Catalyst composition, olefin polymerization method and application

Abstract

The invention relates to the field of catalysis and olefin polymerization, and discloses a catalyst composition, an olefin polymerization method and application. The catalyst composition comprises: a) a transition metal compound having a structure represented by formula (1); b) a cocatalyst component, the cocatalyst component comprises an organic aluminum compound and an organic magnesium compound, in the formula (1), M is a tetravalent transition metal atom; x is respectively and independently alkyloxy or halogen with the carbon atom number of 1 to 10; r1, R2, R3, R4, R5, R6, R7 and R8 are respectively and independently hydrogen atoms, halogen atoms or alkyl with the carbon atom number of 1-16. According to the catalyst composition disclosed by the invention, the non-metallocene transition metal catalyst can be obtained by using cheap raw materials through one-step reaction, and the catalyst composition has extremely high polymerization activity by being matched with a specific cocatalyst. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the fields of catalysis and olefin polymerization, and in particular, to a catalyst composition, an olefin polymerization method and an application thereof. Background Art

[0002] Single-site catalysts for olefin polymerization have been a research hotspot in organometallic chemistry, catalysis, polymer chemistry and materials science in recent decades. By using such catalysts, olefin polymers with uniform molecular weight distribution and chemical composition distribution can be obtained. At the same time, the molecular structure and molecular weight of the polymer can be highly controllable by adjusting the catalyst structure. Since such catalysts have the characteristics of high efficiency and broad spectrum when applied to olefin copolymerization (ChemistrySelect 2020, 5, 7581-7585), olefin polymers that cannot be obtained by traditional Ziegler-Natta catalysts can be obtained by using such catalysts.

[0003] At present, most of the single-site catalysts used require complex design and multiple-step synthesis, with a long synthesis route and low overall yield, resulting in an increase in catalyst cost and a significant reduction in economy. Summary of the Invention

[0004] The purpose of the present invention is to overcome the problems in the prior art that the catalyst preparation is difficult and the activity still needs to be further improved, and to provide a non-metallocene transition metal catalyst composition, an olefin polymerization method and an application thereof. The catalyst composition of the present invention can obtain a non-metallocene transition metal catalyst by a one-step reaction using inexpensive raw materials, and has extremely high polymerization activity by cooperating with a specific cocatalyst.

[0005] To achieve the above purpose, on the one hand, the present invention provides a catalyst composition, wherein the catalyst composition includes the following components,

[0006] a) a transition metal compound having the structure shown in formula (1);

[0007]

[0008] b) a cocatalyst component, and the cocatalyst component includes an organoaluminum compound and an organomagnesium compound,

[0009] In formula (1), M is a tetravalent transition metal atom; X is independently a hydrocarbon oxy group or a halogen having 1-10 carbon atoms; R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 and R 8Each independently is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 16 carbon atoms.

[0010] Preferably, M is titanium, zirconium or hafnium, preferably a titanium atom or a zirconium atom.

[0011] Preferably, X is a hydrocarbon oxy group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; more preferably, X is a hydrocarbon oxy group having 1 to 3 carbon atoms or a chlorine atom; still more preferably, X is a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group or a chlorine atom.

[0012] Preferably, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each independently is a hydrogen atom, a halogen atom or a hydrocarbon group having 3 to 12 carbon atoms; more preferably, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each independently is a hydrogen atom, a halogen atom or a hydrocarbon group having 8 to 10 carbon atoms.

[0013] Preferably, the cocatalyst component is a combination of an organoaluminum compound and an organomagnesium compound.

[0014] Preferably, the organoaluminum compound is a compound having a structure represented by the general formula AlX1X2X3, where X1, X2 and X3 are respectively a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, X1, X2 and X3 may be the same or different, and at least one is an alkyl group having 1 to 8 carbon atoms; more preferably, the organoaluminum compound is a dialkylaluminum chloride, preferably one or more of dimethylaluminum chloride, diethylaluminum chloride and diisobutylaluminum chloride.

[0015] Preferably, the organomagnesium compound is a compound represented by MgR 1 R 2 wherein R 1 , R 2 Each independently is a hydrocarbon oxy group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms or a halogen, and at least one of R 1 and R 2 is a hydrocarbon group; more preferably, the organomagnesium compound is a dialkylmagnesium, preferably dibutylmagnesium.

[0016] Preferably, the molar ratio of the transition metal compound to the organoaluminum compound is 1:(50 - 10000); more preferably, the molar ratio of the transition metal compound to the organoaluminum compound is 1:(100 - 2000).

[0017] Preferably, the molar ratio of the organomagnesium compound to the organoaluminum compound is 1:(1 - 100); more preferably, the molar ratio of the organomagnesium compound to the organoaluminum compound is 1:(2.5 - 30); still more preferably, the molar ratio of the organomagnesium compound to the organoaluminum compound is 1:(3 - 10).

[0018] According to the second aspect of the present invention, there is provided an olefin polymerization method, wherein the method comprises contacting an olefin with the catalyst composition described in the first aspect of the present invention to carry out a polymerization reaction.

[0019] Preferably, the concentration of the transition metal compound in the polymerization reaction system is 1×10 -10 mol / L to 1×10 -3 mol / L, preferably 1×10 -8 mol / L to 1×10 -5 mol / L.

[0020] Preferably, the temperature of the polymerization reaction is -50 to 200 °C, and the time of the polymerization reaction is 1 - 300 minutes; more preferably, the temperature of the polymerization reaction is -20 to 150 °C, and the time of the polymerization reaction is 5 - 60 minutes.

[0021] Preferably, the partial pressure of the olefin is 0.1 - 10 MPa, preferably 0.1 - 4.0 MPa.

[0022] According to the third aspect of the present invention, there is provided the use of the catalyst composition described in the first aspect of the present invention in olefin polymerization.

[0023] By the above technical solutions, the present invention provides a non-metallocene transition metal catalyst composition, an olefin polymerization method and an application. The catalyst composition of the present invention can obtain a non-metallocene transition metal catalyst through a one-step reaction using inexpensive raw materials, and has extremely high polymerization activity by cooperating with a specific cocatalyst. Detailed embodiments

[0024] The endpoints and any values disclosed in this article are not limited to the exact ranges or values. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in this article.

[0025] According to a first aspect of the present invention, there is provided a catalyst composition, wherein the catalyst composition comprises the following components,

[0026] a) a transition metal compound having the structure shown in formula (1);

[0027]

[0028] b) a cocatalyst component, the cocatalyst component comprising an organoaluminum compound and an organomagnesium compound,

[0029] In formula (1), M is a tetravalent transition metal atom; each X is independently a hydrocarbyloxy group having 1 to 10 carbon atoms or a halogen; R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 and R 8 are each independently a hydrogen atom, a halogen atom or a hydrocarbyl group having 1 to 16 carbon atoms.

[0030] For the catalyst composition according to the present invention, in formula (1), M is a tetravalent transition metal atom, preferably, M is a titanium atom, a zirconium atom or a hafnium atom; more preferably, M is a titanium atom or a zirconium atom.

[0031] For the catalyst composition according to the present invention, in formula (1), X is a hydrocarbyloxy group having 1 to 10 carbon atoms or a halogen; preferably, X is a hydrocarbyloxy group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; more preferably, X is a hydrocarbyloxy group having 1 to 3 carbon atoms or a chlorine atom; further preferably, X is a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group or a chlorine atom.

[0032] For the catalyst composition according to the present invention, preferably, in formula (1), R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 and R 8 are each independently a hydrogen atom, a halogen atom or a hydrocarbyl group having 3 to 12 carbon atoms; more preferably, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 and R 8Each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 8 to 10 carbon atoms.

[0033] Examples of the hydrocarbon oxy group having 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, sec-butoxy, isobutoxy, pentyloxy, or hexyloxy. Among them, methoxy, ethoxy, propoxy, or isopropoxy is preferred, ethoxy, propoxy, or isopropoxy is more preferred, and ethoxy or isopropoxy is further preferred.

[0034] Examples of the halogen atom include fluorine, chlorine, bromine, or iodine. Fluorine, chlorine, or bromine is preferred, chlorine or bromine is more preferred, and chlorine is particularly preferred.

[0035] Examples of the hydrocarbon group having 1 to 16 carbon atoms preferably include n-octyl, n-nonyl, n-decyl, etc.

[0036] In a particularly preferred embodiment of the present invention, X is isopropoxy or ethoxy.

[0037] In another particularly preferred embodiment of the present invention, X is a chlorine atom.

[0038] Examples of the specific transition metal compound preferably include the following compounds.

[0039] In formula (1), M is a titanium atom, X is isopropoxy, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 and R 8 are hydrogen atoms;

[0040] In formula (1), M is a titanium atom, X is ethoxy, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 and R 8 are hydrogen atoms;

[0041] In formula (1), M is a titanium atom, X is a chlorine atom, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 and R 8 are hydrogen atoms;

[0042] In formula (1), M is a titanium atom, X is a chlorine atom, and R 1 , R 2 , R 4 , R 5 , R 7 , and R 8 are hydrogen atoms, and R 3 , and R 6 are n-nonyl groups;

[0043] In formula (1), M is a zirconium atom, X is an isopropoxy group, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are hydrogen atoms;

[0044] In formula (1), M is a zirconium atom, X is an ethoxy group, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are hydrogen atoms;

[0045] In formula (1), M is a zirconium atom, X is a chlorine atom, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are hydrogen atoms;

[0046] In formula (1), M is a zirconium atom, X is a chlorine atom, and R 1 , R 2 , R 4 , R 5 , R 7 , and R 8 are hydrogen atoms, and R 3 , and R 6 are n-nonyl groups;

[0047] In formula (1), M is a hafnium atom, X is an isopropoxy group, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are hydrogen atoms;

[0048] In formula (1), M is a hafnium atom, X is an ethoxy group, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are hydrogen atoms;

[0049] In formula (1), M is a hafnium atom, X is a chlorine atom, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are hydrogen atoms;

[0050] In formula (1), M is a hafnium atom, X is a chlorine atom, and R 1 , R 2 , R 4 , R 5 , R 7 and R 8 are hydrogen atoms, and R 3 and R 6 are n-nonyl groups.

[0051] For the catalyst composition according to the present invention, the cocatalyst component includes an organoaluminum compound and an organomagnesium compound; preferably, the cocatalyst component is a combination of an organoaluminum compound and an organomagnesium compound.

[0052] In the present invention, the organoaluminum compound is a compound having a structure represented by the general formula AlX1X2X3, where X1, X2, and X3 are respectively a halogen atom, an alkyl group having 1-8 carbon atoms, an alkoxy group having 1-8 carbon atoms, and an aryloxy group having 6-12 carbon atoms. X1, X2, and X3 may be the same or different, and at least one of them is an alkyl group having 1-8 carbon atoms.

[0053] Examples of the alkyl group having 1-8 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec-butyl, isobutyl, pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, neopentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, hexyl, heptyl, octyl, etc.

[0054] Examples of the alkoxy group having 1-8 carbon atoms include various alkoxy groups having the above-mentioned specific examples of the "alkyl group having 1-8 carbon atoms".

[0055] As the above-mentioned halogen atom, for example, fluorine, chlorine, bromine or iodine can be cited, preferably fluorine, chlorine or bromine, more preferably chlorine or bromine, and particularly preferably chlorine.

[0056] In a preferred embodiment of the present invention, the organoaluminum compound is dialkylaluminum chloride, more preferably one or more of dimethylaluminum chloride, diethylaluminum chloride and diisobutylaluminum chloride.

[0057] In the present invention, the organomagnesium compound is a compound represented by MgR 1 R 2 wherein R 1 and R 2 are each independently a hydrocarbon oxy group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms or a halogen, and at least one of R 1 and R 2 is a hydrocarbon group; more preferably, the organomagnesium compound is dialkylmagnesium. For example, dimethylmagnesium, diethylmagnesium, di-n-propylmagnesium, di-n-butylmagnesium, di-n-pentylmagnesium, di-n-hexylmagnesium, etc. can be cited. Among them, one or more of di-n-propylmagnesium, di-n-butylmagnesium and di-n-pentylmagnesium are preferred, and di-n-butylmagnesium is more preferred.

[0058] For the catalyst composition according to the present invention, preferably, the molar ratio of the transition metal compound to the organoaluminum compound is 1:(50 - 10000); more preferably, the molar ratio of the transition metal compound to the organoaluminum compound is 1:(100 - 2000); further preferably, the molar ratio of the transition metal compound to the organoaluminum compound is 1:(100 - 1000).

[0059] For the catalyst composition according to the present invention, preferably, the molar ratio of the organomagnesium compound to the organoaluminum compound is 1:(1 - 100); more preferably, the molar ratio of the organomagnesium compound to the organoaluminum compound is 1:(2.5 - 30); further preferably, the molar ratio of the organomagnesium compound to the organoaluminum compound is 1:(3 - 10); still further preferably, the molar ratio of the organomagnesium compound to the organoaluminum compound is 1:(3 - 6).

[0060] For the catalyst composition according to the present invention, the transition metal compound having the structure shown in formula (1) is preferably prepared by the following method. That is, in the presence of an organic solvent, the compound having the structure shown in formula (2) is brought into contact reaction with a transition metal halide or an alkoxy transition metal.

[0061]

[0062] In formula (2), R 1 and R 2 and R3 , R 4 , R 5 , R 6 , R 7 and R 8 is the same as the above definition.

[0063] As the compound of the structure shown in the above formula (2), bipyridine or 4,4'-dinonyl-2,2'-bipyridine is preferred.

[0064] As the above organic solvent, a halogenated alkyl solvent can be used, for example, dichloromethane, chloroform, etc. can be used.

[0065] There is no particular limitation on the amount of the above organic solvent used, as long as it can promote the reaction to proceed sufficiently. For example, relative to 100 mg of the compound of the structure shown in formula (2), 1 - 200 ml of the organic solvent can be used, and preferably 3 - 10 ml of the organic solvent.

[0066] The molar ratio of the compound of the structure shown in formula (2) to the transition metal halide or alkoxy transition metal can be 1:1 - 20, preferably 1:2 - 10, and more preferably 1:3 - 6.

[0067] As the transition metal in the above transition metal halide, titanium atom, zirconium atom or hafnium atom can be cited, and titanium atom or zirconium atom is preferred.

[0068] As specific transition metal halides, for example, titanium tetrachloride, zirconium tetrachloride, etc. can be cited.

[0069] As the alkoxy group in the alkoxy transition metal, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, tert-butoxy group, sec-butoxy group, isobutoxy group, pentyloxy group or hexyloxy group can be cited. Among them, methoxy group, ethoxy group, propoxy group or isopropoxy group are preferred, and ethoxy group, propoxy group or isopropoxy group are more preferred, and ethoxy group or isopropoxy group are further preferred.

[0070] As specific alkoxy transition metals, for example, titanium tetramethoxide, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, zirconium tetraethoxide, etc. can be cited.

[0071] As the conditions for the above contact reaction, for example, it can include: the temperature is 5 - 50 °C and the time is 5 - 100 h; preferably, the conditions for the above contact reaction include: the temperature is 15 - 40 °C and the time is 20 - 80 h.

[0072] Preferably, the above contact reaction is carried out under an inert atmosphere.

[0073] As the above inert atmosphere, it can be provided by nitrogen, argon, etc.

[0074] After the contact reaction, purification can be carried out by conventional methods in the art. For example, the target compound can be obtained by removing the solvent.

[0075] According to the second aspect of the present invention, there is provided a method for olefin polymerization, which comprises contacting an olefin with the catalyst composition described in the first aspect of the present invention to carry out a polymerization reaction.

[0076] According to the method of the present invention, preferably, the concentration of the transition metal compound in the polymerization reaction system is 1×10 -10 mol / L to 1×10 -3 mol / L, preferably 1×10 -8 mol / L to 1×10 -5 mol / L.

[0077] According to the method of the present invention, preferably, the polymerization reaction is carried out in an inert organic solvent. The inert organic solvent can be one or a mixture of several of linear aliphatic hydrocarbons, branched aliphatic hydrocarbons, substituted or unsubstituted cyclic aliphatic hydrocarbons, and substituted or unsubstituted aromatic hydrocarbons. Specific examples of the inert organic solvent can include: hexane, heptane, cyclohexane, cyclooctane, toluene, xylene. In addition, the amount of the organic solvent can be determined according to the reaction activity to ensure good dissolution or dispersion of the produced polymer in the system.

[0078] According to the method of the present invention, the polymerization reaction conditions can be the usual conditions for synthesizing polyolefins in the art. Preferably, the temperature of the polymerization reaction is -50 to 200 °C, and the time of the polymerization reaction is 1 - 300 minutes; more preferably, the temperature of the polymerization reaction is -20 to 150 °C, and the time of the polymerization reaction is 5 - 60 minutes.

[0079] According to the method of the present invention, preferably, the partial pressure of the olefin is 0.1 - 10 MPa, preferably 0.1 - 4.0 MPa.

[0080] According to the method of the present invention, the addition amount of the olefin can be, for example, 1000 - 1000000 molar equivalents of the catalyst.

[0081] According to the method of the present invention, the olefin can be ethylene, propylene, etc.

[0082] According to the third aspect of the present invention, there is provided the use of the catalyst composition described in the first aspect of the present invention in olefin polymerization.

[0083] The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.

[0084] For the raw materials used in the following examples and comparative examples, if not specifically defined, they are all disclosed in the prior art, and can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0085] Preparation Example 1

[0086] This preparation example is used to illustrate the synthesis of compound (1-1).

[0087]

[0088] Put a magnetic stir bar into a dry 100 mL three-necked flask. After evacuating the three-necked flask, rinse it with nitrogen three times repeatedly to make it in a nitrogen atmosphere. Dissolve 358 mg of bipyridine in 10 mL of dichloromethane. Dilute 2.4 mL of titanium tetrachloride hexane solution (1.0 mol / L) with 10 mL of dichloromethane and add it slowly. Stir the reaction at room temperature for 24 hours. Filter the reaction mixture, wash the obtained solid thoroughly with hexane, and dry it under vacuum to obtain 736 mg of a yellow solid with a yield of 91%.

[0089] 1 1H-NMR (CDCl3): 9.59 - 9.50 ppm (2H), 8.31 - 8.23 ppm (2H), 8.21 - 8.16 ppm (2H), 7.77 - 7.66 ppm (2H).

[0090] Preparation Example 2

[0091] This preparation example is used to illustrate the synthesis of compound (1-2).

[0092]

[0093] Put a magnetic stir bar into a dry 100 mL three-necked flask. After evacuating the three-necked flask, rinse it with nitrogen three times repeatedly to make it in a nitrogen atmosphere. Dissolve 664 mg of zirconium tetrachloride tetrahydrofuran complex (ZrCl4·2THF) in 10 mL of tetrahydrofuran, and directly add 279 mg of bipyridine solid. Stir the reaction at room temperature for 24 hours. Filter the reaction mixture, wash the obtained solid thoroughly with tetrahydrofuran, and dry it under vacuum to obtain 538 mg of a green solid with a yield of 78%.

[0094] 1 1H-NMR (CDCl3): 9.52 - 9.44 ppm (2H), 8.29 - 8.19 ppm (2H), 8.17 - 8.08 ppm (2H), 7.62 - 7.48 ppm (2H).

[0095] Preparation Example 3

[0096] This preparation example is used to illustrate the synthesis of compound (1-3).

[0097]

[0098] Place the magnetic stir bar into a dry 100 mL three-necked flask. After evacuating the three-necked flask, rinse it three times with nitrogen to make it under a nitrogen atmosphere. Dissolve 389 mg of titanium tetraisopropoxide in 10 mL of dichloromethane, directly add 214 mg of bipyridine solid, and stir the reaction at room temperature for 72 hours. Remove the solvent under vacuum, dissolve the obtained solid in 5 mL of toluene, and freeze it at -20 °C to obtain 519 mg of pale yellow crystals with a yield of 86%.

[0099] 1 1H-NMR (CDCl3): 9.61 - 9.50 ppm (2H), 8.33 - 8.24 ppm (2H), 8.22 - 8.15 ppm (2H), 7.78 - 7.65 ppm (2H), 3.72 - 3.88 (4H), 1.18 - 1.02 (24H).

[0100] Preparation Example 4

[0101] This preparation example is used to illustrate the synthesis of compound (1 - 4).

[0102]

[0103] Place the magnetic stir bar into a dry 100 mL three-necked flask. After evacuating the three-necked flask, rinse it three times with nitrogen to make it under a nitrogen atmosphere. Dissolve 965 mg of 4,4'-dinonyl-2,2'-bipyridine in 10 mL of dichloromethane, dropwise add 2.5 mL of titanium tetrachloride hexane solution, and stir the reaction at room temperature for 24 hours. Remove the solvent under vacuum, wash the obtained solid with 5 mL of hexane, filter to remove hexane, and dry the obtained solid under vacuum to obtain 1188 mg of yellow solid with a yield of 84%.

[0104] 1 1H-NMR (CDCl3): 9.42 - 9.30 ppm (2H), 8.05 - 7.92 ppm (2H), 7.50 - 7.40 ppm (2H), 2.91 - 2.76 ppm (4H), 1.86 - 1.65 (4H), 1.50 - 1.15 (24H), 0.95 - 0.80 (6H).

[0105] Preparation Example 5

[0106] This preparation example is used to illustrate the synthesis of compound (1 - 5).

[0107] Place the magnetic stir bar into a dry 100 mL three-necked flask. After evacuating the three-necked flask, rinse it with nitrogen three times repeatedly to make it under a nitrogen atmosphere. 819 mg of zirconium tetrachloride-tetrahydrofuran complex (1:2) is dispersed in 10 mL of dichloromethane, and 887 mg of 4,4'-dinonyl-2,2'-bipyridine solid is added. Stir the reaction at room temperature for 24 hours. Remove the solvent under vacuum. Wash the obtained solid with 5 mL of hexane, filter off the hexane, and dry the obtained solid under vacuum to obtain 1215 mg of a gray-green solid with a yield of 87%.

[0108] 1 1H-NMR (CDCl3): 9.40 - 9.29 ppm (2H), 8.04 - 7.93 ppm (2H), 7.51 - 7.40 ppm (2H), 2.90 - 2.78 ppm (4H), 1.85 - 1.65 (4H), 1.54 - 1.18 (24H), 0.97 - 0.81 (6H).

[0109] Example 1

[0110] This example is used to illustrate the ethylene polymerization.

[0111] A well-dried 250 mL glass polymerization flask is evacuated and rinsed with nitrogen three times repeatedly. Evacuate and fill with ethylene. The ethylene pressure is 1.05 standard atmospheric pressures. Add 22 mL of toluene and 2.5 mL of a toluene solution of diethylaluminum chloride (containing 2.5 mmol of diethylaluminum chloride) in sequence. Start magnetic stirring and heating, and set the temperature to 70 °C. When the temperature rises to 70 °C, add 5 mL of a toluene solution of the catalyst (containing 5 μmol of compound (1-1)). After 3 minutes, add 0.5 mL of a toluene solution of dibutylmagnesium (containing 0.5 mmol of di-n-butylmagnesium), and start timing. When ethylene is consumed, supplement ethylene to keep the ethylene at a constant 1.05 standard atmospheric pressures all the time. After 20 minutes, turn off the ethylene. Pour the reaction solution into a beaker, add 300 mL of absolute ethanol and 5 mL of concentrated hydrochloric acid, stir for 6 hours, filter to obtain the polymer, and dry it under vacuum at 60 °C for 24 hours to obtain 0.45 g of the polymer with a polymerization activity of 270 kg polymer / mol catalyst / hour.

[0112] Example 2

[0113] This example is used to illustrate the ethylene polymerization.

[0114] A fully dried 100 mL stainless steel polymerization kettle, adjust the temperature control to 50 °C, heat the empty kettle, evacuate for 30 minutes. Charge ethylene and maintain a weak ethylene flow. Add 50 mL of n-hexane, add 2.5 mL of diethylaluminum chloride hexane solution (containing 2.5 mmol of diethylaluminum chloride), start stirring, add 2 mL of catalyst hexane suspension (containing 2 μmol of compound (1-1)), after 3 minutes, add 0.5 mL of dibutylmagnesium hexane solution (containing 0.5 mmol of dibutylmagnesium), close the feeding port. Adjust the ethylene pressure to 6 standard atmospheres. After 30 minutes, turn off the ethylene, cool down, slowly release the pressure, and take out the polymer. Pour the reaction mixture into a beaker, add 300 mL of anhydrous ethanol and 5 mL of concentrated hydrochloric acid, stir for 6 hours, filter to obtain the polymer, and dry it in vacuo at 60 °C for 24 hours to obtain 7.79 g of the polymer, with a polymerization activity of 7790 kg polymer / mol catalyst / hour.

[0115] Example 3

[0116] This example is used to illustrate the polymerization of ethylene.

[0117] A fully dried 100 mL stainless steel polymerization kettle, adjust the temperature control to 50 °C, heat the empty kettle, evacuate for 30 minutes. Charge ethylene and maintain a weak ethylene flow. Add 50 mL of n-hexane, add 2.5 mL of diethylaluminum chloride hexane solution (containing 2.5 mmol of diethylaluminum chloride), start stirring, add 2 mL of catalyst hexane suspension (containing 2 μmol of compound (1-2)), after 3 minutes, add 0.5 mL of dibutylmagnesium hexane solution (containing 0.5 mmol of dibutylmagnesium), close the feeding port. Adjust the ethylene pressure to 6 standard atmospheres. After 30 minutes, turn off the ethylene, cool down, slowly release the pressure, and take out the polymer. Pour the reaction mixture into a beaker, add 300 mL of anhydrous ethanol and 5 mL of concentrated hydrochloric acid, stir for 6 hours, filter to obtain the polymer, and dry it in vacuo at 60 °C for 24 hours to obtain 6.58 g of the polymer. The polymerization activity is 6580 kg polymer / mol catalyst / hour.

[0118] Example 4

[0119] This example is used to illustrate the polymerization of ethylene.

[0120] A fully dried 100 mL stainless steel polymerization kettle, adjust the temperature control to 50 °C, heat the empty kettle, and evacuate for 30 minutes. Fill with ethylene and maintain a weak ethylene flow. Add 50 mL of n-hexane, add 2.5 mL of diethylaluminum chloride hexane solution (containing 2.5 mmol of diethylaluminum chloride), start stirring, add 2 mL of catalyst hexane suspension (containing 2 μmol of compound (1-3)), after 3 minutes, add 0.5 mL of dibutylmagnesium hexane solution (containing 0.5 mmol of dibutylmagnesium), and close the feeding port. Adjust the ethylene pressure to 6 standard atmospheres. After 30 minutes, turn off the ethylene, cool down, slowly release the pressure, and take out the polymer. Pour the reaction mixture into a beaker, add 300 mL of anhydrous ethanol and 5 mL of concentrated hydrochloric acid, stir for 6 hours, filter to obtain the polymer, and dry it under vacuum at 60 °C for 24 hours to obtain 7.45 g of the polymer. The polymerization activity is 7450 kg polymer / mol catalyst / hour.

[0121] Example 5

[0122] This example is used to illustrate the polymerization of ethylene.

[0123] A fully dried 100 mL stainless steel polymerization kettle, adjust the temperature control to 50 °C, heat the empty kettle, and evacuate for 30 minutes. Fill with ethylene and maintain a weak ethylene flow. Add 50 mL of n-hexane, add 2.5 mL of diethylaluminum chloride hexane solution (containing 2.5 mmol of diethylaluminum chloride), start stirring, add 2 mL of catalyst hexane suspension (containing 2 μmol of compound (1-4)), after 3 minutes, add 0.5 mL of dibutylmagnesium hexane solution (containing 0.5 mmol of dibutylmagnesium), and close the feeding port. Adjust the ethylene pressure to 6 standard atmospheres. After 30 minutes, turn off the ethylene, cool down, slowly release the pressure, and take out the polymer. Pour the reaction mixture into a beaker, add 300 mL of anhydrous ethanol and 5 mL of concentrated hydrochloric acid, stir for 6 hours, filter to obtain the polymer, and dry it under vacuum at 60 °C for 24 hours to obtain 9.62 g of the polymer. The polymerization activity is 9620 kg polymer / mol catalyst / hour.

[0124] Example 6

[0125] This example is used to illustrate the polymerization of ethylene.

[0126] A fully dried 100 mL stainless steel polymerization kettle, adjust the temperature control to 50 °C, heat the empty kettle, and evacuate for 30 minutes. Charge ethylene and maintain a weak ethylene flow. Add 50 mL of n-hexane, add 2.5 mL of diethylaluminum chloride hexane solution (containing 2.5 mmol of diethylaluminum chloride), start stirring, add 2 mL of catalyst hexane suspension (containing 2 μmol of compound (1-5)), after 3 minutes, add 0.5 mL of dibutylmagnesium hexane solution (containing 0.5 mmol of dibutylmagnesium), and close the feeding port. Adjust the ethylene pressure to 6 standard atmospheres. After 30 minutes, turn off the ethylene, cool down, slowly release the pressure, and take out the polymer. Pour the reaction mixture into a beaker, add 300 mL of anhydrous ethanol and 5 mL of concentrated hydrochloric acid, stir for 6 hours, filter to obtain the polymer, and dry it under vacuum at 60 °C for 24 hours to obtain 8.83 g of the polymer. The polymerization activity is 8830 kg polymer / mol catalyst / hour.

[0127] Example 7

[0128] This example is used to illustrate the ethylene-1-hexene copolymerization.

[0129] A fully dried 100 mL stainless steel polymerization kettle, adjust the temperature control to 50 °C, heat the empty kettle, and evacuate for 30 minutes. Charge ethylene and maintain a weak ethylene flow. Add 5 mL of 1-hexene and 45 mL of n-hexane, add 2.5 mL of diethylaluminum chloride hexane solution (containing 2.5 mmol of diethylaluminum chloride), start stirring, add 2 mL of catalyst hexane solution (containing 2 μmol of compound (1-4)), after 3 minutes, add 0.5 mL of dibutylmagnesium hexane solution (containing 0.5 mmol of dibutylmagnesium), and close the feeding port. Adjust the ethylene pressure to 6 standard atmospheres. After 30 minutes, turn off the ethylene, cool down, slowly release the pressure, and take out the polymer. Pour the reaction mixture into a beaker, add 300 mL of anhydrous ethanol and 5 mL of concentrated hydrochloric acid, stir for 6 hours, filter to obtain the polymer, and dry it under vacuum at 60 °C for 24 hours to obtain 11.94 g of the polymer. The polymerization activity is 11940 kg polymer / mol catalyst / hour.

[0130] Example 8

[0131] This example is used to illustrate the ethylene-1-hexene copolymerization.

[0132] A 100 mL stainless steel polymerization kettle that has been fully dried is adjusted to a temperature control of 50 °C, heated with the empty kettle, and evacuated for 30 minutes. Ethylene is charged and a weak ethylene flow is maintained. 5 mL of 1-hexene and 45 mL of n-hexane are added. 2.5 mL of a diethylaluminum chloride hexane solution (containing 2.5 mmol of diethylaluminum chloride) is added, stirring is started, and 2 mL of a catalyst hexane solution (containing 2 μmol of compound (1-5)) is added. After 3 minutes, 0.5 mL of a di-n-butylmagnesium hexane solution (containing 0.5 mmol of di-n-butylmagnesium) is added, and the feeding port is closed. The ethylene pressure is adjusted to 6 standard atmospheres. After 30 minutes, the ethylene is turned off, the temperature is lowered, the pressure is slowly released, and the polymer is taken out. The reaction mixture is poured into a beaker, 300 mL of anhydrous ethanol and 5 mL of concentrated hydrochloric acid are added, stirred for 6 hours, filtered to obtain the polymer, and vacuum dried at 60 °C for 24 hours to obtain 12.39 g of the polymer. The polymerization activity is 12,390 kg of polymer / mol of catalyst / hour.

[0133] Comparative Example 1

[0134] This example is used to illustrate the polymerization of ethylene.

[0135] A 100 mL stainless steel polymerization kettle that has been fully dried is adjusted to a temperature control of 50 °C, heated with the empty kettle, and evacuated for 30 minutes. Ethylene is charged and a weak ethylene flow is maintained. 50 mL of n-hexane is added. 3 mL of a methylaluminoxane toluene solution (containing 5 mmol of methylaluminoxane) is added, stirring is started, and 2 mL of a catalyst hexane suspension (containing 2 μmol of compound (1-1)) is added, and the feeding port is closed. The ethylene pressure is adjusted to 6 standard atmospheres. After 30 minutes, the ethylene is turned off, the temperature is lowered, the pressure is slowly released, and the polymer is taken out. The reaction mixture is poured into a beaker, 300 mL of anhydrous ethanol and 5 mL of concentrated hydrochloric acid are added, stirred for 6 hours, filtered to obtain the polymer, and vacuum dried at 60 °C for 24 hours to obtain 0.47 g of the polymer. The polymerization activity is 470 kg of polymer / mol of catalyst / hour.

[0136] Comparative Example 2

[0137] This example is used to illustrate the copolymerization of ethylene-1-hexene.

[0138] A fully dried 100 mL stainless steel polymerization kettle, adjust the temperature control to 50 °C, heat the empty kettle, evacuate for 30 minutes. Charge ethylene and maintain a weak ethylene flow. Add 5 mL of 1-hexene and 45 mL of n-hexane, add 3 mL of methylaluminoxane toluene solution (containing 5 mmol of methylaluminoxane), start stirring, add 2 mL of catalyst hexane solution (containing 2 μmol of compound (1-4)), and close the feeding port. Adjust the ethylene pressure to 6 standard atmospheres. After 30 minutes, close the ethylene, cool down, slowly release the pressure, and take out the polymer. Pour the reaction mixture into a beaker, add 300 mL of anhydrous ethanol and 5 mL of concentrated hydrochloric acid, stir for 6 hours, filter to obtain the polymer, and dry it in vacuo at 60 °C for 24 hours to obtain 0.62 g of the polymer. The polymerization activity is 620 kg polymer / mol catalyst / hour.

[0139] Comparative Example 3

[0140] This example is used to illustrate the copolymerization of ethylene and 1-hexene.

[0141] A fully dried 100 mL stainless steel polymerization kettle, adjust the temperature control to 50 °C, heat the empty kettle, evacuate for 30 minutes. Charge ethylene and maintain a weak ethylene flow. Add 5 mL of 1-hexene and 45 mL of n-hexane, add 3 mL of methylaluminoxane toluene solution (containing 5 mmol of methylaluminoxane), start stirring, add 2 mL of catalyst hexane solution (containing 2 μmol of compound (1-5)), and close the feeding port. Adjust the ethylene pressure to 6 standard atmospheres. After 30 minutes, close the ethylene, cool down, slowly release the pressure, and take out the polymer. Pour the reaction mixture into a beaker, add 300 mL of anhydrous ethanol and 5 mL of concentrated hydrochloric acid, stir for 6 hours, filter to obtain the polymer, and dry it in vacuo at 60 °C for 24 hours to obtain 0.59 g of the polymer. The polymerization activity is 590 kg polymer / mol catalyst / hour.

[0142] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the technical concept scope of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A catalyst composition, characterized in that, The catalyst composition comprises the following components, a) a transition metal compound having the structure shown in formula (1); b) a cocatalyst component, said cocatalyst component comprising an organoaluminum compound and an organomagnesium compound, In formula (1), M is a tetravalent transition metal atom; each X is independently an alkoxy group having 1 to 10 carbon atoms or a halogen; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 16 carbon atoms.

2. The catalyst composition according to claim 1, wherein M is titanium, zirconium or hafnium, preferably a titanium atom or a zirconium atom.

3. The catalyst composition according to claim 1, wherein, X is a hydrocarbyloxy group having 1-6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; or X is a hydrocarbyloxy group having 1-3 carbon atoms or a chlorine atom; or X is a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group or a chlorine atom.

4. The catalyst composition according to claim 1, wherein, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 and R 8 each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 3 to 12 carbon atoms; or R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 and R 8 each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 8 to 10 carbon atoms.

5. The catalyst composition according to any one of claims 1-4, wherein, The cocatalyst component is a combination of an organoaluminum compound and an organomagnesium compound.

6. The catalyst composition according to any one of claims 1-4, wherein The organoaluminum compound is a compound having the structure shown by the general formula AlX1X2X3, where X1, X2 and X3 are respectively a halogen atom, an alkyl group having 1-8 carbon atoms, an alkoxy group having 1-8 carbon atoms, an aryloxy group having 6-12 carbon atoms, X1, X2 and X3 may be the same or different, and at least one is an alkyl group having 1-8 carbon atoms; or The organoaluminum compound is a dialkylaluminum chloride, preferably one or more of dimethylaluminum chloride, diethylaluminum chloride and diisobutylaluminum chloride.

7. The catalyst composition according to any one of claims 1-4, wherein, The organomagnesium compound is MgR 1 R 2 represents a compound, where R 1 and R 2 are each independently an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen, and at least one of R 1 and R 2 is a hydrocarbon group; or The organomagnesium compound is a dialkylmagnesium, preferably di-n-butylmagnesium.

8. The catalyst composition according to any one of claims 1-4, wherein, The molar ratio of the transition metal compound to the organoaluminum compound is 1:(50 - 10000); or The molar ratio of the transition metal compound to the organoaluminum compound is 1:(100 - 2000).

9. The catalyst composition according to any one of claims 1-4, wherein The molar ratio of the organomagnesium compound to the organoaluminum compound is 1:(1 - 100); or The molar ratio of the organomagnesium compound to the organoaluminum compound is 1:(2.5 - 30); or The molar ratio of the organomagnesium compound to the organoaluminum compound is 1:(3 - 10).

10. A process for olefin polymerization, characterized in that, The method comprises contacting an olefin with the catalyst composition according to any one of claims 1-9 to carry out a polymerization reaction.

11. The method according to claim 10, wherein, The concentration of the transition metal compound in the polymerization reaction system is 1×10 -10 mol / L to 1×10 -3 mol / L, preferably 1×10 -8 mol / L to 1×10 -5 mol / L.

12. The method according to claim 10, wherein, The temperature of the polymerization reaction is -50 to 200 °C, and the time of the polymerization reaction is 1-300 minutes; Preferably, the temperature of the polymerization reaction is -20 to 150 °C, and the time of the polymerization reaction is 5-60 minutes.

13. The method according to claim 10, wherein The partial pressure of the olefin is 0.1-10 MPa, preferably 0.1-4.0 MPa.

14. Use of the catalyst composition according to any one of claims 1-9 in olefin polymerization.

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