Phosphine-phenol late transition metal complexes, and methods for their preparation and use - Patent Application 20070122997

Abstract

The present invention relates to the technical field of olefin polymerization catalysts and discloses a phosphine-phenol late transition metal complex, as well as a method for preparing and using the same. The structural formula of the phosphine-phenol late transition metal complex is shown in formula (I), wherein R1 is selected from substituted or unsubstituted C1-C20 hydrocarbyl, R3 and R4 are each independently selected from halogen, C1-C10 hydrocarbyl, -P(R5) 3、 wherein R5 is a substituted or unsubstituted C1-C10 alkyl or aryl, R6, R7, R8, and R9 are each independently selected from C1-C10 hydrocarbyl, and R6 and R7, and R8 and R9 are optionally interconnected to form a 5- or 6-membered ring. Under similar polymerization conditions, by using the metal complex of the present invention as an olefin polymerization catalyst, higher homopolymerization / copolymerization activity can be achieved, and the resulting polymers have obviously higher molecular weights and narrower molecular weight distributions. [Formula 1] JPEG2025535088000015.jpg59169

Description

Detailed Description of the Invention

[0001] [Technical field] The present invention relates to the technical field of olefin polymerization catalysis, and in particular to phosphine-phenol late transition metal complexes, as well as methods for their preparation and use.

[0002] [Background technology] Polyolefin resins are widely used in industry and daily life due to their environmental friendliness compared to other resin materials. Polyethylene resins are an important polyolefin resin. Industrialized polyethylene catalysts include Ziegler-Natta catalysts (e.g., DE Pat. 889229 (1953); IT Pat. 545332 (1956) and IT Pat. 536899 (1955); Chem. Rev., 2000, 100, 1169 and related literature in the special feature), Phillips catalysts (e.g., Belg. Pat. 530617 (1955); Chem. Rev. 1996, 96, 3327), and metallocene catalysts (e.g., W. Kaminsky, Metalorganic Catalysts for Synthesis and Polymerization, Berlin: Springer, 1999). Highly efficient ethylene oligomerization and polymerization catalysts based on late transition metal complexes have also been rapidly developed in recent years. For example, in 1995, Brookhart et al. reported a type of α-diimine Ni(II) complex capable of polymerizing ethylene with high activity. However, this type of catalyst apparently exhibits "chain walking," resulting in highly branched polymers. Furthermore, neutral palladium phosphine sulfonate complexes are also classic catalysts for ethylene homopolymerization / copolymerization, and have attracted widespread attention since their first report by Pugh's research group in 2002. Research groups including Mecking, Nozaki, and Jordon have conducted detailed studies on the ethylene copolymerization reaction behavior and catalytic mechanism initiated by this type of catalyst, further promoting the development of late transition metal catalysts.

[0003] Existing ethylene gas-phase polymerization processes typically require polymerization temperatures of 85°C or higher, while ethylene solution polymerization processes typically require polymerization temperatures of 130 to 250°C. Therefore, to meet the requirements of existing gas-phase and solution ethylene polymerization equipment, it is necessary to develop late transition metal catalysts suitable for use at high temperatures, for example, above 80°C.

[0004] [Summary of the Invention] The object of the present invention is to provide a phosphine-phenol late transition metal complex, as well as a method for preparing the same and its use, which has good thermal stability, in particular, the metal complex can still maintain a higher ethylene polymerization activity even at higher temperatures, and the resulting polymer has a narrower molecular weight distribution.

[0005] To achieve the above object, in a first aspect, the present invention provides a phosphine-phenol late transition metal complex, the structural formula of which is represented by formula (I):

[0006] [ka]

[0007] wherein M is selected from a Group VIII metal, R1 is selected from substituted or unsubstituted C6-C20 aryl, R3 and R4 are each independently selected from halogen, C1-C10 hydrocarbyl, P(R5)3, NR6R7 and OR8R9, or R3 and R4 are linked together to form an 8-membered ring, wherein R5 is selected from substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C10 aryl, and R6, R7, R8 and R9 are each independently selected from C1-C10 hydrocarbyl, or R6, R7 and N are linked together to form a 5- or 6-membered ring, or R8, R9 and O are linked together to form a 5- or 6-membered ring.

[0008] Preferably, R5 includes C1 to C6 alkyl (such as methyl, ethyl, propyl, or a combination thereof), C6 to C10 aryl (such as phenyl, phenylmethyl, phenylethyl, or a combination thereof), or a combination thereof.

[0009] Preferably, the C6 to C20 aryl (including C6 to C15 aryl) is selected from phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, vinylphenyl, anthryl, naphthyl, or biphenyl.

[0010] Preferably, for a substituted C6-C20 aryl, the substituents are selected from H, halogen, hydroxy, substituted or unsubstituted alkoxy (preferably C1-C6 alkoxy), substituted or unsubstituted C1-C20 hydrocarbyl.

[0011] Preferably, for substituted alkoxy and substituted C1-C20 hydrocarbyl, the substituents are selected from halogen, hydroxy, C1-C6 alkyl, halo-substituted C1-C6 alkyl, C1-C6 alkoxy and halo-substituted C1-C6 alkoxy.

[0012] Preferably, said halo is selected from fluoro, chloro, bromo, or iodo.

[0013] Preferably, said halo includes monohalo, dihalo or perhalo, for example monofluoro, difluoro or perfluoro.

[0014] Preferably, the C1-C10 hydrocarbyl includes a C1-C8 hydrocarbyl (such as a C1-C6 alkyl) or a C7-C10 aralkyl, including, but not limited to, phenylmethyl, phenylethyl, phenyl-n-propyl, phenylisopropyl, phenyl-n-butyl, and phenyl tert-butyl.

[0015] Preferably, the C1 to C20 hydrocarbyl includes C1 to C8 hydrocarbyl (such as C1 to C6 alkyl), preferably methyl, ethyl or propyl, and / or C6 to C15 aryl.

[0016] Preferably, the C1-C6 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl and 3,3-dimethylbutyl.

[0017] Preferably, the C1-C6 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, isohexyloxy and 3,3-dimethylbutoxy.

[0018] Preferably, the halogen is selected from fluorine, chlorine, bromine and iodine.

[0019] Unless otherwise indicated, the above radical definitions also apply to radical definitions in other preferred or related structures where the context dictates otherwise.

[0020] Preferably, the structural formula of the phosphine-phenol late transition metal complex is shown in formula (II):

[0021] [ka]

[0022] In the formula, R 11 ~R 15 are each independently selected from H, halogen, hydroxy, substituted or unsubstituted alkoxy, or substituted or unsubstituted C1-C20 hydrocarbyl. Preferably, for substituted alkoxy and substituted C1-C20 hydrocarbyl, the substituents are selected from halogen, hydroxy, C1-C6 alkyl, halo-substituted C1-C6 alkyl, C1-C6 alkoxy, and halo-substituted C1-C6 alkoxy.

[0023] Preferably, M is selected from nickel and palladium.

[0024] Preferably, R 11 ~R 15 are each independently selected from H, halogen, hydroxy, substituted or unsubstituted alkoxy, or substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C15 aryl.

[0025] Preferably, at least one of R3 and R4 is selected from halogen and C1-C8 hydrocarbyl, or R3 and R4 are linked together to form an 8-membered ring.

[0026] Preferably, for substituted alkoxy and substituted C1-C10 alkyl and substituted C6-C15 aryl, the substituents are independently selected from halogen, hydroxy, C1-C6 alkyl, halo-substituted C1-C6 alkyl, C1-C6 alkoxy and halo-substituted C1-C6 alkoxy.

[0027] Preferably, said halo is selected from fluoro, chloro, bromo, or iodo.

[0028] Preferably, the halo includes monohalo, dihalo or perhalo. Preferably, the C1-C6 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl and 3,3-dimethylbutyl.

[0029] Preferably, the C1-C6 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, isohexyloxy and 3,3-dimethylbutoxy.

[0030] Preferably, the halogen is selected from fluorine, chlorine, bromine and iodine. In a second aspect, the present invention provides a method for preparing the above phosphine-phenol late transition metal complexes, said method comprising: (1) reacting a compound of formula (III) with a compound of formula (IV) to obtain a ligand; (2) reacting the ligand with an M metal compound;

[0031] [ka]

[0032] wherein the M metal is selected from the Group VIII metals, preferably nickel and / or palladium, and R1 is defined as above.

[0033] Preferably, the M metal compound is dimethyldipyridinylnickel, bis(1,5-cyclooctadienyl)nickel, tetrapyridinylnickel dichloride, ethylene glycol dimethyl ether nickel bromide, ethylene glycol dimethyl ether nickel chloride, di(trimethylphosphino)nickel dichloride, di(pyridinyl)di[(trimethylsilyl)methyl]nickel, (phenyl)(N,N,N',N'-tetramethyl-1,2-ethylenediamine)nickel chloride, dibenzyl ... diphenyldi(trimethylphosphino)nickel, phenyl(trimethylphosphino)nickel bromide, phenyl(triethylphosphino)nickel chloride, diphenyldi(trimethylphosphino)nickel, di(trimethylphosphino)nickel dichloride, dimethyldipyridinylpalladium, dipyridinylpalladium dichloride, di(pyridinyl)di[(trimethylsilyl)methyl]palladium, dibenzyldipyridinylpalladium, and methyl-1,5-cyclooctadiene-palladium chloride.

[0034] Preferably, the reaction in step (2) is carried out in the presence of a reaction solvent, and the reaction solvent is tetrahydrofuran.

[0035] In a third aspect, the present invention provides the use of the above-described phosphine-phenol late transition metal complexes in olefin polymerization.

[0036] In a fourth aspect, the present invention provides a method for polymerizing olefins, comprising the step of conducting an olefin polymerization reaction in the presence of the phosphine-phenol late transition metal complex described above.

[0037] Preferably, the olefin polymerization reaction has a temperature of -78°C to 200°C, preferably -20°C to 150°C, and a pressure of 0.01 to 10 MPa, preferably 0.01 to 5 MPa.

[0038] When used as an olefin polymerization catalyst, the phosphine-phenol late transition metal complex has higher homopolymerization / copolymerization activity and can catalyze olefin polymerization at higher temperatures, resulting in olefin polymers with significantly higher molecular weights.

[0039] Compared with the prior art, the technical solution of the present invention has the following advantages: (1) The synthesis of the phosphine-phenol late transition metal complexes described herein is simple and easy to carry out.

[0040] (2) The phosphine-phenol late transition metal complexes described herein can catalyze the polymerization of ethylene with high activity, and in particular can maintain high polymerization activity at higher polymerization temperatures.

[0041] (3) The described phosphine-phenol late transition metal complexes as olefin polymerization catalysts exhibit higher performance in the copolymerization of ethylene with α-olefins or polar monomers.

[0042] Detailed Description of Specific Embodiments Specific embodiments of the present invention will now be described in detail, but it should be understood that the specific embodiments described herein are merely for the purpose of illustrating and explaining the present invention and are not intended to limit the present invention.

[0043] The endpoints of ranges and any values ​​disclosed herein are not intended to be limiting to the exact ranges or values, and these ranges or values ​​should be understood to encompass values ​​close to these ranges or values. For numerical ranges, values ​​between the endpoints of each range, values ​​between the endpoints of each range and each individual point, and values ​​between the individual point values ​​can be combined with each other to obtain one or more new numerical ranges. These numerical ranges should be considered to be specifically disclosed herein. The structural formula of the phosphine-phenol late transition metal complex according to the present invention is shown in formula (I):

[0044] [ka]

[0045] wherein M is selected from a Group VIII metal, R1 is selected from substituted or unsubstituted C6-C20 aryl, R3 and R4 are each independently selected from halogen, C1-C10 hydrocarbyl, P(R5)3, NR6R7 and OR8R9, or R3 and R4 are joined together to form an 8-membered ring, wherein R5 is selected from substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C10 aryl, and R6, R7, R8 and R9 are each independently selected from C1-C10 hydrocarbyl, or R6, R7 and N are joined together to form a 5- or 6-membered ring, or R8, R9 and O are joined together to form a 5- or 6-membered ring.

[0046] In a more preferred embodiment, the structural formula of the phosphine-phenol late transition metal complex is shown in formula (II):

[0047] [ka]

[0048] In the formula, R 11 ~R15 are each independently selected from H, halogen, hydroxy, substituted or unsubstituted alkoxy, or substituted or unsubstituted C1-C20 hydrocarbyl. 11 ~R 15 are each independently selected from H, halogen, hydroxy, substituted or unsubstituted C1-C6 alkoxy, or substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C15 aryl.

[0049] In formula (I) and formula (II), in preferred cases, M is selected from nickel and palladium.

[0050] In Formula (I) and Formula (II), in preferred cases, at least one of R3 and R4 is selected from halogen and C1-C8 hydrocarbyl, or R3 and R4 are linked together to form an 8-membered ring. In one embodiment, R3 and R4 are each independently selected from halogen and C1-C8 hydrocarbyl (such as C1-C8 alkyl or aryl). In another embodiment, R3 is selected from halogen and C1-C8 hydrocarbyl (such as C1-C8 alkyl or aryl), and R4 is selected from P(R5)3, NR6R7, and OR8R9. wherein R5 is selected from substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C10 aryl, R6, R7, R8, and R9 are each selected from C1-C6 hydrocarbyl, R6, R7, and N are linked together to form a 5- or 6-membered ring, and R8, R9, and O are linked together to form a 5- or 6-membered ring. In yet another embodiment, R3 and R4 are linked together to form an 8-membered ring.

[0051] In the present invention, when R3 and R4 are bonded to each other to form an 8-membered ring, R3 and R4 may be bonded to each other to form cyclooctenyl, etc. When R3 and / or R4 are each independently selected from P(R5)3, R3 and / or R4 are, for example, PMe3, PPh 3、PEt3, etc. When R3 and / or R4 are each independently selected from NR6R7, R3 and / or R4 may be, for example, pyridine (C5H5N), 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, etc. When R3 and / or R4 are each independently selected from OR8R9, R3 and / or R4 may be, for example, tetrahydrofuranyl (C4H8O), 2-methyltetrahydrofuranyl, 3-methyltetrahydrofuranyl, 2,5-dimethyltetrahydrofuranyl, 2,2-dimethyltetrahydrofuranyl, etc. As used herein, "Me" represents methyl, "Ph" represents phenyl, and "Et" represents ethyl.

[0052] In the present invention, the term "substituted" in the phrase "substituted or unsubstituted" is meant to include substituent(s), wherein the substituent(s) may be independently selected from halogen, hydroxy, C1-C6 alkyl, halo-substituted C1-C6 alkyl, C1-C6 alkoxy, and halo-substituted C1-C6 alkoxy. Preferably, halo is selected from fluoro, chloro, bromo, or iodo.

[0053] In the present invention, alkyl (such as C1-C6 alkyl, C1-C8 alkyl or C1-C10 alkyl) may be independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl and 3,3-dimethylbutyl.

[0054] In the present invention, alkoxy (such as C1-C6 alkoxy) may be independently selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, isohexyloxy, and 3,3-dimethylbutoxy.

[0055] In the present invention, aryl (such as C6-C10 aryl or C6-C15 aryl) may be independently selected from phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, vinylphenyl, anthryl, naphthyl, biphenyl, and the like.

[0056] In the present invention, the halogens are independently selected from fluorine, chlorine, bromine and iodine.

[0057] In a further preferred embodiment, the phosphine-phenol late transition metal complex is selected from the group consisting of the following complexes: Complex 1: A complex of formula (II) where M is Ni and R 11 ~R 15 is H, R3 is methyl, and R4 is pyridinyl (wherein N on pyridinyl coordinates with metallic Ni); Complex 2: A complex of formula (II) where M is Ni and R 11 ~R 15 is F, R3 is methyl, and R4 is pyridinyl; Complex 3: A complex of formula (II) where M is Ni and R 11 is phenyl and R 12 ~R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 4: A complex of formula (II) where M is Ni, R 11 is methyl and R 12 ~R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 5: A complex of formula (II) where M is Ni and R 13 is methyl and R 11 , R 12 , R 14 and R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 6: A complex of formula (II) where M is Ni and R 13 is -CF3 and R 11 , R 12 , R14 and R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 7: A complex of formula (II) where M is Ni and R 13 is F and R 11 , R 12 , R 14 and R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 8: A complex of formula (II) where M is Ni and R 13 is Cl and R 11 , R 12 , R 14 and R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 9: A complex of formula (II) where M is Ni and R 11 , R 13 and R 15 is methyl and R 12 and R 14 is H, R3 is methyl, and R4 is pyridinyl; Complex 10: A complex of formula (II) where M is Ni and R 13 is methoxy and R 11 , R 12 , R 14 and R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 11: A complex of formula (II) where M is Ni and R 12 and R 14 is methyl and R 11 , R 13 and R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 12: A complex of formula (II) where M is Ni and R 12 and R 14 is methyl and R 13 is methoxy and R 11 and R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 13: A complex of formula (II) where M is Ni and R 12 and R 14 is -CF3 and R 11 , R 13 and R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 14: A complex of formula (II), wherein M is Ni and R 11 and R 15 is methoxy and R 12 ~R 14 is H, R3 is methyl, and R4 is pyridinyl; Complex 15: A complex of formula (II) where M is Ni and R 11 is methoxy and R 12 ~R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 16: A complex of formula (II) where M is Ni and R 11 ~R 15 is H, R3 is phenyl, and R4 is PMe3; Complex 17: A complex of formula (II) where M is Ni and R 11 and R 15 is F, R3 is phenyl, and R4 is PMe3; Complex 18: A complex of formula (II) where M is Ni and R 11 is phenyl and R 12 ~R 15 is H, R3 is phenyl, and R4 is PMe3; Complex 19: A complex of formula (II) where M is Ni and R 11 is methyl and R 12 ~R 15 is H, R3 is phenyl, and R4 is PMe3; Complex 20: A complex of formula (II) where M is Ni and R 13 is methyl and R 11 , R 12 , R 14 and R 15 is H, R3 is phenyl, and R4 is PMe3; Complex 21: A complex of formula (II) where M is Ni and R 13 is -CF3 and R 11 , R 12 , R 14 and R 15 is H, R3 is phenyl, and R4 is PMe3; Complex 22: A complex of formula (II) where M is Ni and R 13 is F and R 11 , R 12 , R 14 and R 15 is H, R3 is phenyl, and R4 is PMe3; Complex 23: A complex of formula (II) where M is Ni and R 13 is Cl and R 11 , R 12 , R 14 and R 15 is H, R3 is phenyl, and R4 is PMe3; Complex 24: A complex of formula (II) where M is Ni and R 11 , R 13 and R 15 is methyl and R 12 and R 14 is H, R3 is phenyl, and R4 is PMe3; Complex 25: A complex of formula (II) where M is Ni and R 13 is methoxy and R 11 , R 12 , R 14 and R 15 is H, R3 is phenyl, and R4 is PMe3; Complex 26: A complex of formula (II) where M is Ni and R 12 and R 14 is methyl and R 11 , R 13 and R 15 is H, R3 is phenyl, and R4 is PMe3; Complex 27: A complex of formula (II) where M is Ni and R 12 and R 14 is methyl and R 13is methoxy and R 11 and R 15 is H, R3 is phenyl, and R4 is PMe3; Complex 28: A complex of formula (II) where M is Ni and R 12 and R 14 is -CF3 and R 11 , R 13 and R 15 is H, R3 is phenyl, and R4 is PMe3; Complex 29: A complex of formula (II) where M is Ni and R 11 and R 15 is methoxy and R 12 ~R 14 is H, R3 is phenyl, and R4 is PMe3; Complex 30: A complex of formula (II) where M is Ni and R 11 is methoxy and R 12 ~R 15 is H, R3 is phenyl, and R4 is PMe3; Complex 31: A complex of formula (II) where M is Ni and R 11 ~R 15 is H, and R3 and R4 are linked together to form a cyclooctenyl; Complex 32: A complex of formula (II) where M is Ni and R 11 is phenyl and R 12 ~R 15 is H, and R3 and R4 are linked together to form a cyclooctenyl; Complex 33: A complex of formula (II) where M is Ni and R 11 is phenyl and R 12 ~R 15 is H, and R3 and R4 are linked together to form a cyclooctenyl; Complex 34: A complex of formula (II) where M is Ni and R 13 is methoxy and R 11 , R 12 , R 14 and R 15 is H, and R3 and R4 are linked together to form a cyclooctenyl; Complex 35: A complex of formula (II) where M is Ni and R 12 and R 14 is -CF3 and R 11 , R 13 and R 15 is H, and R3 and R4 are linked together to form a cyclooctenyl; Complex 36: A complex of formula (II) where M is Ni and R 11 and R 15 is methoxy and R 12 ~R 14 is H, and R3 and R4 are linked together to form a cyclooctenyl; Complex 37: A complex of formula (II) where M is Ni and R 11 is methoxy and R 12 ~R 15 is H, and R3 and R4 are linked together to form a cyclooctenyl; Complex 38: A complex of formula (II) where M is Ni and R 11 ~R 15 is H, R3 is Cl, and R4 is tetrahydrofuranyl (wherein O on the tetrahydrofuranyl is coordinated with metallic Ni); Complex 39: A complex of formula (II) where M is Ni and R 11 ~R 15 is F, R3 is Cl, and R4 is tetrahydrofuranyl; Complex 40: A complex of formula (II) where M is Ni and R 11 is phenyl and R 12 ~R 15 is H, R3 is Cl, and R4 is tetrahydrofuranyl; Complex 41: A complex of formula (II) where M is Ni and R 11 is methyl and R 12 ~R 15 is H, R3 is Cl, and R4 is tetrahydrofuranyl; Complex 42: A complex of formula (II) where M is Ni and R 13 is methyl and R 11 , R 12, R 14 and R 15 is H, R3 is Cl, and R4 is tetrahydrofuranyl; Complex 43: A complex of formula (II) where M is Ni and R 13 is -CF3 and R 11 , R 12 , R 14 and R 15 is H, R3 is Cl, and R4 is tetrahydrofuranyl; Complex 44: A complex of formula (II) where M is Ni and R 13 is F and R 11 , R 12 , R 14 and R 15 is H, R3 is Cl, and R4 is tetrahydrofuranyl; Complex 45: A complex of formula (II) where M is Ni and R 13 is Cl and R 11 , R 12 , R 14 and R 15 is H, R3 is Cl, and R4 is tetrahydrofuranyl; Complex 46: A complex of formula (II) where M is Ni and R 11 , R 13 and R 15 is methyl and R 12 and R 14 is H, R3 is Cl, and R4 is tetrahydrofuranyl; Complex 47: A complex of formula (II) where M is Ni and R 13 is methoxy and R 11 , R 12 , R 14 and R 15 is H, R3 is Cl, and R4 is tetrahydrofuranyl; Complex 48: A complex of formula (II) where M is Ni and R 12 and R 14 is methyl and R 11 , R 13 and R 15is H, R3 is Cl, and R4 is tetrahydrofuranyl; Complex 49: A complex of formula (II) where M is Ni and R 12 and R 14 is methyl and R 13 is methoxy and R 11 and R 15 is H, R3 is Cl, and R4 is tetrahydrofuranyl; Complex 50: A complex of formula (II) where M is Ni and R 12 and R 14 is -CF3 and R 11 , R 13 and R 15 is H, R3 is Cl, and R4 is tetrahydrofuranyl; Complex 51: A complex of formula (II) where M is Ni and R 11 and R 15 is methoxy and R 12 ~R 14 is H, R3 is Cl, and R4 is tetrahydrofuranyl; Complex 52: A complex of formula (II) where M is Ni and R 11 is methoxy and R 12 ~R 15 is H, R3 is Cl, and R4 is tetrahydrofuranyl; Complex 53: A complex of formula (II) where M is Ni and R 11 ~R 15 is H, R3 is Br, and R4 is tetrahydrofuranyl; Complex 54: A complex of formula (II) where M is Ni and R 11 ~R 15 is F, R3 is Br, and R4 is tetrahydrofuranyl; Complex 55: A complex of formula (II) where M is Ni and R 11 is phenyl and R 12 ~R 15 is H, R3 is Br, and R4 is tetrahydrofuranyl; Complex 56: A complex of formula (II) where M is Ni and R11 is methyl and R 12 ~R 15 is H, R3 is Br, and R4 is tetrahydrofuranyl; Complex 57: A complex of formula (II) where M is Ni and R 13 is methyl and R 11 , R 12 , R 14 and R 15 is H, R3 is Br, and R4 is tetrahydrofuranyl; Complex 58: A complex of formula (II) where M is Ni and R 13 is -CF3 and R 11 , R 12 , R 14 and R 15 is H, R3 is Br, and R4 is tetrahydrofuranyl; Complex 59: A complex of formula (II) where M is Ni and R 13 is F and R 11 , R 12 , R 14 and R 15 is H, R3 is Br, and R4 is tetrahydrofuranyl; Complex 60: A complex of formula (II) where M is Ni and R 13 is Cl and R 11 , R 12 , R 14 and R 15 is H, R3 is Br, and R4 is tetrahydrofuranyl; Complex 61: A complex of formula (II) where M is Ni and R 11 , R 13 and R 15 is methyl and R 12 and R 14 is H, R3 is Br, and R4 is tetrahydrofuranyl; Complex 62: A complex of formula (II) where M is Ni and R 13 is methoxy and R 11 , R 12 , R 14 and R 15is H, R3 is Br, and R4 is tetrahydrofuranyl; Complex 63: A complex of formula (II) where M is Ni and R 12 and R 14 is methyl and R 11 , R 13 and R 15 is H, R3 is Br, and R4 is tetrahydrofuranyl; Complex 64: A complex of formula (II) where M is Ni and R 12 and R 14 is methyl and R 13 is methoxy and R 11 and R 15 is H, R3 is Br, and R4 is tetrahydrofuranyl; Complex 65: A complex of formula (II) where M is Ni and R 12 and R 14 is -CF3 and R 11 , R 13 and R 15 is H, R3 is Br, and R4 is tetrahydrofuranyl; Complex 66: A complex of formula (II) where M is Ni and R 11 and R 15 is methoxy and R 12 ~R 14 is H, R3 is Br, and R4 is tetrahydrofuranyl; Complex 67: A complex of formula (II) where M is Ni and R 11 is methoxy and R 12 ~R 15 is H, R3 is Br, and R4 is tetrahydrofuranyl; Complex 68: A complex of formula (II) where M is Pd and R 11 ~R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 69: A complex of formula (II) where M is Pd and R 11 ~R 15 is F, R3 is methyl, and R4 is pyridinyl; Complex 70: A complex of formula (II) where M is Pd and R 11 is phenyl and R 12 ~R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 71: A complex of formula (II) where M is Pd and R 11 is phenyl and R 12 ~R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 72: A complex of formula (II) where M is Pd and R 11 is methyl and R 12 ~R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 73: A complex of formula (II) where M is Pd and R 13 is methyl and R 11 , R 12 , R 14 and R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 74: A complex of formula (II) where M is Pd and R 13 is -CF3 and R 11 , R 12 , R 14 and R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 75: A complex of formula (II) where M is Pd and R 13 is F and R 11 , R 12 , R 14 and R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 76: A complex of formula (II) where M is Pd and R 13 is Cl and R 11 , R 12 , R 14 and R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 77: A complex of formula (II) where M is Pd and R11 , R 13 and R 15 is methyl and R 12 and R 14 is H, R3 is methyl, and R4 is pyridinyl; Complex 78: A complex of formula (II) where M is Pd and R 13 is methoxy and R 11 , R 12 , R 14 and R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 79: A complex of formula (II) where M is Pd and R 12 and R 14 is methyl and R 11 , R 13 and R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 80: A complex of formula (II) where M is Pd and R 12 and R 14 is methyl and R 13 is methoxy and R 11 and R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 81: A complex of formula (II) where M is Pd and R 12 and R 14 is -CF3 and R 11 , R 13 and R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 82: A complex of formula (II) where M is Pd and R 11 and R 15 is methoxy and R 12 ~R 14 is H, R3 is methyl, and R4 is pyridinyl; Complex 83: A complex of formula (II) where M is Pd and R 11 is methoxy and R 12 ~R 15 is H, R3 is methyl, and R4 is pyridinyl; Complex 84: A complex of formula (II) where M is Pd and R 11 ~R 15 is H, R3 is methyl, and R4 is Cl; Complex 85: A complex of formula (II) where M is Pd and R 11 is phenyl and R 12 ~R 15 is H, R3 is methyl, and R4 is Cl; Complex 86: A complex of formula (II) where M is Pd and R 13 is methoxy and R 11 , R 12 , R 14 and R 15 is H, R3 is methyl, and R4 is Cl; Complex 87: A complex of formula (II) where M is Pd and R 12 and R 14 is -CF3 and R 11 , R 13 and R 15 is H, R3 is methyl, and R4 is Cl; Complex 88: A complex of formula (II) where M is Pd and R 11 and R 15 is methoxy and R 12 ~R 14 is H, R3 is methyl, and R4 is Cl; Complex 89: A complex of formula (II) where M is Pd and R 11 is methoxy and R 12 ~R 15 is H, R3 is methyl, and R4 is Cl.

[0058] The method for preparing the above phosphine-phenol late transition metal complexes may include: (1) reacting a compound of formula (III) with a compound of formula (IV) to obtain a ligand; (2) reacting the ligand with an M metal compound;

[0059] [ka]

[0060] wherein the M metal is selected from Group VIII metals, preferably nickel and / or palladium, and R1 is defined as above.

[0061] In the method of the present invention, the M metal compound may be dimethyldipyridinylnickel (PyNiMe), bis(1,5-cyclooctadienyl)nickel (Ni(COD)), tetrapyridinylnickel dichloride (NiClPy), ethylene glycol dimethyl ether nickel bromide ((DME)NiBr), ethylene glycol dimethyl ether nickel chloride ((DME)NiCl), di(trimethylphosphino)nickel dichloride (NiCl(PMe)), di(pyridinyl)di[(trimethylsilyl)methyl]nickel (Ni(Py)(CHSiMe)), (phenyl)(N,N,N',N'-tetramethyl-1,2-ethylenediamine)nickel chloride (NiArBr(TMEDA)), dibenzyldipyridinylnickel (Ni(CHPh)), Py2), phenyl(trimethylphosphino)nickel bromide (NiPhBr(PMe3)2, phenyl(triethylphosphino)nickel chloride (NiPhCl(PEt3)2), diphenyldi(trimethylphosphino)nickel (NiPh2(PMe3)2), di(trimethylphosphino)nickel dichloride (NiCl2(PMe3)2), dimethyldipyridinylpalladium (Pd(Me)2Py2), dipyridinylpalladium dichloride (PdCl2Py2), di(pyridinyl)di[(trimethylsilyl)methyl]palladium (Pd(Py)2(CH2SiMe3)2), dibenzyldipyridinylpalladium (Pd(CH2Ph)2Py2), and methyl-1,5-cyclooctadiene-palladium chloride (Pd(COD)ClMe).

[0062] In the method of the present invention, the reaction of step (2) is carried out in the presence of a reaction solvent. In a specific embodiment, the reaction solvent may be selected from toluene and tetrahydrofuran. Preferably, the reaction solvent is tetrahydrofuran.

[0063] In a more preferred embodiment, the reaction process of step (1) and step (2) is shown in the following formula:

[0064] [ka]

[0065] In the formula, M, R3, R4, R 11 ~R 15 The definition of is the same as above.

[0066] In a specific embodiment, the preparation process of step (1) includes the following steps: under a protective gas (such as nitrogen) atmosphere, dissolving the compound of formula (III) in anhydrous diethyl ether, adding a hydrogen abstracting agent (such as n-butyllithium) at room temperature, stirring at room temperature, adding tetrahydrofuran, and then further stirring the resulting black solution containing precipitates; then adding the compound of formula (V), stirring at room temperature, and adding aqueous NHCl solution to quench; then extracting the organic phase with ethyl acetate, drying the resulting organic phase over anhydrous sodium sulfate, and recrystallizing it with dichloromethane / hexane to obtain a yellow crystalline compound; then adding methanol and concentrated hydrochloric acid, and reacting under reflux. After the reaction is complete, the organic solvent is removed, the product is dissolved in ethyl acetate, neutralized with aqueous NaHCO, and the organic phase is extracted, followed by drying, filtration, concentration, and column chromatography to obtain the ligand.

[0067] In a specific embodiment, the preparation process of step (2) includes the following steps: dissolving the ligand obtained in step (1) and the M metal compound in an organic solvent (toluene, tetrahydrofuran, etc.) under a protective gas (such as nitrogen) atmosphere, then mixing the ligand solution with the M metal compound solution with stirring, reacting them at room temperature, filtering, concentrating the filtrate, and then recrystallizing it with heptane to obtain the phosphine-phenol late transition metal complex of the present invention.

[0068] The present invention also provides the use of the above-described phosphine-phenol late transition metal complexes in the polymerization of olefins, preferably including ethylene and α-olefins containing polar groups.

[0069] The phosphine-phenol late transition metal complex of the present invention can be used as a catalyst for the homopolymerization or copolymerization of olefins, and is particularly suitable for the homopolymerization of ethylene or the copolymerization of ethylene with other α-olefins and olefins having polar functional groups such as hydroxyl groups, carboxyl groups, and ester groups, where the α-olefins are independently selected from at least one of propylene, butene, pentene, hexene, octene, and 4-methyl-1-pentene. The olefin having a polar functional group is a vinyl monomer containing one or more of hydroxyl groups, carboxyl groups, and ester groups, and the vinyl monomer can contain multiple different polar groups in the same molecule.

[0070] In the present invention, another embodiment of the method for preparing an α-olefin polymer is to copolymerize (a) an α-olefin with (b) a (meth)acrylate monomer, a vinyl monomer, or an allylic monomer in the presence of the above-mentioned phosphine-phenol late transition metal complex. The (meth)acrylate monomer in the present invention has the general formula CH═C(R 31 )CO2(R 32 ), where R 31 may be H or a C1-C10 hydrocarbyl having branched, cyclic, and / or unsaturated bonds, and R 32may be a C1 to C30 hydrocarbyl having branched, cyclic, and / or unsaturated bonds, and R 32 R may contain heteroatoms at any position therein. 31 If the number of carbon atoms in R is 11 or more, the polymerization activity tends to decrease. 31 is H or C1-C10 hydrocarbyl. In preferred cases, R 31 is H or C1-C5 hydrocarbyl. More preferably, R 31 is H or methyl.

[0071] Similarly, R 32 If the number of carbon atoms in R exceeds 30, the polymerization activity tends to decrease. 32 The number of carbon atoms is 1 to 30, preferably 1 to 12, and more preferably 1 to 8.

[0072] Furthermore, R 32 The heteroatom optionally contained in R 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. Furthermore, R which does not contain a heteroatom may be selected from oxygen, sulfur, selenium, phosphorus, nitrogen, silicon, fluorine, boron, etc. 32 is also preferred.

[0073] More preferred specific examples of the (meth)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, pentyl (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. Examples of the (meth)acrylate monomer include, but are not limited to, hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-aminoethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, glycidyl (meth)acrylate, oxiranyl (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 (meth)acrylate monomers may be used alone or in combination of two or more.

[0074] In the present invention, the olefin is a C2 to C16 olefin. Preferably, the olefin is selected from ethylene and α-olefins or cycloolefins having 3 to 16 carbon atoms. Examples of the cycloolefin include, but are not limited to, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and norbornene.

[0075] The present invention also provides a method for polymerizing olefins, which comprises carrying out an olefin polymerization reaction in the presence of the above-described phosphine-phenol late transition metal complex. The olefin polymerization reaction may be homopolymerization or copolymerization.

[0076] The olefin polymerization reaction may be carried out at a temperature of -78°C to 200°C, preferably -20°C to 150°C, and at a pressure of 0.01 to 10 MPa, preferably 0.01 to 5 MPa. Here, the term "pressure" refers to the ethylene pressure in the polymerization system and is expressed in absolute pressure.

[0077] In the olefin polymerization method according to the present invention, the olefin is a C2 to C16 olefin.

[0078] According to one embodiment of the present invention, the olefin includes a C2-C16 α-olefin or a cycloolefin.

[0079] According to one embodiment of the present invention, the olefin comprises ethylene.

[0080] According to one embodiment of the present invention, the olefin includes ethylene and an α-olefin or cycloolefin containing a polar group.

[0081] According to one embodiment of the present invention, the olefin polymerization reaction is carried out with an olefin monomer in a solvent, and the polymerization solvent is selected from one or more of alkanes, aromatic hydrocarbons, and halogenated hydrocarbons. In particular, the polymerization solvent is selected from one or more of hexane, pentane, heptane, benzene, toluene, dichloromethane, chloroform, chlorobenzene, and dichloroethane, and preferably from one or more of hexane, toluene, and heptane.

[0082] In the present invention, alkyl means straight chain alkyl, branched alkyl, or cyclic alkyl, 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.

[0083] In the present invention, alkenyl means straight chain alkenyl, branched alkenyl or cycloalkenyl, including, but not limited to, vinyl, allyl, butenyl.

[0084] In the present invention, examples of aralkyl include, but are not limited to, phenylmethyl, phenylethyl, phenyl-n-propyl, phenylisopropyl, phenyl-n-butyl, and phenyl-tert-butyl.

[0085] In the present invention, examples of alkaryl include, but are not limited to, tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, and tert-butylphenyl.

[0086] The phosphine-phenol late transition metal complexes of the present invention, as well as their preparation methods and uses, are further illustrated by the following examples.These examples are carried out on the premise of the technical solutions of the present invention, and provide detailed embodiments and specific operation processes.However, the protection scope of the present invention is not limited to the following examples.

[0087] The experimental methods in the following examples are conventional in the art unless otherwise specified. The experimental materials used in the following examples are commercially available unless otherwise specified.

[0088] The analytical property evaluation equipment and test methods used in the following examples and comparative examples are as follows: (1) Nuclear magnetic resonance spectrometer: Bruker DMX 300 (300 MHz), tetramethylsilane (TMS) as an internal standard.

[0089] (2) Molecular weight and molecular weight distribution (PDI) of polymer (PDIMw / Mn): Measurement is carried out at 150°C using a PL-GPC220 chromatograph with trichlorobenzene as the solvent (standard: PS, flow rate: 1.0 mL / min, chromatography column: 3 x PLgel 10 μm M1 x ED-B, 300 x 7.5 nm).

[0090] (3) Activity measurement method: The polymer is washed with a hydrochloric acid-ethanol solution, dried in vacuum, and then weighed. The polymerization activity is calculated by polymer weight (g) / metal (mol) × 60 / polymerization time (min).

[0091] (4) Analysis of polymer comonomer content: Polymer samples were dissolved in 1,2,4-trichlorobenzene at 120°C and analyzed on a 400 MHz Bruker Avance 400 nuclear magnetic resonance spectrometer using a 10 mm PASEX 13 probe. 1 H NMR, 13 Analyze by C NMR spectroscopy.

[0092] Example 1 Complex 1: A complex of formula (II) where M is Ni and R 11 ~R 15 is H, R3 is methyl, and R4 is pyridinyl.

[0093] Under a nitrogen atmosphere, the compound of formula (III) (11.23 g, 30 mmol, S-configuration) was dissolved in anhydrous diethyl ether (150 mL). n-Butyllithium solution (2.7 M, 33.3 mL, 90 mmol) was added dropwise at room temperature, and the solution was stirred at room temperature for 4 hours. After adding tetrahydrofuran (150 mL), the resulting black solution containing a precipitate was stirred for an additional hour. Diphenylphosphine chloride (PPhCl) (90 mmol, 16.7 mL) was added at 0 °C. The solution was stirred at room temperature for 1 hour and then quenched by adding aqueous NHCl (5 mL). The organic phase was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and recrystallized from dichloromethane / hexane to obtain a yellow crystalline compound (15.54 g). Methanol (100 mL) and 5 mL of concentrated hydrochloric acid (37 wt%) were added, and the mixture was allowed to react under reflux for 16 hours. After the reaction was completed, which was monitored by thin layer chromatography (TLC), the organic solvent was removed, and the product was dissolved in ethyl acetate and neutralized with aqueous NaHCO. The organic phase was extracted, dried over anhydrous MgSO, filtered, concentrated, and separated by column chromatography (dichloromethane as solvent) to give ligand L1 in 67% yield. 1 H NMR (400MHz, CDCl3): δ=5.41(s,2H),7.13~7.15(m,2H),7.24~7.29(m,4H),7.38~7.45(m,22H),7.62~7.64(m,2H). 31 P NMR (162 MHz, CDCl3): δ = -17.19 (s). High-resolution mass spectrometry: calculated: 654.19, tested: 655.20.

[0094] Ligand L1 (0.654 g, 1 mmol) and the nickel metal source (PyNiMe2) (0.49 g, 2 mmol) were dissolved in toluene (10 mL) under a nitrogen atmosphere. The ligand solution was then added dropwise to the nickel metal source solution and reacted for 10 hours with vigorous stirring at room temperature. The mixture was then filtered to obtain a yellow-brown solution. The solution was concentrated and freeze-crystallized at -30 °C to obtain the naphthol-phosphine neutral nickel complex 1 in 76% yield. 1H NMR (400MHz, CDCl3): δ:7.92(m,8H),7.58~7.63(m,2H),7.32~7.50(m,22H),7.22~7.34(m,4H),7.10~7.15(m,2H),6.60(m,2H),-0.41(d,6H). 31 P NMR (162MHz, CDCl3)δ:30.98. Elemental analysis test C 56 H 46 N2Ni2O2P2: Theoretical calculation: C, 70.19; H, 4.84; N, 2.92; Tested values: C, 69.94; H, 4.92; N, 2.84.

[0095] A 1-liter stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of toluene was charged to the polymerization kettle, and 9.6 mg (10 μmol) of complex 1 was added. The reaction was carried out at 50°C for 20 minutes with vigorous stirring, while maintaining the ethylene pressure at 10 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid acidified ethanol solution to obtain polyethylene. The polymer was dried, weighed, and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0096] Example 2 Complex 1: A complex of formula (II) where M is Ni and R 11 ~R 15 is H, R3 is methyl, and R4 is pyridinyl.

[0097] A 1-liter stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of hexane was charged to the polymerization kettle, and 9.6 mg (10 μmol) of complex 1 was added. The reaction was carried out at 70°C for 30 minutes with vigorous stirring, while maintaining the ethylene pressure at 10 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid acidified ethanol solution to obtain polyethylene. The polymer was dried, weighed, and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0098] Example 3 Complex 1: A complex of formula (II) where M is Ni and R 11 ~R 15 is H, R3 is methyl, and R4 is pyridinyl.

[0099] A 1-liter stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried at 130°C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of hexane was charged to the polymerization kettle, and 9.6 mg (10 μmol) of complex 1 was added. The reaction was carried out at 100°C for 30 minutes with vigorous stirring while maintaining the ethylene pressure at 14 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid acidified ethanol solution to obtain polyethylene. The polymer was dried, weighed, and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0100] Example 4 Complex 1: A complex of formula (II) where M is Ni and R 11 ~R 15 is H, R3 is methyl, and R4 is pyridinyl.

[0101] A 100 mL stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130 °C for 6 hours, then evacuated while hot and purged with N2 three times. 50 mL of toluene and 0.9 mL (10 mmol) of methyl acrylate were charged to the polymerization kettle, and 9.6 mg (10 μmol) of complex 1 was added. The reaction was carried out at 70 °C for 60 minutes with vigorous stirring, while maintaining the ethylene pressure at 15 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid solution in ethanol to obtain a polymer. The polymer was dried, weighed, and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, polymerization activity, and comonomer content of the resulting polymer are shown in Table 1.

[0102] Example 5 Complex 1: A complex of formula (II) where M is Ni and R 11 ~R 15is H, R3 is methyl, and R4 is pyridinyl.

[0103] A 100 mL stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130 °C for 6 hours, then evacuated while hot and purged with N2 three times. 50 mL of toluene and 1.4 mL (10 mmol) of butyl acrylate were charged to the polymerization kettle, and 9.6 mg (10 μmol) of complex 1 was added. The reaction was carried out at 70 °C for 60 minutes with vigorous stirring, while maintaining the ethylene pressure at 15 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid solution in ethanol to obtain a polymer. The polymer was dried, weighed, and the polymerization activity was measured. The test data for the weight-average molecular weight, molecular weight distribution, polymerization activity, and comonomer content of the resulting polymer are shown in Table 1.

[0104] Example 6 Complex 16: A complex of formula (II) where M is Ni and R 11 ~R 15 is H, R3 is phenyl, and R4 is PMe3.

[0105] Ligand L1 was prepared by the method of Example 1.

[0106] Under a nitrogen atmosphere, ligand L1 (0.654 g, 1 mmol) and PMe3 (1 mol / L, 2 mL) were dissolved in 20 mL of toluene, and 30 mL of a toluene solution of Ni(COD)2 (0.55 g, 2 mmol) was added dropwise at 0 °C. The solution was reacted at room temperature for 16 hours, then heated at 50 °C for 2 hours, and the solvent was evaporated. 5 mL of toluene was added, and the resulting solution was filtered. 100 mL of heptane was added, and the resulting solution was freeze-crystallized to obtain complex 16 in 72% yield. Elemental analysis test C 62 H 58 Ni2O2P4: Theoretical calculation: C, 69.18; H, 5.43; Tested values: C, 79.02; H, 5.71.

[0107] A 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130 °C for 6 h, then evacuated while hot and purged with N2 three times. 500 mL of toluene was charged into the polymerization kettle, and 10.8 mg (10 μmol) of complex 16 was added. After the reaction was carried out at 50 °C for 20 min with vigorous stirring while maintaining the ethylene pressure at 10 atm, the resulting product was a C4–C24 oligomer.

[0108] Example 7 Complex 53: A complex of formula (II) where M is Ni and R 11 ~R 15 is H, R3 is Br, and R4 is tetrahydrofuranyl.

[0109] Ligand L1 was prepared according to the method of Example 1.

[0110] Under a nitrogen atmosphere, ligand L1 (0.654 g, 1 mmol) was dissolved in tetrahydrofuran, excess NaH (0.072 g, 3 mmol) was added, and the solution was stirred at room temperature for 10 hours, after which the NaH was removed by filtration. A solution of (DME)NiBr2 (0.617 g, 2 mmol) in tetrahydrofuran was added dropwise and allowed to react at room temperature overnight. The solvent was removed by suction, and the product was dissolved in dichloromethane (40 mL). The solution was filtered to remove the cake, and the filtrate was concentrated and recrystallized from heptane to give complex 53 in 79% yield. Elemental Analysis Test C 52 H 46 Br2Ni2O4P2: Theoretical calculation: C, 58.15; H, 4.32; Tested values: C, 58.01; H, 4.53.

[0111] A 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130 °C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of toluene was charged to the polymerization kettle, and 10.7 mg (10 μmol) of complex 53 was added. The reaction was carried out at 30 °C for 20 minutes with vigorous stirring, while maintaining the ethylene pressure at 10 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid acidified ethanol solution to obtain polyethylene. The polymer was dried, weighed, and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0112] Example 8 Complex 53: A complex of formula (II) where M is Ni and R 11 ~R 15 is H, R3 is Br, and R4 is tetrahydrofuranyl.

[0113] A 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130 °C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of hexane was charged to the polymerization kettle, and 10.7 mg (10 μmol) of complex 53 was added. The reaction was carried out at 80 °C for 30 minutes with vigorous stirring while maintaining the ethylene pressure at 10 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid acidified ethanol solution to obtain polyethylene. The polymer was dried, weighed, and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0114] Example 9 Complex 53: A complex of formula (II) where M is Ni and R 11 ~R 15 is H, R3 is Br, and R4 is tetrahydrofuranyl.

[0115] A 100 mL stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130 °C for 6 hours, then evacuated while hot and purged with N2 three times. 50 mL of toluene and 0.9 mL (0.01 mol) of methyl acrylate were charged to the polymerization kettle, and 10.7 mg (10 μmol) of complex 53 was added. The reaction was carried out at 70 °C for 60 minutes with vigorous stirring, while maintaining the ethylene pressure at 15 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid solution in ethanol to obtain a polymer. The polymer was dried, weighed, and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, polymerization activity, and comonomer content of the resulting polymer are shown in Table 1.

[0116] Example 10 Complex 65: A complex of formula (II) where M is Ni and R 12 and R 14 is -CF3 and R 11 , R 13 and R 15 is H, R3 is Br, and R4 is tetrahydrofuranyl.

[0117] Under a nitrogen atmosphere, the compound of formula (III) (3.74 g, 10 mmol, R-configuration) was dissolved in anhydrous diethyl ether (120 mL). n-Butyllithium solution (2.7 M, 11.1 mL, 30 mmol) was added dropwise at room temperature, and the solution was stirred at room temperature for 4 hours. After adding tetrahydrofuran (120 mL), the resulting black solution containing a precipitate was stirred for an additional hour. Bis(3,5-di(trifluoromethyl)phenyl)phosphine chloride (30 mmol, 14.78 g) was added at 0°C. The solution was stirred at room temperature for 1 hour and then quenched by adding aqueous NH4Cl (5 mL). The organic phase was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and recrystallized from dichloromethane / hexane to obtain a white crystalline compound. Methanol (100 mL) and 5 mL of concentrated hydrochloric acid (37 wt%) were added, and the mixture was allowed to react under reflux for 16 hours. After the reaction was completed, which was monitored by TLC, the organic solvent was removed, and the product was dissolved in ethyl acetate and neutralized with aqueous NaHCO. The organic phase was extracted, dried over anhydrous MgSO, filtered, concentrated, and separated by column chromatography (dichloromethane as solvent) to obtain 4.78 g of ligand L2 in 40% yield. 1 H NMR(400MHz,DMSO)δ:9.10(s,2H),8.17(s,2H),8.13(s,2H),8.08(dd,J=13.3,6.5Hz, 8H), 7.81(d,J=7.6Hz,2H),7.56(d,J=8.4Hz,2H),7.27(dd,4H),6.90(d,J=8.2Hz,2H). High-resolution mass spectrometry test: Theoretical calculation value: 1198.09, Test value: 1198.95. 31 P NMR (162MHz, DMSO): δ=-8.37(s). 1 H NMR(400MHz,CDCl3)δ5.14(s,2H),7.08~7.11(m,2H),7.41~7.46(m,4H),7.63( d, 2H), 7.78~7.81 (m, 2H), 7.84 (d, 4H), 7.86 (d, 4H), 7.91 (s, 2H), 7.94 (s, 2H).

[0118] Under a nitrogen atmosphere, ligand L2 (1.20 g, 1 mmol) was dissolved in tetrahydrofuran, excess NaH (0.072 g, 3 mmol) was added, and the solution was stirred at room temperature for 10 hours, after which the NaH was removed by filtration. A solution of (DME)NiBr2 (0.617 g, 2 mmol) in tetrahydrofuran was added dropwise and allowed to react at room temperature overnight. The solvent was removed by suction, and the product was dissolved in dichloromethane (40 mL). The solution was filtered to remove the cake, and the filtrate was concentrated and recrystallized from heptane to give complex 65 in 76% yield. Elemental Analysis Test C 60 H 38 Br2F 24 Ni2O4P2: Theoretical calculation: C, 44.54; H, 2.37; Tested values: C, 44.31; H, 2.51.

[0119] A 1-liter stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of toluene was charged to the polymerization kettle, and 8.1 mg (5 μmol) of complex 65 was added. The reaction was carried out at 30°C for 20 minutes with vigorous stirring, while maintaining the ethylene pressure at 10 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid solution in ethanol to obtain polyethylene. The polymer was dried, weighed, and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0120] Example 11 Complex 65: A complex of formula (II) where M is Ni and R 12 and R 14 is -CF3 and R 11 , R 13 and R 15 is H, R3 is Br, and R4 is tetrahydrofuranyl.

[0121] A 1-liter stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried at 130°C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of hexane was charged to the polymerization kettle, and 8.1 mg (5 μmol) of complex 65 was added. The reaction was carried out at 80°C for 30 minutes with vigorous stirring, while maintaining the ethylene pressure at 10 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid acidified ethanol solution to obtain polyethylene. The polymer was dried, weighed, and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0122] Example 12 Complex 65: A complex of formula (II) where M is Ni and R 12 and R 14 is -CF3 and R 11 , R 13 and R 15 is H, R3 is Br, and R4 is tetrahydrofuranyl.

[0123] A 100 mL stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130 °C for 6 hours, then evacuated while hot and purged with N2 three times. 50 mL of toluene and 0.9 mL (10 mmol) of methyl acrylate were charged to the polymerization kettle, and 8.1 mg (5 μmol) of complex 65 was added. The reaction was carried out at 50 °C for 60 minutes with vigorous stirring, while maintaining the ethylene pressure at 15 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid solution in ethanol to obtain a polymer. The polymer was dried, weighed, and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, polymerization activity, and comonomer content of the resulting polymer are shown in Table 1.

[0124] Example 13 Complex 11: A complex of formula (II) where M is Ni and R 12 and R 14 is methyl and R 11 , R 13 and R 15 is H, R3 is methyl, and R4 is pyridinyl.

[0125] The synthesis steps were similar to that of Complex 1 in Example 1 above, except that diphenylphosphine chloride was replaced with di(3,5-dimethylphenyl)phosphine chloride.

[0126] Under a nitrogen atmosphere, the compound of formula (III) (3.74 g, 10 mmol, R-configuration) was dissolved in anhydrous diethyl ether (120 mL). A solution of n-butyllithium (2.5 M, 12 mL, 30 mmol) was added dropwise at room temperature and stirred for 4 hours. After adding tetrahydrofuran (120 mL), the resulting black solution containing a precipitate was stirred for an additional hour. Di(3,5-dimethylphenyl)phosphine chloride (30 mmol, 8.30 g) was added at 0°C. The solution was stirred at room temperature for 1 hour and then quenched by adding aqueous NH₄Cl (5 mL). The organic phase was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and recrystallized from dichloromethane / hexane to obtain a white crystalline compound. Methanol (100 mL) and 5 mL of concentrated hydrochloric acid (37 wt%) were added, and the mixture was refluxed for 16 hours. After the reaction was completed as monitored by TLC, the organic solvent was removed, and the product was dissolved in ethyl acetate and neutralized with aqueous NaHCO. The organic phase was extracted, dried over anhydrous MgSO, filtered, concentrated, and then separated by column chromatography (dichloromethane as solvent) to give ligand L3 in 58% yield. 1 H NMR (400MHz, CDCl3) δ: 2.28 (s, 24H), 5.43 (s, 2H), 6.96~7.05 (m, 12H), 7.17 (m, 2H), 7.24 ~ 7.29 (m, 4H), 7.43 (d, 2H), 7.65 (m, 2H). High-resolution mass spectrometry test: Theoretical calculation value: 766.31, Test value: 767.32. 31 P NMR(162MHz, CDCl3)δ=-15.4(s).

[0127] Under a nitrogen atmosphere, ligand L3 (0.77 g, 1 mmol) was dissolved in tetrahydrofuran, excess NaH (0.072 g, 3 mmol) was added, and the solution was stirred at room temperature for 10 hours, after which the NaH was removed by filtration. A solution of (DME)NiBr2 (0.617 g, 2 mmol) in tetrahydrofuran was added dropwise and allowed to react at room temperature overnight. The solvent was removed by suction, and the product was dissolved in dichloromethane (40 mL). The solution was filtered to remove the cake, and the filtrate was concentrated and recrystallized from heptane to give complex 11 in 76% yield. Elemental Analysis Test C 60 H 62 Br2Ni2O4P2: Theoretical calculation: C, 60.75; H, 5.27; Tested values: C, 60.37; H, 5.51.

[0128] A 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130 °C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of toluene was charged to the polymerization kettle, and 11.8 mg (10 μmol) of complex 11 was added. The reaction was carried out at 50 °C for 20 minutes with vigorous stirring while maintaining the ethylene pressure at 10 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid acidified ethanol solution to obtain polyethylene. The polymer was dried, weighed, and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0129] Example 14 Complex 68: A complex of formula (II) where M is Pd and R 11 ~R 15 is H, R3 is methyl, and R4 is pyridinyl.

[0130] Ligand L1 was prepared by the method of Example 1.

[0131] Under a nitrogen atmosphere, ligand L1 (0.65 g, 1 mmol) was dissolved in toluene (20 mL) and added dropwise to a toluene (15 mL) solution containing the metal palladium source (TMEDA) PdMe2 (0.51 g, 2 mmol). The ligand solution was then added dropwise to the metal palladium source solution. The resulting solution was reacted at room temperature with vigorous stirring for 5 hours, 0.6 mL of pyridine was added, and the resulting solution was reacted overnight and then filtered to obtain a black solution. The solvent was removed under vacuum to give palladium complex 68 in 84% yield. 1 H NMR(400MHz,C6D6)δ:8.92(m,4H),7.79(m,6H,),7.33(m,2H),7.07~7.18(m,22H),6.94~7.00(m,4H),6.81~6.86(m,2H),0.73(d,6H). Elemental analysis test C 56 H 46 N2O2P2Pd2: Theoretical calculation: C, 63.83; H, 4.40; N, 2.66; Tested values: C, 63.62; H, 4.60; N, 2.73.

[0132] A 100 mL glass polymerization tube equipped with a mechanical stirrer was dried continuously at 130 °C for 6 hours, then evacuated while hot and purged with N2 three times. 5.0 mL of toluene and 5.0 mL of norbornene were charged into the polymerization vessel, and 4.2 mg (4 μmol) of complex 68 was added. 40 μmol of B(CF)3 was added, and the reaction was carried out at 60 °C for 10 minutes with vigorous stirring. The reaction solution was neutralized with a 10 wt% ethanolic solution of hydrochloric acid to obtain polynorbornene. The polymer was dried, weighed, and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0133] Example 15 Complex 62: A complex of formula (II) where M is Ni and R 13 is methoxy and R 11 , R 12 , R 14 and R 15 is H, R3 is Br, and R4 is tetrahydrofuranyl.

[0134] Under a nitrogen atmosphere, compound (III) (3.74 g, 10 mmol, S-configuration) was dissolved in anhydrous diethyl ether (120 mL). A solution of n-butyllithium in hexane (2.7 M, 11.1 mL, 30 mmol) was added dropwise at room temperature, and the solution was stirred at room temperature for 4 hours. Tetrahydrofuran (120 mL) was added, and the resulting black solution containing a precipitate was stirred for an additional hour. Di(4-methoxy)phosphine chloride (30 mmol, 8.42 g) was added at 0 °C. The solution was stirred at room temperature for 1 hour and then quenched by the addition of aqueous NH4Cl (5 mL). The organic phase was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and recrystallized from dichloromethane / hexane to obtain a white crystalline compound. Methanol (100 mL) and 5 mL of concentrated hydrochloric acid (37 wt%) were added, and the mixture was allowed to react under reflux for 16 hours. After the reaction was completed, which was monitored by TLC, the organic solvent was removed, and the compound was dissolved in ethyl acetate and neutralized with aqueous NaHCO3. The organic phase was extracted, dried over anhydrous MgSO4, filtered, concentrated, and separated by column chromatography (dichloromethane as solvent) to obtain ligand L4 in 56% yield. Elemental analysis test C 48 H 40 O6P2: Theoretical calculation: C, 74.41; H, 5.20; Tested values: C, 74.32; H, 5.38.

[0135] Under a nitrogen atmosphere, ligand L4 (0.77 g, 1 mmol) was dissolved in tetrahydrofuran, excess NaH (0.072 g, 3 mmol) was added, and the solution was stirred at room temperature for 10 hours, after which the NaH was removed by filtration. A solution of (DME)NiBr2 (0.617 g, 2 mmol) in tetrahydrofuran was added dropwise and allowed to react at room temperature overnight. The solvent was removed by suction, and the product was dissolved in dichloromethane (40 mL). The solution was filtered to remove the cake, and the filtrate was concentrated and recrystallized from heptane to give complex 62 in 77% yield. Elemental Analysis Test C 56 H 54 Br2Ni2O8P2: Theoretical calculation: C, 56.32; H, 4.56; Tested values: C, 56.31; H, 5.11.

[0136] A 1-liter stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried at 130°C for 6 hours, then evacuated while hot and purged with N2 three times. 500 mL of toluene was charged to the polymerization kettle, and 6.0 mg (5 μmol) of complex 62 was added. The reaction was carried out at 30°C for 20 minutes with vigorous stirring, while maintaining the ethylene pressure at 10 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid acidified ethanol solution to obtain polyethylene. The polymer was dried, weighed, and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0137] Comparative Example 1 A 1-liter stainless steel polymerization kettle equipped with a mechanical stirrer and 10 atm of ethylene was heated at 130°C for 6 hours, then evacuated while hot and purged with N2 three times. The kettle was filled with 500 mL of hexane, and 5.0 mL of methylaluminoxane (MAO) (1.53 mol / L toluene solution) and 10.1 mg (20 μmol) of Complex A (see Acta Agron. Sin. 2012, 29, 1381; ACS Catalysis 2021, 11, 5, 2902-2911 for the synthesis process) were added. The reaction was carried out at 70°C for 30 minutes with vigorous stirring, while maintaining the ethylene pressure at 10 atm. The reaction solution was neutralized with a 10 wt% hydrochloric acid solution in ethanol to obtain polyethylene. The polymer was dried, weighed, and the polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity data for the resulting polymer are shown in Table 1.

[0138] [ka]

[0139] Comparative Example 2 A 100 mL stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130 °C for 6 hours, then evacuated while hot and purged with N2 three times. 50 mL of toluene and 0.9 mL (10.0 mmol) of methyl acrylate were charged to the polymerization kettle, and 10.1 mg (10 μmol) of Complex A was added. The reaction was carried out at 70 °C for 60 minutes with vigorous stirring, while maintaining the ethylene pressure at 15 atm. The reaction solution was neutralized with a 10 wt% ethanolic solution of hydrochloric acid to obtain a polymer. The polymer was dried, weighed, and the polymerization activity was measured. The test data for the weight-average molecular weight, molecular weight distribution, polymerization activity, and comonomer content of the resulting polymer are shown in Table 1.

[0140] Comparative Example 3 A 100 mL glass polymerization tube equipped with a mechanical stirrer was dried continuously at 130 °C for 6 hours, then evacuated while hot and purged with N2 three times. The polymerization tube was filled with 5.0 mL of toluene and 5.0 mL of norbornene, and 4.3 mg (8 μmol) of complex B (see Appl. Organometal. Chem. 2017; e4013) was added. 40 μmol of B(CF)3 was added, and the reaction was carried out at 60 °C for 10 minutes with vigorous stirring. The reaction solution was neutralized with a 10 wt% ethanolic solution of hydrochloric acid to obtain polynorbornene. The polymer was dried, weighed, and its polymerization activity was measured. The weight-average molecular weight, molecular weight distribution, and polymerization activity of the resulting polymer are shown in Table 1.

[0141] [ka]

[0142] [Table 1]

[0143] As can be seen from the data in Table 1, under similar polymerization conditions, by using the metal complexes of the present invention as olefin polymerization catalysts, higher homopolymerization / copolymerization activity can be achieved, and the resulting polymers have obviously higher molecular weights and narrower molecular weight distributions.

[0144] Although the preferred embodiments of the present invention have been described in detail above, the present invention is not limited thereto. Within the technical spirit of the present invention, many simple modifications can be made to the technical solutions of the present invention, including various technical features combined in any other suitable manner, and these simple modifications and combinations should also be considered as the disclosure of the present invention, and all fall within the scope of the present invention.

Claims

1. It has a structural formula shown in formula (I): 【Chemical 1】 wherein M is selected from Group VIII metals; R １ is selected from substituted or unsubstituted C6-C20 aryl, R ３ and R ４ are each independently halogen, C1 to C10 hydrocarbyl, P(R ５ ) ３ , N.R. ６ R ７ and OR ８ R ９ or R ３ and R ４ are linked together to form an 8-membered ring, where R ５ is selected from substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C10 aryl; R ６ , R ７ , R ８ and R ９ are each independently selected from C1 to C10 hydrocarbyl, or R ６ , R ７ and N are linked together to form a 5- or 6-membered ring, or R ８ , R ９ and O are linked together to form a 5- or 6-membered ring; Preferably, the C6-C20 aryl is selected from phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, vinylphenyl, anthryl, naphthyl, or biphenyl; Preferably, for the substituted C6-C20 aryl, the substituents are selected from H, halogen, hydroxy, substituted or unsubstituted alkoxy, substituted or unsubstituted C1-C20 hydrocarbyl, preferably, the alkoxy is C1-C6 alkoxy; Preferably, for substituted alkoxy and substituted C1-C20 hydrocarbyl, the substituents are selected from halogen, hydroxy, C1-C6 alkyl, halo-substituted C1-C6 alkyl, C1-C6 alkoxy and halo-substituted C1-C6 alkoxy; Preferably, the C1 to C10 hydrocarbyl is selected from C1 to C8 hydrocarbyl, and / or Preferably, the phosphine-phenol late transition metal complex is characterized in that the C1-C20 hydrocarbyl is selected from C1-C10 alkyl or C6-C15 aryl.

2. It has a structural formula shown in formula (II), 【Chemistry 2】 In the formula, R １１ ~R １５ are each independently selected from H, halogen, hydroxy, substituted or unsubstituted alkoxy, substituted or unsubstituted C1-C20 hydrocarbyl, preferably for substituted alkoxy and substituted C1-C20 hydrocarbyl, the substituents thereof are selected from halogen, hydroxy, C1-C6 alkyl, halo-substituted C1-C6 alkyl, C1-C6 alkoxy and halo-substituted C1-C6 alkoxy.

3. 3. A phosphine-phenol late transition metal complex according to claim 1, wherein M is selected from nickel and palladium.

4. R １１ ~R １５ are each independently selected from H, halogen, hydroxy, substituted or unsubstituted alkoxy, or substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C15 aryl; Preferably, R ３ and R ４ at least one of R is selected from halogen and C1-C8 hydrocarbyl; ３ and R ４ are linked together to form an 8-membered ring, Preferably, for substituted alkoxy, substituted C1-C10 alkyl and substituted C6-C15 aryl, the substituents are independently selected from halogen, hydroxy, C1-C6 alkyl, halo-substituted C1-C6 alkyl, C1-C6 alkoxy and halo-substituted C1-C6 alkoxy; Preferably, said C1-C6 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl and 3,3-dimethylbutyl; Preferably, said C1-C6 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, isohexyloxy and 3,3-dimethylbutoxy; A phosphine-phenol late transition metal complex according to any one of claims 1 to 3, characterized in that the halogen is preferably selected from fluorine, chlorine, bromine and iodine.

5. The phosphine-phenol late transition metal complex according to any one of claims 1 to 4, characterized in that it is selected from the group consisting of the following complexes: Complex 1: A complex of formula (II) where M is Ni and R １１ ~R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 2: A complex of formula (II) where M is Ni and R １１ ~R １５ is F and R ３ is methyl, and R ４ is pyridinyl; Complex 3: A complex of formula (II) where M is Ni and R １１ is phenyl, and R １２ ~R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 4: Complex of formula (II) where M is Ni, R １１ is methyl, and R １２ ~R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 5: A complex of formula (II) where M is Ni and R １３ is methyl, and R １１ , R １２ , R １４ and R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 6: A complex of formula (II) where M is Ni and R １３ Ha-CF ３ and R １１ , R １２ , R １４ and R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 7: A complex of formula (II) where M is Ni and R １３ is F and R １１ , R １２ , R １４ and R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 8: A complex of formula (II) where M is Ni and R １３ is Cl, and R １１ , R １２ , R １４ and R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 9: A complex of formula (II) where M is Ni and R １１ , R １３ and R １５ is methyl, and R １２ and R １４ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 10: A complex of formula (II) where M is Ni and R １３ is methoxy, and R １１ , R １２ , R １４ and R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 11: A complex of formula (II) where M is Ni and R １２ and R １４ is methyl, and R １１ , R １３ and R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 12: A complex of formula (II) where M is Ni and R １２ and R １４ is methyl, and R １３ is methoxy, and R １１ and R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 13: A complex of formula (II) where M is Ni and R １２ and R １４ Ha-CF ３ and R １１ , R １３ and R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 14: A complex of formula (II) where M is Ni and R １１ and R １５ is methoxy, and R １２ ~R １４ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 15: A complex of formula (II) where M is Ni and R １１ is methoxy, and R １２ ~R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 16: A complex of formula (II) where M is Ni and R １１ ~R １５ is H and R ３ is phenyl, and R ４ is PMe ３ is; Complex 17: A complex of formula (II) where M is Ni and R １１ and R １５ is F and R ３ is phenyl, and R ４ is PMe ３ is; Complex 18: Complex of formula (II) where M is Ni and R １１ is phenyl, and R １２ ~R １５ is H and R ３ is phenyl, and R ４ is PMe ３ is; Complex 19: A complex of formula (II) where M is Ni and R １１ is methyl, and R １２ ~R １５ is H and R ３ is phenyl, and R ４ is PMe ３ is; Complex 20: A complex of formula (II) where M is Ni and R １３ is methyl, and R １１ , R １２ , R １４ and R １５ is H and R ３ is phenyl, and R ４ is PMe ３ is; Complex 21: A complex of formula (II) where M is Ni and R １３ Ha-CF ３ and R １１ , R １２ , R １４ and R １５ is H and R ３ is phenyl, and R ４ is PMe ３ is; Complex 22: A complex of formula (II) where M is Ni and R １３ is F and R １１ , R １２ , R １４ and R １５ is H and R ３ is phenyl, and R ４ is PMe ３ is; Complex 23: A complex of formula (II) where M is Ni and R １３ is Cl, and R １１ , R １２ , R １４ and R １５ is H and R ３ is phenyl, and R ４ is PMe ３ is; Complex 24: A complex of formula (II) where M is Ni and R １１ , R １３ and R １５ is methyl, and R １２ and R １４ is H and R ３ is phenyl, and R ４ is PMe ３ is; Complex 25: A complex of formula (II) where M is Ni and R １３ is methoxy, and R １１ , R １２ , R １４ and R １５ is H and R ３ is phenyl, and R ４ is PMe ３ is; Complex 26: A complex of formula (II) where M is Ni and R １２ and R １４ is methyl, and R １１ , R １３ and R １５ is H and R ３ is phenyl, and R ４ is PMe ３ is; Complex 27: A complex of formula (II) where M is Ni and R １２ and R １４ is methyl, and R １３ is methoxy, and R １１ and R １５ is H and R ３ is phenyl, and R ４ is PMe ３ is; Complex 28: A complex of formula (II) where M is Ni and R １２ and R １４ Ha-CF ３ and R １１ , R １３ and R １５ is H and R ３ is phenyl, and R ４ is PMe ３ is; Complex 29: A complex of formula (II) where M is Ni and R １１ and R １５ is methoxy, and R １２ ~R １４ is H and R ３ is phenyl, and R ４ is PMe ３ is; Complex 30: A complex of formula (II) where M is Ni and R １１ is methoxy, and R １２ ~R １５ is H and R ３ is phenyl, and R ４ is PMe ３ is; Complex 31: A complex of formula (II) where M is Ni and R １１ ~R １５ is H and R ３ , R ４ are linked together to form a cyclooctenyl; Complex 32: A complex of formula (II) where M is Ni and R １１ is phenyl, and R １２ ~R １５ is H and R ３ , R ４ are linked together to form a cyclooctenyl; Complex 33: A complex of formula (II) where M is Ni and R １１ is phenyl, and R １２ ~R １５ is H and R ３ , R ４ are linked together to form a cyclooctenyl; Complex 34: A complex of formula (II) where M is Ni and R １３ is methoxy, and R １１ , R １２ , R １４ and R １５ is H and R ３ , R ４ are linked together to form a cyclooctenyl; Complex 35: A complex of formula (II) where M is Ni and R １２ and R １４ Ha-CF ３ and R １１ , R １３ and R １５ is H and R ３ , R ４ are linked together to form a cyclooctenyl; Complex 36: A complex of formula (II) where M is Ni and R １１ and R １５ is methoxy, and R １２ ~R １４ is H and R ３ , R ４ are linked together to form a cyclooctenyl; Complex 37: A complex of formula (II) where M is Ni and R １１ is methoxy, and R １２ ~R １５ is H and R ３ , R ４ are linked together to form a cyclooctenyl; Complex 38: A complex of formula (II) where M is Ni and R １１ ~R １５ is H and R ３ is Cl, and R ４ is tetrahydrofuranyl; Complex 39: A complex of formula (II) where M is Ni and R １１ ~R １５ is F and R ３ is Cl, and R ４ is tetrahydrofuranyl; Complex 40: A complex of formula (II) where M is Ni and R １１ is phenyl, and R １２ ~R １５ is H and R ３ is Cl, and R ４ is tetrahydrofuranyl; Complex 41: A complex of formula (II) where M is Ni and R １１ is methyl, and R １２ ~R １５ is H and R ３ is Cl, and R ４ is tetrahydrofuranyl; Complex 42: A complex of formula (II) where M is Ni and R １３ is methyl, and R １１ , R １２ , R １４ and R １５ is H and R ３ is Cl, and R ４ is tetrahydrofuranyl; Complex 43: A complex of formula (II) where M is Ni and R １３ Ha-CF ３ and R １１ , R １２ , R １４ and R １５ is H and R ３ is Cl, and R ４ is tetrahydrofuranyl; Complex 44: A complex of formula (II) where M is Ni and R １３ is F and R １１ , R １２ , R １４ and R １５ is H and R ３ is Cl, and R ４ is tetrahydrofuranyl; Complex 45: A complex of formula (II) where M is Ni and R １３ is Cl, and R １１ , R １２ , R １４ and R １５ is H and R ３ is Cl, and R ４ is tetrahydrofuranyl; Complex 46: A complex of formula (II) where M is Ni and R １１ , R １３ and R １５ is methyl, and R １２ and R １４ is H and R ３ is Cl, and R ４ is tetrahydrofuranyl; Complex 47: A complex of formula (II) where M is Ni and R １３ is methoxy, and R １１ , R １２ , R １４ and R １５ is H and R ３ is Cl, and R ４ is tetrahydrofuranyl; Complex 48: A complex of formula (II) where M is Ni and R １２ and R １４ is methyl, and R １１ , R １３ and R １５ is H and R ３ is Cl, and R ４ is tetrahydrofuranyl; Complex 49: A complex of formula (II) where M is Ni and R １２ and R １４ is methyl, and R １３ is methoxy, and R １１ and R １５ is H and R ３ is Cl, and R ４ is tetrahydrofuranyl; Complex 50: A complex of formula (II) where M is Ni and R １２ and R １４ Ha-CF ３ and R １１ , R １３ and R １５ is H and R ３ is Cl, and R ４ is tetrahydrofuranyl; Complex 51: A complex of formula (II) where M is Ni and R １１ and R １５ is methoxy, and R １２ ~R １４ is H and R ３ is Cl, and R ４ is tetrahydrofuranyl; Complex 52: A complex of formula (II) where M is Ni and R １１ is methoxy, and R １２ ~R １５ is H and R ３ is Cl, and R ４ is tetrahydrofuranyl; Complex 53: A complex of formula (II) where M is Ni and R １１ ~R １５ is H and R ３ is Br, and R ４ is tetrahydrofuranyl; Complex 54: A complex of formula (II) where M is Ni and R １１ ~R １５ is F and R ３ is Br, and R ４ is tetrahydrofuranyl; Complex 55: A complex of formula (II) where M is Ni and R １１ is phenyl, and R １２ ~R １５ is H and R ３ is Br, and R ４ is tetrahydrofuranyl; Complex 56: A complex of formula (II) where M is Ni and R １１ is methyl, and R １２ ~R １５ is H and R ３ is Br, and R ４ is tetrahydrofuranyl; Complex 57: A complex of formula (II) where M is Ni and R １３ is methyl, and R １１ , R １２ , R １４ and R １５ is H and R ３ is Br, and R ４ is tetrahydrofuranyl; Complex 58: A complex of formula (II) where M is Ni and R １３ Ha-CF ３ and R １１ , R １２ , R １４ and R １５ is H and R ３ is Br, and R ４ is tetrahydrofuranyl; Complex 59: A complex of formula (II) where M is Ni and R １３ is F and R １１ , R １２ , R １４ and R １５ is H and R ３ is Br, and R ４ is tetrahydrofuranyl; Complex 60: A complex of formula (II) where M is Ni and R １３ is Cl, and R １１ , R １２ , R １４ and R １５ is H and R ３ is Br, and R ４ is tetrahydrofuranyl; Complex 61: A complex of formula (II) where M is Ni and R １１ , R １３ and R １５ is methyl, and R １２ and R １４ is H and R ３ is Br, and R ４ is tetrahydrofuranyl; Complex 62: A complex of formula (II) where M is Ni and R １３ is methoxy, and R １１ , R １２ , R １４ and R １５ is H and R ３ is Br, and R ４ is tetrahydrofuranyl; Complex 63: A complex of formula (II) where M is Ni and R １２ and R １４ is methyl, and R １１ , R １３ and R １５ is H and R ３ is Br, and R ４ is tetrahydrofuranyl; Complex 64: A complex of formula (II) where M is Ni and R １２ and R １４ is methyl, and R １３ is methoxy, and R １１ and R １５ is H and R ３ is Br, and R ４ is tetrahydrofuranyl; Complex 65: A complex of formula (II) where M is Ni and R １２ and R １４ Ha-CF ３ and R １１ , R １３ and R １５ is H and R ３ is Br, and R ４ is tetrahydrofuranyl; Complex 66: A complex of formula (II) where M is Ni and R １１ and R １５ is methoxy, and R １２ ~R １４ is H and R ３ is Br, and R ４ is tetrahydrofuranyl; Complex 67: A complex of formula (II) where M is Ni and R １１ is methoxy, and R １２ ~R １５ is H and R ３ is Br, and R ４ is tetrahydrofuranyl; Complex 68: A complex of formula (II) where M is Pd and R １１ ~R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 69: A complex of formula (II) where M is Pd and R １１ ~R １５ is F and R ３ is methyl, and R ４ is pyridinyl; Complex 70: A complex of formula (II) where M is Pd and R １１ is phenyl, and R １２ ~R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 71: A complex of formula (II) where M is Pd and R １１ is phenyl, and R １２ ~R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 72: A complex of formula (II) where M is Pd and R １１ is methyl, and R １２ ~R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 73: A complex of formula (II) where M is Pd and R １３ is methyl, and R １１ , R １２ , R １４ and R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 74: A complex of formula (II) where M is Pd and R １３ Ha-CF ３ and R １１ , R １２ , R １４ and R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 75: A complex of formula (II) where M is Pd and R １３ is F and R １１ , R １２ , R １４ and R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 76: A complex of formula (II) where M is Pd and R １３ is Cl, and R １１ , R １２ , R １４ and R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 77: A complex of formula (II) where M is Pd and R １１ , R １３ and R １５ is methyl, and R １２ and R １４ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 78: A complex of formula (II) where M is Pd and R １３ is methoxy, and R １１ , R １２ , R １４ and R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 79: A complex of formula (II) where M is Pd and R １２ and R １４ is methyl, and R １１ , R １３ and R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 80: A complex of formula (II) where M is Pd and R １２ and R １４ is methyl, and R １３ is methoxy, and R １１ and R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 81: A complex of formula (II) where M is Pd and R １２ and R １４ Ha-CF ３ and R １１ , R １３ and R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 82: A complex of formula (II) where M is Pd and R １１ and R １５ is methoxy, and R １２ ~R １４ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 83: A complex of formula (II) where M is Pd and R １１ is methoxy, and R １２ ~R １５ is H and R ３ is methyl, and R ４ is pyridinyl; Complex 84: A complex of formula (II) where M is Pd and R １１ ~R １５ is H and R ３ is methyl, and R ４ is Cl; Complex 85: A complex of formula (II) where M is Pd and R １１ is phenyl, and R １２ ~R １５ is H and R ３ is methyl, and R ４ is Cl; Complex 86: A complex of formula (II) where M is Pd and R １３ is methoxy, and R １１ , R １２ , R １４ and R １５ is H and R ３ is methyl, and R ４ is Cl; Complex 87: A complex of formula (II) where M is Pd and R １２ and R １４ Ha-CF ３ and R １１ , R １３ and R １５ is H and R ３ is methyl, and R ４ is Cl; Complex 88: A complex of formula (II) where M is Pd and R １１ and R １５ is methoxy, and R １２ ~R １４ is H and R ３ is methyl, and R ４ is Cl; Complex 89: A complex of formula (II) where M is Pd and R １１ is methoxy, and R １２ ~R １５ is H and R ３ is methyl, and R ４ is Cl.

6. A process for preparing a phosphine-phenol late transition metal complex according to any one of claims 1 to 5, characterized in that it comprises the following steps: (1) reacting a compound of formula (III) with a compound of formula (IV) to obtain a ligand; (2) reacting the ligand with an M metal compound; 【Chemistry 3】 wherein M metal is selected from Group VIII metals, preferably nickel and / or palladium; R １ The definitions of are the same as those defined in claim 1.

7. The M metal compound is dimethyldipyridinylnickel, bis(1,5-cyclooctadienyl)nickel, tetrapyridinylnickel dichloride, ethylene glycol dimethyl ether nickel bromide, ethylene glycol dimethyl ether nickel chloride, di(trimethylphosphino)nickel dichloride, di(pyridinyl)di[(trimethylsilyl)methyl]nickel, (phenyl)(N,N,N',N'-tetramethyl-1,2-ethylenediamine)nickel chloride, dibenzyldipyridinylnickel, phenyl( 7. The method of claim 6, wherein the palladium compound is selected from at least one of di(trimethylphosphino)nickel bromide, phenyl(triethylphosphino)nickel chloride, diphenyldi(trimethylphosphino)nickel, di(trimethylphosphino)nickel dichloride, dimethyldipyridinylpalladium, dipyridinylpalladium dichloride, di(pyridinyl)di[(trimethylsilyl)methyl]palladium, dibenzyldipyridinylpalladium, and methyl-1,5-cyclooctadiene-palladium chloride.

8. 8. The method according to claim 6 or 7, wherein the reaction in step (2) is carried out in the presence of a reaction solvent, and the reaction solvent is tetrahydrofuran.

9. Use of the phosphine-phenol late transition metal complexes according to claims 1 to 5 in olefin polymerization.

10. carrying out an olefin polymerization reaction in the presence of the phosphine-phenol late transition metal complex of any one of claims 1 to 5, Preferably, the olefin polymerization reaction is carried out at a temperature of -78°C to 200°C, preferably -20°C to 150°C, and at a pressure of 0.01 to 10 MPa, preferably 0.01 to 5 MPa.

11. The method comprises the step of copolymerizing (a) an α-olefin and (b) a (meth)acrylate monomer, a vinyl monomer, or an allyl monomer in the presence of the phosphine-phenol late transition metal complex according to any one of claims 1 to 5, Preferably, the (meth)acrylate monomer has the general formula CH ２ = C(R ３１ ) CO ２ (R ３２ ) and Preferably, R ３１ is H or C1-C10 hydrocarbyl, optionally with branched, cyclic and / or unsaturated bonds; Preferably, R ３２ is a C1 to C30 hydrocarbyl, optionally having branched, cyclic and / or unsaturated bonds; R ３２ optionally containing a heteroatom at any position thereof.

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