Metal compound containing bipyridine and application of metal compound in preparation of elastomer

Abstract

The invention provides a dipyridyl-containing metal organic compound which is novel in structure and is shown in a formula (I), the dipyridyl-containing metal compound has a structure with a larger steric hindrance ligand, a specific space is given to a catalyst, and a catalyst composition formed by the dipyridyl-containing metal organic compound can efficiently promote olefin copolymerization reaction capacity and high temperature resistance of the catalyst.

Description

Technical Field

[0001] The invention relates to the field of polyolefin catalysis, and in particular to a bipyridine-containing metal compound and application thereof in preparing an elastomer. Background Art

[0002] Ethylene molecules are the simplest molecules containing double bonds. From a thermodynamic point of view, they have a strong tendency to polymerize. However, it was not until the late 1930s that ethylene polymers were obtained (ethylene pressure 150-200MPa, temperature 180-120°C, trace oxygen as initiator conditions). The obtained polymers have many branches, low crystallinity and density, poor mechanical properties, and are suitable for making films, commonly known as high-pressure low-density polyethylene. Later, the advent of Ziegler-Natta catalysts greatly promoted the development of ethylene polymerization. Currently, the gas phase method is mostly used for production (ultra-high molecular weight polyethylene generally uses the slurry method), the temperature is 60-90°C, the ethylene pressure is 0.2-1.5MPa, there are few branches, less chain transfer, regular linearity, crystallinity up to 90-95%, high density, and good mechanical properties, commonly known as low-pressure high-density polyethylene. At a milder temperature, Ziegler-Natta catalyst catalyzes the copolymerization of ethylene with 5% α-olefin (1-butene, 1-hexene or 1-octene), destroying the regularity of the copolymer, reducing the crystallinity, and having a lower density (0.91-0.94 g / cm 3 ), commonly known as linear low-density polyethylene. Linear low-density polyethylene has low transparency, low mechanical strength, high ash content, and high volume resistivity. In order to solve the above shortcomings, polyolefin elastomer (ultra-low-density polyethylene) came into being.

[0003] Polyolefin elastomer is a high-performance polyolefin product that is rubber elastic at room temperature, with low density, large bending, high low-temperature impact resistance, easy processing, and reusability. Thermoplastic polyethylene elastomer is essentially a branched polyethylene in which the polyethylene chain crystal region plays the role of a physical crosslinking point, and the addition of α-olefin weakens the polyethylene chain crystal region, becoming an amorphous region with rubber elasticity, so that the thermoplastic polyethylene elastomer has the properties of an elastomer. According to most of the current information, the thermoplastic polyethylene elastomers of major manufacturers are all produced using metallocene catalysts and solution methods. The only difference between them is the use of metallocene catalysts with different ligands and different production processes.

[0004] In order to obtain polyolefin elastomers with better performance, catalysts have developed from traditional restricted geometry catalysis and bridged dioctenyl catalysts to non-octenyl catalysts. Faced with different requirements for material properties, it is difficult for one catalyst to meet all polymerization needs. Therefore, the development of special catalysts has become a research focus. Summary of the invention

[0005] The first aspect of the present invention provides a bipyridine-containing metal organic compound represented by formula (I):

[0006]

[0007] Wherein, M is selected from the group IVB metals titanium Ti, zirconium Zr, hafnium Hf;

[0008] X1 and X2 are the same or different and are independently selected from: halogen (fluorine, chlorine, bromine, iodine), C 1-20 Alkyl, -(CH2) n -C 6-20 Aryl, C 6-20 Aryl, -(CH2) n -5 to 20 membered heteroaryl, 5 to 20 membered heteroaryl, C 3-20 Cycloalkyl, 3- to 20-membered heterocycloalkyl;

[0009] n is a natural number selected from 1-5 (e.g., 1, 2, 3, 4, 5);

[0010] R1, R2, R3, R4 are the same or different and are independently selected from: hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 6-20 Aryl, 5 to 20 membered heteroaryl; or, R1, R2 and the carbon atom to which they are attached form a C 3-20 Cycloalkyl, 3 to 20-membered cycloalkyl; or, R3, R4 and the carbon atom to which they are connected form C 3-20 Cycloalkyl, 3- to 20-membered heterocycloalkyl;

[0011] R5, R6, R9, R 10 The same or different, each independently selected from: hydrogen, halogen, C 1-20 Alkyl, C 1-20 Alkoxy;

[0012] R7 and R8 are the same or different and are independently selected from: hydrogen, halogen, C 1-20 Alkyl, C 1-20 Alkoxy; or, R7, R8 and the carbon atom on the pyridine ring form a C 6-20 Aryl, 5- to 20-membered heteroaryl.

[0013] According to an embodiment of the present invention, the oxygen atom O in the bipyridine-containing metal organic compound forms a covalent bond with the metal center M, and the nitrogen atom N forms a coordination bond with the metal center M. In space, the ligand is connected to the metal center M through two twisted five-membered rings, which restricts the free rotation of the metal center M, thereby providing a specific space. In the coordination catalysis process, it helps the coordination insertion of olefins. At the same time, the oxygen atom forms a covalent bond, which allows the metal compound to have a higher catalytic activity at high temperatures.

[0014] According to an embodiment of the present invention, X1 and X2 are the same or different and are independently selected from: halogen, C 1-14 Alkyl, -(CH2) n -C 6-14 Aryl, C 6-14 Aryl, -(CH2) n -5 to 14 membered heteroaryl, 5 to 14 membered heteroaryl, C 3-14 Preferably, X1 and X2 are the same or different and are independently selected from: halogen, C 1-10 Alkyl (or C 1-6 Alkyl or C 1-4 Alkyl), -(CH2) n -C 6-10 Aryl, C 6-10 Aryl, -(CH2) n -5 to 10 membered heteroaryl, 5 to 10 membered heteroaryl, C 3-10 Cycloalkyl, 3- to 10-membered heterocycloalkyl; illustratively, X1 and X2 are the same or different, and are each independently selected from: halogen (fluorine, chlorine, bromine, iodine), methyl, ethyl, propyl, butyl, -CH2-phenyl, -CH2-naphthyl.

[0015] According to an embodiment of the present invention, X1 and X2 are the same; preferably, X1 and X2 are both methyl; preferably, X1 and X2 are both -CH2-phenyl. According to an embodiment of the present invention, n is selected from 1.

[0016] According to an embodiment of the present invention, R1, R2, R3, and R4 are the same or different and are independently selected from: hydrogen, C 1-14 Alkyl, C 2-14 Alkenyl, C 2-14 Alkynyl, C 6-14 Aryl, 5 to 14 membered heteroaryl; or, R1, R2 and the carbon atom to which they are attached form a C 3-14 Cycloalkyl, 3 to 14 membered heterocycloalkyl; or, R3, R4 and the carbon atom to which they are attached form C 3-14 Cycloalkyl, 3- to 14-membered heterocycloalkyl;

[0017] Preferably, R1, R2, R3, and R4 are the same or different and are independently selected from: hydrogen, C 1-10 Alkyl (or C 1-6 Alkyl or C 1-4 Alkyl), C 2-10 Alkenyl (or C 2-6 Alkenyl or C 2-4 C 2-10 Alkynyl (or C 2-6 Alkynyl or C 2-4 Alkynyl), C 6-10 Aryl, 5 to 10 membered heteroaryl; or, R1, R2 and the carbon atom to which they are attached form a C 3-10 Cycloalkyl, 3 to 10 membered heterocycloalkyl; or, R3, R4 and the carbon atom to which they are attached form C 3-10 Cycloalkyl, 3- to 10-membered heterocycloalkyl;

[0018] Exemplarily, R1, R2, R3, and R4 are the same or different, and are each independently selected from: H, methyl, ethyl, propyl, butyl, phenyl, naphthyl, vinyl, propenyl, butenyl, pentenyl, ethynyl, propynyl, butynyl; or, R1, R2, and the carbon atoms connected thereto form cyclopentyl, cyclohexyl, or cycloheptyl; or, R3, R4, and the carbon atoms connected thereto form cyclopentyl, cyclohexyl, or cycloheptyl.

[0019] According to an embodiment of the present invention, R1 and R3 are the same. According to an embodiment of the present invention, R2 and R4 are the same. According to an embodiment of the present invention, R1, R2, R3, R4 are not H at the same time.

[0020] According to an embodiment of the present invention, R1 and R3 are selected from: H, methyl, phenyl, butenyl. According to an embodiment of the present invention, R2 and R4 are selected from: H, methyl, phenyl, butenyl. Exemplarily, R1 and R3 are selected from phenyl, and R2 and R4 are selected from phenyl; or, R1 and R3 are selected from methyl, and R2 and R4 are selected from methyl; or, R1 and R3 are selected from H, and R2 and R4 are selected from phenyl; or, R1 and R3 are selected from butenyl, and R2 and R4 are selected from phenyl; or, R1 and R3 are selected from methyl, and R2 and R4 are selected from phenyl; or, R1 and R3 are selected from H, and R2 and R4 are selected from methyl; or, R1 and R3 are selected from butenyl, and R2 and R4 are selected from methyl. According to an embodiment of the present invention, R1, R2 and the carbon atoms connected thereto form a cyclohexyl group; R3, R4 and the carbon atoms connected thereto form a cyclohexyl group.

[0021] According to an embodiment of the present invention, R5, R6, R9, R 10 The same or different, each independently selected from: hydrogen, halogen, C 1-14 Alkyl, C 1-14Alkoxy; preferably, R5, R6, R9, R 10 The same or different, each independently selected from: hydrogen, halogen, C 1-10 Alkyl (or C 1-6 Alkyl or C 1-4 Alkyl), C 1-10 Alkoxy (or C 1-6 Alkoxy or C 1-4 According to an embodiment of the present invention, R5, R6, R9, R 10 For example, R5, R6, R9, R 10 All are hydrogen.

[0022] According to an embodiment of the present invention, R5, R 10 The same; preferably, R5, R 10 R6 and R9 are hydrogen, methoxy, halogen, butyl, and tert-butyl. According to an embodiment of the present invention, R6 and R9 are the same; preferably, R6 and R9 are hydrogen, methoxy, halogen, butyl, and tert-butyl.

[0023] According to an embodiment of the present invention, R7 and R8 are the same or different and are independently selected from: hydrogen, halogen, C 1-14 Alkyl, C 1-14 Alkoxy; or, R7, R8 and the carbon atom on the pyridine ring form a C 6-14 Aryl, 5 to 14 membered heteroaryl; preferably, R7, R8 are the same or different and are independently selected from: hydrogen, halogen, C 1-10 Alkyl, C 1-10 Alkoxy (or C 1-6 Alkoxy or C 1-4 Alkoxy); or, R7, R8 and the carbon atom on the pyridine ring form a C 6-10 Aryl, 5 to 10 membered heteroaryl. According to an embodiment of the present invention, R7 and R8 are the same; preferably, R7 and R8 are both hydrogen. According to an embodiment of the present invention, R7, R8 and the carbon atom on the pyridine ring form a phenyl group or a naphthyl group.

[0024] According to an embodiment of the present invention, when M is Hf, X1 and X2 are -CH2-phenyl. Preferably, R1, R2, R3 and R4 are selected from phenyl. Preferably, R1, R2 and the carbon atoms connected thereto form a cyclohexyl group, and R3, R4 and the carbon atoms connected thereto form a cyclohexyl group. Preferably, R7 and R8 form a phenyl group with the carbon atoms on the pyridine ring.

[0025] According to an embodiment of the present invention, when M is Ti, X1 and X2 are methyl. Preferably, R1 and R3 are selected from phenyl, and R2 and R4 are selected from butenyl. Preferably, R1, R2, R3 and R4 are selected from methyl. Preferably, R1, R2 and the carbon atoms connected thereto form a cyclohexyl group, and R3, R4 and the carbon atoms connected thereto form a cyclohexyl group. Preferably, R7 and R8 form a phenyl group with the carbon atoms on the pyridine ring.

[0026] According to an embodiment of the present invention, when M is Zr, X1 and X2 are methyl. Preferably, R1 and R3 are selected from phenyl, and R2 and R4 are selected from methyl. Preferably, R1 and R3 are selected from phenyl, and R2 and R4 are selected from hydrogen. Preferably, R1, R2, R3 and R4 are selected from methyl. Preferably, R7 and R8 form a phenyl group with the carbon atom on the pyridine ring.

[0027] According to an embodiment of the present invention, the metal organic compound containing bipyridine is selected from:

[0028]

[0029]

[0030]

[0031] The second aspect of the present invention also discloses a method for preparing the bipyridine-containing metal compound represented by the above formula (I), the preparation method comprising the following steps:

[0032] The compound represented by formula (I-1) reacts with compounds X1-M0-X0 and X2-M0-X0 to obtain a bipyridine-containing metal compound represented by formula (I);

[0033] The reaction formula is as follows:

[0034]

[0035] Among them, M, X1, X2, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Having the above definition;

[0036] X is selected from halogen, C 1-10 alkyl;

[0037] X0 is selected from halogen, C 1-10 alkyl;

[0038] M0 is selected from alkali metals (eg, lithium, magnesium, aluminum).

[0039] According to an embodiment of the present invention, the compounds X1-M0-X0, X2-M0-X0 are selected from: C 6-20 Arylmagnesium halides, C6-20 Aryl-(CH2) n -magnesium halide (n is a natural number selected from 1-5, such as 1, 2, 3, 4, 5), C 1-10 Alkyl magnesium halide, etc., preferably C 6-10 Arylmagnesium halides, C 6-10 Aryl-(CH2) n -Magnesium halide, C 1-6 Alkylmagnesium halides; for example, methylmagnesium bromide, benzylmagnesium chloride.

[0040] According to an embodiment of the present invention, X is selected from halogen, C 1-6 Alkyl or C 1-4 According to an embodiment of the present invention, X0 is selected from halogen, C 1-6 Alkyl or C 1-4 alkyl.

[0041] According to an embodiment of the present invention, the preparation method of the compound represented by formula (I-1) is as follows:

[0042] The compound represented by formula (I-2) reacts with the alkali metal compound A-1 to obtain a salt, which is then reacted with the compound MX to obtain the compound represented by formula (I-1);

[0043] The reaction formula is as follows:

[0044]

[0045] Among them, M, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Having the above definition;

[0046] X is selected from halogen, C 1-10 alkyl;

[0047] The alkali metal compound A-1 is selected from C 1-10 Alkyl lithium, C 1-10 Magnesium alkyl, C 6-20 Arylmagnesium halides, C 6-20 Aryl-(CH2) n -magnesium halide (n is a natural number selected from 1-5, such as 1, 2, 3, 4, 5), C 1-10 Alkyl magnesium halide, C 1-10 Alkyl aluminum, etc., preferably C 1-6 Alkyl lithium, C 1-6 Magnesium alkyl, C 6-10 Arylmagnesium halides, C 6-10 Aryl-(CH2) n -Magnesium halide, C 1-6 Alkyl magnesium halide, C 1-6Alkylaluminum; for example, methyllithium, butyllithium, methylmagnesium bromide, butylmagnesium, benzylmagnesium chloride, methylaluminum, triethylaluminum.

[0048] According to an embodiment of the present invention, X is selected from halogen, C 1-6 Alkyl or C 1-4 alkyl.

[0049] According to an embodiment of the present invention, MX is titanium halide, zirconium halide, hafnium halide, C 1-6 Alkyl titanium, C 1-6 Zirconium alkyl, C 1-6 The hafnium alkyl and the like are preferably titanium tetrachloride, zirconium tetrachloride, and hafnium tetrachloride.

[0050] According to an embodiment of the present invention, the preparation method of the compound represented by formula (I-2) is as follows:

[0051] The compound represented by formula (I-3) undergoes a coupling reaction with the compound represented by formula (I-4) to obtain the compound represented by formula (I-2);

[0052] The reaction formula is as follows:

[0053]

[0054] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Having the above definition;

[0055] X3 and X4 are selected from halogen.

[0056] According to an embodiment of the present invention, the reaction is carried out under a catalyst; preferably, the catalyst is at least one of copper halide, nickel halide, palladium halide, zinc halide, iron halide, magnesium powder, iron powder, zinc powder, copper powder, aluminum powder and the like, preferably at least one of nickel chloride, cuprous chloride, ferrous chloride, magnesium powder and zinc powder.

[0057] According to an embodiment of the present invention, the preparation method of the compound represented by formula (I-3) is as follows: the compound represented by formula (I-5) reacts with an alkali metal compound A-2 to obtain a salt, and then reacts with a compound R1-CO-R2 to obtain a compound represented by formula (I-3);

[0058] The reaction formula is as follows:

[0059]

[0060] Among them, R1, R2, R4, R8, R9, R 10 Having the above definition;

[0061] X3 and X4 are selected from halogen;

[0062] The alkali metal compound A-2 is selected from C 1-10 Alkyl lithium, C 1-10 Magnesium alkyl, C 6-20 Arylmagnesium halides, C 6-20 Aryl-(CH2) n -magnesium halide (n is a natural number selected from 1-5, such as 1, 2, 3, 4, 5), C 1-10 Alkyl magnesium halide, C 1-10 Alkyl aluminum, etc., preferably C 1-6 Alkyl lithium, C 1-6 Magnesium alkyl, C 6-10 Arylmagnesium halides, C 6-10 Aryl-(CH2) n -Magnesium halide, C 1-6 Alkyl magnesium halide, C 1-6 Alkylaluminum; for example, methyllithium, butyllithium, methylmagnesium bromide, butylmagnesium, benzylmagnesium chloride, methylaluminum, triethylaluminum.

[0063] According to an embodiment of the present invention, the preparation method of the compound represented by formula (I-4) is as follows: the compound represented by formula (I-6) reacts with an alkali metal compound A-3 to obtain a salt, and then reacts with a compound R3-CO-R4 to obtain a compound represented by formula (I-4);

[0064] The reaction formula is as follows:

[0065]

[0066] Wherein, R3, R4, R5, R6, and R7 have the above definitions;

[0067] X3 and X4 are selected from halogen;

[0068] The alkali metal compound A-3 is selected from C 1-10 Alkyl lithium, C 1-10 Magnesium alkyl, C 6-20 Arylmagnesium halides, C 6-20 Aryl-(CH2) n -magnesium halide (n is a natural number selected from 1-5, such as 1, 2, 3, 4, 5), C 1-10 Alkyl magnesium halide, C 1-10 Alkyl aluminum, etc., preferably C 1-6 Alkyl lithium, C 1-6 Magnesium alkyl, C 6-10 Arylmagnesium halides, C 6-10 Aryl-(CH2) n -Magnesium halide, C 1-6 Alkyl magnesium halide, C 1-6 Alkylaluminum; for example, methyllithium, butyllithium, methylmagnesium bromide, butylmagnesium, benzylmagnesium chloride, methylaluminum, triethylaluminum.

[0069] The third aspect of the present invention further discloses a catalyst composition, which comprises a bipyridine-containing metal organic compound represented by the above formula (I) and an activator.

[0070] According to an embodiment of the present invention, the bipyridine-containing metal organic compound and the activator are capable of interacting to form an ion pair compound.

[0071] According to an embodiment of the present invention, the molar ratio of the metal organic compound containing bipyridine to the activator is 1:5 to 1000. For example, it can be 1:5 to 10, 1:10 to 20, 1:20 to 30, 1:30 to 40, 1:40 to 50, 1:50 to 60, 1:60 to 70, 1:70 to 80, 1:80 to 90, 1:90 to 100, 1:100 to 200, 1:200 to 300, 1:300 to 400, 1:400 to 500, 1:500 to 600, 1:600 ​​to 700, 1:700 to 800, 1:800 to 900, 1:900 to 1000.

[0072] According to an embodiment of the present invention, the activator contains aluminum and / or boron elements. According to an embodiment of the present invention, the activator is an activator containing aluminum elements, an activator containing boron elements, or an activator containing aluminum elements and boron elements.

[0073] According to an embodiment of the present invention, the activator containing aluminum element is substituted or unsubstituted C 1-20 Alkyl aluminum compounds, C 6-20 Aryl aluminum compounds, C 1-20 Aluminoxane, C 6-20 Preferably, the activator containing aluminum element is substituted or unsubstituted C 1-14 Alkyl aluminum compounds, C 6-14 Aryl aluminum compounds, C 1-14 Aluminoxane, C 6-14 Arylaluminoxane.

[0074] According to an embodiment of the present invention, the activator containing aluminum element is selected from one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, triisopropylaluminum, triisobutylaluminum, tri-tert-butylaluminum, tricyclohexylaluminum, tricyclooctylaluminum, triphenylaluminum and tritolylaluminum. According to an embodiment of the present invention, the activator containing aluminum element is selected from one or more of triisobutylaluminum modified methylaluminoxane, methylaluminoxane, triisobutyldialuminoxane, polyisobutylaluminoxane, tetraethyldialuminoxane, pentaisobutyltrialuminoxane, 1,3-dichloro-1,3-diethyldialuminoxane, 1,3-dichloro-1,3-dimethyldialuminoxane.

[0075] According to an embodiment of the present invention, the boron element is introduced by a borate; more preferably, the cation in the borate is a lithium ion, a sodium ion, a potassium ion, a carbon cation, or an ammonium cation. More preferably, the carbon cation is a triphenylmethyl cation, a tritolylmethyl cation, or a tri(xylyl)methyl cation. More preferably, the ammonium cation is a trimethylammonium cation, a triethylammonium cation, a tripropylammonium cation, a tributylammonium cation, a triisobutylammonium cation, a N,N-dimethylanilinium cation, a N,N-diethylanilinium cation, a N,N-diisopropylanilinium cation, a N,N-2,4,6-pentamethylanilinium cation, a diisopropylammonium cation, or a cyclohexylammonium cation. More preferably, the anion in the borate is tetrafluoroboron anion, tetraphenylboron anion, tetrakis(4-fluorophenyl)boron anion, tetrakis(3.5-difluorophenyl)boron anion, tetrakis(4-fluoromethylphenyl)boron anion, tetrakis(pentafluorophenyl)boron anion, tetrakis(3.5-dimethylphenyl)boron anion.

[0076] According to an embodiment of the present invention, the activator containing the boron element is selected from: [Ph3C][B(C6F5)4].

[0077] According to an embodiment of the present invention, the molar ratio of the aluminum element in the activator to the metal organic compound containing bipyridine represented by the above formula (I) is 5 to 1000:1; for example, it can be 5 to 10:1, 10 to 20:1, 20 to 30:1, 30 to 40:1, 40 to 50:1, 50 to 60:1, 60 to 70:1, 70 to 80:1, 80 to 90:1, 90 to 100:1, 100 to 200:1, 200 to 300:1, 300 to 400:1, 400 to 500:1, 500 to 600:1, 600 to 700:1, 700 to 800:1, 800 to 900:1, 900 to 1000:1.

[0078] According to an embodiment of the present invention, the molar ratio of the boron element in the activator to the metal organic compound containing bipyridine represented by the above formula (I) is 0.1 to 10:1; for example, it can be 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1.

[0079] According to an embodiment of the present invention, the molar ratio of the aluminum element in the activator, the boron element in the activator and the bipyridine-containing metal organic compound represented by the above formula (I) is 100:2:1.

[0080] The fourth aspect of the present invention also discloses the use of the bipyridine-containing metal organic compound represented by the above formula (I) and the above catalyst composition in the elastomer polymerization reaction.

[0081] Preferably, the elastomer is an olefin polymer.

[0082] According to an embodiment of the present invention, the elastomer is an olefin polymer prepared by polymerization of an olefin reaction monomer with ethylene or propylene.

[0083] According to an embodiment of the present invention, the olefin reaction monomer is selected from one or more of 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, and 1-octene.

[0084] According to an embodiment of the present invention, the olefin reactive monomer is an α-olefin.

[0085] The fifth aspect of the present invention also discloses a polymerization method for an elastomer, wherein the polymerization reaction comprises: a polymerization reaction of an elastomer reaction monomer in the presence of a bipyridine-containing metal organic compound represented by the above formula (I) or the above catalyst composition.

[0086] Preferably, the elastomer reactive monomer is an olefin, such as an α-olefin. More preferably, the olefin is selected from one or more of 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, and 1-octene.

[0087] More preferably, the polymerization reaction is a copolymerization reaction of ethylene or propylene with an α-olefin. Exemplarily, the polymerization reaction is a copolymerization reaction of ethylene or propylene with 1-octene. Preferably, the polymerization reaction adopts a batch solution polymerization method or a continuous solution polymerization method.

[0088] Preferably, the polymerization reaction is carried out in the presence of a polymerization solvent. More preferably, the polymerization solvent is an alkane, a cycloalkane, or an aromatic compound. More preferably, the alkane is selected from hexane and heptane. More preferably, the aromatic compound is selected from benzene, toluene, xylene, and substituted toluene.

[0089] Preferably, the polymerization temperature is 80-250° C. For example, it may be 80° C., 85° C., 90° C., 95° C., 100° C., 105° C., 110° C., 115° C., 120° C., 125° C., 130° C., 135° C., 140° C., 145° C., 150° C., 155° C., 160° C., 165° C., 170° C., 175° C., 180° C., 185° C., 190° C., 195° C., 200° C., 205° C., 210° C., 215° C., 220° C., 225° C., 230° C., 235° C., 240° C., 245° C., or 250° C.

[0090] Preferably, the polymerization reaction pressure is 0.1-10 MPa, for example, 0.5 MPa, 1 MPa, 1.5 MPa, 2 MPa, 2.5 MPa, 3 MPa, 3.5 MPa, 4 MPa, 4.5 MPa, 5 MPa, 5.5 MPa, 6 MPa, 6.5 MPa, 7 MPa, 7.5 MPa, 8 MPa, 8.5 MPa, 9 MPa, 9.5 MPa, or 10 MPa.

[0091] According to an embodiment of the present invention, the ratio of the elastomer reaction monomer to the bipyridine-containing metal organic compound represented by the above formula (I) is (10-1000):(1-10) (mL:μmol), preferably 50-800:5, for example 100:5, 200:5, 300:5, 400:5, 500:5, 600:5.

[0092] According to an embodiment of the present invention, after the reaction is completed, an antioxidant (such as antioxidant 1010) is added to the reaction material, and then ethanol is added to precipitate the polymer.

[0093] The sixth aspect of the present invention also discloses an elastomeric polymer prepared by the above polymerization method.

[0094] Preferably, the elastomeric polymer has a melting point of 30°C-180°C.

[0095] According to an embodiment of the present invention, the weight average molecular weight (M w) is 10000-600000 Da (g / mol), for example 30000 Da, 40000 Da, 46000 Da, 49000 Da, 50000 Da, 57000 Da, 60000 Da, 61200 Da, 67000 Da, 70000 Da, 79000 Da, 80000 Da, 86000 Da, 90000 Da, 97000 Da, 98000 Da, 100000 Da, 110000 Da, 115000 Da, 1200 00Da, 128000Da, 130000Da, 140000Da, 145000Da, 150000Da, 153000Da, 160000Da, 170000Da, 180000Da, 181000 Da, 190000Da, 200000Da, 210000Da, 250000Da, 300000Da, 324000Da, 350000Da, 379000Da, 400000Da, 500000Da.

[0096] According to an embodiment of the present invention, the ratio of the weight average molecular weight to the number average molecular weight (M w / M n ) is 1.5-4.0, for example, 2.0, 2.5, 2.7, 2.8, 3.0, 3.1, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9. According to an embodiment of the present invention, the melt index MI of the elastomeric polymer is 0.5-10 g / 10 min, for example, 1.0 g / 10 min, 1.5 g / 10 min, 1.7 g / 10 min, 2.0 g / 10 min, 2.4 g / 10 min, 2.5 g / 10 min, 2.6 g / 10 min, 2.8 g / 10 min, 2.9 g / 10 min, 3 g / 10 min, 3.2 g / 10 min, 3.5 g / 10 min, 3.6 g / 10 min, 3.9 g / 10 min, 4g / 10min, 4.3g / 10min, 4.5g / 10min, 4.7g / 10min, 4.8g / 10min, 5g / 10min, 5.4g / 10min, 5.5g / 10min, 5.7g / 10min, 5.9 g / 10min, 6g / 10min, 6.5g / 10min, 7g / 10min, 7.5g / 10min, 8g / 10min, 8.5g / 10min, 9g / 10min, 9.5g / 10min, 10g / 10min.

[0097] According to an embodiment of the present invention, the mass fraction of the elastomer reaction monomer is 1.0%-10%, for example 2%, 2.5%, 2.8%, 3%, 3.1%, 3.4%, 3.5%, 3.8%, 4%, 4.5%, 5%, 5.1%, 5.7%, 5.9%, 6%, 6.1%, 6.5%, 6.7%, 7%, 7.3%, 7.4%, 7.8%, 8%, 8.9%, 9%.

[0098] Beneficial Effects

[0099] The present invention provides a bipyridine-containing metal organic compound represented by formula (I) with a novel structure. The oxygen atom of the compound forms a covalent bond with a metal center, and the nitrogen atom forms a coordination bond with the metal center. In terms of space, the ligand is connected to the metal center through two twisted five-membered rings, which restricts the free rotation of the metal center, thereby providing a specific space. In the coordination catalysis process, it is helpful for olefin coordination insertion. At the same time, the oxygen atom forms a covalent bond, so that the metal compound has a higher catalytic activity at high temperature.

[0100] The bipyridine-containing metal compound provided by the present invention has a structure with a larger sterically hindered ligand, which gives the catalyst a specific space, and the catalyst combination formed by the bipyridine-containing metal compound can effectively promote the olefin copolymerization reaction ability and the high temperature resistance of the catalyst.

[0101] Definition and explanation of terms

[0102] Unless otherwise specified, the definitions of groups and terms recorded in the specification and claims of this application, including their definitions as examples, exemplary definitions, preferred definitions, definitions recorded in tables, definitions of specific compounds in examples, etc., can be arbitrarily combined and combined with each other. The definitions of groups and compound structures after such combinations and combinations should be understood to be within the scope of the specification and / or claims of this application.

[0103] Unless otherwise specified, the numerical ranges recorded in this specification and claims are equivalent to recording at least each specific integer value therein. For example, the numerical range "1-40" is equivalent to recording each integer value in the numerical range "1-10", namely 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and each integer value in the numerical range "11-40", namely 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40. It should be understood that in the one, two or more used herein when describing substituents, "more" should refer to an integer ≥ 3, such as 3, 4, 5, 6, 7, 8, 9 or 10.

[0104] The term "halogen" or "halo" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

[0105] In general, the term "substituted" means that one or more hydrogen atoms in a given structure are replaced by a specific substituent. Further, when the group is substituted by more than one of the substituents, the substituents are independent of each other, that is, the more than one substituents may be different from each other or the same. Unless otherwise indicated, a substituent group may be substituted at each substitutable position of the substituted group. When more than one position in the given structural formula can be substituted by one or more substituents selected from a specific group, the substituents may be substituted at each position in the same or different manner. The substituents may be, but are not limited to, =O, hydrogen, deuterium, cyano, nitro, halogen, alkyl, haloalkyl, alkoxy, carboxyl, cycloalkyl, cycloalkyloxy, heterocyclyl, heterocyclylalkyl, aryl, arylalkyl, aryloxy, heteroaryl, heteroarylalkyl, heteroaryloxy, etc.

[0106] In addition, it should be noted that, unless otherwise explicitly stated, the description method "...independently selected" used in the present invention should be understood in a broad sense, meaning that the individuals described are independent of each other and can be independently selected from the same or different specific groups. In more detail, the description method "...independently selected" can mean that in different groups, the specific options expressed by the same symbols do not affect each other; it can also mean that in the same group, the specific options expressed by the same symbols do not affect each other.

[0107] In various parts of this specification, the substituents of the compounds disclosed in the present invention are disclosed according to group types or ranges. It is particularly pointed out that the present invention includes each independent subcombination of the individual members of these group types and ranges. For example, the term "C 1-6 The term "alkyl" specifically refers to independently disclosed C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl or C6 alkyl.

[0108] In various parts of the present invention, linking substituents are described. When the structure clearly requires a linking group, the Markush variable listed for that group should be understood as a linking group. For example, if the structure requires a linking group and the Markush group definition for that variable lists "alkyl" or "aryl", it should be understood that the "alkyl" or "aryl" represents an alkylene group or an arylene group, respectively, that is linked.

[0109] The term "C 1-20 "Alkyl" means a straight or branched saturated monovalent hydrocarbon group having 1 to 20 carbon atoms. For example, "C 1-6"Alkyl" means straight chain and branched alkyl groups having 1, 2, 3, 4, 5 or 6 carbon atoms. The alkyl group may be optionally substituted with one or more substituents described herein. In some embodiments, the alkyl group contains 1-12 carbon atoms; in other embodiments, the alkyl group contains 1-6 carbon atoms; in yet other embodiments, the alkyl group contains 1-4 carbon atoms. Examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl butyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl or the like or isomers thereof.

[0110] The term "C 3-20 "Cycloalkyl" is understood to mean a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cycloalkane having 3 to 20 carbon atoms, preferably "C 3-10 The term "Cycloalkyl" 3-10 "Cycloalkyl" is understood to mean a saturated monovalent monocyclic, bicyclic hydrocarbon ring or a bridged cycloalkane having 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. 3-10 The cycloalkyl group may be a monocyclic hydrocarbon group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or a bicyclic hydrocarbon group such as a decalin ring.

[0111] The term "3-20 membered heterocyclyl" is understood to mean a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cycloalkane, which contains 1-5 heteroatoms independently selected from N, O and S, and a total number of ring atoms of 3-20 (such as 3, 4, 5, 6, 7, 8, 9, 10, etc.), preferably a "3-10 membered heterocyclyl". The term "3-10 membered heterocyclyl" means a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cycloalkane, which contains 1-5, preferably 1-3 heteroatoms independently selected from N, O and S, such as 1, 2, 3 heteroatoms independently selected from N, O and S. The heterocyclyl may be attached to the rest of the molecule via any of the carbon atoms or the nitrogen atom (if present). In particular, the heterocyclic group may include, but is not limited to, a 4-membered ring, such as azetidinyl, oxetanyl; a 5-membered ring, such as tetrahydrofuranyl, dioxolyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or a 6-membered ring, such as tetrahydropyranyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl or trithianyl; or a 7-membered ring, such as diazepanyl. Optionally, the heterocyclic group may be benzo-fused. The heterocyclic group may be bicyclic, such as, but not limited to, a 5,5-membered ring, such as a hexahydrocyclopenta [c] pyrrole-2 (1H) -yl ring, or a 5,6-membered bicyclic ring, such as a hexahydropyrrolo [1,2-a] pyrazine-2 (1H) -yl ring. The ring containing the nitrogen atom may be partially unsaturated, i.e., it may contain one or more double bonds, such as but not limited to 2,5-dihydro-1H-pyrrolyl, 4H-[1,3,4]thiadiazinyl, 4,5-dihydrooxazolyl or 4H-[1,4]thiazinyl, or it may be benzo-fused, such as but not limited to dihydroisoquinolinyl. According to the present invention, the heterocyclic group is non-aromatic. When the 3-20-membered heterocyclic group is connected with other groups to form the compound of the present invention, the carbon atom on the 3-20-membered heterocyclic group may be connected with other groups, or the heterocyclic atom on the 3-20-membered heterocyclic group may be connected with other groups. For example, when the 3-20-membered heterocyclic group is selected from piperazinyl, the nitrogen atom on the piperazinyl may be connected with other groups. Or when the 3-20-membered heterocyclic group is selected from piperidinyl, the nitrogen atom on the piperidinyl ring and the carbon atom on the para position thereof may be connected with other groups.

[0112] The term "C 6-20 "Aryl" is understood to mean a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6 to 20 carbon atoms, preferably "C 6-14 The term "C 6-14 The term "aryl" is understood to mean preferably a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring ("C 6-14or a ring having 9 carbon atoms ("C9 aryl"), for example indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 aryl), such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C 13 aryl), such as fluorenyl, or a ring having 14 carbon atoms ("C 14 aryl”), such as anthracenyl. When the C 6-20 When the aryl group is substituted, it may be monosubstituted or polysubstituted. Also, there is no limitation on the substitution position, for example, it may be substituted at the ortho position, para position or meta position.

[0113] The term "5-20 membered heteroaryl" is understood to include monovalent monocyclic, bicyclic or tricyclic aromatic ring systems, including aromatic or partially aromatic ones, having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O and S, for example "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" is understood to include monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: having 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and containing 1 to 5, preferably 1 to 3 heteroatoms each independently selected from N, O and S and, in addition, in each case may be benzo-fused. In particular, the heteroaryl group is selected from thienyl, furanyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and benzo derivatives thereof, such as benzofuranyl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl and the like and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl and the like; or azinyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl and the like. When the 5-20 membered heteroaryl is connected to other groups to form the compound of the present invention, the carbon atom on the 5-20 membered heteroaryl ring may be connected to other groups, or the heteroatom on the 5-20 membered heteroaryl ring may be connected to other groups. When the 5-20 membered heteroaryl is substituted, it may be monosubstituted or polysubstituted. In addition, there is no limitation on the substitution site, for example, the hydrogen connected to the carbon atom on the heteroaryl ring may be substituted, or the hydrogen connected to the heteroatom on the heteroaryl ring may be substituted. DETAILED DESCRIPTION

[0114] The following is a description of the implementation of the present invention by means of specific embodiments. Those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification.

[0115] Before further describing the specific embodiments of the present invention, it should be understood that the scope of protection of the present invention is not limited to the specific embodiments described below; it should also be understood that the terms used in the examples of the present invention are intended to describe specific embodiments, rather than to limit the scope of protection of the present invention. The test methods in the following examples without specifying specific conditions are generally carried out under conventional conditions or under conditions recommended by the manufacturers.

[0116] When the embodiments give numerical ranges, it should be understood that, unless otherwise specified in the present invention, both endpoints of each numerical range and any numerical value between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as those generally understood by those skilled in the art. In addition to the specific methods, equipment, and materials used in the embodiments, according to the grasp of the prior art by those skilled in the art and the record of the present invention, any methods, equipment, and materials of the prior art similar or equivalent to the methods, equipment, and materials described in the embodiments of the present invention can also be used to realize the present invention.

[0117] Unless otherwise specified, the reagents used in the examples of the present invention were purchased directly from the market without any special treatment. The anhydrous and anaerobic conditions were prepared using the Schlenk technique known to those skilled in the art. The water and oxygen content of the solvent involved in the anhydrous and anaerobic reaction must be controlled within 10 ppm, and the dissolved oxygen must be fully replaced with nitrogen.

[0118] Example 1: Preparation of Hf-1 metal compound

[0119] The specific steps are as follows:

[0120] 1) Preparation of Hf-11

[0121]

[0122] Under nitrogen protection, 2,6-dibromopyridine (0.1 mol; 23.69 g) and ether (400.0 mL) were added to a 1000 mL three-necked reaction bottle, cooled to -20°C, n-butyl lithium (0.1 mol; 27.40 g) was added dropwise, and the temperature was controlled to be less than -10°C. After the addition was completed, the mixture was reacted at -20°C for 1 h, and then benzophenone (0.11 mol; 20.04 g) was slowly added, and the temperature was controlled to be less than -10°C, and then the mixture was heated to room temperature for 16 h. The reaction solution was then poured into ice water for quenching, extracted with ethyl acetate, the low boiling point solvent was removed, and separated by column chromatography to obtain 22.81 g of a white solid with a yield of 67.1%.

[0123] The characterization data of Hf-11 are as follows:

[0124] 1 HNMR (400MHz, CDCl3): 7.49 (t, J = 8.0Hz, 1H), 7.42 (d, J = 4.0Hz, 1H), 7.34-7.29 (m, 6H), 7.27-7.24 (m, 4H), 7.02 (d, J = 4.0Hz, 1H), 5.55 (br, 1H); ESIMS: m / z 341.1([M+H] + ).

[0125] 2) Preparation of Hf-12

[0126]

[0127] Under nitrogen protection, nickel chloride (0.0025 mol; 0.60 g), Hf-11 (0.05 mol; 17.01 g), lithium chloride (0.05 mol; 2.15 g), zinc powder (0.06 mol; 3.85 g), and N,N-dimethylformamide (200.0 mL) were added to a 500 mL three-necked reaction bottle, the temperature was raised to 50 ° C and stirred for 30 min, then 2 iodine grains and 5 drops of acetic acid were added, and the temperature was raised to 60 ° C. After the reaction for 4 h, the raw materials reacted completely, and then the unreacted zinc powder was directly filtered out, the filtrate was poured into ice water to quench, and dichloromethane was added for extraction. After removing the low-boiling point solvent, the crude product was obtained, and column chromatography was used for separation to obtain 6.10 g of a white solid with a yield of 47.0%.

[0128] The characterization data of Hf-12 are as follows:

[0129] 1 HNMR (400MHz, CDCl3): 8.36 (d, J = 4.0Hz, 2H), 7.78 (t, J = 8.0Hz, 2H), 7.32-7.28 (m, 20H), 7.15 (d, J = 4.0Hz, 2H), 6.41 (br, 2H); ESIMS: m / z 520.6 ([M+H] + ).

[0130] 3) Preparation of Hf-13

[0131]

[0132] Under nitrogen protection, add Hf-12 (10.00mmol; 5.20g) and ether (40.0mL) to a 250mL three-necked reaction bottle. Cool down to -10℃, add n-butyl lithium (2.5M; 21.00mmol; 5.75g) dropwise, control the temperature below 0℃, and slowly warm to room temperature for reaction after the addition is complete. Cool down to -10℃ after 16h, add hafnium tetrachloride (10.00mmol; 3.20g) and control the temperature below 0℃, and slowly warm to room temperature for reaction after the addition is complete. Remove ether under reduced pressure after 16h, add dichloromethane (80.0mL), stir well, filter to remove insoluble lithium chloride, distill the filtrate under reduced pressure, remove the solvent dichloromethane, add n-pentane (40.0mL), stir well, and filter to obtain 3.99g of slightly yellow solid, with a yield of 51%.

[0133] The characterization data of Hf-13 are as follows:

[0134] 1 HNMR (400MHz,CDCl3):8.47(d,J=4.0Hz,2H),7.89(t,J=8.0Hz,2H),7.45-7.34(m,20H),7.24(d,J=4.0Hz,2H); Elemental analysis theoretical value:HfC 37 H 29 O2Cl2N2: C, 56.75; H, 3.73; N, 3.58. Experimen tal value: C, 56.78; H, 3.76; N, 3.60.

[0135] 4) Preparation of Hf-1

[0136]

[0137] Under nitrogen protection, Hf-13 (5.0mmol; 3.91g) and ether (20.0mL) were added to a 100mL three-necked reaction bottle, cooled to 0°C, and benzylmagnesium chloride solution (2.0M; 15.0mmol; 7.5mL) was added, and the temperature was controlled to be less than 5°C. After the addition was completed, the temperature was raised to room temperature for reaction. After 16 hours, low-boiling substances were removed under reduced pressure, n-pentane was added and stirred thoroughly, and the insoluble matter was removed by filtration. The filtrate was collected, the solvent was concentrated, and recrystallization was performed to obtain 1.01g of a white solid with a yield of 23.0%.

[0138] The characterization data of Hf-1 are as follows:

[0139] 1 HNMR (400MHz, CDCl3): 8.49d, J=4.0Hz, 2H), 7.91 (t, J=8.0Hz, 2H), 7.47-7.36 (m, 20H),

[0140] 7.24 (d, J = 4.0 Hz, 2H), 7.11-7.06 (m, 4H), 6.84-6.74 (m, 2H), 6.61-6.51 (m, 4H), 2.11 (br, 4H); Elemental analysis theoretical value: HfC 50 H 40 O2N2: C, 68.29; H, 4.59; N, 3.19. Exp.: C, 68.24; H, 4.62; N, 3.23.

[0141] Example 2: Preparation of Ti-2 Metal Compound

[0142] The specific steps are as follows:

[0143] 1) Preparation of Ti-21

[0144]

[0145] Under nitrogen protection, 2,6-dibromopyridine (0.1 mol; 23.69 g) and ether (400.0 mL) were added to a 1000 mL three-necked reaction bottle, cooled to -20°C, n-butyl lithium (0.1 mol; 27.40 g) was added dropwise, and the temperature was controlled to be less than -10°C. After the addition was completed, the reaction was carried out at -20°C for 1 hour, and then acetone (0.11 mol; 6.39 g) was slowly added, and the temperature was controlled to be less than -10°C, and then the temperature was raised to room temperature for 16 hours. The reaction solution was then poured into ice water for quenching, extracted with ethyl acetate, the low boiling point solvent was removed, and column chromatography was performed to obtain 15.41 g of a slightly yellow liquid with a yield of 71.3%.

[0146] The characterization data of Ti-21 are as follows:

[0147] 1 H

[0148] NMR (400MHz, CDCl3): 7.52 (t, J = 8.0 Hz, 1H), 7.33 (t, J = 8.0 Hz, 2H), 3.74 (br, 1H), 3.48-3.31 (m, 6H); ESI MS: m / z 217.1 ([M+H] + ).

[0149] 2) Preparation of Ti-22

[0150]

[0151] Under nitrogen protection, nickel chloride (0.0025 mol; 0.60 g), Ti-21 (0.05 mol; 10.80 g), lithium chloride (0.05 mol; 2.15 g), zinc powder (0.06 mol; 3.85 g), and N,N-dimethylformamide (200.0 mL) were added to a 500 mL three-necked reaction bottle, the temperature was raised to 50 ° C and stirred for 30 min, then 2 iodine grains and 5 drops of acetic acid were added, and the temperature was raised to 60 ° C. After reacting for 4 h, the raw materials reacted completely, and then the unreacted zinc powder was directly filtered out, the filtrate was poured into ice water for quenching, and dichloromethane was added for extraction. After removing the low boiling point solvent, the crude product was obtained, and column chromatography was used for separation to obtain 7.23 g of a slightly yellow solid with a yield of 53.1%.

[0152] The characterization data of Ti-22 are as follows:

[0153] 1 HNMR (400MHz, CDCl3): 8.35 (d, J = 4.0Hz, 2H), 7.76 (t, J = 8.0Hz, 2H), 7.13 (d, J = 4.0Hz, 2H), 3.94 (br, 2H), 1.24-1.15 (m, 12H); ESIMS: m / z 273.4 ([M+H] + ).

[0154] 3) Preparation of Ti-23

[0155]

[0156] Under nitrogen protection, Ti-22 (10.00mmol; 2.72g) and ether (40.0mL) were added to a 250mL three-necked reaction bottle. The temperature was lowered to -10℃, and n-butyl lithium (2.5M; 21.00mmol; 5.75g) was added dropwise, and the temperature was controlled to be less than 0℃. After the addition was completed, the temperature was slowly raised to room temperature for reaction. After 16h, the temperature was lowered to -10℃, and titanium tetrachloride tetrahydrofuran complex (10.00mmol; 3.33g) was added and the temperature was controlled to be less than 0℃. After the addition was completed, the temperature was slowly raised to room temperature for reaction. After 16h, the ether was removed under reduced pressure, and dichloromethane (80.0mL) was added. After sufficient stirring, the insoluble lithium chloride was removed by filtration, and the filtrate was distilled under reduced pressure to remove the solvent dichloromethane. N-pentane (40.0mL) was added, and after sufficient stirring, 2.15g of brick red solid was obtained by filtration, with a yield of 53.2%.

[0157] The characterization data of Ti-23 are as follows:

[0158] 1HNMR (400MHz,CDCl3):8.38(d,J=4.0Hz,2H),7.79(t,J=8.0Hz,2H),7.19(d,J=4.0Hz,2H),1.22-1.14(m,12H); Elemental analysis theoretical value: TiC 16 H 18 O2Cl2N2: C, 49.39; H, 4.66; N, 7.20. Experimen tal value: C, 49.42; H, 4.69; N, 7.25.

[0159] 4) Preparation of Ti-2

[0160]

[0161] Under nitrogen protection, Ti-23 (5.0mmol; 2.02g) and ether (20.0mL) were added to a 100mL three-necked reaction bottle. The temperature was lowered to 0°C, and methylmagnesium bromide solution (3.0M; 15.0mmol; 7.5mL) was added. The temperature was controlled to be less than 5°C. After the addition was completed, the temperature was raised to room temperature for reaction. After 16 hours, low-boiling substances were removed under reduced pressure, and n-pentane was added and stirred thoroughly. Insoluble matter was removed by filtration, and the filtrate was collected. The solvent was concentrated and recrystallized to obtain 0.86g of off-white solid with a yield of 47.6%.

[0162] The characterization data of Ti-2 are as follows:

[0163] 1 HNMR (400MHz,CDCl3):8.39(d,J=4.0Hz,2H),7.81(t,J=8.0Hz,2H),7.23(d,J=4.0Hz,2H),1.32-1.24(m,12H),1.23(s,3H),1.43(s,3H); Elemental analysis theoretical value: TiC 18 H 24 O2N2: C, 62.08; H, 6.95; N, 8.04. Experimen tal value: C, 62.13; H, 6.98; N, 8.07.

[0164] Example 3: Preparation of Zr-3 Metal Compound

[0165] The specific steps are as follows:

[0166] 1) Preparation of Zr-31

[0167]

[0168] Under nitrogen protection, 2,6-dibromopyridine (0.1 mol; 23.69 g) and ether (400.0 mL) were added to a 1000 mL three-necked reaction bottle, cooled to -20°C, n-butyl lithium (0.1 mol; 27.40 g) was added dropwise, the temperature was controlled to be less than -10°C, and the reaction was carried out at -20°C for 1 h after the addition was completed, and then benzaldehyde (0.11 mol; 11.67 g) was slowly added, the temperature was controlled to be less than -10°C, and then the temperature was raised to room temperature for 16 h. The reaction solution was then poured into ice water for quenching, extracted with ethyl acetate, the low boiling point solvent was removed, and column chromatography was performed to obtain 19.57 g of a slightly yellow viscous liquid with a yield of 74.1%.

[0169] The characterization data of Zr-31 are as follows:

[0170] 1 HNMR(400MHz, CDCl3):7.49(t,J=8.0Hz,1H),7.41-7.33(m,5H),7.30(d,J=4.0Hz,1H),

[0171] 7.17(d,J=4.0Hz,1H),5.75(s,1H),4.65(br,1H); ESIMS:m / z 265.1([M+H] + ).

[0172] 2) Preparation of Zr-32

[0173]

[0174] Under nitrogen protection, nickel chloride (0.0025 mol; 0.60 g), Zr-31 (0.05 mol; 13.20 g), lithium chloride (0.05 mol; 2.15 g), zinc powder (0.06 mol; 3.85 g), and N,N-dimethylformamide (200.0 mL) were added to a 500 mL three-necked reaction bottle, the temperature was raised to 50 ° C and stirred for 30 min, then 2 iodine grains and 5 drops of acetic acid were added, and the temperature was raised to 60 ° C. After the reaction for 4 h, the raw materials reacted completely, and then the unreacted zinc powder was directly filtered out, the filtrate was poured into ice water to quench, and dichloromethane was added for extraction. After removing the low boiling point solvent, the crude product was obtained, and column chromatography was used for separation to obtain 5.00 g of a slightly yellow solid with a yield of 54.3%.

[0175] The characterization data of Zr-32 are as follows:

[0176] 1HNMR (400MHz, CDCl3): 8.38 (d, J = 4.0Hz, 2H), 7.81 (t, J = 8.0Hz, 2H), 7.42-7.33 (m, 10H), 7.23 (d, J = 4.0Hz, 2H), 5.78 (s, 2H) 5.44 (br, 2H); ESIMS: m / z 369.40([M+H] + ).

[0177] 3) Preparation of Zr-33

[0178]

[0179] Under nitrogen protection, Zr-32 (10.00mmol; 3.68g) and ether (40.0mL) were added to a 250mL three-necked reaction bottle. The temperature was lowered to -10℃, and n-butyl lithium (2.5M; 21.00mmol; 5.75g) was added dropwise, and the temperature was controlled to be less than 0℃. After the addition was completed, the temperature was slowly raised to room temperature for reaction. After 16h, the temperature was lowered to -10℃, and zirconium tetrachloride (10.00mmol; 2.30g) was added to control the temperature to be less than 0℃. After the addition was completed, the temperature was slowly raised to room temperature for reaction. After 16h, the ether was removed under reduced pressure, and dichloromethane (80.0mL) was added. After sufficient stirring, the insoluble lithium chloride was removed by filtration. The filtrate was distilled under reduced pressure, the solvent dichloromethane was removed, and n-pentane (40.0mL) was added. After sufficient stirring, 3.05g of light yellow solid was obtained by filtration, and the yield was 56.1%.

[0180] The characterization data of Zr-33 are as follows:

[0181] 1 HNMR (400MHz,CDCl3):8.41(d,J=4.0Hz,2H),7.91(t,J=8.0Hz,2H),7.52-7.43(m,10H),7.33(d,J=4.0Hz,2H),5.86-5.61(m,2H); Elemental analysis theoretical value:ZrC 24 H 18 O2Cl2N2: C, 55.54; H, 3.43; N, 5.30. Experimen tal value: C, 55.59; H, 3.48; N, 5.33.

[0182] 4) Preparation of Zr-3

[0183]

[0184] Under nitrogen protection, Zr-33 (5.0mmol; 2.72g) and ether (20.0mL) were added to a 100mL three-necked reaction bottle. The temperature was lowered to 0°C, and methylmagnesium bromide solution (3.0M; 15.0mmol; 5.0mL) was added. The temperature was controlled to be less than 5°C. After the addition was completed, the temperature was raised to room temperature for reaction. After 16 hours, low-boiling substances were removed under reduced pressure, and n-pentane was added and stirred thoroughly. Insoluble matter was removed by filtration, and the filtrate was collected. The solvent was concentrated and recrystallized to obtain 1.19g of white solid with a yield of 47.3%.

[0185] The characterization data of Zr-3 are as follows:

[0186] 1 HNMR (400MHz,CDCl3):8.47(d,J=4.0Hz,2H),7.97(t,J=8.0Hz,2H),7.64-7.53(m,10H),7.43(d,J=4.0Hz,2H),5.96-5.71(m,2H),-1.45(s,3H),-1.54(s,3H); Elemental analysis theoretical value:ZrC 26 H 24 O2N2: C, 64.03; H, 5.96; N, 5.74. Experimen tal value: C, 64.08; H, 5.60N, 5.78.

[0187] Example 4: Preparation of Hf-4 Metal Compound

[0188] The specific steps are as follows:

[0189] 1) Preparation of Hf-41

[0190]

[0191] Under nitrogen protection, 2,6-dibromopyridine (0.1 mol; 23.69 g) and ether (400.0 mL) were added to a 1000 mL three-necked reaction bottle, cooled to -20°C, n-butyl lithium (0.1 mol; 27.40 g) was added dropwise, and the temperature was controlled to be less than -10°C. After the addition was completed, the reaction was carried out at -20°C for 1 hour, and then cyclohexanone (0.11 mol; 10.80 g) was slowly added, and the temperature was controlled to be less than -10°C, and then the temperature was raised to room temperature for 16 hours. The reaction solution was then poured into ice water for quenching, extracted with ethyl acetate, the low boiling point solvent was removed, and column chromatography was performed to obtain 17.93 g of a slightly yellow liquid with a yield of 73.2%.

[0192] The characterization data of Hf-41 are as follows: 1H NMR (400MHz, CDCl3): 7.55 (t, J = 8.0 Hz, 1H), 7.37 (t, J = 8.0 Hz, 2H), 3.81 (br, 1H), 3.87-1.74 (m, 5H), 1.74-1.65 (m, 4H), 1.35-1.28 (m, 1H); ESIMS: m / z 257.1([M+H] + ).

[0193] 2) Preparation of Hf-42

[0194]

[0195] Under nitrogen protection, nickel chloride (0.0025 mol; 0.60 g), Hf-41 (0.05 mol; 12.81 g), lithium chloride (0.05 mol; 2.15 g), zinc powder (0.06 mol; 3.85 g), and N,N-dimethylformamide (200.0 mL) were added to a 500 mL three-necked reaction bottle, the temperature was raised to 50 ° C and stirred for 30 min, then 2 iodine grains and 5 drops of acetic acid were added, and the temperature was raised to 60 ° C. After the reaction for 4 h, the raw materials reacted completely, and then the unreacted zinc powder was directly filtered out, the filtrate was poured into ice water for quenching, and dichloromethane was added for extraction. After removing the low boiling point solvent, the crude product was obtained, and column chromatography was used for separation to obtain 4.85 g of a slightly yellow solid with a yield of 55.0%.

[0196] The characterization data of Hf-42 are as follows:

[0197] 1 HNMR (400MHz, CDCl3): 8.16 (d, J = 4.0Hz, 2H), 7.58 (t, J = 8.0Hz, 2H), 7.05 (d, J = 4.0Hz, 2 H),3.91(br,2H),3.97-1.84(m,10H),1.84-1.75(m,8H),1.45-1.38(m,2H); ESIMS:m / z 353.5([M+H] + ).

[0198] 3) Preparation of Hf-43

[0199]

[0200] Under nitrogen protection, Hf-42 (10.00mmol; 3.52g) and ether (40.0mL) were added to a 250mL three-necked reaction bottle. The temperature was lowered to -10℃, and n-butyl lithium (2.5M; 21.00mmol; 5.75g) was added dropwise, and the temperature was controlled to be less than 0℃. After the addition was completed, the temperature was slowly raised to room temperature for reaction. After 16h, the temperature was lowered to -10℃, and hafnium tetrachloride (10.00mmol; 3.20g) was added to control the temperature to be less than 0℃. After the addition was completed, the temperature was slowly raised to room temperature for reaction. After 16h, the ether was removed under reduced pressure, and dichloromethane (80.0mL) was added. After sufficient stirring, the insoluble lithium chloride was removed by filtration, and the filtrate was distilled under reduced pressure to remove the solvent dichloromethane. N-pentane (40.0mL) was added, and after sufficient stirring, 3.52g of light yellow solid was obtained by filtration, with a yield of 57.3%.

[0201] The characterization data of Hf-43 are as follows:

[0202] 1 HNMR (400MHz,CDCl3):8.36(d,J=4.0Hz,2H),7.78(t,J=8.0Hz,2H),7.25(d,J=4.0Hz,2H),4.17-2.04(m,10H),2.04-1.95(m,8H),1.55-1.58(m,2H); Elemental analysis theoretical value:HfC 22 H 26 O2Cl2N2: C, 44.05; H, 4.37; N, 4.67. Experimen tal value: C, 44.08; H, 4.42; N, 4.70.

[0203] 4) Preparation of Hf-4

[0204]

[0205] Under nitrogen protection, Hf-43 (5.0mmol; 3.07g) and ether (20.0mL) were added to a 100mL three-necked reaction bottle. The temperature was lowered to 0°C, and benzylmagnesium chloride solution (2.0M; 15.0mmol; 7.5mL) was added, and the temperature was controlled to be less than 5°C. After the addition was completed, the temperature was raised to room temperature for reaction. After 16 hours, low-boiling substances were removed under reduced pressure, and n-pentane was added and stirred thoroughly. Insoluble matter was removed by filtration, and the filtrate was collected, the solvent was concentrated, and recrystallization was performed to obtain 1.81g of yellow-white solid with a yield of 51.0%.

[0206] The characterization data of Hf-4 are as follows:

[0207] 1HNMR (400MHz,CDCl3):8.46(d,J=4.0Hz,2H),7.88(t,J=8.0Hz,2H),7.35(d,J=4.0Hz,2H),7.11-7.06(m,4H),6.84-6.74(m,2H),6.61-6.51(m,4H),4.27-2.14(m,10H),2.16(br,4H),2.14-2.05(m,8H),1.65-1.58(m,2H); Elemental analysis theoretical value: HfC 36 H 40 O2N2: C, 60.80; H, 5.67; N, 3.94. Experimen tal value: C, 60.83; H, 5.70; N, 3.99.

[0208] Example 5: Preparation of Ti-5 Metal Compound

[0209] The specific steps are as follows

[0210] 1) Preparation of Ti-51

[0211]

[0212] Under nitrogen protection, 2,6-dibromopyridine (0.1 mol; 23.69 g) and ether (400.0 mL) were added to a 1000 mL three-necked reaction bottle, cooled to -20°C, n-butyl lithium (0.1 mol; 27.40 g) was added dropwise, and the temperature was controlled to be less than -10°C. After the addition was completed, the reaction was carried out at -20°C for 1 h, and then phenylbutenyl ketone (0.11 mol; 17.60 g) was slowly added, and the temperature was controlled to be less than -10°C, and then the temperature was raised to room temperature for 16 h. The reaction solution was then poured into ice water for quenching, extracted with ethyl acetate, the low boiling point solvent was removed, and column chromatography was performed to obtain 20.17 g of yellow liquid with a yield of 63.4%.

[0213] The characterization data of Ti-51 are as follows:

[0214] 1 HNMR(400MHz, CDCl3):7.46(t,J=8.0Hz,1H),7.40(d,J=4.0Hz,1H),7.31-7.26(m,5H),

[0215] 7.02(d,J=4.0Hz,1H),5.82(m,1H),5.35(br,1H),5.02(m,2H),2.10(m,2H),1.96(m,2H); ESIMS:m / z

[0216] 319.2([M+H] + ).

[0217] 2) Preparation of Ti-52

[0218]

[0219] Under nitrogen protection, nickel chloride (0.0025 mol; 0.60 g), Ti-51 (0.05 mol; 15.91 g), lithium chloride (0.05 mol; 2.15 g), zinc powder (0.06 mol; 3.85 g), and N,N-dimethylformamide (200.0 mL) were added to a 500 mL three-necked reaction bottle, the temperature was raised to 50 ° C and stirred for 30 min, then 2 iodine grains and 5 drops of acetic acid were added, and the temperature was raised to 60 ° C. After the reaction for 4 h, the raw materials reacted completely, and then the unreacted zinc powder was directly filtered out, the filtrate was poured into ice water for quenching, and dichloromethane was added for extraction. After removing the low-boiling point solvent, the crude product was obtained, and column chromatography was used for separation to obtain 7.30 g of a yellow solid with a yield of 61.3%.

[0220] The characterization data of Ti-52 are as follows:

[0221] 1 HNMR(400MHz, CDCl3):8.34(d,J=4.0Hz,2H),7.74(t,J=8.0Hz,2H),7.30-7.24(m,10H),7.12( d,J=4.0Hz,2H),5.82(m,2H),5.45(br,2H),5.02(m,4H),2.10(m,4H),1.96(m,4H); ESIMS:m / z

[0222] 477.6([M+H] + ).

[0223] 3) Preparation of Ti-53

[0224]

[0225] Under nitrogen protection, Ti-52 (10.00mmol; 4.76g) and ether (40.0mL) were added to a 250mL three-necked reaction bottle. The temperature was lowered to -10℃, and n-butyl lithium (2.5M; 21.00mmol; 5.75g) was added dropwise, and the temperature was controlled to be less than 0℃. After the addition was completed, the temperature was slowly raised to room temperature for reaction. After 16h, the temperature was lowered to -10℃, and titanium tetrachloride tetrahydrofuran complex (10.00mmol; 3.33g) was added and the temperature was controlled to be less than 0℃. After the addition was completed, the temperature was slowly raised to room temperature for reaction. After 16h, the ether was removed under reduced pressure, and dichloromethane (80.0mL) was added. After sufficient stirring, the insoluble lithium chloride was removed by filtration, and the filtrate was distilled under reduced pressure to remove the solvent dichloromethane. N-pentane (40.0mL) was added, and after sufficient stirring, 3.55g of earthy red solid was obtained by filtration, with a yield of 58.3%.

[0226] The characterization data of Ti-53 are as follows:

[0227] 1 HNMR (400MHz,CDCl3):8.44(d,J=4.0Hz,2H),7.84(t,J=8.0Hz,2H),7.41-7.33(m,10H),7.22(d,J=4.0Hz,2H),5.92(m,2H),5.12(m,4H),2.20(m,4H),2.06(m,4H); Elemental analysis theoretical value: TiC 32 H 30 O2Cl2N2: C, 64.77; H, 5.10; N, 4.72. Experimen tal value: C, 64.82; H, 5.15; N, 4.75.

[0228] 4) Preparation of Ti-5

[0229]

[0230] Under nitrogen protection, Ti-53 (5.0mmol; 2.02g) and ether (20.0mL) were added to a 100mL three-necked reaction bottle. The temperature was lowered to 0°C, and methylmagnesium bromide solution (3.0M; 15.0mmol; 7.5mL) was added. The temperature was controlled to be less than 5°C. After the addition was completed, the temperature was raised to room temperature for reaction. After 16 hours, low-boiling substances were removed under reduced pressure, and n-pentane was added and stirred thoroughly. Insoluble matter was removed by filtration, and the filtrate was collected. The solvent was concentrated and recrystallized to obtain 1.07g of light gray solid with a yield of 37.8%.

[0231] The characterization data of Ti-5 are as follows:

[0232] 1 HNMR(400MHz, CDCl3):8.48(d,J=4.0Hz,2H),7.87(t,J=8.0Hz,2H),7.44-7.36m,10H),

[0233] 7.24 (d, J = 4.0 Hz, 2H), 5.95 (m, 2H), 5.15 (m, 4H), 2.24 (m, 4H), 2.08 (m, 4H), -1.24 (s, 3H), -1.46 (s, 3H). Elemental analysis theoretical value: TiC 34 H 36 O2N2: C, 73.91; H, 6.57; N, 5.07. Experimen tal value: C, 73.96; H, 6.62; N, 5.12.

[0234] Example 6: Preparation of Zr-6 Metal Compound

[0235] The specific steps are as follows:

[0236] 1) Preparation of Zr-61

[0237]

[0238] Under nitrogen protection, 2,6-dibromopyridine (0.1 mol; 23.69 g) and ether (400.0 mL) were added to a 1000 mL three-necked reaction bottle, cooled to -20°C, n-butyl lithium (0.1 mol; 27.40 g) was added dropwise, and the temperature was controlled to be less than -10°C. After the addition was completed, the reaction was carried out at -20°C for 1 h, and then acetophenone (0.11 mol; 13.20 g) was slowly added, and the temperature was controlled to be less than -10°C, and then the temperature was raised to room temperature for 16 h. The reaction solution was then poured into ice water for quenching, extracted with ethyl acetate, the low boiling point solvent was removed, and column chromatography was performed to obtain 17.55 g of a slightly yellow viscous liquid with a yield of 63.1%.

[0239] The characterization data of Zr-61 are as follows:

[0240] 1 HNMR(400MHz, CDCl3):7.49(t,J=8.0Hz,1H),7.41-7.33(m,5H),7.30(d,J=4.0Hz,1H),

[0241] 7.17(d,J=4.0Hz,1H),4.65(br,1H),1.87(s,3H); ESIMS:m / z 279.1([M+H] + ).

[0242] 2) Preparation of Zr-62

[0243]

[0244] Under nitrogen protection, nickel chloride (0.0025 mol; 0.60 g), Zr-61 (0.05 mol; 13.90 g), lithium chloride (0.05 mol; 2.15 g), zinc powder (0.06 mol; 3.85 g), and N,N-dimethylformamide (200.0 mL) were added to a 500 mL three-necked reaction bottle, the temperature was raised to 50 ° C and stirred for 30 min, then 2 iodine grains and 5 drops of acetic acid were added, and the temperature was raised to 60 ° C. After the reaction for 4 h, the raw materials reacted completely, and then the unreacted zinc powder was directly filtered out, the filtrate was poured into ice water for quenching, and dichloromethane was added for extraction. After removing the low-boiling point solvent, the crude product was obtained, and column chromatography was used for separation to obtain 6.65 g of light yellow liquid with a yield of 67.1%.

[0245] The characterization data of Zr-62 are as follows:

[0246] 1 HNMR (400MHz, CDCl3): 8.38 (d, J = 4.0Hz, 2H), 7.81 (t, J = 8.0Hz, 2H), 7.42-7.33 (m, 10H), 7.23 (d, J = 4.0Hz, 2H), 5.44 (br, 2H), 1.90 (s, 6H); ESIMS: m / z 397.5([M+H] + ).

[0247] 3) Preparation of Zr-63

[0248]

[0249] Under nitrogen protection, Zr-62 (10.00mmol; 3.96g) and ether (40.0mL) were added to a 250mL three-necked reaction bottle. The temperature was lowered to -10℃, and n-butyl lithium (2.5M; 21.00mmol; 5.75g) was added dropwise, and the temperature was controlled to be less than 0℃. After the addition was completed, the temperature was slowly raised to room temperature for reaction. After 16h, the temperature was lowered to -10℃, and zirconium tetrachloride (10.00mmol; 2.30g) was added to control the temperature to be less than 0℃. After the addition was completed, the temperature was slowly raised to room temperature for reaction. After 16h, the ether was removed under reduced pressure, and dichloromethane (80.0mL) was added. After sufficient stirring, the insoluble lithium chloride was removed by filtration, and the filtrate was distilled under reduced pressure to remove the solvent dichloromethane. N-pentane (40.0mL) was added, and after sufficient stirring, 3.63g of yellow solid was obtained by filtration, with a yield of 63.5%.

[0250] The characterization data of Zr-63 are as follows:

[0251] 1 HNMR(400MHz, CDCl3):8.40(d,J=4.0Hz,2H),7.83(t,J=8.0Hz,2H),7.45-7.35(m,10H),

[0252] 7.24 (d, J = 4.0 Hz, 2H), 1.92 (s, 6H); Elemental analysis theoretical value: ZrC 26 H 22 O2Cl2N2: C, 56.11; H, 3.98; N, 5.03. Experimen tal value: C, 56.16; H, 4.03; N, 5.08.

[0253] 4) Preparation of Zr-6

[0254]

[0255] Under nitrogen protection, Zr-63 (5.0mmol; 2.85g) and ether (20.0mL) were added to a 100mL three-necked reaction bottle. The temperature was lowered to 0°C, and methylmagnesium bromide solution (3.0M; 15.0mmol; 5.0mL) was added. The temperature was controlled to be less than 5°C. After the addition was completed, the temperature was raised to room temperature for reaction. After 16 hours, low-boiling substances were removed under reduced pressure, and n-pentane was added and stirred thoroughly. Insoluble matter was removed by filtration, and the filtrate was collected. The solvent was concentrated and recrystallized to obtain 1.23g of light yellow solid with a yield of 46.5%.

[0256] The characterization data of Zr-6 are as follows:

[0257] 1 HNMR(400MHz, CDCl3):8.50(d,J=4.0Hz,2H),7.93(t,J=8.0Hz,2H),755-7.45(m,10H),

[0258] 7.34 (d, J = 4.0 Hz, 2H), 2.02 (s, 6H), -1.45 (s, 3H), -1.58 (s, 3H); Elemental analysis theoretical value: ZrC 26 H 28 O2N2: C, 65.21; H, 5.47; N, 5.43. Experimen tal value: C, 65.26; H, 5.52; N, 5.48.

[0259] Example 7: Preparation of Hf-7 Metal Compound

[0260] The specific steps are as follows:

[0261] 1) Preparation of Hf-71

[0262]

[0263] Under nitrogen protection, 2,9-dibromo-1,10-phenanthroline (0.1 mol; 23.69 g) and ether (400.0 mL) were added to a 1000 mL three-necked reaction bottle, cooled to -20°C, n-butyl lithium (0.21 mol; 57.54 g) was added dropwise, the temperature was controlled to be less than -10°C, and the temperature was slowly raised to room temperature for reaction after the addition was completed. After 16 hours, benzophenone (0.2 mol; 36.44 g) was slowly added, the temperature was controlled to be less than -10°C, and then the temperature was raised to room temperature for reaction for 16 hours. The reaction solution was then poured into ice water for quenching, extracted with ethyl acetate, the low boiling point solvent was removed, and column chromatography was performed to obtain 40.09 g of a white solid with a yield of 73.6%.

[0264] The characterization data of Hf-71 are as follows:

[0265] 1HNMR (400MHz, CDCl3): 8.36 (d, J = 4.0Hz, 2H), 7.78 (t, J = 8.0Hz, 2H), 7.32-7.28 (m, 22H), 6.45 (br, 2H); ESIMS: m / z 545.6 ([M+H] + ).

[0266] 2) Preparation of Hf-72

[0267]

[0268] Under nitrogen protection, Hf-71 (10.00mmol; 5.44g) and ether (40.0mL) were added to a 250mL three-necked reaction bottle. The temperature was lowered to -10℃, and n-butyl lithium (2.5M; 21.00mmol; 5.75g) was added dropwise, and the temperature was controlled to be less than 0℃. After the addition was completed, the temperature was slowly raised to room temperature for reaction. After 16h, the temperature was lowered to -10℃, and hafnium tetrachloride (10.00mmol; 3.20g) was added to control the temperature to be less than 0℃. After the addition was completed, the temperature was slowly raised to room temperature for reaction. After 16h, the ether was removed under reduced pressure, and dichloromethane (80.0mL) was added. After sufficient stirring, the insoluble lithium chloride was removed by filtration, and the filtrate was distilled under reduced pressure to remove the solvent dichloromethane. N-pentane (40.0mL) was added, and after sufficient stirring, 4.56g of orange-yellow solid was obtained by filtration, with a yield of 57.6%.

[0269] The characterization data of Hf-72 are as follows:

[0270] 1 HNMR (400MHz,CDCl3):8.39(d,J=4.0Hz,2H),7.80(t,J=8.0Hz,2H),7.36-7.31(m,22H); Elemental analysis theoretical value:HfC 38 H 26 O2Cl2N2: C, 57.63; H, 3.31; N, 3.54. Experimen tal value: C, 57.67; H, 3.36; N, 3.59.

[0271] 3) Preparation of Hf-7

[0272]

[0273] Under nitrogen protection, add Hf-72 (5.0mmol; 3.96g) and ether (20.0mL) to a 100mL three-necked reaction bottle. Cool down to 0℃, add benzylmagnesium chloride solution (2.0M; 15.0mmol; 7.5mL), control the temperature below 5℃, and warm to room temperature for reaction after the addition is complete. After 16h, remove low-boiling substances under reduced pressure, add n-pentane and stir thoroughly, filter to remove insolubles, collect the filtrate, concentrate the solvent, and recrystallize to obtain 2.32g of yellow, with a yield of 51.3%.

[0274] The characterization data of Hf-7 are as follows:

[0275] 1 HNMR (400MHz,CDCl3):8.49(d,J=4.0Hz,2H),7.90(t,J=8.0Hz,2H),7.46-7.41(m,22H),7.11-7.06(m,4H),6.84-6.74(m,2H),6.61-6.51(m,4H),2.11(br,4H); Elemental analysis theoretical value: HfC 52 H 40 O2N2: C, 69.14; H, 4.46; N, 3.10. Experimen tal value: C, 69.19; H, 4.51; N, 3.15.

[0276] Example 8: Preparation of Ti-8 Metal Compound

[0277] The specific steps are as follows:

[0278] 1) Preparation of Ti-81

[0279]

[0280] Under nitrogen protection, 2,9-dibromo-1,10-phenanthroline (0.1 mol; 33.80 g) and ether (400.0 mL) were added to a 1000 mL three-necked reaction bottle, cooled to -20°C, n-butyl lithium (0.21 mol; 57.54) was added dropwise, the temperature was controlled to be less than -10°C, and the reaction was carried out at -20°C for 1 h after the addition was completed, and then cyclohexanone (0.20 mol; 19.63 g) was slowly added, the temperature was controlled to be less than -10°C, and then the temperature was raised to room temperature for 16 h. The reaction solution was then poured into ice water for quenching, extracted with ethyl acetate, the low boiling point solvent was removed, and column chromatography was performed to obtain 26.24 g of a slightly yellow liquid with a yield of 69.7%.

[0281] The characterization data of Ti-81 are as follows:

[0282] 1HNMR(400MHz, CDCl3):8.16(d,J=4.0Hz,2H),7.58(t,J=8.0Hz,2H),7.35-7.30(m,2H),3.91 (br,2H),3.97-1.84(m,10H),1.84-1.75(m,8H),1.45-1.38(m,2H); ESIMS:m / z377.5([M+H] + ).

[0283] 2) Preparation of Ti-82

[0284]

[0285] Under nitrogen protection, Ti-81 (10.00mmol; 3.77g) and ether (40.0mL) were added to a 250mL three-necked reaction bottle. The temperature was lowered to -10℃, and n-butyl lithium (2.5M; 21.00mmol; 5.75g) was added dropwise, and the temperature was controlled to be less than 0℃. After the addition was completed, the temperature was slowly raised to room temperature for reaction. After 16h, the temperature was lowered to -10℃, and titanium tetrachloride tetrahydrofuran complex (10.00mmol; 3.33g) was added, and the temperature was controlled to be less than 0℃. After the addition was completed, the temperature was slowly raised to room temperature for reaction. After 16h, the ether was removed under reduced pressure, and dichloromethane (80.0mL) was added. After sufficient stirring, the insoluble lithium chloride was removed by filtration, and the filtrate was distilled under reduced pressure to remove the solvent dichloromethane. N-pentane (40.0mL) was added, and after sufficient stirring, 2.85g of earthy red solid was obtained by filtration, with a yield of 57.8%.

[0286] The characterization data of Ti-82 are as follows:

[0287] 1 HNMR (400MHz,CDCl3):8.19(d,J=4.0Hz,2H),7.61(t,J=8.0Hz,2H),7.39-7.34(m,2H),3.40-1.87(m,10H),1.88-1.77(m,8H),1.48-1.41(m,2H); Elemental analysis theoretical value: TiC 24 H 26 O2Cl2N2: C, 58.44; H, 5.31N, 5.68. Experimen tal value: C, 58.47; H, 5.34; N, 5.72.

[0288] 3) Preparation of Ti-8

[0289]

[0290] Under nitrogen protection, Ti-82 (5.0mmol; 2.47g) and ether (20.0mL) were added to a 100mL three-necked reaction bottle. The temperature was lowered to 0°C, and methylmagnesium bromide solution (3.0M; 15.0mmol; 7.5mL) was added, and the temperature was controlled to be less than 5°C. After the addition was completed, the temperature was raised to room temperature for reaction. After 16 hours, low-boiling substances were removed under reduced pressure, and n-pentane was added and stirred thoroughly. Insoluble matter was removed by filtration, and the filtrate was collected, the solvent was concentrated, and recrystallization was performed to obtain 1.21g of gray solid with a yield of 53.7%.

[0291] The characterization data of Ti-8 are as follows:

[0292] 1 HNMR (400MHz,CDCl3):8.29(d,J=4.0Hz,2H),7.71(t,J=8.0Hz,2H),7.49-7.44(m,2H),3.50-1.97(m,10H),1.98-1.87(m,8H),1.58-1.51(m,2H),-1.43(s,3H),-1.56(s,3H); Elemental analysis theoretical value: TiC 26 H 32 O2N2: C, 69.03; H, 7.13N, 6.19. Experimen tal value: C, 69.43; H, 7.43; N, 6.69.

[0293] Example 9: Preparation of Zr-9 Metal Compound

[0294] The specific steps are as follows:

[0295] 1) Preparation of Zr-91

[0296]

[0297] Under nitrogen protection, 2,9-dibromo-1,10-phenanthroline (0.1 mol; 33.80 g) and ether (400.0 mL) were added to a 1000 mL three-necked reaction bottle, cooled to -20°C, and n-butyl lithium (0.21 mol; 57.54 g) was added dropwise, and the temperature was controlled to be less than -10°C. After the addition was completed, the reaction was carried out at -20°C for 1 hour, and then acetone (0.2 mol; 11.62 g) was slowly added, and the temperature was controlled to be less than -10°C, and then the temperature was raised to room temperature for 16 hours. The reaction solution was then poured into ice water for quenching, extracted with ethyl acetate, the low boiling point solvent was removed, and column chromatography was performed to obtain 20.09 g of a slightly yellow viscous liquid with a yield of 67.8%.

[0298] The characterization data of Zr-91 are as follows:

[0299] 1HNMR(400MHz, CDCl3):8.35(d,J=4.0Hz,2H),7.76(t,J=8.0Hz,2H),7.24-7.20(m,2H),

[0300] 3.94(br,2H),1.24-1.15(m,12H); ESIMS:m / z 297.4([M+H] + ).

[0301] 2) Preparation of Zr-92

[0302]

[0303] Under nitrogen protection, Zr-91 (10.00mmol; 2.96g) and ether (40.0mL) were added to a 250mL three-necked reaction bottle. The temperature was lowered to -10℃, and n-butyl lithium (2.5M; 21.00mmol; 5.75g) was added dropwise, and the temperature was controlled to be less than 0℃. After the addition was completed, the temperature was slowly raised to room temperature for reaction. After 16h, the temperature was lowered to -10℃, and zirconium tetrachloride (10.00mmol; 2.30g) was added to control the temperature to be less than 0℃. After the addition was completed, the temperature was slowly raised to room temperature for reaction. After 16h, the ether was removed under reduced pressure, and dichloromethane (80.0mL) was added. After sufficient stirring, the insoluble lithium chloride was removed by filtration. The filtrate was distilled under reduced pressure, the solvent dichloromethane was removed, and n-pentane (40.0mL) was added. After sufficient stirring, 2.89g of bright yellow solid was obtained by filtration, and the yield was 63.4%.

[0304] The characterization data of Zr-92 are as follows:

[0305] 1 HNMR (400MHz,CDCl3):8.38(d,J=4.0Hz,2H),7.79(t,J=8.0Hz,2H),7.28-7.22(m,2H),1.28-1.19(m,12H); Elemental analysis theoretical value:ZrC 18 H 18 O2Cl2N2: C, 47.36; H, 3.97; N, 6.14. Experimen tal value: C, 47.39; H, 4.01; N, 6.18.

[0306] 3) Preparation of Zr-9

[0307]

[0308] Under nitrogen protection, Zr-92 (5.0mmol; 2.28g) and ether (20.0mL) were added to a 100mL three-necked reaction bottle. The temperature was lowered to 0°C, and methylmagnesium bromide solution (3.0M; 15.0mmol; 5.0mL) was added. The temperature was controlled to be less than 5°C. After the addition was completed, the temperature was raised to room temperature for reaction. After 16 hours, low-boiling substances were removed under reduced pressure, and n-pentane was added and stirred thoroughly. Insoluble matter was removed by filtration, and the filtrate was collected. The solvent was concentrated and recrystallized to obtain 1.01g of light yellow solid with a yield of 48.7%.

[0309] The characterization data of Zr-9 are as follows:

[0310] 1 HNMR (400MHz,CDCl3):8.48(d,J=4.0Hz,2H),7.89(t,J=8.0Hz,2H),7.38-7.32(m,2H),1.38-1.29(m,12H),1.45(s,3H),1.53(s,3H); Elemental analysis theoretical value:ZrC 20 H 24 O2N2: C, 57.79; H, 5.82; N, 6.74. Experimen tal value: C, 57.84; H, 5.85; N, 6.79.

[0311] Example 10 Ethylene / 1-butene batch polymerization

[0312] Catalyst configuration method: a certain amount of the corresponding main catalyst (metal compound prepared in Example 1-9) is dissolved in toluene to prepare a main catalyst solution (5.0%, mass fraction); a certain amount of [Ph3C][B(C6F5)4] is dissolved in toluene to prepare a borate solution (5.0%, mass fraction); triisobutylaluminum modified methylaluminoxane (MMAO) solution (7%, aluminum element mass fraction) is purchased commercially (Nouryon). The polymerization conditions are: the molar ratio of triisobutylaluminum modified methylaluminoxane (MMAO), [Ph3C][B(C6F5)4], and the main catalyst is Al: B: main catalyst = 100:2:1.

[0313] The intermittent polymerization reaction was carried out in a 2L reactor. The reactor was first evacuated at 100°C for 2h, then evacuated and replaced with nitrogen 3 times, evacuated and replaced with ethylene 2 times, and then cooled to room temperature. Stirring was started at 400rpm, and 900mL of Isopar E solvent, 200mL of hydrogen, 300mL of 1-butene, borate solution, MMAO solution, and main catalyst solution were added in sequence. After the addition of each material, ethylene was introduced to adjust the polymerization pressure to 30bar, and the temperature was raised to 120°C within 5 minutes for polymerization. After the reaction was completed, the reaction materials were received by a buffer receiving tank connected to the bottom discharge valve, and antioxidant 1010 (3000ppm) was added, and then ethanol was added to precipitate the polymer. The polymer was filtered, vacuum dried at 60°C overnight, and weighed.

[0314] Product Characterization:

[0315] 1. Polymer molecular weight (M w and M n ) and its molecular weight distribution (M w / M n ) Test: High temperature gel chromatography was used for determination. Test conditions: 1,2,4-trichlorobenzene was used as solvent, 0.1-0.3 wt% polymer solution was prepared at 150°C, narrow molecular weight distribution polystyrene was used as standard sample, and the measurement was carried out at 150°C, with a solvent flow rate of 1.0 mL / min. The parameter K=5.91×10 -4 , α=0.69.

[0316] 2. Test of the branching degree (comonomer content) of the copolymer: Gel chromatography-infrared was used for detection and determination.

[0317] 3. Polymer melt index (MI) test: Zwick Mflow test was used; test method: 190°C, load 2.16 kg.

[0318] Table 1 Results of ethylene / 1-butene copolymerization catalyzed by catalysts

[0319]

[0320] 1. Catalyst dosage: 5 μmol, polymerization temperature: 120°C, reactor pressure: 30 bar.

[0321] 2. F1 a : Mass fraction of 1-butene, obtained by GPC-IR test.

[0322] As shown in Table 1, the bipyridine metal compound provided by the present invention can catalyze the copolymerization of ethylene and 1-butene at 120°C, and the maximum activity can reach 2.7×10 7g polymer g / (mol.h), the 1-butene insertion rate reaches 8.9%, it has high catalytic activity and high temperature resistance, and meets the conditions for industrial application.

[0323] Example 11 Ethylene / 1-octene batch polymerization

[0324] Catalyst configuration method: a certain amount of the corresponding main catalyst (metal compound prepared in Example 1-9) is dissolved in toluene to prepare a main catalyst solution (5.0%, mass fraction); a certain amount of [Ph3C][B(C6F5)4] is dissolved in toluene to prepare a borate solution (5.0%, mass fraction); triisobutylaluminum modified methylaluminoxane (MMAO) solution (7.0%, aluminum element mass fraction) is purchased commercially (Nouryon). The polymerization conditions are: the molar ratio of triisobutylaluminum modified methylaluminoxane (MMAO), [Ph3C][B(C6F5)4], and catalyst is Al: B: catalyst = 100:2:1.

[0325] The intermittent polymerization reaction was carried out in a 2L reactor. The reactor was first evacuated at 100°C for 2h, then evacuated and replaced with nitrogen 3 times, evacuated and replaced with ethylene 2 times, and cooled to room temperature. Stirring was started at 400rpm, and 900mL of Isopar E solvent, 120mL of hydrogen, 350mL of 1-octene, borate solution, MMAO solution, and main catalyst solution were added in sequence. After the addition of each material, ethylene was introduced to adjust the polymerization pressure to 35bar, and the temperature was raised to 145°C within 5 minutes for polymerization. After the reaction was completed, the reaction materials were received by a buffer receiving tank connected to the bottom discharge valve, and antioxidant 1010 (3000ppm) was added, and then ethanol was added to precipitate the polymer. The polymer was filtered, vacuum dried at 60°C overnight, and weighed.

[0326] Table 2 Results of ethylene / 1-octene copolymerization catalyzed by catalysts

[0327]

[0328] 1. Catalyst dosage: 5 μmol, polymerization temperature: 145°C, reactor pressure: 35 bar.

[0329] 2. F1 b : Mass fraction of 1-octene, obtained by GPC-IR test.

[0330] As shown in Table 2, the bipyridine metal compound of the present invention can catalyze the copolymerization of ethylene and 1-octene at 145°C, and the maximum activity can reach 2.17×10 7 g polymer g / (mol.h), the 1-octene insertion rate reaches 7.8%, it has high catalytic activity and high temperature resistance, and meets the conditions for industrial application.

[0331] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A bipyridine-containing metal organic compound represented by formula (I): in, M is selected from the group IVB metals titanium Ti, zirconium Zr, hafnium Hf; X1 and X2 are the same or different and are independently selected from: halogen, C 1-20 Alkyl, -(CH2) n -C 6-20 Aryl, C 6-20 Aryl, -(CH2) n -5 to 20 membered heteroaryl, 5 to 20 membered heteroaryl, C 3-20 Cycloalkyl, 3- to 20-membered heterocycloalkyl; n is a natural number selected from 1 to 5; R1, R2, R3, R4 are the same or different and are independently selected from: hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 6-20 Aryl, 5 to 20 membered heteroaryl; or, R1, R2 and the carbon atom to which they are attached form a C 3-20 Cycloalkyl, 3 to 20-membered cycloalkyl; or, R3, R4 and the carbon atom to which they are connected form C 3-20 Cycloalkyl, 3- to 20-membered heterocycloalkyl; R5, R6, R9, R 10 The same or different, each independently selected from: hydrogen, halogen, C 1-20 Alkyl, C 1-20 Alkoxy; R7 and R8 are the same or different and are independently selected from: hydrogen, halogen, C 1-20 Alkyl, C 1-20 Alkoxy; or, R7, R8 and the carbon atom on the pyridine ring form a C 6-20 Aryl, 5- to 20-membered heteroaryl.

2. The metal organic compound according to claim 1, characterized in that X1 and X2 are the same or different and are independently selected from: halogen, C 1-14 Alkyl, -(CH2) n -C 6-14 Aryl, C 6-14 Aryl, -(CH2) n -5 to 14 membered heteroaryl, 5 to 14 membered heteroaryl, C 3-14 Cycloalkyl, 3- to 14-membered heterocycloalkyl; Preferably, X1 and X2 are the same or different and are independently selected from: halogen, C 1-10 Alkyl, -(CH2) n -C 6-10 Aryl, C 6-10 Aryl, -(CH2) n -5 to 10 membered heteroaryl, 5 to 10 membered heteroaryl, C 3-10 Cycloalkyl, 3- to 10-membered heterocycloalkyl; Preferably, X1 and X2 are the same; preferably, X1 and X2 are both methyl; preferably, X1 and X2 are both -CH2-phenyl; and / or, R1, R2, R3, R4 are the same or different and are independently selected from: hydrogen, C 1-14 Alkyl, C 2-14 Alkenyl, C 2-14 Alkynyl, C 6-14 Aryl, 5 to 14 membered heteroaryl; or, R1, R2 and the carbon atom to which they are attached form a C 3-14 Cycloalkyl, 3 to 14 membered heterocycloalkyl; or, R3, R4 and the carbon atom to which they are attached form C 3-14 Cycloalkyl, 3- to 14-membered heterocycloalkyl; Preferably, R1, R2, R3, and R4 are the same or different and are independently selected from: hydrogen, C 1-10 Alkyl, C 2-10 Alkenyl, C 2-10 Alkynyl, C 6-10 Aryl, 5 to 10 membered heteroaryl; or, R1, R2 and the carbon atom to which they are attached form a C 3-10 Cycloalkyl, 3 to 10 membered heterocycloalkyl; or, R3, R4 and the carbon atom to which they are attached form C 3-10 Cycloalkyl, 3- to 10-membered heterocycloalkyl; Preferably, R1, R2, R3, and R4 are the same or different, and are independently selected from: H, methyl, ethyl, propyl, butyl, phenyl, naphthyl, vinyl, propenyl, butenyl, pentenyl, ethynyl, propynyl, butynyl; or, R1, R2 and the carbon atoms connected thereto form cyclopentyl, cyclohexyl, or cycloheptyl; or, R3, R4 and the carbon atoms connected thereto form cyclopentyl, cyclohexyl, or cycloheptyl.

3. The metal organic compound according to claim 1 or 2, characterized in that: R5, R6, R9, R 10 The same or different, each independently selected from: hydrogen, halogen, C 1-14 Alkyl, C 1-14 Alkoxy; preferably, R5, R6, R9, R 10 The same or different, each independently selected from: hydrogen, halogen, C 1-10 Alkyl, C 1-10 Alkoxy; preferably, R5, R6, R9, R 10 All are hydrogen; and / or, R7 and R8 are the same or different and are independently selected from: hydrogen, halogen, C 1-14 Alkyl, C 1-14 Alkoxy; or, R7, R8 and the carbon atom on the pyridine ring form a C 6-14 Aryl, 5 to 14 membered heteroaryl; preferably, R7, R8 are the same or different and are independently selected from: hydrogen, halogen, C 1-10 Alkyl, C 1-10 Alkoxy; or, R7, R8 and the carbon atom on the pyridine ring form a C 6-10 Aryl, 5- to 10-membered heteroaryl; preferably, R7 and R8 are both hydrogen; preferably, R7, R8 and the carbon atom on the pyridine ring form phenyl or naphthyl.

4. The metal organic compound according to any one of claims 1 to 3, characterized in that When M is Hf, X1 and X2 are -CH2-phenyl; preferably, R1, R2, R3 and R4 are selected from phenyl; preferably, R1, R2 and the carbon atoms connected thereto form a cyclohexyl group, and R3, R4 and the carbon atoms connected thereto form a cyclohexyl group; preferably, R7, R8 and the carbon atoms on the pyridine ring form a phenyl group; and / or, when M is Ti, X1 and X2 are methyl groups; preferably, R1 and R3 are selected from phenyl groups, and R2 and R4 are selected from butenyl groups; preferably, R1, R2, R3 and R4 are selected from methyl groups; preferably, R1, R2 and the carbon atoms connected thereto form a cyclohexyl group, and R3, R4 and the carbon atoms connected thereto form a cyclohexyl group; preferably, R7 and R8 form a phenyl group with the carbon atoms on the pyridine ring; And / or, when M is Zr, X1 and X2 are methyl groups; preferably, R1 and R3 are selected from phenyl groups, and R2 and R4 are selected from methyl groups; preferably, R1 and R3 are selected from phenyl groups, and R2 and R4 are selected from hydrogen groups; preferably, R1, R2, R3 and R4 are selected from methyl groups; preferably, R7 and R8 form a phenyl group with the carbon atoms on the pyridine ring.

5. The metal organic compound according to any one of claims 1 to 4, characterized in that The bipyridine-containing metal organic compound is selected from any one of the following compounds:

6. A method for preparing a bipyridine-containing metal compound represented by formula (I) according to any one of claims 1 to 5, the method comprising the following steps: The compound represented by formula (I-1) reacts with compounds X1-M0-X0 and X2-M0-X0 to obtain a bipyridine-containing metal compound represented by formula (I); The reaction formula is as follows: Among them, M, X1, X2, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Having the definition of any one of claims 1 to 5; X is selected from halogen, C 1-10 alkyl; X0 is selected from halogen, C 1-10 alkyl; M0 is selected from alkali metals.

7. A catalyst composition, comprising a bipyridine-containing metal organic compound represented by formula (I) according to any one of claims 1 to 5 and an activator; Preferably, the molar ratio of the bipyridine-containing metal organic compound to the activator is 1:5 to 1000; Preferably, the activator contains aluminum and / or boron; Preferably, the activator containing aluminum element is substituted or unsubstituted C 1-20 Alkyl aluminum compounds, C 6-20 Aryl aluminum compounds, C 1-20 Aluminoxane, C 6-20 Aryl aluminoxanes; Preferably, the boron element is introduced by borate; preferably, the cations in the borate are lithium ions, sodium ions, potassium ions, carbon ions, and ammonium cations; preferably, the anions in the borate are tetrafluoroboron anions, tetraphenylboron anions, tetrakis(4-fluorophenyl)boron anions, tetrakis(3.5-difluorophenyl)boron anions, tetrakis(4-fluoromethylphenyl)boron anions, tetrakis(pentafluorophenyl)boron anions, and tetrakis(3.5-dimethylphenyl)boron anions.

8. Use of the metal organic compound containing bipyridine represented by formula (I) according to any one of claims 1 to 5 and the catalyst composition according to claim 7 in the polymerization reaction of elastomers; Preferably, the elastomer is an olefin polymer; Preferably, the elastomer is an olefin polymer prepared by polymerization of an olefin reaction monomer with ethylene or propylene; preferably, the olefin reaction monomer is an α-olefin.

9. A method for polymerizing an elastomer, the polymerization reaction comprising: The elastomer reaction monomer is polymerized in the presence of the bipyridine-containing metal organic compound represented by formula (I) as described in any one of claims 1 to 5 or the catalyst composition as described in claim 7; Preferably, the elastomer reactive monomer is an olefin, such as an α-olefin; more preferably, the polymerization reaction is a copolymerization reaction of ethylene or propylene with an α-olefin; Preferably, the polymerization reaction temperature is 80 to 250°C; Preferably, the polymerization reaction pressure is 0.1 to 10 MPa; Preferably, the ratio of the elastomer reactive monomer to the bipyridine-containing metal organic compound represented by formula (I) is (10-1000):(1-10).

10. The elastomeric polymer prepared by the polymerization method according to claim 9; Preferably, the melting point of the elastomeric polymer is 30°C-180°C; Preferably, the weight average molecular weight M of the elastomeric polymer is w 10000-600000Da; Preferably, the ratio of the weight average molecular weight to the number average molecular weight of the elastomeric polymer is w / M n 1.5~4.0; Preferably, the melt index MI of the elastomeric polymer is 0.5 to 10 g / 10 min; Preferably, the mass fraction of the elastomer reactive monomer is 1.0%-10%.

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