Post-transition metal complex as well as preparation method and application thereof

Abstract

The present invention relates to the field of olefin polymerization organic metal catalysts, and discloses a late transition metal complex, the structural formula of the late transition metal complex is represented by formula (I), M is selected from group VIII metals, R1 is selected from substituted or unsubstituted C6-C20 aryl, R3 and R4 are independently selected from halogen, C1-C10 alkyl, P (R5) 3, NR6R7 and OR8R9, or R3 and R4 are connected to form an eight-membered ring; wherein R < 5 > is selected from a substituted or unsubstituted C < 1 > to C < 10 > alkyl group and a substituted or unsubstituted C < 6 > to C < 10 > aryl group; r6 and R7 are independently selected from C1-C10 alkyl, or R6, R7 and N are mutually connected to form a five-membered ring or a six-membered ring; r8 and R9 are independently selected from C1-C10 alkyl, or R8, R9 and O are mutually connected to form a five-membered ring or a six-membered ring. The olefin polymerization catalyst prepared from the late transition metal complex has high polymerization activity under similar polymerization conditions.

Description

Technical Field

[0001] This invention relates to the field of organometallic catalysts for olefin polymerization, specifically to a post-transition metal complex, its preparation method, and its application. Background Technology

[0002] Polyolefin resins have excellent environmental compatibility compared to other resin materials, and are therefore widely used in industry and daily life. Polyethylene resin is an important polyolefin resin. Industrially used polyethylene catalysts include Ziegler-Natta type catalysts (see, for example, DE Pat 889229 (1953); IT Pat 545332 (1956) and IT Pat 536899 (1955); Chem. Rev., 2000, 100, 1169 and related literature in this issue), Phillips type catalysts (for example, Belg. Pat. 530617 (1955); Chem. Rev. 1996, 96, 3327), metallocene catalysts (for example, W. Kaminsky, Metalorganic Catalysts for Synthesis and Polymerization, Berlin: Springer, 1999), and post-transition metal complex ethylene oligomerization / polymerization catalysts that have developed rapidly in recent years. In 2006, the Gibson group of British scientists discovered that group IV phenol-phosphine zirconium complexes have good catalytic ability for olefin polymerization. With the activation of co-catalysts such as methylaluminoxane (MAO), they can effectively carry out ethylene or propylene polymerization reactions (Inorg. Chem, 2006, 45, 511-513, Organometallics 2008, 27, 235-245).

[0003] However, all of the above catalysts have the problem of not being able to maintain high catalytic activity and high polymerization performance at high temperatures. Summary of the Invention

[0004] The purpose of this invention is to overcome the problems existing in the prior art and provide a post-transition metal complex. Catalysts for olefin polymerization prepared using this post-transition metal complex have high polymerization activity at high temperatures.

[0005] To achieve the above objectives, the present invention provides a post-transition metal complex with the structural formula shown in formula (Ⅰ).

[0006]

[0007] M is selected from group VIII metals, R1 is selected from substituted or unsubstituted C6-C20 aryl groups, and R3 and R4 are each independently selected from halogens, C1-C10 hydrocarbon groups, P(R5)3, NR6R7 and OR8R9, or R3 and R4 are connected to each other to form an eight-membered ring.

[0008] R5 is selected from substituted or unsubstituted C1-C10 alkyl groups and substituted or unsubstituted C6-C10 aryl groups;

[0009] R6 and R7 are each independently selected from C1-C10 hydrocarbon groups, or R6 and R7 are connected with N to form a five-membered ring or a six-membered ring;

[0010] R8 and R9 are each independently selected from C1-C10 hydrocarbon groups, or R8 and R9 are connected with O to form a five-membered ring or a six-membered ring.

[0011] Preferably, the structural formula of the post-transition metal complex is shown in formula (ⅠⅠ).

[0012]

[0013] Among them, R 11 -R 15 Each is independently selected from hydrogen, halogen, hydroxyl, and substituted or unsubstituted C1-C20 hydrocarbon groups.

[0014] Preferably, M is selected from nickel or palladium.

[0015] Preferably, at least one of R3 and R4 is selected from halogens or C1-C8 hydrocarbon groups, or R3 and R4 are interconnected to form an eight-membered ring.

[0016] Preferably, R 11 -R 15 Each is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C15 aryl.

[0017] Preferably, the substituent is selected from halogen, hydroxyl, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy.

[0018] Preferably, the C1-C6 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl or 3,3-dimethylbutyl.

[0019] Preferably, the C1-C6 alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexyloxy, isohexyloxy, or 3,3-dimethylbutoxy.

[0020] Preferably, the halogen is selected from fluorine, chlorine, bromine or iodine.

[0021] A second aspect of the present invention provides a method for preparing the above-mentioned post-transition metal complex, the method comprising the following steps:

[0022] (1) The compound shown in formula (III) is reacted with the compound shown in formula (IV) to generate a ligand;

[0023] (2) The ligand is reacted with the metal compound M;

[0024]

[0025] In this compound, the metal M is selected from group VIII metals, preferably nickel or palladium, and the definition of R1 is the same as described above.

[0026] Preferably, the M metal compound is selected from at least one of dimethyl dipyridinium nickel, bis(1,5-cyclooctadiene) nickel, dichlorotetrapyridinium nickel, ethylene glycol dimethyl ether nickel bromide, ethylene glycol dimethyl ether nickel chloride, dichlorodi(trimethylphosphine) nickel, di(pyridinium)bis[(trimethylsilyl)methyl] nickel, chloro(phenyl)(N,N,N',N'-tetramethyl-1,2-ethylenediamine) nickel, dibenzyl dipyridinium nickel, phenyl(trimethylphosphine) nickel bromide, phenyl(triethylphosphine) nickel chloride, diphenyldi(trimethylphosphine) nickel, dichlorodi(trimethylphosphine) nickel, dimethyl dipyridinium palladium, dichlorodipyridinium palladium, di(pyridinium)bis[(trimethylsilyl)methyl] palladium, dimethyl(N,N,N,N-tetramethylethylenediamine) palladium, dibenzyl dipyridinium palladium, and methyl-1,5-cyclooctadiene-palladium chloride.

[0027] A third aspect of the present invention provides the application of the above-mentioned post-transition metal complex in olefin polymerization.

[0028] A fourth aspect of the present invention provides a catalyst composition for olefin polymerization, the catalyst composition comprising a post-transition metal complex, chlorinated hydrocarbon silicon, an organoaluminum compound, and a silica gel support;

[0029] The post-transition metal complex is the aforementioned post-transition metal complex.

[0030] Preferably, based on each gram of silica gel carrier, the amount of chlorinated hydrocarbon silicon is 0.01-3 mmol, the amount of organoaluminum compound is 0.01-30 mmol, and the amount of metal M in the subsequent transition metal complex is 1-1000 μmol.

[0031] Preferably, the general formula of the chlorinated hydrocarbon-based silicon is as follows: Cl n Si(R 16 ) 4-n ;where R 16It is a C1-20 hydrocarbon group, and n is selected from 1 to 4 and n is an integer.

[0032] Preferably, the organoaluminum compound is selected from alkylaluminoxanes, alkylaluminum compounds, or alkylaluminum chloride compounds; wherein the general formula of alkylaluminoxanes is:

[0033]

[0034] Where R is a C1-12 hydrocarbon group, and a is selected from 4 to 30 and a is an integer.

[0035] The fifth aspect of this invention provides a method for preparing a catalyst for olefin polymerization, the method comprising the following steps:

[0036] A1: Under an inert atmosphere, the dispersant S1, the silica gel support and chlorinated hydrocarbon silicon in the above-mentioned catalyst composition for olefin polymerization are reacted at 0-120°C for 3-24 hours;

[0037] A2: Under an inert atmosphere, the intermediate material obtained in step A1, the dispersant S2, and the organoaluminum compound in the above-mentioned catalyst composition for olefin polymerization are reacted at 30-120°C for 3-24 hours.

[0038] A3: Under an inert atmosphere, the intermediate material obtained in step A2, the dispersant S3, and the post-transition metal complex in the above-mentioned catalyst composition for olefin polymerization are reacted at 0-120°C for 0.5-24 h.

[0039] The dispersant S1, dispersant S2 and dispersant S3 are each independently selected from one or more of toluene, benzene, xylene, hexane, heptane and cyclohexane.

[0040] The sixth aspect of the present invention provides a catalyst for olefin polymerization prepared by the above method, wherein, based on the total weight of the catalyst for olefin polymerization, the aluminum content is 1-15 wt% and the metal M content is 0.05-10 wt%.

[0041] A seventh aspect of the present invention provides a method for olefin polymerization, comprising carrying out an olefin polymerization reaction in the presence of the catalyst described above for olefin polymerization.

[0042] Preferably, during the polymerization reaction, the concentration of the catalyst used for olefin polymerization is 1×10⁻⁶. -8 mol / L~1×10 -3 mol / L, preferably 1×10 -8 mol / L~1×10 -5 mol / L;

[0043] Preferably, the polymerization temperature is -78℃ to 150℃, more preferably 0℃ to 90℃; the polymerization pressure is 0.01 to 10MPa, more preferably 0.01 to 2MPa.

[0044] Compared with the prior art, the present invention has the following advantages:

[0045] (1) The method for synthesizing post-transition metal complexes described in this invention is simple, has a high yield, and low cost;

[0046] (2) The catalyst for olefin polymerization described in this invention can catalyze ethylene polymerization or copolymerization with high activity and maintain high polymerization activity even at higher polymerization temperatures;

[0047] (3) The catalyst particles for olefin polymerization described in this invention have good particle morphology, adjustable particle size, and high packing density, and can be applied to slurry polymerization and gas-phase polymerization processes. Detailed Implementation

[0048] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0049] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0050] In the description of this application, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating relative importance or implying the number of technical features indicated. Therefore, unless otherwise stated, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature; "multiple" means two or more. The term "comprising" and any variations thereof mean non-exclusive inclusion, where one or more other features, integers, steps, operations, units, components, and / or combinations thereof may be present or added.

[0051] In one aspect, this invention provides a post-transition metal complex, the structural formula of which is shown in formula (Ⅰ).

[0052]

[0053] M is selected from group VIII metals, R1 is selected from substituted or unsubstituted C6-C20 aryl groups, and R3 and R4 are each independently selected from halogens, C1-C10 hydrocarbon groups, P(R5)3, NR6R7 and OR8R9, or R3 and R4 are connected to each other to form an eight-membered ring.

[0054] R5 is selected from substituted or unsubstituted C1-C10 alkyl groups and substituted or unsubstituted C6-C10 aryl groups;

[0055] R6 and R7 are each independently selected from C1-C10 hydrocarbon groups, or R6 and R7 are connected with N to form a five-membered ring or a six-membered ring;

[0056] R8 and R9 are each independently selected from C1-C10 hydrocarbon groups, or R8 and R9 are connected with O to form a five-membered ring or a six-membered ring.

[0057] In a preferred embodiment, the post-transition metal complex has the structural formula shown in formula (ⅠⅠ).

[0058]

[0059] Among them, R 11 -R 15 Each is independently selected from hydrogen, halogen, hydroxyl, and substituted or unsubstituted C1-C20 hydrocarbon groups.

[0060] In a preferred embodiment, R 11 -R 15 Each is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C15 aryl.

[0061] In a preferred embodiment, M is selected from nickel or palladium.

[0062] In a preferred embodiment, at least one of R3 and R4 is selected from halogens or C1-C8 hydrocarbon groups, or R3 and R4 are interconnected to form an eight-membered ring.

[0063] In a preferred embodiment, R3 and R4 are each independently selected from halogens or C1-C10 hydrocarbon groups (such as C1-C10 alkyl or C6-C10 aryl).

[0064] In a more preferred embodiment, R3 is selected from halogens or C1-C8 hydrocarbon groups (such as C1-C8 alkyl or C6-C8 aryl), R4 is selected from P(R5)3, NR6R7 and OR8R9, wherein R5 is a substituted or unsubstituted C1-C10 alkyl and a substituted or unsubstituted C6-C10 aryl; R6 and R7 are each independently selected from C1-C6 hydrocarbon groups, and R6 and R7 are interconnected with N to form a five-membered ring or a six-membered ring; R8 and R9 are each independently selected from C1-C10 hydrocarbon groups, and R8 and R9 are interconnected with O to form a five-membered ring or a six-membered ring.

[0065] According to some embodiments of the present invention, R3 and R4 are interconnected to form an octet.

[0066] In this invention, "substituted or unsubstituted" means containing a substituent, which can be selected from halogens, hydroxyl groups, C1-C6 alkyl groups, halogenated C1-C6 alkyl groups, C1-C6 alkoxy groups, or halogenated C1-C6 alkoxy groups.

[0067] In a preferred embodiment, the C1-C6 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, or 3,3-dimethylbutyl.

[0068] In a preferred embodiment, the C1-C6 alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexyloxy, isohexyloxy, or 3,3-dimethylbutoxy.

[0069] In this invention, the halogen is selected from fluorine, chlorine, bromine or iodine.

[0070] In a further preferred embodiment, the post-transition metal complex is selected from the group consisting of the following complexes.

[0071] Complex 1: The complex shown in formula (II), where M is Ni and R is... 11 -R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0072] Complex 2: The complex shown in formula (II), where M is Ni and R is... 11 -R 15 F is F, R3 is methyl, and R4 is pyridine;

[0073] Complex 3: The complex shown in formula (II), where M is Ni and R is... 11 It is a phenyl group, R 12 -R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0074] Complex 4: The complex shown in formula (II), where M is Ni and R is... 11 For methyl, R 12 -R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0075] Complex 5: The complex shown in formula (II), where M is Ni and R is... 13 For methyl, R 11 R 12 R 14 and R15 R3 is H, R4 is methyl, and R5 is pyridine.

[0076] Complex 6: The complex shown in formula (II), where M is Ni and R is... 13 For -CF3, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0077] Complex 7: The complex shown in formula (II), where M is Ni and R is... 13 For F, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0078] Complex 8: The complex shown in formula (II), where M is Ni and R is... 13 For Cl, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0079] Complex 9: The complex shown in formula (II), where M is Ni and R is... 11 R 13 and R 15 For methyl, R 12 and R 14 R3 is H, R4 is methyl, and R5 is pyridine.

[0080] Complex 10: The complex shown in formula (II), where M is Ni and R is... 13 It is a methoxy group, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0081] Complex 11: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For methyl, R 11 R 13 and R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0082] Complex 12: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For methyl, R 13 It is a methoxy group, R 11 and R 15R3 is H, R4 is methyl, and R5 is pyridine.

[0083] Complex 13: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For -CF3, R 11 R 13 and R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0084] Complex 14: The complex shown in formula (II), where M is Ni and R is... 11 and R 15 It is a methoxy group, R 12 -R 14 R3 is H, R4 is methyl, and R5 is pyridine.

[0085] Complex 15: The complex shown in formula (II), where M is Ni and R is... 11 It is a methoxy group, R 12 -R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0086] Complex 16: The complex shown in formula (II), where M is Ni and R is... 11 -R 15 R3 is H, R4 is phenyl, and R5 is PMe3.

[0087] Complex 17: The complex shown in formula (II), where M is Ni and R is... 11 and R 15 R3 is F, R4 is phenyl, and R5 is PMe3.

[0088] Complex 18: The complex shown in formula (II), where M is Ni and R is... 11 It is a phenyl group, R 12 -R 15 R3 is H, R4 is phenyl, and R5 is PMe3.

[0089] Complex 19: The complex shown in formula (II), where M is Ni and R is... 11 For methyl, R 12 -R 15 R3 is H, R4 is phenyl, and R5 is PMe3.

[0090] Complex 20: The complex shown in formula (II), where M is Ni and R is... 13 For methyl, R 11 R 12 R 14 and R 15 R3 is H, R4 is phenyl, and R5 is PMe3.

[0091] Complex 21: The complex shown in formula (II), where M is Ni and R is... 13 For -CF3, R 11 R 12 R 14 and R 15 R3 is H, R4 is phenyl, and R5 is PMe3.

[0092] Complex 22: The complex shown in formula (II), where M is Ni and R is... 13 For F, R 11 R 12 R 14 and R 15 R3 is H, R4 is phenyl, and R5 is PMe3.

[0093] Complex 23: The complex shown in formula (II), where M is Ni and R is... 13 For Cl, R 11 R 12 R 14 and R 15 R3 is H, R4 is phenyl, and R5 is PMe3.

[0094] Complex 24: The complex shown in formula (II), where M is Ni and R is... 11 R 13 and R 15 For methyl, R 12 and R 14 R3 is H, R4 is phenyl, and R5 is PMe3.

[0095] Complex 25: The complex shown in formula (II), where M is Ni and R is... 13 It is a methoxy group, R 11 R 12 R 14 and R 15 R3 is H, R4 is phenyl, and R5 is PMe3.

[0096] Complex 26: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For methyl, R 11 R 13 and R 15 R3 is H, R4 is phenyl, and R5 is PMe3.

[0097] Complex 27: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For methyl, R 13 It is a methoxy group, R 11 and R 15 R3 is H, R4 is phenyl, and R5 is PMe3.

[0098] Complex 28: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For -CF3, R 11 R 13 and R 15 R3 is H, R4 is phenyl, and R5 is PMe3.

[0099] Complex 29: The complex shown in formula (II), where M is Ni and R is... 11 and R 15 It is a methoxy group, R 12 -R 14 R3 is H, R4 is phenyl, and R5 is PMe3.

[0100] Complex 30: The complex shown in formula (II), where M is Ni and R is... 11 It is a methoxy group, R 12 -R 15 R3 is H, R4 is phenyl, and R5 is PMe3.

[0101] Complex 31: The complex shown in formula (II), where M is Ni and R is... 11 -R 15 H, R3 and R4 are interconnected to form cyclooctene;

[0102] Complex 32: The complex shown in formula (II), where M is Ni and R is... 11 It is a phenyl group, R 12 -R 15 H, R3 and R4 are interconnected to form cyclooctene;

[0103] Complex 33: The complex shown in formula (II), where M is Ni and R is... 11 It is a phenyl group, R 12 -R 15 H, R3 and R4 are interconnected to form cyclooctene;

[0104] Complex 34: The complex shown in formula (II), where M is Ni and R is... 13 It is a methoxy group, R 11 R 12 R 14 and R 15 H, R3 and R4 are interconnected to form cyclooctene;

[0105] Complex 35: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For -CF3, R 11 R 13 and R 15 H, R3 and R4 are interconnected to form cyclooctene;

[0106] Complex 36: The complex shown in formula (II), where M is Ni and R is... 11 and R 15 It is a methoxy group, R 12 -R 14 H, R3 and R4 are interconnected to form cyclooctene;

[0107] Complex 37: The complex shown in formula (II), where M is Ni and R is... 11 It is a methoxy group, R 12 -R 15 H, R3 and R4 are interconnected to form cyclooctene;

[0108] Complex 38: The complex shown in formula (II), where M is Ni and R is... 11 -R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran.

[0109] Complex 39: The complex shown in formula (II), where M is Ni and R is... 11 -R 15 R3 is F, R4 is Cl, and R5 is tetrahydrofuran.

[0110] Complex 40: The complex shown in formula (II), where M is Ni and R is... 11 It is a phenyl group, R 12 -R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran.

[0111] Complex 41: The complex shown in formula (II), where M is Ni and R is... 11 For methyl, R 12 -R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran.

[0112] Complex 42: The complex shown in formula (II), where M is Ni and R is... 13 For methyl, R 11 R 12 R 14 and R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran.

[0113] Complex 43: The complex shown in formula (II), where M is Ni and R is... 13 For -CF3, R 11 R 12 R 14 and R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran.

[0114] Complex 44: The complex shown in formula (II), where M is Ni and R is... 13 For F, R11 R 12 R 14 and R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran.

[0115] Complex 45: The complex shown in formula (II), where M is Ni and R is... 13 For Cl, R 11 R 12 R 14 and R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran.

[0116] Complex 46: The complex shown in formula (II), where M is Ni and R is... 11 R 13 and R 15 For methyl, R 12 and R 14 R3 is H, R4 is Cl, and R5 is tetrahydrofuran.

[0117] Complex 47: The complex shown in formula (II), where M is Ni and R is... 13 It is a methoxy group, R 11 R 12 R 14 and R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran.

[0118] Complex 48: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For methyl, R 11 R 13 and R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran.

[0119] Complex 49: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For methyl, R 13 It is a methoxy group, R 11 and R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran.

[0120] Complex 50: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For -CF3, R 11 R 13 and R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran.

[0121] Complex 51: The complex shown in formula (II), where M is Ni and R is... 11and R 15 It is a methoxy group, R 12 -R 14 R3 is H, R4 is Cl, and R5 is tetrahydrofuran.

[0122] Complex 52: The complex shown in formula (II), where M is Ni and R is... 11 It is a methoxy group, R 12 -R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran.

[0123] Complex 53: The complex shown in formula (II), where M is Ni and R is... 11 -R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran.

[0124] Complex 54: The complex shown in formula (II), where M is Ni and R is... 11 -R 15 R3 is F, R4 is Br, and R5 is tetrahydrofuran.

[0125] Complex 55: The complex shown in formula (II), where M is Ni and R is... 11 It is a phenyl group, R 12 -R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran.

[0126] Complex 56: The complex shown in formula (II), where M is Ni and R is... 11 For methyl, R 12 -R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran.

[0127] Complex 57: The complex shown in formula (II), where M is Ni and R is... 13 For methyl, R 11 R 12 R 14 and R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran.

[0128] Complex 58: The complex shown in formula (II), where M is Ni and R is... 13 For -CF3, R 11 R 12 R 14 and R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran.

[0129] Complex 59: The complex shown in formula (II), where M is Ni and R is... 13 For F, R 11 R 12 R 14 and R15 R3 is H, R4 is Br, and R5 is tetrahydrofuran.

[0130] Complex 60: The complex shown in formula (II), where M is Ni and R is... 13 For Cl, R 11 R 12 R 14 and R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran.

[0131] Complex 61: The complex shown in formula (II), where M is Ni and R is... 11 R 13 and R 15 For methyl, R 12 and R 14 R3 is H, R4 is Br, and R5 is tetrahydrofuran.

[0132] Complex 62: The complex shown in formula (II), where M is Ni and R is... 13 It is a methoxy group, R 11 R 12 R 14 and R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran.

[0133] Complex 63: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For methyl, R 11 R 13 and R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran.

[0134] Complex 64: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For methyl, R 13 It is a methoxy group, R 11 and R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran.

[0135] Complex 65: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For -CF3, R 11 R 13 and R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran.

[0136] Complex 66: The complex shown in formula (II), where M is Ni and R is... 11 and R 15 It is a methoxy group, R 12 -R14 R3 is H, R4 is Br, and R5 is tetrahydrofuran.

[0137] Complex 67: The complex shown in formula (II), where M is Ni and R is... 11 It is a methoxy group, R 12 -R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran.

[0138] Complex 68: The complex shown in formula (II), where M is Pd and R is... 11 -R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0139] Complex 69: The complex shown in formula (II), where M is Pd and R is... 11 -R 15 F is F, R3 is methyl, and R4 is pyridine;

[0140] Complex 70: The complex shown in formula (II), where M is Pd and R is... 11 It is a phenyl group, R 12 -R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0141] Complex 71: The complex shown in formula (II), where M is Pd and R is... 11 It is a phenyl group, R 12 -R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0142] Complex 72: The complex shown in formula (II), where M is Pd and R is... 11 For methyl, R 12 -R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0143] Complex 73: The complex shown in formula (II), where M is Pd and R is... 13 For methyl, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0144] Complex 74: The complex shown in formula (II), where M is Pd and R is... 13 For -CF3, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0145] Complex 75: The complex shown in formula (II), where M is Pd and R is...13 For F, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0146] Complex 76: The complex shown in formula (II), where M is Pd and R is... 13 For Cl, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0147] Complex 77: The complex shown in formula (II), where M is Pd and R is... 11 R 13 and R 15 For methyl, R 12 and R 14 R3 is H, R4 is methyl, and R5 is pyridine.

[0148] Complex 78: The complex shown in formula (II), where M is Pd and R is... 13 It is a methoxy group, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0149] Complex 79: The complex shown in formula (II), where M is Pd and R is... 12 and R 14 For methyl, R 11 R 13 and R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0150] Complex 80: The complex shown in formula (II), where M is Pd and R is... 12 and R 14 For methyl, R 13 It is a methoxy group, R 11 and R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0151] Complex 81: The complex shown in formula (II), where M is Pd and R is... 12 and R 14 For -CF3, R 11 R 13 and R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0152] Complex 82: The complex shown in formula (II), where M is Pd and R is...11 and R 15 It is a methoxy group, R 12 -R 14 R3 is H, R4 is methyl, and R5 is pyridine.

[0153] Complex 83: The complex shown in formula (II), where M is Pd and R is... 11 It is a methoxy group, R 12 -R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0154] Complex 84: The complex shown in formula (II), where M is Pd and R is... 11 -R 15 R3 is H, R4 is methyl, and R5 is Cl.

[0155] Complex 85: The complex shown in formula (II), where M is Pd and R is... 11 It is a phenyl group, R 12 -R 15 R3 is H, R4 is methyl, and R5 is Cl.

[0156] Complex 86: The complex shown in formula (II), where M is Pd and R is... 13 It is a methoxy group, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is Cl.

[0157] Complex 87: The complex shown in formula (II), where M is Pd and R is... 12 and R 14 For -CF3, R 11 R 13 and R 15 R3 is H, R4 is methyl, and R5 is Cl.

[0158] Complex 88: The complex shown in formula (II), where M is Pd and R is... 11 and R 15 It is a methoxy group, R 12 -R 14 R3 is H, R4 is methyl, and R5 is Cl.

[0159] Complex 89: The complex shown in formula (II), where M is Pd and R is... 11 It is a methoxy group, R 12 -R 15 R3 is H, R4 is methyl, and R5 is Cl.

[0160] A second aspect of the present invention provides a method for preparing the above-mentioned post-transition metal complex, the method comprising the following steps:

[0161] (1) React the compound shown in formula (III) with the compound shown in formula (IV) to generate a ligand;

[0162] (2) The ligand is reacted with the metal compound M;

[0163]

[0164] In this compound, the metal M is selected from group VIII metals, preferably nickel or palladium, and the definition of R1 is the same as described above.

[0165] In the method described in this invention, the M metal compound is selected from nickel dimethyl dipyridinium (Py2NiMe2), bis(1,5-cyclooctadiene)nickel (Ni(COD)2), nickel dichlorotetrapyridinium (Ni2Cl2Py4), nickel dimethyl ether bromide ((DME)NiBr2), nickel dimethyl ether chloride ((DME)NiCl2), nickel dichlorodi(trimethylphosphine) (NiCl2(PMe3)2), bis(pyridinium)bis[(trimethylsilyl)methyl]nickel (Ni(Py)2(CH2SiMe3)2), nickel chloro(phenyl)(N,N,N',N'-tetramethyl-1,2-ethylenediamine) (NiArBr(TMEDA)), nickel dibenzyl dipyridinium (Ni(CH2Ph)2Py2), and phenyl(trimethylphosphine) bromide. The nickel chloride (NiPhBr(PMe3)2, phenyl(triethylphosphine)nickel chloride (NiPhCl(PEt3)2), diphenyldi(trimethylphosphine)nickel (NiPh2(PMe3)2), dichlorodi(trimethylphosphine)nickel (NiCl2(PMe3)2), dimethyldipyridinium palladium (Pd(Me)2Py2), dichlorodipyridinium palladium (PdCl2Py2), di(pyridine)bis[(trimethylsilyl)methyl]palladium (Pd(Py)2(CH2SiMe3)2), dimethyl(N,N,N,N tetramethylethylenediamine)palladium ((TMEDA)PdMe2, (dibenzyldipyridinium palladium (Pd(CH2Ph)2Py2) and methyl-1,5-cyclooctadiene-palladium chloride (Pd(COD)ClMe)).

[0166] In this invention, "Me" refers to methyl, "Ph" refers to phenyl, and "Et" refers to ethyl.

[0167] In the method described in this invention, the reaction process of step (1) is shown in the following reaction formula.

[0168]

[0169] The definition of R1 is the same as described above.

[0170] In a preferred embodiment, the reaction process of step (1) is as shown in the following reaction formula.

[0171]

[0172] Among them, R 11 -R 15 The definition is the same as described above.

[0173] In the method described in this invention, the reaction process of step (2) is shown in the following reaction formula.

[0174]

[0175] The definitions of M, R1, R3, and R4 are the same as those described above.

[0176] In a preferred embodiment, the reaction process of step (2) is shown in the following reaction formula.

[0177]

[0178] Among them, M, R3, R4, R 11 -R 15 The definition is the same as described above.

[0179] In the method described in this invention, the reaction in step (1) is carried out in the presence of a solvent; in a specific embodiment, the solvent may be diethyl ether.

[0180] In the method described in this invention, the reaction in step (2) is carried out in the presence of a reaction solvent; in a preferred embodiment, the reaction solvent may be toluene or tetrahydrofuran; in a preferred case, the reaction solvent is tetrahydrofuran.

[0181] In one specific embodiment, the preparation process of step (1) includes: dissolving the compound shown in formula (III) in anhydrous diethyl ether in a protective gas atmosphere (such as nitrogen), adding a dehydrogenating agent (such as n-butyllithium) at room temperature and stirring, then adding tetrahydrofuran to obtain a black solution containing precipitate, continuing to stir, then adding the compound shown in formula (V), stirring at room temperature, adding NH4Cl aqueous solution to quench, extracting the organic phase with ethyl acetate, drying the obtained organic phase with anhydrous sodium sulfate, recrystallizing with dichloromethane / hexane; then adding methanol and concentrated hydrochloric acid, refluxing the reaction, removing the organic solvent after the reaction is complete, dissolving the product in ethyl acetate, adding NaHCO3 aqueous solution to neutralize, extracting the organic phase, and then sequentially drying, filtering, concentrating, and column chromatography to obtain the ligand.

[0182] In one specific embodiment, the preparation process of step (2) includes: in a protective gas atmosphere (such as nitrogen), dissolving the ligand obtained in step (1) and the M metal compound in an organic solvent (such as toluene, tetrahydrofuran, etc.), then stirring and mixing the ligand solution and the M metal compound solution and reacting at room temperature, filtering, concentrating the filtrate, adding heptane for recrystallization, and obtaining the post-transition metal complex of the present invention.

[0183] A third aspect of the present invention provides the application of the above-mentioned post-transition metal complex in olefin polymerization.

[0184] In a preferred embodiment, the polymerization can be homopolymerization or copolymerization.

[0185] In a preferred embodiment, the olefin is selected from ethylene or α-olefin.

[0186] In a more preferred embodiment, the α-olefin is selected from propylene, butene, pentene, hexene, octene, or 4-methyl-1-pentene.

[0187] A fourth aspect of the present invention provides a catalyst composition for olefin polymerization, the catalyst composition comprising a post-transition metal complex, chlorinated hydrocarbon silicon, an organoaluminum compound, and a silica gel support;

[0188] The post-transition metal complex is the aforementioned post-transition metal complex.

[0189] In a preferred embodiment, based on each gram of silica gel carrier, the amount of chlorinated alkyl silicon is 0.01-3 mmol, the amount of organoaluminum compound is 0.01-30 mmol, and the amount of metallic chromium in the subsequent transition metal complex is 1-1000 μmol. Specifically, the amount of chlorinated alkyl silicon can be 0.01 mmol, 0.05 mmol, 0.1 mmol, 0.5 mmol, 1 mmol, 2 mmol, or 3 mmol; the amount of organoaluminum compound can be 0.01 mmol, 1 mmol, 5 mmol, 10 mmol, 15 mmol, 20 mmol, 25 mmol, or 30 mmol; and the amount of metallic chromium in the subsequent transition metal complex can be 1 μmol, 100 μmol, 200 μmol, 300 μmol, 400 μmol, 500 μmol, 600 μmol, 700 μmol, 800 μmol, 900 μmol, or 1000 μmol.

[0190] In this invention, the general formula of the chlorinated hydrocarbon-based silicon is as follows: Cl n Si(R 16 ) 4-n ;where R 16 It is a C1-20 hydrocarbon group, and n is selected from 1 to 4 and n is an integer.

[0191] In a preferred embodiment, the chlorinated hydrocarbon silicon is selected from trimethylchlorosilane, triethylchlorosilane, triisopropylchlorosilane, dimethylethylchlorosilane, diethylpropylchlorosilane, dipropylmethylchlorosilane, dichlorodimethylsilane, dichlorodiethylsilane, dichlorodiphenylsilane, dichloromethyl-n-propylsilane, dichloromethylphenylsilane, trichloromethylsilane, trichloroethylsilane, phenyltrichlorosilane, and silicon tetrachloride, preferably trimethylchlorosilane, triethylchlorosilane, dichlorodiethylsilane, dichlorodiphenylsilane, trichloromethylsilane, trichloroethylsilane, or silicon tetrachloride.

[0192] In this invention, the organoaluminum compound is selected from alkylaluminoxanes, alkylaluminum compounds, or alkylaluminum chloride compounds; wherein the general formula of alkylaluminoxanes is:

[0193]

[0194] Where R is a C1-12 hydrocarbon group, and a is selected from 4 to 30 and a is an integer.

[0195] In a preferred embodiment, R in alkylaluminoxane is methyl, and a is selected from 10-30 and a is an integer.

[0196] In a specific embodiment, the alkylaluminoxane is methylaluminoxane (MAO) or modified methylaluminoxane (MMAO).

[0197] In a preferred embodiment, the alkylaluminum compound is selected from trialkylaluminum, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, or tri-n-octylaluminum.

[0198] In a preferred embodiment, the alkylaluminum chloride compound is selected from diethylaluminum chloride, ethylaluminum dichloride, or ethylaluminum sesquichloride.

[0199] The fifth aspect of this invention provides a method for preparing a catalyst for olefin polymerization, the method comprising the following steps:

[0200] A1: Under an inert atmosphere, the dispersant S1, the silica gel support and chlorinated hydrocarbon silicon in the above-mentioned catalyst composition for olefin polymerization are reacted at 0-120°C for 3-24 hours;

[0201] A2: Under an inert atmosphere, the intermediate material obtained in step A1, the dispersant S2, and the organoaluminum compound in the above-mentioned catalyst composition for olefin polymerization are reacted at 30-120°C for 3-24 hours.

[0202] A3: Under an inert atmosphere, the intermediate material obtained in step A2, the dispersant S3, and the post-transition metal complex in the above-mentioned catalyst composition for olefin polymerization are reacted at 0-120°C for 0.5-24 h.

[0203] The dispersant S1, dispersant S2 and dispersant S3 are each independently selected from one or more of toluene, benzene, xylene, hexane, heptane and cyclohexane.

[0204] In a preferred embodiment, the reaction temperature is 20-100°C in step A1; 30-100°C in step A2; and 20-100°C in step A3.

[0205] In a specific embodiment, step A1 includes: under nitrogen protection, adding the silica gel support in the above-mentioned catalyst composition for olefin polymerization into a reactor, then adding dispersant S1 to disperse it into a suspension, then adding chlorinated hydrocarbon silicon in the above-mentioned catalyst composition for olefin polymerization, heating to 20-100°C, stirring and reacting for 3-24 hours, then washing several times with dispersant S1 and vacuum drying.

[0206] In a specific embodiment, step A2 includes: under nitrogen protection, adding the intermediate material obtained in step A1 into the reactor, then adding dispersant S2 to disperse it into a suspension, then adding the organoaluminum compound from the above-mentioned catalyst composition for olefin polymerization, heating to 30-100°C, stirring and reacting for 3-24 hours, then washing several times with dispersant S2 and vacuum drying.

[0207] In a specific embodiment, step A3 includes: under nitrogen protection, adding the intermediate material obtained in step A2 to dispersant S3 to form a slurry, then slowly adding the aqueous solution of the monochromium metal complex in the above-mentioned olefin polymerization catalyst composition to the above-mentioned slurry, reacting at 20-100°C for 0.5-24 hours to obtain the above-mentioned olefin polymerization catalyst slurry, or removing the solvent from the obtained olefin polymerization catalyst slurry and washing and drying it.

[0208] The sixth aspect of this invention provides a catalyst for olefin polymerization prepared by the above method, wherein, based on the total weight of the catalyst for olefin polymerization, the aluminum content is 1-15 wt%; the metal M content is 0.05-10 wt%; the aluminum content can be 1 wt%, 5 wt%, 10 wt%, 10.5 wt%, 11 wt%, or 15 wt%; and the metal M content can be 0.05 wt%, 0.1 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 2 wt%, 4 wt%, 6 wt%, 8 wt%, or 10 wt%.

[0209] A seventh aspect of the present invention provides a method for olefin polymerization, comprising carrying out an olefin polymerization reaction in the presence of the catalyst described above for olefin polymerization.

[0210] In this invention, the olefin polymerization process can be gas-phase polymerization or slurry polymerization; in the gas-phase polymerization process, alkyl aluminum can also be added as a co-catalyst for olefin polymerization; in the slurry polymerization process, the addition of alkyl aluminum can remove impurities in the system and improve the polymerization activity to a certain extent, without the need to add expensive MAO as a co-catalyst.

[0211] In a preferred embodiment, during the olefin polymerization process, the concentration of the catalyst used for olefin polymerization is 1 × 10⁻⁶. -8 mol / L~1×10 -3 mol / L, preferably 1×10 -8 mol / L~1×10 -5 mol / L.

[0212] In a preferred embodiment, the polymerization temperature is -78°C to 150°C, more preferably 0°C to 90°C; the polymerization pressure is 0.01 to 10 MPa, more preferably 0.01 to 2 MPa.

[0213] In this invention, "polymerization pressure" refers to the ethylene pressure in the polymerization system, expressed as absolute pressure.

[0214] According to some embodiments of the present invention, the polymerization reaction is carried out by olefin monomers in a solvent, the solvent being independently selected from one or more of alkanes, aromatic hydrocarbons and halogenated hydrocarbons.

[0215] According to some specific embodiments of the present invention, the polymerization solvent is independently selected from one or more of hexane, pentane, heptane, benzene, toluene, dichloromethane, chloroform and dichloroethane, more preferably from one or more of hexane, toluene and heptane.

[0216] In this invention, 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.

[0217] Examples of aryl groups in this invention include, but are not limited to, phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, and vinylphenyl.

[0218] The following examples further illustrate the post-transition metal complex, its preparation method, and its application according to the present invention. These examples are implemented based on the technical solution of the present invention, providing detailed implementation methods and specific operating procedures; however, the scope of protection of the present invention is not limited to the following examples.

[0219] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods in the art. Unless otherwise specified, the experimental materials used in the following embodiments are commercially available.

[0220] The analytical characterization instruments and testing methods used in the following examples and comparative examples are as follows:

[0221] (1) Nuclear magnetic resonance spectrometer: Bruker DMX 300 (300MHz), with tetramethylsilicon (TMS) as internal standard;

[0222] (2) ICP (Inductively Coupled Plasma Emission Spectrometry) characterization: quantitative determination of the weight percentage of metals in catalysts used for olefin polymerization; the instrument used was a P1000 ICP-AES plasma emission spectrometer manufactured by PE Corporation, USA.

[0223] (3) Characterization of polymer molecular weight and molecular weight distribution: Molecular weight and its distribution were determined by gel permeation chromatography (GPC) using a Waters Alliance GPCV 2000 instrument. The polymer samples were dissolved in 1,2,4-trichlorobenzene at 150℃, with a sample concentration of 1 mg / mL and a solvent flow rate of 1.0 mL / min. Each sample was measured twice.

[0224] (4) Activity measurement method: The polymer was washed with hydrochloric acid ethanol solution, vacuum dried, and the weight of the polymer was obtained; the polymerization activity was calculated as: polymer weight (g) / metal M (mol) × 60 / polymerization time (min).

[0225] Example 1

[0226] Complex 1: The complex shown in formula (II), where M is Ni and R is... 11 -R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0227] In a nitrogen atmosphere, the compound shown in formula (III) (11.23 g, 30 mmol, S type) was dissolved in anhydrous diethyl ether (150 mL). A solution of n-butyllithium (2.7 M, 33.3 mL, 90 mmol) was added dropwise at room temperature and stirred for 4 h. Then, tetrahydrofuran (150 mL) was added to obtain a black solution containing a precipitate. Stirring continued for 1 h. Diphenylphosphine chloride (PPh₂Cl) (90 mmol, 16.7 mL) was added at 0 °C. After stirring at room temperature for 1 h, NH₄⁺ was added. Quenching with 4Cl aqueous solution (5 mL), the organic phase was extracted with ethyl acetate, dried with anhydrous sodium sulfate, recrystallized with dichloromethane / hexane, methanol (100 mL) and 5 mL concentrated hydrochloric acid were added, and the reaction was refluxed for 16 h. After the reaction was completed by TLC, the organic solvent was removed, the product was dissolved in ethyl acetate, neutralized with NaHCO3 aqueous solution, the organic phase was extracted, dried with anhydrous MgSO4, filtered, concentrated, and column chromatography (dichloromethane as solvent) was performed to obtain ligand L1 with a yield of 67%. 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 (162MHz, CDCl3): δ=-17.19(s); High-resolution mass spectrometry test: theoretical value: 654.19; measured value: 655.20;

[0228] In a nitrogen atmosphere, ligand L1 (0.654 g, 1 mmol) and nickel source (Py2NiMe2) (0.49 g, 2 mmol) were dissolved in toluene (10 mL), respectively. Then, the ligand solution was added dropwise to the nickel source solution, and the mixture was stirred vigorously. The reaction was carried out at room temperature for 10 h. The solution was filtered to obtain a brownish-yellow solution. The solvent was concentrated and the solution was frozen at -30 °C to obtain complex 1 with a yield of 76%. 1 H 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 values: C, 70.19; H, 4.84; N, 2.92; Test values: C, 69.94; H, 4.92; N, 2.84;

[0229] Catalyst M1 for the preparation of olefin polymerization:

[0230] A1: Under nitrogen protection, 10g of dry silica gel support was added to a glass reactor, followed by 150ml of dry hexane to disperse it into a suspension. Then, 1ml of SiCl2(n-Bu)2 was added, stirred and heated to 30℃, reacted for 4h and then dried under vacuum.

[0231] A2: Under nitrogen protection, take 5g of the intermediate material obtained in step A1 and add it to a glass reactor. Then add 60ml of dry toluene and disperse it into a suspension. Then add 18ml of 10wt% MAO (methylaluminoxane) toluene solution, heat to 50℃, stir and react for 4h. Then wash three times with 50ml of toluene, then wash with hexane and vacuum dry.

[0232] A3: Under nitrogen protection, 2g of the intermediate material obtained in step A2 was added to a glass reactor, and then 30ml of dry toluene was added to make a slurry. 0.192g (0.2mmol) of complex 1 was dissolved in 20ml of toluene, and then the toluene solution of complex 2 was added dropwise to the reactor. The reaction was carried out at 30℃ for 30min, and then washed with 30ml of toluene and vacuum dried. ICP characterization showed that the content of Ni in catalyst M1 for olefin polymerization was 0.71wt% and the content of Al was 10.24wt%.

[0233] Example 2

[0234] Complex 53: The complex shown in formula (II), where M is Ni and R is... 11 -R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran.

[0235] Ligand L1 was prepared according to the method described in Example 1;

[0236] Under a nitrogen atmosphere, ligand L1 (0.654 g, 1 mmol) was dissolved in tetrahydrofuran, and excess NaH (0.072 g, 3 mmol) was added. The mixture was stirred at room temperature for 10 h, and the NaH was removed by filtration. A tetrahydrofuran solution of (DME)NiBr2 (0.617 g, 2 mmol) was added dropwise, and the mixture was reacted overnight at room temperature. The solvent was dried under vacuum, and the mixture was dissolved in dichloromethane (40 mL). The filter cake was removed by filtration, and the filtrate was concentrated. Heptane was added for recrystallization to obtain complex 53, with a yield of 79%. Elemental analysis showed that C... 52 H 46 Br2Ni2O4P2: Theoretical values: C, 58.15; H, 4.32; Test values: C, 58.01; H, 4.53;

[0237] Catalyst M2 for the preparation of olefin polymerization:

[0238] The experiment was carried out in accordance with Example 1, except that in step A2, 13 mL of 2M diethylaluminum chloride was used to replace 18 mL of 10 wt% MAO, and in step A3, the same molar amount of complex 53 was used to replace complex 1. According to ICP characterization, the content of Ni in catalyst M2 for olefin polymerization was 0.68 wt%, and the content of Al was 10.24 wt%.

[0239] Example 3

[0240] Complex 65: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For -CF3, R 11 R 13 and R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran.

[0241] In a nitrogen atmosphere, the compound shown in formula (III) (3.74 g, 10 mmol, type R) was dissolved in anhydrous diethyl ether (120 mL). A solution of n-butyllithium (2.7 M, 11.1 mL, 30 mmol) was added dropwise at room temperature and stirred for 4 h. Then, tetrahydrofuran (120 mL) was added to obtain a black solution containing a precipitate. Stirring continued for 1 h. Then, bis(3,5-bis(trifluoromethyl)phenyl)chlorophosphine (30 mmol, 14.78 g) was added at 0 °C. After stirring at room temperature for 1 h, [further steps were taken]. Quenching was performed with 5 mL of NH4Cl aqueous solution. The organic phase was extracted with ethyl acetate and dried with anhydrous sodium sulfate. The product was recrystallized with dichloromethane / hexane, and methanol (100 mL) and 5 mL of concentrated hydrochloric acid were added. The mixture was refluxed for 16 h. After the reaction was completed by TLC, the organic solvent was removed, the product was dissolved in ethyl acetate, neutralized with NaHCO3 aqueous solution, and the organic phase was extracted. The product was dried with anhydrous MgSO4, filtered, concentrated, and column chromatography (with dichloromethane as solvent) was performed to obtain ligand L2 in 40% yield. 31 P NMR (162MHz, DMSO): δ = -8.37 (s); 1 ¹H NMR (400MHz, CDCl₃) δ 5.14 (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); High-resolution mass spectrometry: Theoretical calculated value: 1198.09; Measured value: 1198.95;

[0242] Under a nitrogen atmosphere, ligand L2 (1.20 g, 1 mmol) was dissolved in tetrahydrofuran, and excess NaH (0.072 g, 3 mmol) was added. The mixture was stirred at room temperature for 10 h, and the NaH was removed by filtration. A solution of (DME)NiBr2 (0.617 g, 2 mmol) in tetrahydrofuran was added dropwise, and the reaction was carried out overnight at room temperature. The solvent was dried under vacuum, and the mixture was dissolved in dichloromethane (40 mL). The filter cake was removed by filtration, the filtrate was concentrated, and heptane was added for recrystallization to give complex 65, with a yield of 76%. Elemental analysis showed that C... 60 H 38 Br2F 24 Ni2O4P2: Theoretical values: C, 44.54; H, 2.37; Test values: C, 44.31; H, 2.51;

[0243] Catalyst M3 for the preparation of olefin polymerization:

[0244] The process was carried out in accordance with Example 1, except that in step A1, an equimolar amount of CH3SiCl3 was used to replace SiCl2(n-Bu)2, and in step A3, an equal molar amount of complex 65 was used to replace complex 1. According to ICP characterization, the content of Ni in catalyst M3 for olefin polymerization was 0.70 wt%, and the content of Al was 10.28 wt%.

[0245] Example 4

[0246] Complex 63: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For methyl, R 11 R 13 and R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran.

[0247] In a nitrogen atmosphere, the compound shown in formula (III) (3.74 g, 10 mmol, R type) was dissolved in anhydrous diethyl ether (120 mL). A 2.5 M, 12 mL, 30 mmol solution of n-butyllithium was added dropwise at room temperature and stirred for 4 h. Then, tetrahydrofuran (120 mL) was added to obtain a black solution containing a precipitate. Stirring continued for 1 h. At 0 °C, 30 mmol, 8.30 g of dichloro(3,5-dimethylphenyl)phosphine was added. After stirring at room temperature for 1 h, NH₄C was added. Quenching with 5 mL of aqueous solution, the organic phase was extracted with ethyl acetate, dried with anhydrous sodium sulfate, recrystallized with dichloromethane / hexane, and then refluxed with 100 mL of methanol and 5 mL of concentrated hydrochloric acid for 16 h. After the reaction was completed by TLC, the organic solvent was removed, the product was dissolved in ethyl acetate, neutralized with NaHCO3 aqueous solution, the organic phase was extracted, dried with anhydrous MgSO4, filtered, concentrated, and column chromatography (with dichloromethane as solvent) was performed to obtain 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); 31 P NMR (162MHz, CDCl3) δ=-15.4(s); High-resolution mass spectrometry test: theoretical calculated value: 766.31; measured value: 767.32;

[0248] Under a nitrogen atmosphere, ligand L3 (0.77 g, 1 mmol) was dissolved in tetrahydrofuran, and excess NaH (0.072 g, 3 mmol) was added. The mixture was stirred at room temperature for 10 h, and the NaH was removed by filtration. A solution of (DME)NiBr2 (0.617 g, 2 mmol) in tetrahydrofuran was added dropwise, and the reaction was carried out overnight at room temperature. The solvent was dried under vacuum, and the mixture was dissolved in dichloromethane (40 mL). The filter cake was removed by filtration, and the filtrate was concentrated. Heptane was added for recrystallization to obtain complex 63, with a yield of 76%. Elemental analysis showed that C... 60 H 62 Br2Ni2O4P2: Theoretical values: C, 60.75; H, 5.27; Test values: C, 60.37; H, 5.51;

[0249] Catalyst M4 for the preparation of olefin polymerization:

[0250] The process was carried out as described in Example 1. In step A3, SiCl2(n-Bu)2 was replaced with an equimolar amount of SiCl4, and complex 1 was replaced with an equal molar amount of complex 63. According to ICP characterization, the content of Ni in catalyst M4 for olefin polymerization was 0.69 wt%, and the content of Al was 10.42 wt%.

[0251] Example 5

[0252] Complex 62: The complex shown in formula (II), where M is Ni and R is... 13 It is a methoxy group, R 11 R 12 R 14 and R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran.

[0253] In a nitrogen atmosphere, the compound shown in formula (III) (3.74 g, 10 mmol, S type) was dissolved in anhydrous diethyl ether (120 mL). A solution of n-butyllithium hexane (2.7 M, 11.1 mL, 30 mmol) was added dropwise at room temperature. The mixture was stirred at room temperature for 4 h. Tetrahydrofuran (120 mL) was added to obtain a black solution containing a precipitate. The mixture was stirred for another 1 h. Di(4-methoxy)phosphine chloride (30 mmol, 8.42 g) was added at 0 °C. After stirring at room temperature for 1 h, the mixture was quenched with an aqueous solution of NH4Cl (5 mL). The organic phase was extracted with ethyl acetate, dried with anhydrous sodium sulfate, and recrystallized from dichloromethane / hexane to obtain a white crystalline compound. Methanol (100 mL) and 5 mL concentrated hydrochloric acid were added, and the mixture was refluxed for 16 h. After the reaction was completed by TLC, the organic solvent was removed, the compound was dissolved in ethyl acetate, neutralized with NaHCO3 aqueous solution, the organic phase was extracted, dried with anhydrous MgSO4, filtered, concentrated, and column chromatography (using dichloromethane as solvent) was performed to give ligand L4 in 56% yield. Elemental analysis showed that C... 48 H 40 O6P2: Theoretical values: C, 74.41; H, 5.20; Test values: C, 74.32; H, 5.38;

[0254] Under a nitrogen atmosphere, ligand L4 (0.77 g, 1 mmol) was dissolved in tetrahydrofuran, and excess NaH (0.072 g, 3 mmol) was added. The mixture was stirred at room temperature for 10 h, and the NaH was removed by filtration. A solution of (DME)NiBr2 (0.617 g, 2 mmol) in tetrahydrofuran was added dropwise, and the reaction was carried out overnight at room temperature. The solvent was dried under vacuum, and the mixture was dissolved in dichloromethane (40 mL). The filter cake was removed by filtration, the filtrate was concentrated, and heptane was added for recrystallization to give complex 62, with a yield of 77%. Elemental analysis showed C... 56 H 54Br2Ni2O8P2: Theoretical values: C, 56.32; H, 4.56; Test values: C, 56.31; H, 5.11;

[0255] Catalyst M5 for the preparation of olefin polymerization:

[0256] The process was carried out in accordance with Example 1. In step A3, SiCl2(n-Bu)2 was replaced with an equimolar amount of SiCl4, and complex 1 was replaced with an equal amount of complex 62. According to ICP characterization, the content of Ni in catalyst M5 for olefin polymerization was 0.63 wt%, and the content of Al was 10.52 wt%.

[0257] Example 6

[0258] Complex 68: The complex shown in formula (II), where M is Pd and R is... 11 -R 15 R3 is H, R4 is methyl, and R5 is pyridine.

[0259] Ligand L1 was prepared according to the method described in Example 1;

[0260] In 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 of palladium source (TMEDA) PdMe2 (0.51 g, 2 mmol). Then, the ligand solution was added dropwise to the palladium source solution. The mixture was stirred vigorously 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 68 with a yield of 84%. 1 ¹H 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 showed C 56 H 46 N₂O₂P₂Pd₂: Theoretical values: C, 63.83; H, 4.40; N, 2.66; Test values: C, 63.62; H, 4.60; N, 2.73;

[0261] Catalyst M6 for the preparation of olefin polymerization:

[0262] The process was carried out as described in Example 4. In step A3, complex 63 was replaced with the same molar amount of complex 68. According to ICP characterization, the content of Pd in ​​catalyst M6 for olefin polymerization was 0.97 wt% and the content of Al was 10.88 wt%.

[0263] Comparative Example 1

[0264] Catalyst S1 for the preparation of olefin polymerization:

[0265] The procedure was carried out as described in Example 1, except that in step A3, 0.4 mmol of the comparative complex 1* (its structure is shown below, and the synthesis process is referenced in Acta Agron. Sin. 2012, 29, 1381; ACSCatalysis 2021, 11, 5, 2902-2911) was used instead of 0.2 mmol of complex 1. ICP characterization showed that the catalyst S1 for olefin polymerization contained 0.52 wt% Ni and 10.43 wt% Al.

[0266] Comparative complex 1*

[0267] Comparative Example 2

[0268] Catalyst S2 for the preparation of olefin polymerization:

[0269] The process was carried out in accordance with Example 2, except that in step A3, 0.4 mmol of the comparative complex 2* (the structure of which is shown below, and the synthesis process is referenced in Appl Organometal Chem. 2017; e4013) was used instead of 0.2 mmol of complex 16. ICP characterization showed that the content of Pd in ​​the catalyst S2 for olefin polymerization was 0.82 wt% and the content of Al was 10.64 wt%.

[0270] Comparative complex 2*

[0271] Test case

[0272] In a 1L stainless steel high-pressure polymerization reactor, nitrogen and ethylene were used to replace the polymer three times each. Then, 500mL of hexane solvent was added, followed by 2mL of 1mol / L triethylaluminum (TEA) hexane solution. Then, about 30mg of the olefin polymerization catalyst prepared in the examples and comparative examples was added. The temperature was raised to 80℃, the polymerization pressure was increased to 1MPa and maintained for 1h. After the polymerization reaction was completed, the temperature was lowered, the polyethylene granules were collected, weighed and the polymerization activity was tested. The weight-average molecular weight, molecular weight distribution and polymerization activity test data of the obtained polymer are shown in Table 1.

[0273] Table 1

[0274] serial number coordination compounds Polymerization activity (g / mol M.h) <![CDATA[M w ×10 -4 ]]> <![CDATA[M w / M n ]]> Example 1 Complex 1 <![CDATA[3.71×10 6 ]]> 8.9 4.2 Example 2 Complex 53 <![CDATA[3.05×10 6 ]]> 21.4 4.4 Example 3 Complex 65 <![CDATA[4.22×10 6 ]]> 18.4 4.3 Example 4 Complex 63 <![CDATA[2.71×10 6 ]]> 14.3 4.2 Example 5 Complex 62 <![CDATA[4.01×10 6 ]]> 32.6 4.4 Example 6 Complex 68 <![CDATA[1.45×10 6 ]]> 5.2 4.3 Comparative Example 1 Comparative complex 1* <![CDATA[1.29×10 6 ]]> 2.3 4.5 Comparative Example 2 Comparative complex 2* <![CDATA[7.12×10 5 ]]> 2.2 4.5

[0275] As can be seen from the results in Table 1, the catalyst for olefin polymerization prepared using the post-transition metal complex of the present invention has high polymerization activity under similar polymerization conditions, and the molecular weight of the resulting polymer is higher than that of the polymer obtained in the comparative example.

[0276] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A post-transition metal complex, characterized in that, Its structural formula is shown in equation (Ⅰ). M is selected from group VIII metals, R1 is selected from substituted or unsubstituted C6-C20 aryl groups, and R3 and R4 are each independently selected from halogens, C1-C10 hydrocarbon groups, P(R5)3, NR6R7 and OR8R9, or R3 and R4 are connected to each other to form an eight-membered ring. R5 is selected from substituted or unsubstituted C1-C10 alkyl groups and substituted or unsubstituted C6-C10 aryl groups; R6 and R7 are each independently selected from C1-C10 hydrocarbon groups, or R6 and R7 are connected with N to form a five-membered ring or a six-membered ring; R8 and R9 are each independently selected from C1-C10 hydrocarbon groups, or R8 and R9 are connected with O to form a five-membered ring or a six-membered ring.

2. The post-transition metal complex according to claim 1, characterized in that, Its structural formula is shown in equation (ⅠⅠ). Among them, R 11 -R 15 Each is independently selected from hydrogen, halogen, hydroxyl, and substituted or unsubstituted C1-C20 hydrocarbon groups; Preferably, M is selected from nickel or palladium; Preferably, at least one of R3 and R4 is selected from halogens or C1-C8 hydrocarbon groups, or R3 and R4 are interconnected to form an eight-membered ring.

3. The post-transition metal complex according to claim 2, characterized in that, R 11 -R 15 Each is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C15 aryl; Preferably, the substituent is selected from halogen, hydroxyl, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy; Preferably, the C1-C6 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl or 3,3-dimethylbutyl; Preferably, the C1-C6 alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexyloxy, isohexyloxy, or 3,3-dimethylbutoxy. Preferably, the halogen is selected from fluorine, chlorine, bromine or iodine.

4. The post-transition metal complex according to any one of claims 1-3, characterized in that, It is selected from the group consisting of the following coordination compounds. Complex 1: The complex shown in formula (II), where M is Ni and R is... 11 -R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 2: The complex shown in formula (II), where M is Ni and R is... 11 -R 15 F is F, R3 is methyl, and R4 is pyridine; Complex 3: The complex shown in formula (II), where M is Ni and R is... 11 It is a phenyl group, R 12 -R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 4: The complex shown in formula (II), where M is Ni and R is... 11 For methyl, R 12 -R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 5: The complex shown in formula (II), where M is Ni and R is... 13 For methyl, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 6: The complex shown in formula (II), where M is Ni and R is... 13 For -CF3, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 7: The complex shown in formula (II), where M is Ni and R is... 13 For F, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 8: The complex shown in formula (II), where M is Ni and R is... 13 For Cl, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 9: The complex shown in formula (II), where M is Ni and R is... 11 R 13 and R 15 For methyl, R 12 and R 14 R3 is H, R4 is methyl, and R5 is pyridine. Complex 10: The complex shown in formula (II), where M is Ni and R is... 13 It is a methoxy group, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 11: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For methyl, R 11 R 13 and R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 12: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For methyl, R 13 It is a methoxy group, R 11 and R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 13: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For -CF3, R 11 R 13 and R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 14: The complex shown in formula (II), where M is Ni and R is... 11 and R 15 It is a methoxy group, R 12 -R 14 R3 is H, R4 is methyl, and R5 is pyridine. Complex 15: The complex shown in formula (II), where M is Ni and R is... 11 It is a methoxy group, R 12 -R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 16: The complex shown in formula (II), where M is Ni and R is... 11 -R 15 R3 is H, R4 is phenyl, and R5 is PMe3. Complex 17: The complex shown in formula (II), where M is Ni and R is... 11 and R 15 R3 is F, R4 is phenyl, and R5 is PMe3. Complex 18: The complex shown in formula (II), where M is Ni and R is... 11 It is a phenyl group, R 12 -R 15 R3 is H, R4 is phenyl, and R5 is PMe3. Complex 19: The complex shown in formula (II), where M is Ni and R is... 11 For methyl, R 12 -R 15 R3 is H, R4 is phenyl, and R5 is PMe3. Complex 20: The complex shown in formula (II), where M is Ni and R is... 13 For methyl, R 11 R 12 R 14 and R 15 R3 is H, R4 is phenyl, and R5 is PMe3. Complex 21: The complex shown in formula (II), where M is Ni and R is... 13 For -CF3, R 11 R 12 R 14 and R 15 R3 is H, R4 is phenyl, and R5 is PMe3. Complex 22: The complex shown in formula (II), where M is Ni and R is... 13 For F, R 11 R 12 R 14 and R 15 R3 is H, R4 is phenyl, and R5 is PMe3. Complex 23: The complex shown in formula (II), where M is Ni and R is... 13 For Cl, R 11 R 12 R 14 and R 15 R3 is H, R4 is phenyl, and R5 is PMe3. Complex 24: The complex shown in formula (II), where M is Ni and R is... 11 R 13 and R 15 For methyl, R 12 and R 14 R3 is H, R4 is phenyl, and R5 is PMe3. Complex 25: The complex shown in formula (II), where M is Ni and R is... 13 It is a methoxy group, R 11 R 12 R 14 and R 15 R3 is H, R4 is phenyl, and R5 is PMe3. Complex 26: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For methyl, R 11 R 13 and R 15 R3 is H, R4 is phenyl, and R5 is PMe3. Complex 27: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For methyl, R 13 It is a methoxy group, R 11 and R 15 R3 is H, R4 is phenyl, and R5 is PMe3. Complex 28: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For -CF3, R 11 R 13 and R 15 R3 is H, R4 is phenyl, and R5 is PMe3. Complex 29: The complex shown in formula (II), where M is Ni and R is... 11 and R 15 It is a methoxy group, R 12 -R 14 R3 is H, R4 is phenyl, and R5 is PMe3. Complex 30: The complex shown in formula (II), where M is Ni and R is... 11 It is a methoxy group, R 12 -R 15 R3 is H, R4 is phenyl, and R5 is PMe3. Complex 31: The complex shown in formula (II), where M is Ni and R is... 11 -R 15 H, R3 and R4 are interconnected to form cyclooctene; Complex 32: The complex shown in formula (II), where M is Ni and R is... 11 It is a phenyl group, R 12 -R 15 H, R3 and R4 are interconnected to form cyclooctene; Complex 33: The complex shown in formula (II), where M is Ni and R is... 11 It is a phenyl group, R 12 -R 15 H, R3 and R4 are interconnected to form cyclooctene; Complex 34: The complex shown in formula (II), where M is Ni and R is... 13 It is a methoxy group, R 11 R 12 R 14 and R 15 H, R3 and R4 are interconnected to form cyclooctene; Complex 35: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For -CF3, R 11 R 13 and R 15 H, R3 and R4 are interconnected to form cyclooctene; Complex 36: The complex shown in formula (II), where M is Ni and R is... 11 and R 15 It is a methoxy group, R 12 -R 14 H, R3 and R4 are interconnected to form cyclooctene; Complex 37: The complex shown in formula (II), where M is Ni and R is... 11 It is a methoxy group, R 12 -R 15 H, R3 and R4 are interconnected to form cyclooctene; Complex 38: The complex shown in formula (II), where M is Ni and R is... 11 -R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran. Complex 39: The complex shown in formula (II), where M is Ni and R is... 11 -R 15 R3 is F, R4 is Cl, and R5 is tetrahydrofuran. Complex 40: The complex shown in formula (II), where M is Ni and R is... 11 It is a phenyl group, R 12 -R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran. Complex 41: The complex shown in formula (II), where M is Ni and R is... 11 For methyl, R 12 -R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran. Complex 42: The complex shown in formula (II), where M is Ni and R is... 13 For methyl, R 11 R 12 R 14 and R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran. Complex 43: The complex shown in formula (II), where M is Ni and R is... 13 For -CF3, R 11 R 12 R 14 and R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran. Complex 44: The complex shown in formula (II), where M is Ni and R is... 13 For F, R 11 R 12 R 14 and R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran. Complex 45: The complex shown in formula (II), where M is Ni and R is... 13 For Cl, R 11 R 12 R 14 and R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran. Complex 46: The complex shown in formula (II), where M is Ni and R is... 11 R 13 and R 15 For methyl, R 12 and R 14 R3 is H, R4 is Cl, and R5 is tetrahydrofuran. Complex 47: The complex shown in formula (II), where M is Ni and R is... 13 It is a methoxy group, R 11 R 12 R 14 and R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran. Complex 48: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For methyl, R 11 R 13 and R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran. Complex 49: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For methyl, R 13 It is a methoxy group, R 11 and R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran. Complex 50: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For -CF3, R 11 R 13 and R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran. Complex 51: The complex shown in formula (II), where M is Ni and R is... 11 and R 15 It is a methoxy group, R 12 -R 14 R3 is H, R4 is Cl, and R5 is tetrahydrofuran. Complex 52: The complex shown in formula (II), where M is Ni and R is... 11 It is a methoxy group, R 12 -R 15 R3 is H, R4 is Cl, and R5 is tetrahydrofuran. Complex 53: The complex shown in formula (II), where M is Ni and R is... 11 -R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran. Complex 54: The complex shown in formula (II), where M is Ni and R is... 11 -R 15 R3 is F, R4 is Br, and R5 is tetrahydrofuran. Complex 55: The complex shown in formula (II), where M is Ni and R is... 11 It is a phenyl group, R 12 -R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran. Complex 56: The complex shown in formula (II), where M is Ni and R is... 11 For methyl, R 12 -R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran. Complex 57: The complex shown in formula (II), where M is Ni and R is... 13 For methyl, R 11 R 12 R 14 and R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran. Complex 58: The complex shown in formula (II), where M is Ni and R is... 13 For -CF3, R 11 R 12 R 14 and R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran. Complex 59: The complex shown in formula (II), where M is Ni and R is... 13 For F, R 11 R 12 R 14 and R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran. Complex 60: The complex shown in formula (II), where M is Ni and R is... 13 For Cl, R 11 R 12 R 14 and R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran. Complex 61: The complex shown in formula (II), where M is Ni and R is... 11 R 13 and R 15 For methyl, R 12 and R 14 R3 is H, R4 is Br, and R5 is tetrahydrofuran. Complex 62: The complex shown in formula (II), where M is Ni and R is... 13 It is a methoxy group, R 11 R 12 R 14 and R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran. Complex 63: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For methyl, R 11 R 13 and R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran. Complex 64: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For methyl, R 13 It is a methoxy group, R 11 and R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran. Complex 65: The complex shown in formula (II), where M is Ni and R is... 12 and R 14 For -CF3, R 11 R 13 and R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran. Complex 66: The complex shown in formula (II), where M is Ni and R is... 11 and R 15 It is a methoxy group, R 12 -R 14 R3 is H, R4 is Br, and R5 is tetrahydrofuran. Complex 67: The complex shown in formula (II), where M is Ni and R is... 11 It is a methoxy group, R 12 -R 15 R3 is H, R4 is Br, and R5 is tetrahydrofuran. Complex 68: The complex shown in formula (II), where M is Pd and R is... 11 -R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 69: The complex shown in formula (II), where M is Pd and R is... 11 -R 15 F is F, R3 is methyl, and R4 is pyridine; Complex 70: The complex shown in formula (II), where M is Pd and R is... 11 It is a phenyl group, R 12 -R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 71: The complex shown in formula (II), where M is Pd and R is... 11 It is a phenyl group, R 12 -R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 72: The complex shown in formula (II), where M is Pd and R is... 11 For methyl, R 12 -R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 73: The complex shown in formula (II), where M is Pd and R is... 13 For methyl, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 74: The complex shown in formula (II), where M is Pd and R is... 13 For -CF3, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 75: The complex shown in formula (II), where M is Pd and R is... 13 For F, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 76: The complex shown in formula (II), where M is Pd and R is... 13 For Cl, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 77: The complex shown in formula (II), where M is Pd and R is... 11 R 13 and R 15 For methyl, R 12 and R 14 R3 is H, R4 is methyl, and R5 is pyridine. Complex 78: The complex shown in formula (II), where M is Pd and R is... 13 It is a methoxy group, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 79: The complex shown in formula (II), where M is Pd and R is... 12 and R 14 For methyl, R 11 R 13 and R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 80: The complex shown in formula (II), where M is Pd and R is... 12 and R 14 For methyl, R 13 It is a methoxy group, R 11 and R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 81: The complex shown in formula (II), where M is Pd and R is... 12 and R 14 For -CF3, R 11 R 13 and R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 82: The complex shown in formula (II), where M is Pd and R is... 11 and R 15 It is a methoxy group, R 12 -R 14 R3 is H, R4 is methyl, and R5 is pyridine. Complex 83: The complex shown in formula (II), where M is Pd and R is... 11 It is a methoxy group, R 12 -R 15 R3 is H, R4 is methyl, and R5 is pyridine. Complex 84: The complex shown in formula (II), where M is Pd and R is... 11 -R 15 R3 is H, R4 is methyl, and R5 is Cl. Complex 85: The complex shown in formula (II), where M is Pd and R is... 11 It is a phenyl group, R 12 -R 15 R3 is H, R4 is methyl, and R5 is Cl. Complex 86: The complex shown in formula (II), where M is Pd and R is... 13 It is a methoxy group, R 11 R 12 R 14 and R 15 R3 is H, R4 is methyl, and R5 is Cl. Complex 87: The complex shown in formula (II), where M is Pd and R is... 12 and R 14 For -CF3, R 11 R 13 and R 15 R3 is H, R4 is methyl, and R5 is Cl. Complex 88: The complex shown in formula (II), where M is Pd and R is... 11 and R 15 It is a methoxy group, R 12 -R 14 R3 is H, R4 is methyl, and R5 is Cl. Complex 89: The complex shown in formula (II), where M is Pd and R is... 11 It is a methoxy group, R 12 -R 15 R3 is H, R4 is methyl, and R5 is Cl.

5. A method for preparing the post-transition metal complex according to any one of claims 1-4, characterized in that, The method includes the following steps: (1) The compound shown in formula (III) is reacted with the compound shown in formula (IV) to generate a ligand; (2) The ligand is reacted with the metal compound M; Wherein, the metal M in the M metal compound is selected from group VIII metals, preferably nickel or palladium, and the definition of R1 is the same as in claim 1.

6. The method according to claim 5, characterized in that, The M metal compound is selected from at least one of dimethyl dipyridinium nickel, bis(1,5-cyclooctadiene) nickel, dichlorotetrapyridinium nickel, ethylene glycol dimethyl ether nickel bromide, ethylene glycol dimethyl ether nickel chloride, dichlorodi(trimethylphosphine) nickel, di(pyridine)bis[(trimethylsilyl)methyl] nickel, chloro(phenyl)(N,N,N',N'-tetramethyl-1,2-ethylenediamine) nickel, dibenzyl dipyridinium nickel, phenyl(trimethylphosphine) nickel bromide, phenyl(triethylphosphine) nickel chloride, diphenyldi(trimethylphosphine) nickel, dichlorodi(trimethylphosphine) nickel, dimethyl dipyridinium palladium, dichlorodipyridinium palladium, di(pyridine)bis[(trimethylsilyl)methyl] palladium, dimethyl(N,N,N,N-tetramethylethylenediamine) palladium, dibenzyl dipyridinium palladium, and methyl-1,5-cyclooctadiene-palladium chloride.

7. The application of the post-transition metal complex according to any one of claims 1-4 in olefin polymerization.

8. A catalyst composition for olefin polymerization, characterized in that, The catalyst composition for olefin polymerization includes a post-transition metal complex, chlorinated hydrocarbon silicon, an organoaluminum compound, and a silica support. The post-transition metal complex is the post-transition metal complex according to any one of claims 1-4.

9. The catalyst composition for olefin polymerization according to claim 8, characterized in that, Based on each gram of silica gel carrier, the amount of chlorinated hydrocarbon silicon used was 0.01-3 mmol, the amount of organoaluminum compound used was 0.01-30 mmol, and the amount of metal M in the subsequent transition metal complex was 1-1000 μmol.

10. A catalyst composition for olefin polymerization according to claim 8 or 9, characterized in that, The general formula of the chlorinated hydrocarbon-based silicon is as follows: Cl n Si(R 16 ) 4-n ;where R 16 It is a C1-20 hydrocarbon group, and n is selected from 1 to 4 and n is an integer; Preferably, the organoaluminum compound is selected from alkylaluminoxanes, alkylaluminum compounds, or alkylaluminum chloride compounds; The general formula for alkylaluminoxanes is: Where R is a C1-12 hydrocarbon group, and a is selected from 4 to 30 and a is an integer.

11. A method for preparing a catalyst for olefin polymerization, characterized in that, The method includes the following steps: A1: Under an inert atmosphere, the dispersant S1, the silica gel support and chlorinated hydrocarbon silicon in the catalyst composition for olefin polymerization according to any one of claims 8-10 are reacted at 0-120°C for 3-24 hours; A2: Under an inert atmosphere, the intermediate material obtained in step A1, the dispersant S2, and the organoaluminum compound in the catalyst composition for olefin polymerization according to any one of claims 8-10 are reacted at 30-120°C for 3-24 hours. A3: Under an inert atmosphere, the intermediate material obtained in step A2, the dispersant S3, and the post-transition metal complex in the catalyst composition for olefin polymerization according to any one of claims 8-10 are reacted at 0-120°C for 0.5-24 h. The dispersant S1, dispersant S2 and dispersant S3 are each independently selected from one or more of toluene, benzene, xylene, hexane, heptane and cyclohexane.

12. A catalyst for olefin polymerization prepared by the method of claim 11, characterized in that, Based on the total weight of the catalyst used for olefin polymerization, the aluminum content is 1-15 wt% and the metal M content is 0.05-10 wt%.

13. A method for olefin polymerization, characterized in that, Includes carrying out an olefin polymerization reaction in the presence of the catalyst for olefin polymerization as described in claim 12; Preferably, during the polymerization reaction, the concentration of the catalyst used for olefin polymerization is 1×10⁻⁶. -8 mol / L~1×10 - 3 mol / L, preferably 1×10 -8 mol / L~1×10 -5 mol / L; Preferably, the polymerization temperature is -78℃ to 150℃, more preferably 0℃ to 90℃; the polymerization pressure is 0.01 to 10MPa, more preferably 0.01 to 2MPa.

Images