A [ONO] tridentate imine vanadium complex, a preparation method thereof, and applications thereof

Abstract

The present invention relates to the technical field of olefin polymerization catalysts, and particularly to an [ONO] tridentate imine vanadium complex and its preparation method and application. The novel [ONO] tridentate imine vanadium complex provided by the present invention has a simple structure, is easy to modify and regulate, and has the advantages of a simple synthesis route, a simple purification method, a high yield, and being conducive to large-scale production. As the main catalyst, under the activation of cocatalysts such as Et2AlCl, EtAlCl2 or alkylaluminoxane, this type of metal complex can catalyze the homopolymerization reaction of ethylene, showing high catalytic activity, good thermal stability, long service life, etc., and highly linear polyethylene can be obtained; when it catalyzes the copolymerization reaction of ethylene and norbornene, it can catalyze with high activity to obtain polymer products with a high comonomer insertion rate; at the same time, this type of metal complex can also catalyze the copolymerization reaction of ethylene and polar monomers containing hydroxyl groups to obtain functionalized polyolefin products.

Description

Technical Field

[0001] The present invention relates to the technical field of olefin polymerization catalysts, and particularly to an [ONO] tridentate imine vanadium complex and its preparation method and application. Background Art

[0002] Polyolefin products are the most widely used synthetic resin materials in the world at present. Their extensive applications in industry, agriculture, national defense, transportation and people's daily lives have brought revolutionary changes to people's lives. Catalysts are the soul of the polyolefin industry. Therefore, a large number of scientific researchers are committed to developing transition metal catalytic systems with high activity and high control over the product structure. Traditional vanadium-based catalysts have the characteristics of a single active center and strong olefin copolymerization ability, but their catalytic activity is low, they are easy to deactivate, and their high-temperature tolerance is poor. Therefore, effective molecular structure design of their ligands to improve the performance of catalysts occupies a core position in the field of catalyst research and development.

[0003] Although the existing arylacyl monoimine vanadium catalysts can catalyze ethylene homopolymerization, copolymerization of ethylene with cycloolefins and polar monomers containing hydroxyl groups, their high-temperature resistance is poor (the optimal temperature is 0 - 40 °C), their catalytic activity is not high, and their copolymerization ability is not strong; although some reported Schiff base pentavalent imine vanadium catalysts show relatively high activity and temperature resistance in catalyzing ethylene polymerization, when they catalyze the copolymerization of ethylene with cycloolefins and polar monomers containing hydroxyl groups, there are generally problems of low catalytic activity and poor copolymerization ability.

[0004] The present invention aims to change the structures of these types of catalysts, and design a catalyst with simple synthesis, convenient purification, easy characterization, easy structure regulation, good high-temperature tolerance, long lifespan and excellent catalytic performance, while reducing the use cost. Summary of the Invention

[0005] The object of the present invention is to provide an [ONO] tridentate imine vanadium complex and its preparation method and application to solve the problems existing in the above-mentioned prior art. Through reasonable modification, these catalysts have the advantages of high catalytic activity, good thermal stability and long service life when in use; at the same time, these catalysts can also efficiently catalyze the copolymerization of ethylene with cycloolefins and polar monomers to obtain polymer products with a high comonomer content, so as to realize the application in catalyzing ethylene homopolymerization and copolymerization of ethylene with cycloolefins and polar monomers.

[0006] To achieve the above object, the present invention provides the following solutions:

[0007] One of the technical solutions of the present invention: an [ONO] tridentate imine vanadium complex, the structural formula of which is shown in Formula 1;

[0008]

[0009] Wherein:

[0010] R1 is selected from any one of the following structures: an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a phenyl group having a substituent, a carbazolyl group, an adamantyl group, a cumyl group, a diphenylmethyl group, a trityl group;

[0011] R2 is selected from any one of the following structures: an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a cumyl group;

[0012] R3 is selected from any one of the following structures: an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a phenyl group having a substituent, a carbazolyl group, an adamantyl group, a cumyl group, a diphenylmethyl group, a trityl group;

[0013] R4 is selected from any one of the following structures: hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a phenyl group having a substituent, a cumyl group;

[0014] R5 is selected from any one of the following structures: an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a hydrogen atom, a halogen atom;

[0015] R6 is selected from any one of the following structures: an alkyl group having 1 to 4 carbon atoms, a hydrogen atom, a halogen atom, a halogen-containing substituent;

[0016] R7 is selected from any one of the following structures: an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a hydrogen atom, a halogen atom, a halogen-containing substituent.

[0017] Furthermore, in the [ONO] tridentate imine vanadium complex: R1 is methyl, tert-butyl, phenyl, adamantyl, cumyl or trityl; R2 is methyl, tert-butyl, tert-octyl, methoxy or cumyl; R3 is methoxy, tert-butyl, phenyl, adamantyl, cumyl or trityl; R4 is hydrogen, methyl, tert-butyl, tert-octyl, methoxy or cumyl; R5 is H, methyl or isopropyl; R6 is H, a halogen atom or a halogen-containing substituent; R7 is H, a halogen atom or a halogen-containing substituent.

[0018] Furthermore, the structural formula of the [ONO] tridentate imine vanadium complex is any one of Formula C1 to Formula C11:

[0019]

[0020] In the second technical solution of the present invention, the preparation method of the above [ONO] tridentate imine vanadium complex is obtained by reacting the ligand shown in Formula 2 and

[0021] the complex shown in Formula 3 as raw materials; wherein:

[0022]

[0023] Furthermore, the reaction uses benzene as the reaction solvent and triethylamine as the acid-binding agent, and the reaction temperature is room temperature.

[0024] Furthermore, in Formula 2 and Formula 3:

[0025] R1 is selected from any one of the following structures: alkyl containing 1 to 10 carbons, alkoxy containing 1 to 10 carbons, phenyl, phenyl with substituents, carbazolyl, adamantyl, cumyl, diphenylmethyl, trityl;

[0026] R2 is selected from any one of the following structures: alkyl containing 1 to 10 carbons, alkoxy containing 1 to 10 carbons, phenyl, cumyl;

[0027] R3 is selected from any one of the following structures: alkyl containing 1 to 10 carbons, alkoxy containing 1 to 10 carbons, phenyl, phenyl with substituents, carbazolyl, adamantyl, cumyl, diphenylmethyl, trityl;

[0028] R4 is selected from any one of the following structures: hydrogen, alkyl containing 1 to 10 carbons, alkoxy containing 1 to 10 carbons, phenyl, phenyl with substituents, cumyl;

[0029] R5 is selected from any one of the following structures: alkyl containing 1 to 4 carbons, alkoxy, hydrogen atom, halogen atom;

[0030] R6 is selected from any one of the following structures: alkyl containing 1 to 4 carbons, hydrogen atom, halogen atom, halogen-containing substituent;

[0031] R7 is selected from any one of the following structures: alkyl containing 1 to 4 carbons, alkoxy, hydrogen atom, halogen atom, halogen-containing substituent.

[0032] The third technical solution of the present invention is the application of the above [ONO] tridentate imine vanadium complex in the catalytic ethylene polymerization reaction.

[0033] Furthermore, the ethylene polymerization reaction is specifically an ethylene homopolymerization reaction, a copolymerization reaction of ethylene and cycloolefin, or a copolymerization reaction of ethylene and a polar monomer containing a hydroxyl group.

[0034] Furthermore, the ethylene polymerization reaction uses the [ONO] tridentate imine vanadium complex as the main catalyst, and an alkylaluminoxane, a modified alkylaluminoxane or a haloalkylaluminum as the co-catalyst. The molar ratio of aluminum in the co-catalyst to the metal in the main catalyst is 5 - 10000:1, and the pressure of ethylene gas during polymerization is 0.1 - 10.0 MPa.

[0035] Furthermore, in the ethylene polymerization reaction, the [ONO] tridentate imine vanadium complex is used as the main catalyst, and diethylaluminum chloride, ethylaluminum dichloride or methylaluminoxane is used as the cocatalyst. The molar ratio of aluminum in the cocatalyst to the metal in the main catalyst is 100 - 5000:1, and the pressure of ethylene gas during polymerization is 0.1 - 1.0 MPa.

[0036] Furthermore, when the ethylene polymerization reaction is a copolymerization reaction of ethylene and a polar monomer containing a hydroxyl group, the molar ratio of the organoaluminum used for hydroxyl protection to the polar monomer is 1:1.

[0037] Furthermore, the copolymerization reaction of ethylene and cycloolefin is specifically a copolymerization reaction of ethylene and norbornene.

[0038] Furthermore, the copolymerization reaction of ethylene and a polar monomer containing a hydroxyl group is specifically a copolymerization reaction of ethylene and undecenol. The [ONO] tridentate imine vanadium complex is used as the main catalyst, and diethylaluminum chloride is used as the cocatalyst. The molar ratio of the organoaluminum used for hydroxyl protection to the polar monomer is 1:1.

[0039] The present invention discloses the following technical effects:

[0040] The present invention relates to a novel [ONO] tridentate imine vanadium complex, which has a simple structure, is easy to modify and regulate, and has the advantages of a short synthesis route, a simple purification method, a high yield, and being conducive to large-scale production. As the main catalyst, this type of metal complex can catalyze the homopolymerization reaction of ethylene under the activation of cocatalysts such as Et2AlCl, EtAlCl2 or alkylaluminoxane, showing high catalytic activity, good thermal stability, long lifespan, etc., and highly linear polyethylene can be obtained; when it catalyzes the copolymerization reaction of ethylene and norbornene, it can catalyze with high activity to obtain polymer products with a high comonomer insertion rate; at the same time, this type of metal complex can also catalyze the copolymerization reaction of ethylene and a polar monomer containing a hydroxyl group to obtain functionalized polyolefin products.

[0041] The catalyst of the present invention has very good heat resistance and can still maintain good catalytic activity under higher temperature conditions.

[0042] The metal center of the catalyst of the present invention is stable and the catalytic lifespan is long.

[0043] The catalyst of the present invention catalyzes the copolymerization reaction of ethylene and norbornene with very high activity, and the comonomer insertion rate in the polymer is also very high.

[0044] The catalyst of the present invention catalyzes the copolymerization reaction of ethylene and undecenol with very high activity and can obtain functionalized polyolefin products. Description of the Drawings

[0045] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0046] Figure 1 1H NMR spectrum of complex C1 provided in Example 2 of the present invention;

[0047] Figure 2 1H NMR spectrum of complex C2 provided in Example 2 of the present invention;

[0048] Figure 3 13C NMR spectrum of the copolymer of ethylene and norbornene when complex C2 is used as the main catalyst provided in Test Example 2 of the present invention;

[0049] Figure 4 1H NMR spectrum of the copolymer of ethylene and 1 - undecenol when complex C5 is used as the main catalyst provided in Test Example 3 of the present invention. Detailed implementation manners

[0050] Now, various exemplary implementation manners of the present invention will be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, characteristics, and implementation schemes of the present invention.

[0051] It should be understood that the terms described in the present invention are only for describing specific implementation manners and are not used to limit the present invention. Additionally, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.

[0052] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0053] Without departing from the scope or spirit of the present invention, various modifications and variations can be made to the specific embodiments of the description of the present invention, which are obvious to those skilled in the art. Other embodiments obtained from the description of the present invention are obvious to those skilled in the art. The description and examples of the present invention are merely exemplary.

[0054] Regarding the use of "comprising", "including", "having", "containing", etc. herein, they are all open-ended terms, meaning including but not limited to.

[0055] As used in the present invention, "room temperature" refers to 25°C unless otherwise specified.

[0056] The raw materials used in the present invention are all obtained by purchasing on the market.

[0057] The [ONO] tridentate imine vanadium complex provided by the present invention has a structural formula as shown in Formula 1;

[0058]

[0059] Wherein:

[0060] R1 is selected from any one of the following structures: an alkyl group containing 1 to 10 carbons, an alkoxy group containing 1 to 10 carbons, a phenyl group, a phenyl group with substituents, a carbazolyl group, an adamantyl group, a cumyl group, a diphenylmethyl group, a triphenylmethyl group;

[0061] R2 is selected from any one of the following structures: an alkyl group containing 1 to 10 carbons, an alkoxy group containing 1 to 10 carbons, a phenyl group, a cumyl group;

[0062] R3 is selected from any one of the following structures: an alkyl group containing 1 to 10 carbons, an alkoxy group containing 1 to 10 carbons, a phenyl group, a phenyl group with substituents, a carbazolyl group, an adamantyl group, a cumyl group, a diphenylmethyl group, a triphenylmethyl group;

[0063] R4 is selected from any one of the following structures: hydrogen, an alkyl group containing 1 to 10 carbons, an alkoxy group containing 1 to 10 carbons, a phenyl group, a phenyl group with substituents, a cumyl group;

[0064] R5 is selected from any one of the following structures: an alkyl group containing 1 to 4 carbons, an alkoxy group, a hydrogen atom, a halogen atom;

[0065] R6 is selected from any one of the following structures: an alkyl group containing 1 to 4 carbons, a hydrogen atom, a halogen atom, a halogen-containing substituent;

[0066] R7 is selected from any one of the following structures: an alkyl group containing 1 to 4 carbons, an alkoxy group, a hydrogen atom, a halogen atom, a halogen-containing substituent.

[0067] In some preferred embodiments of the present invention, in the [ONO] tridentate imine vanadium complex: R1 is methyl, tert-butyl, phenyl, adamantyl, cumyl or trityl; R2 is methyl, tert-butyl, tert-octyl, methoxy or cumyl; R3 is methoxy, tert-butyl, phenyl, adamantyl, cumyl or trityl; R4 is hydrogen, methyl, tert-butyl, tert-octyl, methoxy or cumyl; R5 is H, methyl or isopropyl; R6 is H, a halogen atom or a halogen-containing substituent; R7 is H, a halogen atom or a halogen-containing substituent.

[0068] In some preferred embodiments of the present invention, the structural formula of the [ONO] tridentate imine vanadium complex is any one of Formulas C1 to C11:

[0069]

[0070] The [ONO] tridentate imine vanadium complex of the present invention can be synthesized by various methods known to those skilled in the art. Ligands and transition metal complexes with similar structures can also be synthesized with reference to Example 1 and Example 2 of the present invention.

[0071] In some preferred embodiments of the present invention, the preparation method of the above [ONO] tridentate imine vanadium complex is obtained by reacting the ligand shown in Formula 2 and the complex shown in Formula 3 as raw materials; wherein:

[0072]

[0073] In some preferred embodiments of the present invention, the reaction uses benzene as the reaction solvent, triethylamine as the acid-binding agent, and the reaction temperature is room temperature.

[0074] In some preferred embodiments of the present invention, in Formulas 2 and 3:

[0075] R1 is selected from any one of the following structures: an alkyl group containing 1 to 10 carbons, an alkoxy group containing 1 to 10 carbons, phenyl, phenyl with a substituent, carbazolyl, adamantyl, cumyl, diphenylmethyl, trityl;

[0076] R2 is selected from any one of the following structures: an alkyl group containing 1 to 10 carbons, an alkoxy group containing 1 to 10 carbons, phenyl, cumyl;

[0077] R3 is selected from any one of the following structures: an alkyl group containing 1 to 10 carbons, an alkoxy group containing 1 to 10 carbons, phenyl, phenyl with a substituent, carbazolyl, adamantyl, cumyl, diphenylmethyl, trityl;

[0078] R4 is selected from any one of the following structures: hydrogen, an alkyl group containing 1 to 10 carbons, an alkoxy group containing 1 to 10 carbons, phenyl, phenyl with a substituent, cumyl;

[0079] R5 is selected from any one of the following structures: an alkyl group having 1 to 4 carbons, an alkoxy group, a hydrogen atom, a halogen atom;

[0080] R6 is selected from any one of the following structures: an alkyl group having 1 to 4 carbons, a hydrogen atom, a halogen atom, a halogen-containing substituent;

[0081] R7 is selected from any one of the following structures: an alkyl group having 1 to 4 carbons, an alkoxy group, a hydrogen atom, a halogen atom, a halogen-containing substituent.

[0082] In some preferred embodiments of the present invention, the structure of Formula 2 is prepared by using the structures of Formula A and Formula B as raw materials, methanol as the reaction solvent, glacial acetic acid as the acid-binding agent, and heating and reacting at 60 °C under a nitrogen atmosphere;

[0083]

[0084] The present invention uses the above [ONO] tridentate imine vanadium complex for catalyzing the ethylene polymerization reaction.

[0085] In some preferred embodiments of the present invention, the ethylene polymerization reaction is specifically an ethylene homopolymerization reaction, a copolymerization reaction of ethylene and a cycloolefin, or a copolymerization reaction of ethylene and a polar monomer containing a hydroxyl group.

[0086] In some preferred embodiments of the present invention, the ethylene polymerization reaction uses the [ONO] tridentate imine vanadium complex as the main catalyst, and an alkylaluminoxane, a modified alkylaluminoxane or a haloalkylaluminum as the cocatalyst. The molar ratio of aluminum in the cocatalyst to the metal in the main catalyst is 5 - 10000:1, and the pressure of ethylene gas during polymerization is 0.1 - 10.0 MPa.

[0087] In some preferred embodiments of the present invention, the ethylene polymerization reaction uses the [ONO] tridentate imine vanadium complex as the main catalyst, and diethylaluminum chloride, dichloroethylaluminum or methylaluminoxane as the cocatalyst. The molar ratio of aluminum in the cocatalyst to the metal in the main catalyst is 100 - 5000:1, and the pressure of ethylene gas during polymerization is 0.1 - 1.0 MPa;

[0088] In some preferred embodiments of the present invention, when the ethylene polymerization reaction is a copolymerization reaction of ethylene and a polar monomer containing a hydroxyl group, the polar monomer containing a hydroxyl group is pretreated with an alkylaluminoxane, a modified alkylaluminoxane or a haloalkylaluminum (cocatalyst) before reacting with ethylene to protect the hydroxyl group of the polar monomer containing a hydroxyl group. The molar ratio of the organoaluminum used for hydroxyl protection to the polar monomer is 1:1.

[0089] In some preferred embodiments of the present invention, the copolymerization reaction of ethylene and a cycloolefin is specifically a copolymerization reaction of ethylene and norbornene;

[0090] In some preferred embodiments of the present invention, the copolymerization reaction of ethylene with a polar monomer containing a hydroxyl group is specifically the copolymerization reaction of ethylene with undecenol. Using the [ONO] tridentate imine vanadium complex as the main catalyst and diethylaluminum chloride as the cocatalyst, undecenol is pretreated with diethylaluminum chloride before reacting with ethylene to protect the hydroxyl group of undecenol. The molar ratio of the organoaluminum used for undecenol to the polar monomer is 1:1.

[0091] In the following examples of the present invention, a ligand having the structure shown in Formula 2 is used as a raw material to prepare the [ONO] tridentate imine vanadium complex shown in Formula 1. Specifically, ligands having the structures of L1 to L11 are used as raw materials to prepare [ONO] tridentate imine vanadium complexes having the structural formulas of C1 to C11.

[0092] The ligands having the structures of L1 to L11 are specifically as follows:

[0093]

[0094] Example 1: Preparation of ligand

[0095]

[0096] (1) Referring to the following method, a series of substituted 2-amino-4-R2-6-R1-phenol compounds (A) are synthesized:

[0097] Place 2-R1-4-R2-phenol (0.145 mol, eq = 1.00) in a 500 mL round-bottom flask, add 270 mL of dichloromethane and 30 mL of glacial acetic acid, stir and mix evenly, cool to -15 °C, and then slowly drop 11 mL of concentrated nitric acid (mass fraction 65 - 68%) into the above system. The system immediately turns dark red-brown. After the dropping is complete, raise the temperature to room temperature and react for 1 h; add 100 mL of water to quench the reaction, carefully add sodium bicarbonate to adjust the pH to 5.0 - 7.0, extract with CH2Cl2, separate and retain the organic phase, dry it with anhydrous magnesium sulfate, rotary evaporate to remove the solvent, and separate with a silica gel column (the eluent is CH2Cl2:petroleum ether = 1:50) to obtain 2-nitro-4-R2-6-R1-phenol;

[0098] Place the prepared 2-nitro-4-R2-6-R1-phenol in a 500 mL two-necked round-bottom flask, add ethanol (200 mL) and 1 g of Pd / C (5%) catalyst, start stirring, carefully drop 20 mL of hydrazine monohydrate solution into it, and then heat to reflux for 12 h. After cooling to room temperature, filter off the Pd / C (5%) catalyst, concentrate, precipitate a grayish-white solid, filter and wash with a small amount of cold ethanol, and drain to obtain a white solid, which is 2-amino-4-R2-6-R1-phenol;

[0099] 2-Amino-4,6-dimethylphenol, 2-amino-4,6-di-tert-butylphenol, 2-amino-4-tert-butyl-6-adamantylphenol, 2-amino-4-tert-butyl-6-cumylphenol, and 2-amino-4-tert-butyl-6-triphenylmethylphenol in the present invention are all synthesized by the above method.

[0100] (2) Synthesize a series of substituted 3-R3-5-R4-salicylaldehyde compounds (B) with reference to the following method:

[0101] Add 2-R3-4-R4-phenol (0.2 mol, eq = 1.00), anhydrous MgCl2 (0.22 mol, eq = 1.10), and dry paraformaldehyde (0.22 mol, eq = 1.10) into a 500 mL Schlenck flask in sequence, displace it into a nitrogen atmosphere, introduce dry THF (300 mL) into it, keep stirring at room temperature, and dropwise add dry triethylamine (0.24 mol, eq = 1.20); heat the reaction mixture to 60 °C and react for 5 h, cool to room temperature, add 100 mL of water to quench the reaction, extract with CH2Cl2, separate and retain the organic phase, dry it with anhydrous magnesium sulfate, rotary evaporate to remove most of the solvent, concentrate to 80 mL, and add anhydrous methanol (300 mL) to it, stir rapidly, and precipitate solid powder, which is 3-R3-5-R4-salicylaldehyde;

[0102] 3-Adamantyl-5-tert-butylsalicylaldehyde, 3,5-dicumylsalicylaldehyde, 3-phenylsalicylaldehyde, 3,5-di-tert-butylsalicylaldehyde, and 3-methoxysalicylaldehyde in the present invention are all synthesized by the above method.

[0103] (3) Synthesis of ligands

[0104] Add compound (A) (21.87 mmol, eq = 1.00), compound (B) (21.87 mmol, eq = 1.00), and 50 mL of anhydrous methanol into a 100 mL Schlenck flask in sequence, displace the system into an N2 atmosphere, add 3 - 5 drops of glacial acetic acid to it with a syringe, heat to 60 °C and react for 12 h, stop heating, cool to room temperature, at this time, a large amount of precipitate appears in the flask, filter, and wash the filter cake with 20 mL of cold methanol twice, and drain to obtain the ligand; Ligands L1 - L11 preferred in the present invention are all synthesized by the above method.

[0105] The experimental results are as follows:

[0106] L1: Light yellow powdery solid, yield: 95.1%. 11H NMR (400 MHz, CDCl3) δ 12.72 (s, 1H, -OH), 8.68 (s, 1H, N=C-H), 7.48 (d, J=2.3 Hz, 1H, Ar-H), 7.25 (s, 1H, Ar-H), 6.89 (s, 1H, Ar-H), 6.81 (s, 1H, Ar-H), 5.77 (s, 1H, -OH), 2.28 (d, J=5.7 Hz, 6H, Ar-CH3), 1.47 (s, 9H, -C(CH3)3), 1.33 (s, 9H, -C(CH3)3);

[0107] L2: Light yellow powdery solid, yield: 89.7%. 1 1H NMR (400 MHz, CDCl3) δ 12.64 (s, 1H, -OH), 8.68 (s, 1H, N=C-H), 7.48 (d, J=1.9 Hz, 1H, Ar-H), 7.27 (dd, J=5.4, 1.8 Hz, 2H, Ar-H), 7.00 (d, J=1.7 Hz, 1H, Ar-H), 6.12 (s, 1H, -OH), 1.46 (d, J=6.5 Hz, 18H, -C(CH3)3), 1.35 (s, 18H, -C(CH3)3);

[0108] L3: Light yellow powdery solid, yield: 95.6%. 1 1H NMR (400 MHz, CDCl3) δ 12.63 (s, 1H, -OH), 8.68 (s, 1H, N=C-H), 7.48 (d, J=2.2 Hz, 1H, Ar-H), 7.27 (d, J=2.1 Hz, 1H, Ar-H), 7.21 (d, J=1.7 Hz, 1H, Ar-H), 7.00 (d, J=1.8 Hz, 1H, Ar-H), 6.15 (s, 1H, -OH), 2.18 (s, 6H, Ad-H), 2.10 (s, 3H, Ad-H), 1.85 - 1.75 (m, 6H, Ad-H), 1.46 (s, 9H, -C(CH3)3), 1.34 (s, 18H, -C(CH3)3);

[0109] L4: Orange powdery solid, yield: 94.5%. 11H NMR (400 MHz, CDCl3) δ 12.75 (s, 1H, -OH), 8.65 (s, 1H, N=C-H), 7.43 (dd, J=6.8, 2.0 Hz, 2H, Ar-H), 7.27 (t, J=4.2 Hz, 4H, Ar-H), 7.23 (d, J=2.2 Hz, 1H, Ar-H), 7.20 - 7.16 (m, 1H, Ar-H), 7.07 (d, J=1.9 Hz, 1H, Ar-H), 5.58 (s, 1H, -OH), 1.75 (s, 6H, Cumyl-CH3), 1.41 (s, 9H, -C(CH3)3), 1.39 (s, 9H, -C(CH3)3), 1.32 (s, 9H, -C(CH3)3);

[0110] L5: Bright yellow crystalline solid, yield: 94.2%. 1 1H NMR (400 MHz, CDCl3) δ 12.84 (s, 1H, -OH), 8.67 (s, 1H, N=C-H), 7.42 (d, J=2.2 Hz, 1H, Ar-H), 7.29 - 7.17 (m, 16H, Ar-H), 7.15 (d, J=1.9 Hz, 1H, Ar-H), 7.11 (d, J=2.0 Hz, 1H, Ar-H), 5.50 (s, 1H, -OH), 1.40 (s, 9H, -C(CH3)3), 1.32 (s, 9H, -C(CH3)3), 1.21 (s, 9H, -C(CH3)3);

[0111] L6: Light yellow powdery solid, yield: 89.4%. 1 1H NMR (400 MHz, CDCl3) δ 12.67 (s, 1H, -OH), 8.68 (s, 1H, N=C-H), 7.42 (d, J=2.2 Hz, 1H, Ar-H), 7.25 (s, 2H, Ar-H), 7.00 (d, J=2.1 Hz, 1H, Ar-H), 6.11 (s, 1H, -OH), 2.20 (s, 6H, Ad-H), 2.11 (s, 3H, Ad-H), 1.85 - 1.77 (m, 6H, Ad-H), 1.45 (s, 9H, -C(CH3)3), 1.34 (d, J=2.1 Hz, 18H, -C(CH3)3);

[0112] L7: Light yellow powdery solid, yield: 92.9%. 11H NMR (400 MHz, CDCl3) δ 12.69 (s, 1H, -OH), 8.69 (s, 1H, N=C-H), 7.42 (d, J=2.1 Hz, 1H, Ar-H), 7.26 (d, J=2.1 Hz, 1H, Ar-H), 7.20 (d, J=1.7 Hz, 1H, Ar-H), 7.00 (d, J=1.9 Hz, 1H, Ar-H), 6.15 (s, 1H, -OH), 2.19 (s, 12H, Ad-H), 2.10 (s, 6H, Ad-H), 1.80 (s, 12H, Ad-H), 1.34 (s, 18H, -C(CH3)3);

[0113] L8: Yellow powdery solid, yield: 90.6%. 1 1H NMR (400 MHz, CDCl3) δ 12.23 (s, 1H, -OH), 8.55 (s, 1H, N=C-H), 7.45 (d, J=2.1 Hz, 1H, Ar-H), 7.32 - 7.28 (m, 4H, Ar-H), 7.24 - 7.18 (m, 7H, Ar-H), 7.13 (t, J=6.9 Hz, 1H, Ar-H), 6.89 (d, J=2.1 Hz, 1H, Ar-H), 5.96 (s, 1H, -OH), 1.75 (s, 6H, Cumyl-CH3), 1.69 (s, 6H, Cumyl-CH3), 1.39 (s, 9H, -C(CH3)3), 1.30 (s, 9H, -C(CH3)3);

[0114] L9: Orange-yellow crystalline solid, yield: 93.6%. 1 1H NMR (400 MHz, CDCl3) δ 12.28 (s, 1H, -OH), 8.51 (s, 1H, N=C-H), 7.41 (d, J=2.3 Hz, 1H, Ar-H), 7.31 - 7.27 (m, 4H, Ar-H), 7.24 - 7.13 (m, 21H, Ar-H), 7.11 (d, J=7.2 Hz, 1H, Ar-H), 7.10 - 7.08 (m, 1H, Ar-H), 6.96 (d, J=2.2 Hz, 1H, Ar-H), 5.35 (s, 1H, -OH), 1.72 (s, 6H, Cumyl-CH3), 1.63 (s, 6H, Cumyl-CH3), 1.16 (s, 9H, -C(CH3)3);

[0115] L10: Yellow powdery solid, yield: 92.0%. 11H NMR (400 MHz, CDCl3) δ 12.77 (s, 1H, -OH), 8.74 (s, 1H, N=C-H), 7.64 (d, J = 7.3 Hz, 2H, Ar-H), 7.47 (dd, J = 14.9, 7.5 Hz, 4H, Ar-H), 7.37 (t, J = 7.4 Hz, 1H, Ar-H), 7.29 (d, J = 1.8 Hz, 1H, Ar-H), 7.07 (t, J = 7.6 Hz, 1H, Ar-H), 7.03 (d, J = 2.1 Hz, 1H, Ar-H), 6.00 (s, 1H, -OH), 1.43 (s, 9H, -C(CH3)3), 1.35 (s, 9H, -C(CH3)3);

[0116] L11: Pale yellow powdery solid, yield: 83.1%. 1 1H NMR (400 MHz, CDCl3) δ 12.29 (s, 1H, -OH), 8.69 (s, 1H, N=C-H), 7.29 (d, J = 2.2 Hz, 1H, Ar-H), 7.10 (dd, J = 7.8, 1.3 Hz, 1H, Ar-H), 7.05 - 6.98 (m, 2H, Ar-H), 6.94 (t, J = 7.9 Hz, 1H, Ar-H), 6.05 (s, 1H, -OH), 3.95 (s, 3H, -OCH3), 1.44 (s, 9H, -C(CH3)3), 1.34 (s, 9H, -C(CH3)3).

[0117] Example 2: Preparation of [ONO] tridentate imine vanadium complex

[0118]

[0119] General synthesis method: Under an inert gas atmosphere, 0.5000 g (1.81 mmol, eq = 1.02) of V(N-2,6-Me2C6H3)Cl3 and 30 mL of dry benzene were successively added to a 100 mL Schlenk flask, and the mixture was stirred at room temperature for 3 min to dissolve the solid. Subsequently, a powder of one of the ligands L1 - L11 (1.77 mmol, eq = 1.00) was directly added to the above system, and the flask wall was rinsed with 20 mL of dry benzene. After stirring for 10 min, 0.60 mL (4.26 mmol, eq = 2.40) of triethylamine was added thereto, and the reaction was stirred at room temperature overnight. The triethylamine hydrochloride was removed by filtration, the filtrate was concentrated to 15 mL, then 30 mL of n-hexane was added thereto, and the mixture was rapidly stirred for 20 min to precipitate a large amount of solid, which was filtered and dried to obtain the metal complex. (The preferred catalysts C1 - C11 in the present invention are all prepared and purified by this method).

[0120] The experimental results are as follows:

[0121] C1: 0.8455 g of yellow powdery solid, yield: 85.6%. 1 H NMR (400 MHz, C6D6) δ 8.30 (s, 1H, C=N-H), 7.79 (d, J = 2.4 Hz, 1H, Ar-H), 7.15 - 7.14 (m, 1H, Ar-H), 6.83 (s, 1H, Ar-H), 6.61 (s, 1H, Ar-H), 6.25 (s, 3H, Ar-H), 2.45 (s, 3H, Ar-CH3), 2.17 (s, 3H, Ar-CH3), 1.96 (s, 6H, Ar-CH3), 1.74 (s, 9H, -C(CH3)3), 1.33 (s, 9H, -C(CH3)3);

[0122] C2: 0.9073 g of yellowish green solid, yield: 79.8%. 1 H NMR (400 MHz, C6D6) δ 8.57 (s, 1H, N=C-H), 7.77 (d, J = 2.3 Hz, 1H, Ar-H), 7.54 (d, J = 1.9 Hz, 1H, Ar-H), 7.24 (d, J = 1.8 Hz, 1H, Ar-H), 7.07 (d, J = 2.2 Hz, 1H, Ar-H), 6.26 (s, 3H, Ar-H), 1.96 (s, 6H, Ar-CH3), 1.74 (d, J = 1.7 Hz, 18H, -C(CH3)3), 1.31 (s, 9H, -C(CH3)3), 1.27 (s, 9H, -C(CH3)3);

[0123] C3: 1.0267 g of yellowish green solid, yield: 80.5%. 1 H NMR (400 MHz, C6D6) δ 8.56 (s, 1H, N=C-H), 7.77 (d, J = 2.0 Hz, 1H, Ar-H), 7.52 (s, 1H, Ar-H), 7.24 (s, 1H, Ar-H), 7.07 (s, 1H, Ar-H), 6.27 (s, 3H, Ar-H), 2.62 - 2.52 (m, 6H, Ad-H), 2.22 (s, 3H, Ad-H), 2.03 (d, J = 11.8 Hz, 3H, Ad-H), 1.98 (s, 6H, Ar-CH3), 1.85 (d, J = 11.5 Hz, 3H, Ad-H), 1.75 (s, 9H, -C(CH3)3), 1.34 (s, 9H, -C(CH3)3), 1.27 (s, 9H, -C(CH3)3);

[0124] C4: 1.0649 g of yellowish green solid, yield: 85.4%. 11H NMR (400 MHz, C6D6) δ 8.48 (s, 1H, N=C-H), 7.74 (d, J=2.3 Hz, 1H, Ar-H), 7.65 (d, J=7.4 Hz, 2H, Ar-H), 7.49 (d, J=1.9 Hz, 1H, Ar-H), 7.27 (t, J=7.8 Hz, 2H, Ar-H), 7.21 (d, J=1.9 Hz, 1H, Ar-H), 7.06 (d, J=7.3 Hz, 1H, Ar-H), 7.02 (d, J=2.3 Hz, 1H, Ar-H), 6.26 (d, J=4.3 Hz, 3H, Ar-H), 2.08 (d, J=5.7 Hz, 6H, Cumyl-CH3), 1.86 (s, 6H, Ar-CH3), 1.70 (s, 9H, -C(CH3)3), 1.29 (s, 9H, -C(CH3)3), 1.25 (s, 9H, -C(CH3)3);

[0125] C5: Yellowish green solid, 1.2074 g, yield: 82.3%. 1 1H NMR (400 MHz, C6D6) δ 8.68 (s, 1H, N=C-H), 7.87 (d, J=1.8 Hz, 1H, Ar-H), 7.72 (d, J=2.3 Hz, 1H, Ar-H), 7.68 (d, J=7.5 Hz, 6H, Ar-H), 7.40 (d, J=1.8 Hz, 1H, Ar-H), 7.13 (s, 1H, Ar-H), 7.08 (t, J=7.8 Hz, 6H, Ar-H), 6.93 (t, J=7.3 Hz, 3H, Ar-H), 6.36 - 6.32 (m, 3H, Ar-H), 2.00 (s, 6H, Ar-CH3), 1.65 (s, 9H, -C(CH3)3), 1.31 (s, 9H, -C(CH3)3), 1.23 (s, 9H, -C(CH3)3);

[0126] C6: Yellowish green solid, 0.9617 g, yield: 75.4%. 11H NMR (400 MHz, C6D6) δ 8.56 (s, 1H, N=C-H), 7.76 (d, J=2.3 Hz, 1H, Ar-H), 7.54 (d, J=2.0 Hz, 1H, Ar-H), 7.23 (d, J=1.9 Hz, 1H, Ar-H), 7.08 (d, J=2.2 Hz, 1H, Ar-H), 6.26 (s, 3H, Ar-H), 2.62 (d, J=12.2 Hz, 3H, Ad-H), 2.50 (d, J=11.3 Hz, 3H, Ad-H), 2.28 (s, 3H, Ad-H), 2.14 (d, J=12.0 Hz, 3H, Ad-H), 1.97 (s, 6H, Ar-CH3), 1.89 (d, J=12.2 Hz, 3H, Ad-H), 1.74 (s, 9H, -C(CH3)3), 1.31 (d, J=4.0 Hz, 18H, -C(CH3)3);

[0127] C7: Yellowish green solid, 1.2669 g, yield: 89.6%. 1 1H NMR (400 MHz, CDCl3) δ 9.22 (s, 1H, N=C-H), 7.66 (d, J=2.1 Hz, 1H, Ar-H), 7.55 (d, J=2.1 Hz, 1H, Ar-H), 7.47 (d, J=1.6 Hz, 1H, Ar-H), 7.27 (d, J=1.7 Hz, 1H, Ar-H), 6.70 - 6.61 (m, 3H, Ar-H, Ar-H), 2.37 - 2.20 (m, 12H, Ad-H), 2.14 (d, J=12.1 Hz, 6H, Ad-H), 1.89 (s, 6H, Ar-CH3), 1.82 (t, J=11.0 Hz, 8H, Ad-H), 1.42 (d, J=7.3 Hz, 4H, Ad-H), 1.40 (s, 9H, -C(CH3)3), 1.37 (s, 9H, -C(CH3)3);

[0128] C8: Yellowish green solid, 1.0083 g, yield: 74.3%. 11H NMR (400 MHz, C6D6) δ 8.32 (s, 1H, N=C-H), 7.72 (d, J=2.1 Hz, 1H, Ar-H), 7.59 (d, J=7.5 Hz, 2H, Ar-H), 7.46 (s, 1H, Ar-H), 7.26 - 7.18 (m, 7H, Ar-H), 7.08 (t, J=4.9 Hz, 2H, Ar-H), 7.01 (d, J=1.6 Hz, 1H, Ar-H), 6.93 (t, J=7.4 Hz, 1H, Ar-H), 6.29 (q, J=4.4 Hz, 3H, Ar-H), 2.14 (s, 3H, Cumyl-CH3), 1.94 (s, 6H, Ar-CH3), 1.80 (s, 3H, Cumyl-CH3), 1.65 (s, 12H, Cumyl-CH3 and -C(CH3)3), 1.63 (s, 3H, Cumyl-CH3), 1.26 (s, 9H, -C(CH3)3);

[0129] C9: Orange-yellow solid, 1.3650 g, yield: 80.9%. 1 1H NMR (400 MHz, C6D6) δ 8.43 (s, 1H, N=C-H), 7.78 (d, J=1.5 Hz, 1H, Ar-H), 7.65 (dd, J=15.6, 4.8 Hz, 7H, Ar-H), 7.39 (d, J=7.7 Hz, 2H, Ar-H), 7.21 (dd, J=16.8, 7.8 Hz, 5H, Ar-H), 7.08 (t, J=7.7 Hz, 7H, Ar-H), 6.98 (dt, J=14.5, 7.4 Hz, 6H, Ar-H), 6.73 (t, J=7.4 Hz, 1H, Ar-H), 6.41 (s, 3H, Ar-H), 1.96 (s, 6H, Ar-CH3), 1.86 (s, 3H, Cumyl-CH3), 1.78 (s, 3H, Cumyl-CH3), 1.62 (s, 6H, Cumyl-CH3), 1.24 (s, 9H, -C(CH3)3);

[0130] C10: Orange-yellow solid, 0.9441 g, yield: 88.0%. 11H NMR (400 MHz, CDCl3) δ 9.28 (s, 1H, N=C-H), 7.91 (d, J=7.6 Hz, 2H, Ar-H), 7.84 (d, J=6.6 Hz, 1H, Ar-H), 7.74 (d, J=7.7 Hz, 1H, Ar-H), 7.55 - 7.50 (m, 3H, Ar-H), 7.39 (dd, J=15.4, 7.8 Hz, 3H, Ar-H), 7.29 - 7.25 (m, 1H, Ar-H), 6.66 (dt, J=12.9, 5.7 Hz, 3H, Ar-H), 1.91 (s, 6H, Ar-CH3), 1.50 (s, 9H, -C(CH3)3), 1.39 (s, 9H, -C(CH3)3);

[0131] C11: Yellow solid, 0.8048 g, yield: 81.2%. 1 1H NMR (400 MHz, C6D6) δ 8.51 (s, 1H, N=C-H), 7.53 (s, 1H, Ar-H), 7.23 (s, 1H, Ar-H), 6.80 (d, J=7.6 Hz, 1H, Ar-H), 6.67 (t, J=7.8 Hz, 1H, Ar-H), 6.60 (d, J=7.8 Hz, 1H, Ar-H), 6.24 (s, 3H, Ar-H), 3.66 (s, 3H, -OCH3), 2.01 (s, 6H, Ar-CH3), 1.71 (s, 9H, -C(CH3)3), 1.33 (s, 9H, -C(CH3)3).

[0132] Test Example 1: Study on High-Pressure Polymerization of Ethylene

[0133] The polymerization reaction was carried out in a 250 mL stainless steel high-pressure reactor. The polymerization kettle equipped with mechanical stirring was heated to 200 °C, evacuated for 1 h, adjusted to the temperature conditions required for polymerization, filled with ethylene gas at 0.1 MPa, and a toluene solution (total volume of 200 mL) containing an aluminum-based cocatalyst and a reactivator (ethyl trichloroacetate) was added to the polymerization kettle. After maintaining the temperature for a period of time until it was constant, ethylene gas at a certain pressure was introduced, waited for 10 min to reach the dissolution equilibrium of ethylene, then the main catalyst was added, and the stirring reaction was carried out for a period of time. After the polymerization reaction was completed, the residual ethylene gas was released, the reaction kettle was opened, and the obtained polymerization reaction mixture was poured into a mixed solution of 3M hydrochloric acid and ethanol with a volume ratio of 1:1, stirred for 30 min and then filtered, and the polyethylene product was dried in a vacuum oven. Weigh its mass and measure its molecular weight, molecular weight distribution and melting point. The results are shown in Table 1.

[0134] Table 1 Data of High-Pressure Homopolymerization of Ethylene Catalyzed by C1 - C11 as the Main Catalyst

[0135]

[0136]

[0137] a Polymerization conditions: The dosage of the main catalyst C1 - C11 is 2 μmol, the cocatalyst is Et2AlCl: 4 mmol, the reactivator is ethyl trichloroacetate: 0.3 mmol, the polymerization temperature is 75 °C, the polymerization pressure is 0.50 MPa, and the time is 10 min;

[0138] b Polymerization activity × 10 6 g Polymer / (mol V·h);

[0139] c The molecular weight and molecular weight distribution are measured by high-temperature GPC, molecular weight: × 10 4 g / mol;

[0140] d The melting point is measured by DSC;

[0141] e The cocatalyst is MAO: 4 mmol, and the rest is the same as a ;

[0142] f The cocatalyst is EtAlCl2: 4 mmol, and the rest is the same as a ;

[0143] k Polymerization temperature: 100 °C, and the rest is the same as a ;

[0144] g The polymerization time is 20 min, and the rest is the same as a ;

[0145] h The polymerization time is 30 min, and the rest is the same as a ;

[0146] j The polymerization time is 60 min, and the rest is the same as a .

[0147] During the high-pressure polymerization of ethylene catalyzed, the role of the reactivator is to prevent the central metal vanadium of the catalyst from being reduced to a low valence state, and the range can be 100 - 1000 times that of the main catalyst.

[0148] Test Example 2: Study on the copolymerization of ethylene and cycloolefin

[0149] The polymerization reaction was carried out in a 250 mL stainless steel autoclave. The autoclave equipped with mechanical stirring was heated to 200 °C, evacuated under vacuum for 1 h, adjusted to the temperature condition required for polymerization, filled with ethylene gas at 0.1 MPa, and a toluene solution (with a final total volume of 200 mL) containing a certain amount of diethylaluminum chloride, a reactivator (ethyl trichloroacetate), and a certain concentration of cycloolefin (norbornene) was added to the autoclave. It was kept warm for a period of time until the temperature was constant, then ethylene gas at 0.5 MPa was introduced, waited for 10 min to make ethylene reach the dissolution equilibrium, and then the main catalyst was added, and the stirring reaction was carried out for a period of time. After the polymerization reaction was completed, the residual ethylene gas was released, the autoclave was opened, and the obtained polymerization reaction mixture was poured into a mixed solution of 3 M hydrochloric acid and ethanol with a volume ratio of 1:1, stirred for 30 min and then filtered, and the polymer product was dried in a vacuum oven. Weighed its mass, measured its molecular weight and molecular weight distribution, and measured the comonomer insertion rate by carbon nuclear magnetic resonance spectroscopy. The results are shown in Table 2.

[0150] Table 2 C1 - C11 are the copolymerization data of ethylene and norbornene catalyzed by the main catalyst

[0151]

[0152] a Polymerization conditions: The dosage of the main catalysts C1 - C11 was 2 μmol, the cocatalyst was Et2AlCl: 2 mmol, the reactivator was ethyl trichloroacetate: 0.3 mmol, the polymerization temperature was 75 °C, the polymerization pressure was 0.50 MPa, and the polymerization time was 10 min;

[0153] b Polymerization activity × 10 6 g Polymer / (mol V·h);

[0154] c The molecular weight and molecular weight distribution were measured by high - temperature GPC, molecular weight: × 10 4 g / mol;

[0155] d By 13 CNMR measured;

[0156] The NB concentration refers to the concentration of norbornene in the reaction system;

[0157] The NB insertion rate refers to the norbornene insertion rate.

[0158] Experimental Example 3: Study on the copolymerization of ethylene and polar monomers

[0159] The polymerization reaction was carried out in a 250 mL stainless steel autoclave. The autoclave equipped with mechanical stirring was heated to 200 °C, evacuated under vacuum for 1 h, adjusted to the temperature conditions required for polymerization, filled with ethylene gas at 0.1 MPa, and a toluene solution (with a final total volume of 60 mL) containing a certain amount of diethylaluminum chloride, a reactivator (ethyl trichloroacetate), and a polar monomer (undecenol) with a certain concentration pretreated with diethylaluminum chloride was added to the autoclave. It was kept warm for a period of time until the temperature was constant, then ethylene gas at 0.5 MPa was introduced, waited for 10 min to reach the dissolution equilibrium of ethylene, and then the main catalyst was added, and the stirring reaction was carried out for a period of time. After the polymerization reaction was completed, the residual ethylene gas was released, the autoclave was opened, and the obtained polymerization reaction mixture was poured into a mixed solution of 3M hydrochloric acid and ethanol with a volume ratio of 1:1. After stirring for 30 min, it was filtered, and the polymer product was dried in a vacuum oven. Its mass was weighed, its molecular weight and molecular weight distribution were measured, and the comonomer insertion rate was measured by 1H NMR. The results are shown in Table 3.

[0160] Table 3 Copolymerization data of ethylene and undecenol catalyzed by the main catalyst

[0161]

[0162] a Polymerization conditions: The dosage of the selected main catalyst was 2 μmol, the cocatalyst was Et2AlCl, the reactivator was ethyl trichloroacetate: 0.3 mmol, the polymerization temperature was 75 °C, the polymerization pressure was 0.50 MPa, and the polymerization time was 10 min;

[0163] b The molar ratio of diethylaluminum chloride used for pretreatment of the polar monomer to the polar monomer was 1:1, and the pretreatment time was 20 min. The amount of cocatalyst added in the table was the total amount of diethylaluminum chloride added to the reaction system, and the remaining amount after removing the amount used for pretreatment of the polar monomer played a cocatalytic role;

[0164] c Polymerization activity × 10 6 g Polymer / (mol V·h);

[0165] d The molecular weight and molecular weight distribution were measured by high-temperature GPC, molecular weight: × 10 4 g / mol;

[0166] e From 1 1H NMR measurement.

[0167] The experimental results show that:

[0168] 1. The highest activity of the novel [ONO] tridentate imine vanadium complex provided by the present invention for ethylene homopolymerization (0.5 MPa) can reach 28.0×10 6 g Polymer / (mol V·h), and still has catalytic activity when the reaction proceeds to 60 min and at 100 °C;

[0169] 2. The activity of the novel [ONO] tridentate imine vanadium complex provided by the present invention for copolymerization of ethylene and norbornene (concentration: 1.0 mol / L) can reach 19.5×10 6 g Polymer / (mol V·h), the highest molecular weight of the obtained polymer can reach 15.7×10 4 g / mol, and the highest molar insertion rate of norbornene is 31.6%; when the concentration of norbornene is 1.5 mol / L and C2 is used as the main catalyst, the molar insertion rate of norbornene in the obtained polymer is 34.8%;

[0170] 3. The activity of the novel [ONO] tridentate imine vanadium complex provided by the present invention for copolymerization of ethylene and undecenol (concentration: 0.3 mol / L) can reach 6.3×10 6 g Polymer / (mol V·h), the highest molecular weight of the obtained polymer can reach 15.5×10 4 g / mol, and the highest molar insertion rate of undecenol is 3.3%; when the concentration of undecenol is 0.5 mol / L and C9 is used as the main catalyst, the molar insertion rate of undecenol in the obtained polymer is 4.7%.

[0171] As can be seen from the above examples, the present invention provides a class of novel [ONO] tridentate imine vanadium complexes, which have high catalytic activity, long lifespan, and good temperature resistance when catalyzing ethylene polymerization, and can maintain high catalytic activity at 100 °C; when catalyzing the copolymerization of ethylene and norbornene, it shows extremely high activity, and the comonomer insertion rate in the obtained polymer is very high; when catalyzing the copolymerization of ethylene and undecenol, it has high catalytic activity, and the molecular weight and comonomer content are also relatively high, obtaining functionalized polymer products.

[0172] The above-described embodiments are only descriptions of the preferred embodiments of the present invention, and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, various deformations and improvements made by those of ordinary skill in the art to the technical solutions of the present invention shall fall within the protection scope determined by the claims of the present invention.

Claims

1. A [ONO] tridentate imine vanadium complex, characterized in that, The structural formula is any one of Formula C1 to Formula C11; 2. A preparation method of the [ONO] tridentate imine vanadium complex according to claim 1, characterized in that, It is obtained by reacting the ligand shown in Formula 2 and the complex shown in Formula 3; wherein: Formula 2 is one of the following structures: Equation 3 is as follows:

3. The preparation method according to claim 2, characterized in that, In the said reaction, benzene is used as the reaction solvent, triethylamine is used as the acid-binding agent, and the reaction temperature is room temperature.

4. An application of the [ONO] tridentate imine vanadium complex according to claim 1 in the catalytic ethylene polymerization reaction.

5. The application according to claim 4, wherein The said ethylene polymerization reaction is specifically an ethylene homopolymerization reaction, a copolymerization reaction of ethylene and cycloolefin, or a copolymerization reaction of ethylene and a polar monomer containing a hydroxyl group.

6. The application according to claim 5, characterized in that, In the said ethylene polymerization reaction, the [ONO] tridentate imine vanadium complex is used as the main catalyst, and an alkylaluminoxane, a modified alkylaluminoxane or a haloalkylaluminum is used as the cocatalyst. The molar ratio of aluminum in the cocatalyst to the metal in the main catalyst is 5 - 10000:1, and the pressure of ethylene gas during polymerization is 0.1 - 10.0 MPa.

7. The application according to claim 6, wherein, In the said ethylene polymerization reaction, the [ONO] tridentate imine vanadium complex is used as the main catalyst, and diethylaluminum chloride, diethylaluminum dichloride or methylaluminoxane is used as the cocatalyst. The molar ratio of aluminum in the cocatalyst to the metal in the main catalyst is 100 - 5000:1, and the pressure of ethylene gas during polymerization is 0.1 - 1.0 MPa; When the said ethylene polymerization reaction is a copolymerization reaction of ethylene and a polar monomer containing a hydroxyl group, the molar ratio of the organoaluminum used for hydroxyl protection to the polar monomer is 1:

1.

8. The application according to claim 5, wherein, The said copolymerization reaction of ethylene and cycloolefin is specifically a copolymerization reaction of ethylene and norbornene; The said copolymerization reaction of ethylene and a polar monomer containing a hydroxyl group is specifically a copolymerization reaction of ethylene and undecenol. The [ONO] tridentate imine vanadium complex is used as the main catalyst, and diethylaluminum chloride is used as the cocatalyst. The molar ratio of the organoaluminum used for hydroxyl protection to the polar monomer is 1:1.

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