5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complexes, and methods for preparing and using same

Abstract

The present invention relates to the technical field of olefin polymerization catalysts and discloses a 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complex, as well as its preparation and use. The structure of the complex of the present invention is shown in formula (I), where R7 to R 11 is selected from hydrogen, halogen, hydroxy, and substituted or unsubstituted C1-C15 hydrocarbon groups, and R2 and R3 are selected from halogen, C1-C10 hydrocarbon groups, P(R4)3, NR5R6, and OR 12 R 13 wherein R4 is selected from a substituted or unsubstituted C1 to C10 hydrocarbon group, and R5, R6, R 12 , and R 13 are selected from C1 to C6 hydrocarbon groups, or R5 and R6 are linked to N to form a 5-membered or 6-membered ring, or R 12 , R 13 is linked to O to form a 5- or 6-membered ring. The complex of the present invention has good thermal stability, relatively high ethylene polymerization activity at relatively high temperatures, and relatively high copolymerization properties with acrylate monomers, and the prepared polymers have relatively good properties. [Formula 1] TIFF2026505664000013.tif39169

Description

Detailed Description of the Invention

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of Chinese Patent Application No. 202310573961.0, filed on May 19, 2023, the contents of which are incorporated herein by reference.

[0002] [Technical Field] The present invention relates to the technical field of olefin polymerization catalysts, in particular to 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complexes, and methods for their preparation and use.

[0003] [Background technology] Polyethylene materials are widely used due to their excellent chemical resistance, low cost, ease of preparation, low density, and excellent mechanical properties. Late transition metal catalysts, in particular, have attracted widespread attention in the scientific research community due to their relatively high ethylene homopolymerization activity, good tolerance to polar groups, and the ability to directly copolymerize olefins with polar monomers under relatively mild conditions (see, for example, SD Ittel, Chem Rev, 2000, 100(4), 1169-1203; H. Mu, Coord Chem Rev, 2021, 435, 213802).

[0004] In 1995, Brookhart et al. reported an α-diimine Ni(II) complex capable of polymerizing ethylene with high activity. The cationic α-diimine palladium complex they developed successfully copolymerized ethylene or propylene with acrylates. The complex's unique "β-H elimination" and "chain walking" properties resulted in highly branched copolymers in which polar groups were mostly located at the chain ends (see, for example, M. Brookhart, J Am Chem Soc, 1996, 118(1), 267-268). In 2000, Grubbs et al. developed a salicylaldehyde imine neutral nickel catalyst with excellent heteroatom tolerance, which enabled the copolymerization of ethylene with functionalized norbornenes to form linear copolymers with high insertion yields (see, for example, R.H. Grubbs, Science, 2000, 287, 460-462). In 2002, Drent et al. reported that an electronically asymmetric neutral palladium phosphine sulfonate complex is another classic catalyst for ethylene homopolymerization / copolymerization (see, for example, E. Drent, Chem Commun, 2002, 7, 744-745), and that it can catalyze the copolymerization of ethylene with various simple industrial bulk polar monomers (e.g., acrylonitrile, vinyl acetate, acrylic acid, and acrylates) to form linear copolymers (see, for example, E. Drent, Chem. Commun. 2002, 7, 744-745). Several research groups, including Mecking, Nozaki, and Jordon, conducted detailed studies on the reaction behavior and catalytic mechanism of ethylene copolymerization initiated by this type of catalyst, further promoting the development of late transition metal catalysts.

[0005] However, the above catalysts have low ethylene polymerization activity when used at high temperatures, cannot directly homopolymerize with ethylene, and cannot coordinately copolymerize with acrylates. In addition, the preparation method is complicated and expensive.

[0006] Summary of the Invention [Problem to be solved by the invention] The present invention aims to overcome the problem of low ethylene polymerization activity at high temperatures associated with prior art catalysts and to provide a 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complex, as well as a preparation method and use thereof. The 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complex has good thermal stability, high ethylene polymerization activity at high temperatures, and good copolymerization properties with acrylate monomers, and the polymers prepared therefrom have good properties, such as narrow molecular weight distributions.

[0007] [Means for solving the problem] In order to achieve the above object, one aspect of the present invention provides a 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complex having a structural formula represented by formula (I). [ka] (M is selected from Group VIII metals, R to R 11 are each selected from hydrogen, halogen, hydroxy, and a substituted or unsubstituted C1-C15 hydrocarbon group; R2 and R3 are each selected from halogen, a C1-C10 hydrocarbon group, P(R4)3, NR5R6, and OR 12 R 13 is selected from wherein R4 is selected from substituted or unsubstituted C1 to C10 alkyl and substituted or unsubstituted C6 to C10 aryl; R5 and R6 are each selected from C1 to C10 hydrocarbon groups; or R5 and R6 are connected to N to form a 5- or 6-membered ring; 12 and R 13 are each selected from a C1 to C10 hydrocarbon group, or R 12 , R 13 are linked to each other to form a 5- or 6-membered ring.

[0008] A second aspect of the present invention provides a method for preparing a 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complex, the method comprising: (1) reacting a compound represented by formula (II) with a compound represented by formula (III) to obtain a ligand; (2) reacting the ligand with an M metal compound. [ka] wherein the metal M in said M metal compound is selected from Group VIII metals; In formula (III), X is a halogen, and R to R 11 are each selected from hydrogen, halogen, hydroxy, and a substituted or unsubstituted C1-C15 hydrocarbon group; R2 and R3 are each selected from halogen, a C1-C10 hydrocarbon group, P(R4)3, NR5R6, and OR 12 R 13 wherein R4 is selected from substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C10 aryl; R5 and R6 are each selected from C1-C10 hydrocarbon groups; or R5 and R6 are connected to N to form a 5- or 6-membered ring; 12 and R 13 are each selected from a C1 to C10 hydrocarbon group, or R 12 , R 13 are linked to each other to form a 5- or 6-membered ring. A third aspect of the present invention provides a method for olefin polymerization, comprising the step of carrying out an olefin polymerization reaction in the presence of the 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complex provided by the present invention.

[0009] According to the technical solution of the present invention, the 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complex has good thermal stability, relatively high ethylene polymerization activity at relatively high temperatures, and relatively high copolymerization properties with acrylate monomers, and the prepared polymer has relatively good properties such as narrow molecular weight distribution.

[0010] [Effects of the Invention] Compared with the prior art, the technical solution of the present invention has the following advantages: (1) The 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complexes described in the present invention can be synthesized in a simple manner, with high yields and low costs. (2) The 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complex described in the present invention can catalyze ethylene polymerization with high activity, has relatively high polymerization activity even at high temperatures, and can prepare linear polyethylene with adjustable relative molecular weight. (3) The 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complexes described in the present invention have relatively high copolymerization properties with acrylate monomers.

[0011] [Mode for Carrying Out the Invention] Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described herein are for the purpose of explaining and interpreting the present invention, and are not intended to limit the present invention.

[0012] The structural formula of the 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complex according to the present invention is shown in formula (I). [ka] (M is selected from Group VIII metals, R to R 11 are each selected from hydrogen, halogen, hydroxy, and a substituted or unsubstituted C1-C15 hydrocarbon group; R2 and R3 are each selected from halogen, a C1-C10 hydrocarbon group, P(R4)3, NR5R6, and OR 12 R 13 is selected from wherein R4 is selected from substituted or unsubstituted C1 to C10 alkyl and substituted or unsubstituted C6 to C10 aryl; R5 and R6 are each selected from C1 to C10 hydrocarbon groups; or R5 and R6 are connected to N to form a 5- or 6-membered ring; 12 and R 13 are each selected from a C1 to C10 hydrocarbon group, or R 12 , R 13 are linked to each other to form a 5- or 6-membered ring.

[0013] In a preferred embodiment, R to R 11 are each selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C15 alkyl, and substituted or unsubstituted C6-C15 aryl, and the substituents are selected from halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, or halogenated C1-C10 alkoxy.

[0014] In a preferred embodiment, M is nickel or palladium.

[0015] In a preferred embodiment, R2 and R3 are each a halogen, a C1-C8 hydrocarbon group, P(R4)3, NR5R6, or OR 12 R 13 wherein R4 is selected from substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C10 aryl; R5 and R6 are each selected from C1-C6 hydrocarbon groups; or R5 and R6 are connected to N to form a 5- or 6-membered ring; 12 and R 13 are each selected from a C1 to C6 hydrocarbon group, or R 12 , R 13 are linked together to O to form a 5- or 6-membered ring.

[0016] Preferably, at least one of R2 and R3 is selected from halogen or a C1-C10 hydrocarbon group.

[0017] In some embodiments, R2 and R3 are each selected from halogen and a C1-C10 hydrocarbon group (eg, C1-C10 alkyl or C6-C10 aryl).

[0018] In some other embodiments, R2 is selected from halogen or a C1-C8 hydrocarbon group (e.g., C1-C8 alkyl or C6-C8 aryl), and R3 is P(R4)3, NR5R6, or OR 12 R 13 wherein R4 is selected from substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C10 aryl; R5 and R6 are each selected from C1-C6 hydrocarbon groups; and R5 and R6 are connected to N to form a 5- or 6-membered ring; 12 and R 13 are each selected from a C1 to C10 hydrocarbon group, and R 12 , R 13 are linked together to O to form a 5- or 6-membered ring.

[0019] In a preferred embodiment, when R2 and R3 are each selected from P(R4)3, P(R4)3 may be PMe3, PPh3, or PEt3; when R2 and R3 are each selected from NR5R6, NR5R6 may be pyridine (C5H5N), 2-methylpyridine, 3-methylpyridine, or 4-methylpyridine; and when R2 and R3 are each selected from OR 12 R 13 If selected from OR 12 R 13 may be tetrahydrofuran (C4H8O), 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, or 2,2-dimethyltetrahydrofuran.

[0020] As used herein, "Me" refers to methyl, "Ph" refers to phenyl, and "Et" refers to ethyl.

[0021] In the present invention, the term "substituted" in "substituted or unsubstituted" means containing a substituent, and the substituent here may be selected from halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, or halogenated C1-C6 alkoxy.

[0022] In preferred cases, the C1-C6 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, or 3,3-dimethylbutyl.

[0023] In preferred cases, the C1-C6 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, isohexyloxy, or 3,3-dimethylbutoxy.

[0024] In the present invention, said halogen is selected from fluorine, chlorine, bromine or iodine.

[0025] In a more preferred embodiment, the 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complex is selected from the group consisting of the following complexes: Complex 1: A complex represented by formula (I) (wherein M is Ni and R7 to R 11 is H, R2 is methyl, and R3 is -NC5H5. Complex 2: A complex represented by formula (I) (wherein M is Ni and R7 to R 11 is H, R2 is phenyl, and R3 is PMe3. Complex 3: A complex represented by formula (I) (wherein M is Ni and R7 to R 11 is H, R2 is Cl, and R3 is -OC4H8. Complex 4: A complex represented by formula (I) (wherein M is Ni and R7 to R 11 is H, R2 is Br, and R3 is -OC4H8. Complex 5: A complex shown in formula (I) where M is Ni and R, R and R 10 is H, R8 is methyl, and R 11 is isopropyl, R2 is methyl, and R3 is -NC5H5. Complex 6: A complex shown in formula (I) where M is Ni and R, R and R 10 is H, R8 is methyl, and R 11 is isopropyl, R2 is phenyl, and R3 is PMe3. Complex 7: A complex shown in formula (I) (wherein M is Ni and R, R and R 10 is H, R8 is methyl, and R 11 is isopropyl, R2 is Cl, and R3 is -OC4H8. Complex 8: A complex shown in formula (I) (wherein M is Ni and R7, R9 and R 10 is H, R8 is methyl, and R 11 is isopropyl, R2 is Br, and R3 is -OC4H8. Complex 9: A complex represented by formula (I) (wherein M is Pd and R7 to R 11 is H, R2 is methyl, and R3 is -NC5H5. Complex 10: A complex represented by formula (I) (wherein M is Pd and R7 to R 11 is H, R2 is Cl, and R3 is PMe3. Complex 11: A complex as shown in formula (I) where M is Pd and R7, R9 and R 10 is H, R8 is methyl, and R 11 is isopropyl, R2 is methyl, and R3 is -NC5H5. Complex 12: A complex of formula (I) where M is Pd and R, R and R 10 is H, R8 is methyl, and R 11 is isopropyl, R2 is Cl, and R3 is PMe3.

[0026] The method for preparing the 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complex according to the present invention may include the following steps: (1) A compound represented by formula (II) is reacted with a compound represented by formula (III) to obtain a ligand represented by formula (IV). (2) The ligand is reacted with the M metal compound. [ka]

[0027] In formula (III), X is a halogen, particularly for example chlorine or bromine, most preferably chlorine.

[0028] In formula (III), R to R 11 The definition of is the same as above.

[0029] In the method according to the present invention, the metal M in said M metal compound is selected from the Group VIII metals, preferably nickel or palladium.

[0030] In a preferred embodiment, the M metal compound is dimethyldipyridine nickel (Py2NiMe2), bis(1,5-cyclooctadiene)nickel (Ni(COD)2), dichlorotetrakis(pyridine)nickel (Ni2Cl2Py4), nickel(II) bromide ethylene glycol dimethyl ether ((DME)NiBr2), nickel(II) chloride ethylene glycol dimethyl ether ((DME)NiCl2), dichlorobis(trimethylphosphine)nickel(II) (NiCl2(PMe3)2), bis(pyridine)bis[(trimethylsilyl)methyl]nickel (Ni(Py)2(CH2SiMe3)2), bromo(phenyl)(N,N,N',N'-tetramethyl-1,2-ethylenediamine)nickel (NiArBr(TMEDA)), dibenzyldipyridinenickel (Ni(CH2Ph)2Py2), phenyl(trimethylphosphine)nickel NiPhBr(PMe3)2), phenyl(triethylphosphine)nickel chloride (NiPhCl(PEt3)2), diphenylbis(trimethylphosphine)nickel (NiPh2(PMe3)2), dichlorobis(trimethylphosphine)nickel(II) (NiCl2(PMe3)2), dimethyldipyridinepalladium (Pd(Me)2Py2), dichlorodipyridinepalladium (PdCl2Py2), bis(pi and one or more selected from N,N,N',N'-tetramethyl-1,2-ethylenediamine)palladium ((TMEDA)PdMe2).

[0031] In the method according to the present invention, the reaction process of step (1) is shown in the following reaction scheme: [ka] (where X and R7 to R 11 The definitions are the same as above.)

[0032] In the method according to the present invention, the reaction process of step (2) is shown in the following reaction scheme: [ka] (Here, M, R2, R3, R7~R 11 The definitions are the same as above.)

[0033] In a preferred embodiment, the reaction of step (1) is carried out in the presence of a solvent. In a specific example, the solvent may be ethyl ether.

[0034] In a preferred embodiment, the reaction of step (2) is carried out in the presence of a reaction solvent. In a specific example, the reaction solvent may be toluene or tetrahydrofuran.

[0035] In a preferred embodiment, in step (2), the molar ratio of the M metal compound to the ligand is 1.1-1.3:1.

[0036] In a specific embodiment, the preparation process of step (1) includes dissolving the compound of formula (II) in anhydrous ethyl ether under a protective gas (e.g., nitrogen gas) atmosphere, adding n-BuLi (n-butyllithium) solution dropwise at -78°C, and gradually warming to room temperature after the reaction; then adding an anhydrous ethyl ether solution (ice-water bath) of the compound of formula (III) dropwise, slowly warming to room temperature, and reacting overnight with stirring; quenching with water, extracting the organic phase with anhydrous ethyl ether, concentrating the obtained organic phase, repeatedly freezing and deoxygenating, adding 15 mL of concentrated hydrochloric acid under a nitrogen gas atmosphere, and reacting; when the reaction is completed by TLC monitoring, adding aqueous NaHCO3 solution to neutralize, quenching with water, extracting the organic phase with anhydrous ethyl ether, drying with anhydrous MgSO4, filtering and concentrating, and obtaining the ligand of formula (IV) by column chromatography.

[0037] In a specific embodiment, the preparation process of step (2) involves dissolving the ligand obtained in step (1) and the M metal compound in a reaction solvent (e.g., toluene, tetrahydrofuran, etc.) in a protective gas (e.g., nitrogen gas) atmosphere, then mixing the ligand solution and the M metal compound solution by stirring and reacting at room temperature for 8 to 10 hours, filtering, concentrating the filtrate, and adding heptane for recrystallization to obtain the 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complex described in the present invention.

[0038] The present invention also provides a method for polymerizing olefins, comprising the step of carrying out an olefin polymerization reaction in the presence of the 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complex provided by the present invention.

[0039] In the olefin polymerization process according to the present invention, the olefin polymerization reaction may be homopolymerization or copolymerization.

[0040] In some embodiments, the polymerized monomer is ethylene. In this embodiment, the olefin polymerization reaction is the homopolymerization of ethylene.

[0041] In some other embodiments, the polymerizable monomers include ethylene and an α-olefin. In this embodiment, the olefin polymerization reaction is a copolymerization reaction. The α-olefin may be a C3 to C16 α-olefin, specifically, but not limited to, at least one selected from propylene, butene, pentene, hexene, octene, and 4-methylpentene-1. Optionally, the α-olefin may have one or more polar functional groups, and the polar functional groups may be, for example, hydroxy, carboxy, or ester groups.

[0042] In some other embodiments, the polymerized monomers include ethylene and an acrylate monomer. In this embodiment, the olefin polymerization reaction is a copolymerization reaction. The acrylate monomer has the general formula CH═C(R 31 )CO2(R 32 ), where R 31 may be H or a C1-C10 hydrocarbon group, and may have a branched chain, a ring, and / or an unsaturated bond; R 32 may be a C1 to C30 hydrocarbon group, which may have a branched chain, a ring, and / or an unsaturated bond, and R 32 may contain heteroatoms at any position thereof.

[0043] R 31 If the number of carbon atoms in R is 11 or more, the polymerization activity tends to be low. 31 is H or a C1 to C10 hydrocarbon group. 31 is H or a C1 to C5 hydrocarbon group. More preferably, R 31 is H or methyl.

[0044] Similarly, R 32 If the number of carbon atoms in R is greater than 30, the polymerization activity tends to be low. 32 The number of carbon atoms is 1 to 30, preferably 1 to 12, and more preferably 1 to 8.

[0045] Furthermore, R 32 The heteroatom optionally contained in may be selected from oxygen, sulfur, selenium, phosphorus, nitrogen, silicon, fluorine, boron, etc. Among these heteroatoms, oxygen, silicon, and fluorine are preferred, and oxygen is more preferred. In addition, R which does not contain a heteroatom 32 is also preferred.

[0046] More preferably, specific examples of the acrylate monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, and benzyl (meth)acrylate. , hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-aminoethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, glycidyl (meth)acrylate, ethylene oxide (meth)acrylate, trifluoromethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, perfluoroethyl (meth)acrylate, (meth)acrylamide, (meth)acryloyldimethylamide, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. The above acrylate monomers may be used alone or in combination.

[0047] In the olefin polymerization method described in the present invention, the temperature of the olefin polymerization reaction may be -78°C to 200°C, and preferably -20°C to 150°C. The 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complex described in the present invention has relatively high polymerization activity even at high temperatures, and therefore the olefin polymerization method of the present invention is particularly suitable for olefin polymerization reactions at high temperatures. In some embodiments, the temperature of the olefin polymerization reaction is 30 to 100°C, and preferably 70 to 100°C.

[0048] In the olefin polymerization method according to the present invention, the polymerization pressure of the olefin polymerization reaction may be 0.01 to 10 MPa, and is preferably 0.01 to 5 MPa.

[0049] In the olefin polymerization method according to the present invention, the polymerization reaction time of the olefin polymerization reaction may be 5 to 60 minutes.

[0050] In the present invention, the "polymerization pressure" refers to the ethylene pressure in the polymerization system, and is expressed as an absolute pressure.

[0051] In the olefin polymerization method according to the present invention, the polymerization is carried out in a solvent containing the polymerizable monomers. The polymerization solvent may be one or more selected from alkanes, aromatic hydrocarbons, and halogenated hydrocarbons. In a preferred case, the polymerization solvent may be one or more selected from hexane, pentane, heptane, benzene, toluene, dichloromethane, chloroform, and ethylene dichloride, and more preferably one or more selected from hexane, toluene, and heptane.

[0052] As used herein, alkyl refers to straight chain alkyl, branched alkyl, or cycloalkyl, including, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, and 4-n-butylcyclohexyl.

[0053] In the present invention, examples of aryl include, but are not limited to, phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, and vinylphenyl.

[0054] As used herein, alkenyl refers to straight chain alkenyl, branched chain alkenyl, or cycloalkenyl, including, but not limited to, vinyl, allyl, butenyl, and the like.

[0055] In the present invention, examples of aralkyl include, but are not limited to, phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-isopropyl, phenyl-n-butyl, phenyl-t-butyl, and the like.

[0056] In the present invention, examples of alkylaryl include, but are not limited to, tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, tert-butylphenyl, and the like.

[0057] The following examples further illustrate the phosphine-phenol late transition metal complexes according to the present invention, as well as their preparation methods and uses. These examples are carried out on the basis of the technical concept of the present invention, and provide detailed embodiments and specific operation processes, but the scope of protection of the present invention is not limited to the following examples.

[0058] Unless otherwise specified, all experimental methods in the following examples are conventional methods in the art, and all experimental materials used in the following examples are commercially available unless otherwise specified.

[0059] The analytical property evaluation instruments and test methods used in the following examples and comparative examples are as follows: (1) Nuclear magnetic resonance spectrometer: Avance III HD 500 (500 MHz), tetramethylsilane (TMS) was used as the internal standard. (2) Molecular weight and molecular weight distribution (PDI) of polymer (PDI = Mw / Mn): Measured using a PL-GPC220 chromatograph at 150°C using trichlorobenzene as the solvent (standard sample: PS, flow rate: 1.0 mL / min, chromatographic column: 3 x PLgel 10 um M1 x ED-B, 300 x 7.5 nm). (3) Activity measurement method: The polymer was washed with a hydrochloric acid ethanol solution, dried in vacuum, and the weight of the polymer was measured, and the polymerization activity was calculated as follows: polymer weight (g) / metal (mol)×60 / polymerization time (min). (4) Analysis of comonomer content in polymer: 1 H NMR and 13 C NMR spectra were examined by dissolving polymer samples in 1,2,4-trichlorobenzene at 120 °C and analyzing them using a 400 MHz Bruker Avance 400 NMR spectrometer with a 10 mm PASEX13 probe.

[0060] Example 1 Complex 1: A complex represented by formula (I) (wherein M is Ni and R7 to R 11 is H, R2 is methyl, and R3 is -NC5H5. In a nitrogen gas atmosphere, the compound represented by formula (II) (2.32 g, 10 mmol) was dissolved in anhydrous ethyl ether (20 mL), and n-butyllithium solution (2.7 M, 4.0 mL, 11 mmol) was added dropwise at -78°C. The reaction mixture was gradually warmed to room temperature and stirred for 12 hours to obtain a white precipitate. Dicyclohexylchlorophosphine (10 mmol, 2.32 g) was uniformly dispersed in 10 mL of anhydrous ethyl ether, and the mixture was added dropwise to the original reaction mixture in an ice-water bath. The mixture was then slowly warmed to room temperature. The mixture was heated to room temperature, stirred overnight, quenched with water, and the organic phase was extracted with anhydrous ethyl ether. The resulting organic phase was concentrated, frozen, and repeatedly deoxygenated. 5 mL of concentrated hydrochloric acid was added under a nitrogen atmosphere and the reaction was continued for 5 hours. When the reaction was complete as monitored by TLC, an aqueous solution of NaHCO3 was added to neutralize the mixture, quenched with water, and the organic phase was extracted with anhydrous ethyl ether. The mixture was then dried over anhydrous MgSO4, filtered, concentrated, and purified by column chromatography to obtain ligand L1 in a 31% yield. 1H NMR (500 MHz,CDCl3,TMS): δ 11.65 (s,0.9H),6.72-6.68 (m,1H),6.58-6.56 (m,1H),2.74-2.72 (t,J = 5.8 Hz,2H),2.65-2.63 (t,J = 6.3 Hz, 2H), 2.06-1.96 (m, 4H), 1.86-1.68 (m, 12H), 1.45-1.13 (m, 10H). 13 C NMR (126 MHz,CDCl3) δ 163.26,143.18,143.16,126.63,126.58, 125.86,125.79,119.39,119.30,104.10,103.39,77.28,77.03,76.77,36.01,35.49,29. 98,26.41,26.31,26.27,26.17,25.76,25.27,25.25,24.10,24.08,22.78,22.59,22.54. 31 P NMR (202 MHz, CDCl3) δ 60.52. Ligand L1 (0.517 g, 1.5 mmol) and the nickel metal source (PyNiMe) (0.366 g, 1.5 mmol) were dissolved in toluene (10 mL) under a nitrogen gas atmosphere. The ligand solution was then added dropwise to the nickel metal source solution, vigorously stirred, and reacted at room temperature for 10 h. The reaction mixture was filtered to obtain a brown solution. The solvent was concentrated and the solution was frozen at -30 °C for crystallization, yielding complex 1 in 72% yield. 31 P NMR (202 MHz, CDCl3) δ 60.61. Elemental analysis test C 28 H 40 NNiOP: Theoretical calculation: C, 67.76; H, 8.12; N, 2.82; Measured: C, 67.45; H, 8.42; N, 2.67. A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While hot, the mixture was evacuated and replaced with N2 gas three times. 500mL of toluene was poured into the polymerization kettle, and 5.0mg (10µmol) of complex 1 was added. The reaction was carried out at 70°C with vigorously stirring for 30 minutes while maintaining an ethylene pressure of 10atm. The mixture was then neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed to determine its polymerization activity. The test data for the weight average molecular weight, molecular weight distribution, polymerization activity, and copolymerization monomer content of the obtained polymer are shown in Table 1.

[0061] Example 2 Complex 1: A complex represented by formula (II) (wherein M is Ni and R7 to R 11 is H, R2 is methyl, and R3 is -NC5H5. A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While hot, the mixture was evacuated and replaced with N2 gas three times. 500mL of toluene was poured into the polymerization kettle, and 5.0mg (10µmol) of complex 1 was added. The ethylene pressure was maintained at 80°C and 10atm. The reaction was carried out with vigorous stirring for 30 minutes. The mixture was then neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed to determine its polymerization activity. The test data for the weight average molecular weight, molecular weight distribution, polymerization activity, and copolymerization monomer content of the obtained polymer are shown in Table 1.

[0062] Example 3 Complex 1: A complex represented by formula (II) (wherein M is Ni and R7 to R 11 is H, R2 is methyl, and R3 is -NC5H5. A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While hot, the mixture was evacuated and replaced with N2 gas three times. 500mL of toluene was poured into the polymerization kettle, and 5.0mg (10µmol) of complex 1 was added. The ethylene pressure was maintained at 100°C and 10atm. The reaction was carried out with vigorous stirring for 30 minutes. The mixture was then neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed to determine its polymerization activity. The test data for the weight average molecular weight, molecular weight distribution, polymerization activity, and copolymerization monomer content of the obtained polymer are shown in Table 1.

[0063] Example 4 Complex 1: A complex represented by formula (II) (wherein M is Ni and R7 to R 11 is H, R2 is methyl, and R3 is -NC5H5. A 100 mL stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130 °C for 6 h. While hot, the kettle was evacuated and replaced with N2 gas three times. 50 mL of toluene and 0.45 mL (5 mmol) of methyl acrylate were added to the polymerization kettle, and 5.0 mg (10 μmol) of complex 1 were added. The reaction was carried out at 70 °C with 15 atm of ethylene pressure and vigorously stirred for 60 min. The reaction was then neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain an ethylene-acrylate copolymer. The polymer was dried and weighed to determine its polymerization activity. The test data for the weight average molecular weight, molecular weight distribution, polymerization activity, and copolymerization monomer content of the obtained polymer are shown in Table 1.

[0064] Example 5 Complex 1: A complex represented by formula (II) (wherein M is Ni and R7 to R 11 is H, R2 is methyl, and R3 is -NC5H5. A 100 mL stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130 °C for 6 h. While hot, the kettle was evacuated and replaced with N2 gas three times. 50 mL of toluene and 0.72 mL (5 mmol) of butyl acrylate were added to the polymerization kettle, and 5.0 mg (10 μmol) of complex 1 were added. The reaction was carried out at 70 °C with 15 atm of ethylene pressure and vigorously stirred for 60 min. The reaction was then neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain an ethylene-acrylate copolymer. The polymer was dried and weighed to determine its polymerization activity. The test data for the weight average molecular weight, molecular weight distribution, polymerization activity, and copolymerization monomer content of the obtained polymer are shown in Table 1.

[0065] Example 6 Complex 4: A complex represented by formula (I) (wherein M is Ni and R7 to R 11 is H, R2 is Br, and R3 is -OC4H8. Ligand L1 was prepared according to the method of Example 1. In a nitrogen gas atmosphere, ligand L1 (0.688 g, 2 mmol) was dissolved in tetrahydrofuran, and excess NaH (0.072 g, 3 mmol) was added. The mixture was stirred at room temperature for 10 hours. The NaH was removed by filtration, and a solution of NiBr2 (0.617 g, 2 mmol) in tetrahydrofuran (DME) was added dropwise. The mixture was allowed to react overnight at room temperature. The solvent was then vacuum-dried, and the mixture was dissolved in dichloromethane (40 mL). The mixture was filtered to remove the filter cake. The filtrate was concentrated and recrystallized with heptane to obtain complex 4 in a 72% yield. Elemental analysis test C 26 H 40 BrNiO2P: Theoretical calculation: C, 56.35; H, 7.28; Tested values: C, 56.74; H, 7.41. A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While hot, the mixture was evacuated and replaced with N2 gas three times. 500mL of toluene was poured into the polymerization kettle, and 5.5mg (10µmol) of complex 4 was added. The ethylene pressure was maintained at 30°C and 10atm. The reaction was carried out with vigorous stirring for 30 minutes. The mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed to determine its polymerization activity. The test data for the weight average molecular weight, molecular weight distribution, polymerization activity, and copolymerization monomer content of the obtained polymer are shown in Table 1.

[0066] Example 7 Complex 4: A complex represented by formula (I) (wherein M is Ni and R7 to R 11 is H, R2 is Br, and R3 is -OC4H8. A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While hot, the mixture was evacuated and replaced with N2 gas three times. 500mL of toluene was poured into the polymerization kettle, and 5.5mg (10µmol) of complex 4 was added. The ethylene pressure was maintained at 80°C and 10atm. The reaction was carried out with vigorous stirring for 30 minutes. The mixture was then neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed to determine its polymerization activity. The test data for the weight average molecular weight, molecular weight distribution, polymerization activity, and copolymerization monomer content of the obtained polymer are shown in Table 1.

[0067] Example 8 Complex 4: A complex represented by formula (I) (wherein M is Ni and R7 to R 11 is H, R2 is Br, and R3 is -OC4H8. A 100 mL stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130 °C for 6 h. While hot, the kettle was evacuated and replaced with N2 gas three times. 50 mL of toluene and 0.45 mL (5 mmol) of methyl acrylate were added to the polymerization kettle, and 5.5 mg (10 μmol) of complex 4 were added. The reaction was carried out at 70 °C, maintaining an ethylene pressure of 15 atm, with vigorous stirring for 60 min. The reaction was then neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain an ethylene-acrylate copolymer. The polymer was dried and weighed to determine its polymerization activity. The test data for the weight average molecular weight, molecular weight distribution, polymerization activity, and copolymerization monomer content of the obtained polymer are shown in Table 1.

[0068] Example 9 Complex 11: A complex represented by formula (I) (wherein M is Pd and R7 to R 11 is H, R2 is methyl, and R3 is -NC5H5. Ligand L1 was prepared according to the method of Example 1. In a nitrogen gas atmosphere, ligand L1 (0.688 g, 2 mmol) was dissolved in toluene (20 mL), and the metal palladium source (TMEDA) PdMe2 (0.51 g, 2 mmol) was dissolved in toluene (15 mL). The ligand solution was then added dropwise to the metal palladium source solution, vigorously stirred, and reacted at room temperature for 5 h. 0.6 mL of pyridine was added, and the reaction was allowed to proceed overnight. The mixture was filtered to obtain a black solution, and the solvent was removed under vacuum to obtain complex 11 in a 77% yield. Elemental analysis test C 28 H 40 NOPPd: Theoretical calculated values: C, 61.82; H, 7.41; N, 2.57; Tested values: C, 62.03; H, 7.58; N, 2.36. A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While hot, the mixture was evacuated and replaced with N2 gas three times. 500mL of toluene was poured into the kettle, and 5.4mg (10µmol) of complex 11 and 40µmol of B(C6F5)3 were added. The mixture was heated to 80°C under an ethylene pressure of 10atm and reacted for 30 minutes with vigorous stirring. The mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed to determine its polymerization activity. The test data for the weight average molecular weight, molecular weight distribution, polymerization activity, and copolymerization monomer content of the obtained polymer are shown in Table 1.

[0069] Comparative Example 1 A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While hot, the kettle was evacuated and replaced with N2 gas three times. 500mL of toluene was poured into the kettle. 5.0mL of methylaluminoxane (MAO) (1.53mol / L toluene solution) and 5.1mg (10µmol) of Complex A (Chem Cat Chem 2022, 14, e202101736) were then added. The mixture was heated to 80°C under an ethylene pressure of 10atm and reacted for 30 minutes with vigorous stirring. The mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed to determine its polymerization activity. The test data for the weight average molecular weight, molecular weight distribution, polymerization activity, and copolymerization monomer content of the resulting polymer are shown in Table 1. [ka]

[0070] Comparative Example 2 A 100 mL stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While hot, the kettle was evacuated and replaced with N2 gas three times. 50 mL of toluene and 0.45 mL (5 mmol) of methyl acrylate were added to the polymerization kettle, and 5.1 mg (10 μmol) of complex A were added. The reaction was carried out at 70°C, maintaining an ethylene pressure of 15 atm, and vigorously stirred for 60 minutes. The reaction was then neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain an ethylene-acrylate copolymer. The polymer was dried and weighed to determine its polymerization activity. The test data for the weight-average molecular weight, molecular weight distribution, polymerization activity, and copolymerization monomer content of the obtained polymer are shown in Table 1.

[0071] Comparative Example 3 Complex B was prepared according to the method disclosed in patent application CN102197040A. [ka] A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While hot, the kettle was evacuated and replaced with N2 gas three times. 500mL of toluene was poured into the polymerization kettle, and 6.2mg (10µmol) of complex B was added. The ethylene pressure was maintained at 80°C and 10atm. The reaction was carried out with vigorously stirring for 30 minutes. The reaction was then neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed to determine its polymerization activity. The test data for the weight average molecular weight, molecular weight distribution, polymerization activity, and copolymerization monomer content of the obtained polymer are shown in Table 1.

[0072] [Table 1]

[0073] Table 1 shows that the 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complexes described in the present invention have relatively high polymerization activity at relatively high temperatures, and the polymers prepared have excellent properties. Specifically, comparing Examples 1 to 3, 6 to 7, and 9 with Comparative Examples 1 and 3, it was found that the complexes according to the present invention have significantly high ethylene polymerization activity, and the polyethylenes prepared have significantly high molecular weights and narrow molecular weight distributions. Comparing Examples 4 to 5 and 8 with Comparative Example 2, it was found that the complexes according to the present invention have significantly high copolymerization activity with acrylate monomers, and the copolymers prepared have significantly high molecular weights and narrow molecular weight distributions.

[0074] Although the preferred embodiments of the present invention have been described in detail above, the present invention is not limited thereto, and various simple modifications can be made to the technical solutions of the present invention, including combining each technical feature in any other appropriate manner within the scope of the technical concept of the present invention, and these simple modifications and combinations should also be considered as the disclosure content of the present invention, and all fall within the protection scope of the present invention.

Claims

1. A 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complex, characterized in that the structural formula is represented by formula (I). 【Chemistry 1】 (M is selected from Group VIII metals, R ７ ~R １１ are each selected from hydrogen, halogen, hydroxy, and a substituted or unsubstituted C1 to C15 hydrocarbon group; R ２ and R ３ are halogen, C1-C10 hydrocarbon group, P(R ４ ) ３ , N.R. ５ R ６ , and OR １２ R １３ is selected from Here, R ４ is selected from substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C10 aryl; R ５ and R ６ are each independently selected from a C1 to C10 hydrocarbon group, or R ５ , R ６ are linked to N to form a 5- or 6-membered ring, and R １２ and R １３ are each independently selected from a C1 to C10 hydrocarbon group, or R １２ , R １３ are linked to each other with O to form a 5- or 6-membered ring.

2. 2. The 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complex according to claim 1, wherein M is nickel or palladium.

3. R ７ ~R １１ are each selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1 to C15 alkyl, and substituted or unsubstituted C6 to C15 aryl, and the substituents are selected from halogen, hydroxy, C1 to C10 alkyl, halogenated C1 to C10 alkyl, C1 to C10 alkoxy, and halogenated C1 to C10 alkoxy.

4. R ２ and R ３ are halogen, C1 to C8 hydrocarbon group, P(R ４ ) ３ , N.R. ５ R ６ , or OR １２ R １３ where R ４ is selected from substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C10 aryl; R ５ and R ６ are each selected from a C1 to C6 hydrocarbon group, or R ５ , R ６ are linked to N to form a 5- or 6-membered ring, and R １２ and R １３ are each selected from a C1 to C6 hydrocarbon group, or R １２ , R １３ are linked to each other with O to form a 5-membered ring or a 6-membered ring.

5. 5. The 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complex according to claim 1, which is selected from the group consisting of the following complexes: Complex 1: A complex of formula (I) where M is Ni and R ７ ~R １１ is H and R ２ is methyl, and R ３ Ha-NC ５ H ５ It is.) Complex 2: A complex of formula (I) where M is Ni and R ７ ~R １１ is H and R ２ is phenyl, and R ３ is PMe ３ It is.) Complex 3: A complex of formula (I) where M is Ni and R ７ ~R １１ is H and R ２ is Cl, and R ３ Ha-OC ４ H ８ It is.) Complex 4: A complex of formula (I) where M is Ni and R ７ ~R １１ is H and R ２ is Br, and R ３ Ha-OC ４ H ８ It is.) Complex 5: A complex of formula (I) where M is Ni and R ７ , R ９ and R １０ is H and R ８ is methyl, and R １１ is isopropyl, and R ２ is methyl, and R ３ Ha-NC ５ H ５ It is.) Complex 6: A complex of formula (I) where M is Ni and R ７ , R ９ and R １０ is H and R ８ is methyl, and R １１ is isopropyl, and R ２ is phenyl, and R ３ is PMe ３ It is.) Complex 7: A complex of formula (I) where M is Ni and R ７ , R ９ and R １０ is H and R ８ is methyl, and R １１ is isopropyl, and R ２ is Cl, and R ３ Ha-OC ４ H ８ It is.) Complex 8: A complex of formula (I) where M is Ni and R ７ , R ９ and R １０ is H and R ８ is methyl, and R １１ is isopropyl, and R ２ is Br, and R ３ Ha-OC ４ H ８ It is.) Complex 9: A complex of formula (I) where M is Pd and R ７ ~R １１ is H and R ２ is methyl, and R ３ Ha-NC ５ H ５ It is.) Complex 10: A complex of formula (I) where M is Pd and R ７ ~R １１ is H and R ２ is Cl, and R ３ is PMe ３ It is.) Complex 11: A complex of formula (I) where M is Pd and R ７ , R ９ and R １０ is H and R ８ is methyl, and R １１ is isopropyl, and R ２ is methyl, and R ３ Ha-NC ５ H ５ It is.) Complex 12: A complex of formula (I) where M is Pd and R ７ , R ９ and R １０ is H and R ８ is methyl, and R １１ is isopropyl, and R ２ is Cl, and R ３ is PMe ３ It is.)

6. (1) reacting a compound represented by formula (II) with a compound represented by formula (III) to obtain a ligand; (2) A method for preparing a 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complex, comprising the step of reacting the ligand with an M metal compound. 【Chemistry 2】 wherein the metal M in said M metal compound is selected from Group VIII metals; In formula (III), X is a halogen and R ７ ~R １１ are each selected from hydrogen, halogen, hydroxy, and a substituted or unsubstituted C1 to C15 hydrocarbon group; R ２ and R ３ are halogen, C1-C10 hydrocarbon group, P(R ４ ) ３ , N.R. ５ R ６ , and OR １２ R １３ where R ４ is selected from substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C10 aryl; R ５ and R ６ are each selected from a C1 to C10 hydrocarbon group, or R ５ , R ６ are linked to N to form a 5- or 6-membered ring, and R １２ and R １３ are each selected from a C1 to C10 hydrocarbon group, or R １２ , R １３ are linked to each other with O to form a 5- or 6-membered ring.

7. 7. The method of claim 6, wherein the metal M is nickel or palladium.

8. The M metal compounds include dimethyldipyridine nickel, bis(1,5-cyclooctadiene)nickel, dichlorotetrakis(pyridine)nickel, nickel(II) bromide ethylene glycol dimethyl ether, nickel(II) chloride ethylene glycol dimethyl ether, dichlorobis(trimethylphosphine)nickel(II), bis(pyridine)bis[(trimethylsilyl)methyl]nickel, bromo(phenyl)(N,N,N',N'-tetramethyl-1,2-ethylenediamine)nickel, dibenzyldipyridine nickel, and phenyl(trimethylphosphine)nickel bromide.

8. The method of claim 7, wherein the palladium compound is one or more selected from the group consisting of phenyl(triethylphosphine)nickel chloride, diphenylbis(trimethylphosphine)nickel, dichlorobis(trimethylphosphine)nickel(II), dimethyldipyridinepalladium, dichlorodipyridinepalladium, bis(pyridine)bis[(trimethylsilyl)methyl]palladium, dibenzyldipyridinepalladium, methyl-1,5-cyclooctadienepalladium chloride, and dimethyl(N,N,N',N'-tetramethyl-1,2-ethylenediamine)palladium.

9. The method according to any one of claims 6 to 8, wherein the reaction in step (2) is carried out in the presence of a reaction solvent, and the reaction solvent is toluene and / or tetrahydrofuran.

10. 1. A process for olefin polymerization comprising: The method for olefin polymerization, comprising a step of carrying out an olefin polymerization reaction in the presence of the 5,6,7,8-tetrahydro-1-naphthol-phosphine late transition metal complex according to any one of claims 1 to 5.

11. 11. The method of claim 10, wherein the olefin polymerization reaction is a homopolymerization or copolymerization.

12. 12. The method of claim 10 or 11, wherein the polymerized monomer is ethylene.

13. 12. The method of claim 10 or 11, wherein the polymerized monomers include ethylene and an α-olefin.

14. 12. The method of claim 10 or 11, wherein the polymerized monomers include ethylene and acrylate monomers.

15. Examples of the acrylate monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, and hydroxyethyl (meth)acrylate. , dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-aminoethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, glycidyl (meth)acrylate, ethylene oxide (meth)acrylate, trifluoromethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, perfluoroethyl (meth)acrylate, (meth)acrylamide, (meth)acryloyldimethylamide, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

16. 16. The method according to any one of claims 10 to 15, wherein the temperature of the olefin polymerization reaction is from 30 to 100°C.

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