluminium-containing cocatalyst; preferably the cocatalyst is an organoaluminum compound; more preferably, the co-catalyst is at least one selected from the group consisting of aluminum alkyl, aluminum alkoxy and aluminum alkyl halide; also preferably the cocatalyst is at least one selected from the group consisting of methylalumoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, ethylalumoxane and modified methylalumoxane; even more preferably, the cocatalyst is at least one selected from the group consisting of modified methylalumoxane, methylalumoxane and triethylaluminum. 9. The composition of the catalyst for the oligomerization of ethylene containing a halogenated compound according to any one of paragraphs. 1, 2, transition metal compound and co-catalyst. 10. The composition of claim 9, wherein the molar ratio of halogenated compound to transition metal compound is 1:0.1-10, preferably 1:0.25-2, more preferably 1:0.5-2. 11. Composition according to claim 9 or 10, wherein the molar ratio of halogenated compound to cocatalyst is 1:1-1000, preferably 1:10-700, more preferably 1:100-500. 12. Composition according to any one of paragraphs. 9-11, wherein 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 selected from the group, consisting of chromium acetylacetonate, chromium isooctanate, tris(tetrahydrofuran)chromium trichloride and bis(tetrahydrofuran)chromium dichloride. 13. Composition according to any one of paragraphs. 9-12, wherein the cocatalyst is an aluminium-containing cocatalyst; preferably the cocatalyst is an organoaluminum compound; more preferably, the co-catalyst is at least one selected from the group consisting of aluminum alkyl, aluminum alkoxy and aluminum alkyl halide; also preferably the cocatalyst is at least one selected from the group consisting of methylalumoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, ethylalumoxane and modified methylalumoxane; even more preferably, the cocatalyst is at least one selected from the group consisting of modified methylalumoxane, methylalumoxane and triethylaluminum. 14. The method of oligomerization of ethylene, including the step of bringing ethylene into contact with the composition of the catalyst according to any one of paragraphs. 9-13. 15. The method of claim 14 wherein the contacting is carried out in at least one organic solvent. 16. The method according to p. 15, in which the organic solvent is at least one selected from the group consisting of C ₆ -C ₁₂ alkane, C ₆ -C ₁₂ cycloalkane, and C ₆ -C ₁₂ aromatic hydrocarbon; preferably the organic solvent is at least one selected from the group consisting of methylcyclohexane, heptane, cyclohexane, toluene and xylene. 17. The method according to claim 15 or 16, wherein the organic solvent is used in such an amount that the concentration of the catalyst composition, in terms of the transition metal element in the transition metal compound, is 1-20 µmol/L. 18. The method according to any one of paragraphs. 14-17, in which bringing into contact is carried out at a temperature of 0-200°C, preferably 0-100°C, more preferably 30-90°C. 19. The method according to any one of paragraphs. 14-18, wherein the ethylene pressure is 0.1-20 MPa, preferably 0.5-10 MPa, more preferably 2-8 MPa. 20. The method of trimerization of ethylene, including the step of bringing ethylene into contact with the composition of the catalyst according to any one of paragraphs. 9-13 at 60° C. or higher. 21. The trimerization method of claim 20, wherein the contacting is carried out in at least one organic solvent. 22. The trimerization method according to claim 21, in which the organic solvent is at least one selected from the group consisting of C ₆ -C ₁₂ alkane, C ₆ -C ₁₂ cycloalkane and C ₆ -C ₁₂ aromatic hydrocarbon; preferably the organic solvent is at least one selected from the group consisting of methylcyclohexane, heptane, cyclohexane, toluene and xylene. 23. The trimerization process according to claim 21 or 22, wherein the organic solvent is used in such an amount that the concentration of the catalyst composition, in terms of the transition metal element in the transition metal compound, is 1-20 µmol/L. 24. The method of trimerization according to any one of paragraphs. 20-23, wherein the ethylene pressure is 0.1-20 MPa, preferably 0.5-5 MPa, more preferably 1-4 MPa, even more preferably 2-3 MPa. 25. The method of trimerization according to any one of paragraphs. 20-24, in which bringing into contact is carried out at a temperature of 60-90°C. 26. The method of tetramerization of ethylene, including the step of bringing ethylene into contact with the composition of the catalyst according to any one of paragraphs. 9-14 at temperatures below 60°C. 27. The tetramerization process according to claim 26, wherein the contacting is carried out in at least one organic solvent. 28. The method of tetramerization according to claim 27, in which the organic solvent is at least one selected from the group consisting of C ₆ -C ₁₂ alkane, C ₆ -C ₁₂ cycloalkane and C ₆ -C ₁₂ aromatic hydrocarbon; preferably the organic solvent is at least one selected from methylcyclohexane, heptane, cyclohexane, toluene and xylene. 29. The method according to claim 27 or 28, wherein the organic solvent is used in such an amount that the concentration of the catalyst composition, in terms of the transition metal element in the transition metal compound, is 1-20 µmol/L. 30. Tetramerization method according to any one of paragraphs. 26-29, wherein the ethylene pressure is 0.1-20 MPa, preferably 0.5-8 MPa, more preferably 3-6 MPa, even more preferably 4-5 MPa. 31. The method of tetramerization according to any one of paragraphs. 26-30, in which bringing into contact is carried out at a temperature of 30-50°C.