A phosphine-phenol transition metal complex and its preparation method and application

Abstract

The present invention relates to the technical field of olefin polymerization catalysts, and discloses a phosphine-phenol transition metal complex, its preparation method, and application. The structural formula of the phosphine-phenol transition metal complex is shown in Formula (I), wherein M is selected from a Group IVB metal; Ar is selected from a substituted or unsubstituted C6-C20 aryl group; X is selected from a halogen or a C1-C10 hydrocarbon group, and n is 1 or 2. The phosphine-phenol transition metal complex of the present invention is used as a main catalyst for an olefin polymerization catalyst, can achieve high activity in catalyzing olefin polymerization, and the resulting polymer has a high molecular weight, a narrow molecular weight distribution, and excellent copolymerization performance.

Description

Technical Field

[0001] The present invention relates to the technical field of olefin polymerization catalysts, and in particular to a phosphine-phenol transition metal complex and a preparation method and application thereof. Background Art

[0002] Polyolefin resin has excellent environmental compatibility compared to other resin materials and is therefore widely used in industry and life. Polyethylene resin is an important polyolefin resin. Industrial 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 documents of this special edition), Phillips type catalysts (see, for example, Belg. Pat. 530617 (1955); Chem. Rev. 1996, 96, 3327) and metallocene type catalysts (see, for example, W. Kaminsky, Metalorganic Catalysts for Synthesis and Polymerization, Berlin: Springer, 1999), as well as the high-efficiency ethylene oligomerization and polymerization catalysts of late transition metal complex type that have developed rapidly in recent years. In 2006, the Gibson team of British scientists discovered that Group IV phenol-phosphine zirconium complexes have good catalytic ability for olefin polymerization. When activated by 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] Currently, in the production of high-end polyolefins, there is an urgent need for olefin polymerization catalysts with good performance. Therefore, the development of new catalysts with good catalytic activity is of great significance. Summary of the Invention

[0004] The object of the present invention is to provide a phosphine-phenol transition metal complex and a preparation method and application thereof. The phosphine-phenol transition metal complex has excellent olefin homopolymerization / copolymerization performance, and the obtained polymer has a narrow molecular weight distribution.

[0005] In order to achieve the above object, the present invention provides a phosphine-phenol transition metal complex, the structural formula of which is shown in formula (I):

[0006]

[0007] wherein M is selected from a Group IVB metal; Ar is selected from a substituted or unsubstituted C6-C20 aryl group; X is selected from a halogen, a C1-C10 hydrocarbon group, and n is 1 or 2.

[0008] Preferably, the structural formula of the phosphine-phenol transition metal complex is as shown in formula (II),

[0009]

[0010] Among them, R 11 -R 15 Each is independently selected from hydrogen, halogen, hydroxyl, and substituted or unsubstituted C1-C20 hydrocarbon groups.

[0011] Preferably, M is selected from titanium, zirconium and hafnium.

[0012] Preferably, R 11 -R 15 Each is independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C15 aryl; X is selected from halogen, C1-C8 hydrocarbon group.

[0013] Preferably, the substituents are selected from halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkoxy.

[0014] Preferably, the C1-C6 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl and 3,3-dimethylbutyl.

[0015] Preferably, the C1-C6 alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy and 3,3-dimethylbutoxy.

[0016] Preferably, the halogen is selected from fluorine, chlorine, bromine and iodine.

[0017] A second aspect of the present invention provides a method for preparing the above-mentioned phosphine-phenol transition metal complex, the method comprising:

[0018] (1) reacting the compound represented by formula (III) with the compound represented by formula (IV) to obtain the ligand represented by formula (V);

[0019] (2) reacting the ligand with a hydrogen extraction agent, and then reacting with an M metal compound, wherein the transition metal M in the M metal compound is selected from Group IVB metals;

[0020]

[0021] Here, the definition of Ar is the same as described above.

[0022] Preferably, the M metal compound is at least one selected from titanium tetrachloride, bis(tetrahydrofuran)titanium tetrachloride, tris(tetrahydrofuran)titanium trichloride, zirconium tetrachloride, bis(tetrahydrofuran)zirconium tetrachloride, hafnium tetrachloride and bis(tetrahydrofuran)hafnium tetrachloride.

[0023] Preferably, the hydrogen withdrawal agent is selected from at least one of NaH, KH, n-butyl lithium and methyl lithium.

[0024] The third aspect of the present invention provides the use of the above-mentioned phosphine-phenol transition metal complex in olefin polymerization.

[0025] The fourth aspect of the present invention provides an olefin polymerization catalyst comprising the above-mentioned phosphine-phenol transition metal complex and a co-catalyst.

[0026] Preferably, the co-catalyst is an organoaluminum compound and / or an organoboron compound.

[0027] Preferably, the organoaluminum compound is one or more selected from alkylaluminoxane, alkylaluminum and alkylaluminum halide.

[0028] Preferably, the organic boron compound is one or more selected from organic boron and organic borate.

[0029] A fifth aspect of the present invention provides an olefin polymerization method, comprising carrying out an olefin polymerization reaction in the presence of the above-mentioned olefin polymerization catalyst.

[0030] Preferably, the temperature of the olefin polymerization reaction is -78°C to 200°C, preferably -20°C to 150°C, and the pressure is 0.01 to 10 MPa, preferably 0.01 to 5 MPa.

[0031] The phosphine-phenol transition metal complex of the present invention is used as a main catalyst of an olefin polymerization catalyst, can achieve high-activity catalytic olefin polymerization, and the obtained polymer has a high molecular weight, a narrow molecular weight distribution, and excellent copolymerization performance.

[0032] Compared with the prior art, the technical solution of the present invention has the following advantages:

[0033] (1) The method for synthesizing the phosphine-phenol transition metal complex described in the present invention is simple and easy.

[0034] (2) The phosphine-phenol transition metal complex of the present invention can catalyze olefin polymerization with high activity, and in particular, can maintain high polymerization activity at relatively high polymerization temperatures.

[0035] (3) The phosphine-phenol transition metal complex of the present invention has higher copolymerization performance of ethylene and α-olefin or cycloolefin (such as norbornene) when used as a main catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is a diagram of the single crystal structure of the phosphine-phenol transition metal complex prepared in Example 1. DETAILED DESCRIPTION

[0037] The following is a detailed description of the specific embodiments of the present invention. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention and are not intended to limit the present invention.

[0038] The endpoints of the ranges and any values ​​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 endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0039] The structural formula of the phosphine-phenol transition metal complex of the present invention is shown in formula (I),

[0040]

[0041] Wherein, Ar is selected from substituted or unsubstituted C6-C20 aryl groups, preferably substituted or unsubstituted C6-C15 aryl groups, and more preferably substituted or unsubstituted C6-C8 aryl groups.

[0042] In a preferred embodiment, the structural formula of the phosphine-phenol transition metal complex is as shown in formula (II),

[0043]

[0044] Among them, R 11 -R 15 Each is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C20 hydrocarbon group. 11 -R 15 Each is independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C10 alkyl, and substituted or unsubstituted C6-C15 aryl.

[0045] In formula (I) and formula (II), M is selected from Group IVB metals. Preferably, M is selected from titanium, zirconium and hafnium.

[0046] In formula (I) and formula (II), X is selected from halogen, C1-C10 hydrocarbon group. Preferably, X is selected from halogen, C1-C8 hydrocarbon group (such as C1-C6 alkyl group).

[0047] In formula (I) and formula (II), n is 1 or 2, indicating that the number of X groups bonded to the transition metal M is n.

[0048] In the present invention, the "substituted" in "substituted or unsubstituted" refers to containing substituents, and the substituents here can be selected from halogen, hydroxyl, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkoxy.

[0049] In the present invention, the alkyl group (such as C1-C6 alkyl or C1-C10 alkyl) can be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl and 3,3-dimethylbutyl.

[0050] In the present invention, the alkoxy group (such as C1-C6 alkoxy group) can be selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy and 3,3-dimethylbutoxy.

[0051] In the present invention, the aryl group (such as a C6-C8 aryl group, a C6-C15 aryl group, or a C6-C20 aryl group) may be selected from a phenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, a dimethylphenyl group, and a vinylphenyl group.

[0052] In the present invention, the halogen is selected from fluorine, chlorine, bromine and iodine.

[0053] In a more preferred embodiment, the phosphine-phenol transition metal complex is selected from the group consisting of the following complexes:

[0054] Complex 1: Complex represented by formula (II), wherein M is Ti, R 11 -R 15 is H, X is Cl, n=1; Complex 2: Complex represented by formula (II), wherein M is Ti, R 11 -R 15 is H, X is Cl, n=2; Complex 3: Complex represented by formula (II), wherein M is Ti, R 11 -R 15 is H, X is methyl, n=1;

[0055] Complex 4: Complex represented by formula (II), wherein M is Ti, R 11 -R 15 is H, X is -CH2C6H5, n=2;

[0056] Complex 5: Complex represented by formula (II), wherein M is Ti, R 11 、R 12 、R 14 and R 15 H, R 13 is -CF3, X is Cl, n=1;

[0057] Complex 6: Complex represented by formula (II), wherein M is Ti, R 11 、R 12 、R 14 and R 15 H, R 13 is -CF3, X is Cl, n=2;

[0058] Complex 7: Complex represented by formula (II), wherein M is Ti, R 11 、R 12 、R 14 and R 15 H, R 13 is -CF3, X is methyl, n=2;

[0059] Complex 8: Complex represented by formula (II), wherein M is Ti, R 11 、R 12 、R 14 and R 15 H, R 13 is -CF3, X is -CH2C6H5, n=2;

[0060] Complex 9: Complex represented by formula (II), wherein M is Ti, R 12 -R 15 H, R 11 is a methoxy group, X is Cl, and n=1;

[0061] Complex 10: Complex represented by formula (II), wherein M is Ti, R 12 -R 15 H, R 11 is a methoxy group, X is Cl, and n=2;

[0062] Complex 11: Complex represented by formula (II), wherein M is Ti, R 12 -R 15 H, R 11 is a methoxy group, X is a methyl group, and n=2;

[0063] Complex 12: Complex represented by formula (II), wherein M is Ti, R 12 -R 15 H, R 11 is a methoxy group, X is -CH2C6H5, n=2;

[0064] Complex 13: Complex represented by formula (II), wherein M is Ti, R 11 、R 12 、R 14 and R 15 H, R 13 is a methoxy group, X is Cl, and n=1;

[0065] Complex 14: Complex represented by formula (II), wherein M is Ti, R 11 、R 12 、R 14 and R 15 H, R 13 is a methoxy group, X is Cl, and n=2;

[0066] Complex 15: Complex represented by formula (II), wherein M is Ti, R 11 、R 12 、R 14 and R 15 H, R 13 is a methoxy group, X is a methyl group, and n=2;

[0067] Complex 16: Complex represented by formula (II), wherein M is Ti, R 11 、R 12 、R 14 and R 15 H, R 13 is a methoxy group, X is -CH2C6H5, n=2;

[0068] Complex 17: Complex represented by formula (II), wherein M is Ti, R 11 、R 13 and R 15 H, R 12 and R 14 is -CF3, X is Cl, n=1;

[0069] Complex 18: Complex represented by formula (II), wherein M is Ti, R 11 、R 13 and R 15 H, R 12 and R 14 is -CF3, X is Cl, n=2;

[0070] Complex 19: Complex represented by formula (II), wherein M is Ti, R 11 、R 13 and R 15 H, R 12 and R 14 is -CF3, X is methyl, n=2;

[0071] Complex 20: Complex represented by formula (II), wherein M is Ti, R 11 、R 13 and R 15 H, R 12 and R 14 is -CF3, X is -CH2C6H5, n=2;

[0072] Complex 21: Complex represented by formula (II), wherein M is Ti, R 11 、R 13 and R 15 H, R 12 and R 14 is methyl, X is Cl, n=1;

[0073] Complex 22: Complex represented by formula (II), wherein M is Ti, R 11 、R 13 and R 15 H, R 12 and R 14 is methyl, X is Cl, n=2;

[0074] Complex 23: Complex represented by formula (II), wherein M is Ti, R 11 、R 13 and R 15 H, R 12 and R 14 is a methyl group, X is a methyl group, and n=2;

[0075] Complex 24: Complex represented by formula (II), wherein M is Ti, R 11 、R 13 and R 15 H, R 12 and R 14 is methyl, X is -CH2C6H5, n=2;

[0076] Complex 25: Complex represented by formula (II), wherein M is Zr, R 11 -R 15 is H, X is Cl, n=2; Complex 26: Complex represented by formula (II), wherein M is Zr, R 11 -R 15 is H, X is methyl, n=2;

[0077] Complex 27: Complex represented by formula (II), wherein M is Zr, R 11 -R 15 is H, X is -CH2C6H5, n=2;

[0078] Complex 28: Complex represented by formula (II), wherein M is Zr, R 11 、R12 、R 14 and R 15 H, R 13 is -CF3, X is Cl, n=2;

[0079] Complex 29: Complex represented by formula (II), wherein M is Zr, R 11 、R 12 、R 14 and R 15 H, R 13 is -CF3, X is methyl, n=2;

[0080] Complex 30: Complex represented by formula (II), wherein M is Zr, R 11 、R 12 、R 14 and R 15 H, R 13 is -CF3, X is -CH2C6H5, n=2;

[0081] Complex 31: Complex represented by formula (II), wherein M is Zr, R 12 -R 15 H, R 11 is a methoxy group, X is Cl, and n=2;

[0082] Complex 32: Complex represented by formula (II), wherein M is Zr, R 12 -R 15 For R 11 is a methoxy group, X is a methyl group, and n=2;

[0083] Complex 33: Complex represented by formula (II), wherein M is Zr, R 12 -R 15 For R 11 is a methoxy group, X is -CH2C6H5, n=2;

[0084] Complex 34: Complex represented by formula (II), wherein M is Zr, R 11 、R 12 、R 14 and R 15 H, R 13 is a methoxy group, X is Cl, and n=2;

[0085] Complex 35: Complex represented by formula (II), wherein M is Zr, R 11 、R 12 、R 14 and R 15 H, R 13 is a methoxy group, X is a methyl group, and n=2;

[0086] Complex 36: Complex represented by formula (II), wherein M is Zr, R 11 、R 12 、R 14 and R 15 H, R 13 is a methoxy group, X is -CH2C6H5, n=2;

[0087] Complex 37: Complex represented by formula (II), wherein M is Zr, R 11 、R 13 and R 15 H, R 12 and R 14 is -CF3, X is Cl, n=2;

[0088] Complex 38: Complex represented by formula (II), wherein M is Zr, R 11 、R 13 and R 15 H, R 12 and R 14 is -CF3, X is methyl, n=2;

[0089] Complex 39: Complex represented by formula (II), wherein M is Zr, R 11 、R 13 and R 15 H, R 12 and R 14 is -CF3, X is -CH2C6H5, n=2;

[0090] Complex 40: Complex represented by formula (II), wherein M is Zr, R 11 、R 13 and R 15 H, R 12 and R 14 is methyl, X is Cl, n=2;

[0091] Complex 41: Complex represented by formula (II), wherein M is Zr, R 11 、R 13 and R 15 H, R 12 and R 14 is a methyl group, X is a methyl group, and n=2;

[0092] Complex 42: Complex represented by formula (II), wherein M is Zr, R 11 、R 13 and R 15 H, R 12 and R 14 is methyl, X is -CH2C6H5, n=2;

[0093] Complex 43: A complex represented by formula (II), wherein M is Hf, R 11 -R 15 is H, X is Cl, n=2; Complex 44: a complex represented by formula (II), wherein M is Hf, R 11 -R 15 is H, X is methyl, n=2;

[0094] Complex 45: A complex represented by formula (II), wherein M is Hf, R 11 -R 15 is H, X is -CH2C6H5, n=2;

[0095] Complex 46: A complex represented by formula (II), wherein M is Hf, R 11 、R 12 、R 14 and R 15 H, R 13 is -CF3, X is Cl, n=2;

[0096] Complex 47: A complex represented by formula (II), wherein M is Hf, R 11 、R 12 、R 14 and R 15 H, R 13 is a methoxy group, X is Cl, and n=2;

[0097] Complex 48: A complex represented by formula (II), wherein M is Hf, R 11 、R 13 and R 15 H, R 12 and R 14 is -CF3, X is Cl, n=2;

[0098] Complex 49: A complex represented by formula (II), wherein M is Hf, R 11 、R 13 and R 15 H, R 12 and R 14 is methyl, X is Cl, n=2;

[0099] Complex 50: A complex represented by formula (II), wherein M is Hf, R 11 、R 13 and R 15 H, R 12 and R 14 is -CF3, X is -CH2C6H5, n=2;

[0100] Complex 51: A complex represented by formula (II), wherein M is Hf, R 11 、R12 、R 14 and R 15 H, R 13 is -CF3, X is -CH2C6H5, n=2;

[0101] Complex 52: A complex represented by formula (II), wherein M is Hf, R 11 、R 12 、R 14 and R 15 H, R 13 is a methoxy group, X is -CH2C6H5, n=2;

[0102] Complex 53: A complex represented by formula (II), wherein M is Hf, R 11 、R 13 and R 15 H, R 12 and R 14 is methyl, X is -CH2C6H5, n=2;

[0103] Complex 54: A complex represented by formula (II), wherein M is Hf, R 11 、R 13 and R 15 H, R 12 and R 14 is -CF3, X is -CH2C6H5, and n=2.

[0104] The preparation method of the above-mentioned phosphine-phenol transition metal complex may include:

[0105] (1) reacting the compound represented by formula (III) with the compound represented by formula (IV) to obtain the ligand represented by formula (V);

[0106] (2) reacting the ligand with a hydrogen extraction agent, and then reacting with an M metal compound, wherein the transition metal M in the M metal compound is selected from Group IVB metals;

[0107]

[0108]

[0109] Here, the definition of Ar is the same as described above.

[0110] In a more preferred embodiment, the reaction process of step (1) is shown in the following reaction formula.

[0111]

[0112] Among them, R 11 -R 15 The definition of is the same as described above.

[0113] In the method of the present invention, preferably, the transition metal M in the M metal compound is selected from titanium, zirconium and hafnium. Further preferably, the M metal compound is selected from at least one of titanium tetrachloride, bis(tetrahydrofuran)titanium tetrachloride, tris(tetrahydrofuran)titanium trichloride, zirconium tetrachloride, bis(tetrahydrofuran)zirconium tetrachloride, hafnium tetrachloride and bis(tetrahydrofuran)hafnium tetrachloride.

[0114] In the method of the present invention, preferably, during the reaction of step (1), the compound represented by formula (III) is first reacted with a hydrogen-withdrawing agent and then reacted with the compound represented by formula (IV).

[0115] In step (1) and step (2), the hydrogen extraction agents used may be the same or different, and are each independently selected from at least one of NaH, KH, n-butyllithium and methyllithium.

[0116] In a specific embodiment, the preparation process of step (1) comprises: dissolving the compound represented by formula (III) in anhydrous ether in a protective gas (such as nitrogen) atmosphere, adding a hydrogen extraction agent (such as n-butyl lithium) at room temperature, stirring at room temperature, adding tetrahydrofuran, and further stirring the obtained black solution containing the precipitate; then adding the compound represented by formula (VI), stirring at room temperature, and quenching by adding NH4Cl aqueous solution; then extracting the organic phase with ethyl acetate, drying the obtained organic phase with anhydrous sodium sulfate, and recrystallizing it with dichloromethane / hexane to obtain a yellow crystalline compound; then adding methanol and concentrated hydrochloric acid, reflux reaction, removing the organic solvent after the reaction is completed, dissolving the product in ethyl acetate, adding NaHCO3 aqueous solution to neutralize it, extracting the organic phase, and then drying, filtering, concentrating, and column chromatography in sequence to obtain the ligand represented by formula (VII).

[0117] In one embodiment, the preparation process of step (2) comprises: dissolving the ligand obtained in step (1) in tetrahydrofuran in a protective gas (such as nitrogen) atmosphere, adding an excess of a hydrogen extraction agent (such as NaH, KH, etc.), stirring at room temperature, filtering to remove the hydrogen extraction agent, then adding a tetrahydrofuran solution of the M metal compound, reacting overnight, draining the solvent, adding dichloromethane to dissolve, filtering to remove the filter cake, concentrating the filtrate, and adding heptane for recrystallization to obtain the phosphine-phenol transition metal complex of the present invention.

[0118] The present invention also provides the use of the above-mentioned phosphine-phenol transition metal complex in olefin polymerization. Preferably, the olefin includes ethylene, α-olefin and cycloolefin.

[0119] The present invention also provides an olefin polymerization catalyst containing the above phosphine-phenol transition metal complex as a main catalyst.

[0120] The olefin polymerization catalyst further contains a cocatalyst. The cocatalyst is an organoaluminum compound and / or an organoboron compound.

[0121] The organoaluminum compound is selected from alkylaluminoxanes or organoaluminum compounds (alkylaluminum or alkylaluminum halides) of the general formula AlR n X 1 3-n In the general formula AlR n X 1 3-n , R is H, a C1-C20 hydrocarbon group or a C1-C20 hydrocarbon oxy group, preferably a C1-C20 alkyl group, a C1-C20 alkoxy group, a C7-C20 aralkyl group or a C6-C20 aryl group; X 1 is a halogen, preferably chlorine or bromine; 0 < n ≤ 3. Specific examples of the organoaluminum compound include, but are not limited to: trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, diethylaluminum dichloride, methylaluminoxane (MAO) and modified methylaluminoxane (MMAO). Preferably, the organoaluminum compound is methylaluminoxane (MAO).

[0122] The organoboron compound is selected from arylborons and / or borates. The arylboron is preferably a substituted or unsubstituted phenylboron, more preferably tris(pentafluorophenyl)boron. The borate is preferably N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and / or triphenylmethyl tetrakis(pentafluorophenyl)borate.

[0123] According to a preferred embodiment of the present invention, when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to the transition metal M in the main catalyst is (10 - 10 7):1, for example, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1, 2000:1, 3000:1, 5000:1, 10000:1, 10000000:1 and any value therebetween, preferably (10-100000):1, more preferably (100-10000):1; when the catalyst is When the catalyst is an organic boron compound, the molar ratio of boron in the co-catalyst to the transition metal M in the main catalyst is (0.1-1000):1, for example, 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 3:1, 5:1, 8:1, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1 and any value therebetween, preferably (0.1-500):1.

[0124] In the present invention, the olefin is a C2-C16 olefin. Preferably, the olefin is ethylene or an α-olefin having 3-16 carbon atoms.

[0125] The present invention also provides an olefin polymerization method, comprising carrying out an olefin polymerization reaction in the presence of the above-mentioned olefin polymerization catalyst. The olefin polymerization reaction can be homopolymerization or copolymerization.

[0126] The temperature of the olefin polymerization reaction can be -78°C to 200°C, preferably -20°C to 150°C, and the pressure can be 0.01 to 10 MPa, preferably 0.01 to 5 MPa. Here, "pressure" refers to the ethylene pressure in the polymerization system, expressed as absolute pressure.

[0127] In the olefin polymerization method of the present invention, the olefin is a C2-C16 olefin.

[0128] According to one embodiment of the present invention, the olefin comprises ethylene.

[0129] According to one embodiment of the present invention, the olefins include ethylene, propylene, α-olefins, and cycloolefins.

[0130] According to one embodiment of the present invention, the olefin polymerization reaction is carried out by reacting olefin monomers in a solvent, and the polymerization solvent is selected from one or more of alkanes, aromatic hydrocarbons, and halogenated hydrocarbons. Specifically, the polymerization solvent is selected from one or more of hexane, pentane, heptane, benzene, toluene, dichloromethane, chloroform, chlorobenzene, and dichloroethane, preferably one or more of hexane, toluene, and heptane.

[0131] In the present invention, alkyl refers to a straight-chain alkyl, a branched-chain alkyl or a 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.

[0132] In the present invention, examples of the aryl group include, but are not limited to, phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, and vinylphenyl.

[0133] In the present invention, alkenyl refers to straight-chain alkenyl, branched-chain alkenyl or cycloalkenyl, including but not limited to vinyl, allyl and butenyl.

[0134] In the present invention, examples of the aralkyl group include, but are not limited to, phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-isopropyl, phenyl-n-butyl, and phenyl-t-butyl.

[0135] In the present invention, examples of the alkaryl group include, but are not limited to, tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, and tert-butylphenyl.

[0136] The following examples further illustrate the phosphine-phenol transition metal complex, its preparation method, and application of the present invention. The examples are implemented based on the technical solution of the present invention, and provide detailed implementation methods and specific operating processes, but the scope of protection of the present invention is not limited to the following examples.

[0137] The experimental methods in the following examples, unless otherwise specified, are all conventional methods in the art. The experimental materials used in the following examples, unless otherwise specified, are all commercially available.

[0138] The analytical characterization instruments and test methods used in the following examples and comparative examples are as follows:

[0139] (1) Nuclear magnetic resonance instrument: Bruker DMX 300 (300 MHz), with tetramethylsilane (TMS) as the internal standard.

[0140] (2) Molecular weight and molecular weight distribution (PDI) of polymers (PDI = Mw / Mn): The molecular weights were measured at 150°C using a PL-GPC220 chromatograph with trichlorobenzene as solvent (standard: PS, flow rate: 1.0 mL / min, column: 3 × PLgel 10 μm M1 × ED-B, 300 × 7.5 nm).

[0141] (3) Activity measurement method: The polymer was washed with hydrochloric acid and ethanol solution, dried under vacuum, and the polymer weight was measured. The polymerization activity was calculated as follows: polymer weight (g) / metal (mol) × 60 / polymerization time (min).

[0142] (4) Complex structure analysis: Single crystal analysis was performed using a Rigaku RAXIS Rapid IP diffractometer.

[0143] (5) Analysis of comonomer content of polymer: using 1 H NMR, 13 C NMR spectroscopy was performed on a 400 MHz Bruker Avance 400 NMR spectrometer using a 10 mm PASEX 13 probe. The polymer samples were dissolved in 1,2,4-trichlorobenzene at 120°C for analysis.

[0144] Example 1

[0145] Complex 2: Complex represented by formula (II), wherein M is Ti, R 11 -R 15 is H, X is Cl, and n=2.

[0146] In a nitrogen atmosphere, the compound represented by formula (III) (11.23 g, 30 mmol, S type) was dissolved in anhydrous ether (150 mL), and n-butyl lithium solution (2.7 M, 33.3 mL, 90 mmol) was added dropwise at room temperature. The mixture was stirred at room temperature for 4 h, and tetrahydrofuran (150 mL) was added. The resulting black solution containing the precipitate was further stirred for 1 h. Diphenylphosphine chloride (PPh2Cl) (90 mmol, 16.7 mL) was added at 0 ° C. After stirring at room temperature for 1 h, NH4Cl aqueous solution (5 mL) was added to quench the mixture. 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 were added, and the reaction was refluxed for 16 h. After completion of the reaction, TLC was used to track the reaction. The organic solvent was removed, and the product was dissolved in ethyl acetate and neutralized by adding aqueous NaHCO3. The organic phase was extracted, dried over anhydrous MgSO4, filtered, concentrated, and purified by column chromatography (dichloromethane as solvent) 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). 31P NMR (162 MHz, CDCl3): δ = -17.19 (s). High-resolution mass spectrometry: Theoretical calculated value: 654.19; measured value: 655.20.

[0147] In 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 mixture was stirred at room temperature for 10 h. The NaH was removed by filtration. A tetrahydrofuran solution of TiCl4(THF)2 (0.334 g, 1 mmol) was added dropwise, and the mixture was reacted overnight at room temperature. The solvent was drained, and dichloromethane (40 mL) was added to dissolve the mixture. The filter cake was removed by filtration, and the filtrate was concentrated and recrystallized by adding heptane to obtain a red complex 2 (its single crystal structure is shown in the figure). Figure 1 The yield was 74%. 1 HNMR (300 MHz, CDCl3): δ = 6.80-6.91 (m, 4H), 6.93-7.15 (m, 22H), 7.18-7.20 (m, 4H), 7.26-7.36 (m, 22H), 7.47-7.60 (m, 4H), 7.88-7.92 (m, 4H). Elemental analysis test C 88 H 60 Cl4O4P4Ti2: Theoretical calculated values ​​are: C, 68.51; H, 3.92; tested values ​​are: C, 68.37; H, 4.14.

[0148] A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While still hot, the mixture was evacuated and replaced with N2 three times. 500mL of toluene was injected into the polymerization kettle, and methylaluminoxane (6.5mL, 10mmol) and 7.7mg (5μmol) of complex 2 were added. The reaction was stirred vigorously at 30°C for 20 minutes while maintaining an ethylene pressure of 1.0atm. The mixture was neutralized with ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried, weighed, and tested for polymerization activity. The weight-average molecular weight, molecular weight distribution, and polymerization activity of the resulting polymer are shown in Table 1.

[0149] Example 2

[0150] Complex 2: Complex represented by formula (II), wherein M is Ti, R 11 -R 15 is H, X is Cl, and n=2.

[0151] A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While still hot, the mixture was evacuated and replaced with N2 three times. 500mL of toluene was injected into the polymerization kettle, and methylaluminoxane (6.5mL, 10mmol) and 7.7mg (5μmol) of complex 2 were added. The reaction was stirred vigorously at 30°C for 30 minutes while maintaining an ethylene pressure of 10atm. The mixture was neutralized with ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried, weighed, and tested for polymerization activity. The weight-average molecular weight, molecular weight distribution, and polymerization activity of the resulting polymer are shown in Table 1.

[0152] Example 3

[0153] Complex 2: Complex represented by formula (II), wherein M is Ti, R 11 -R 15 is H, X is Cl, and n=2.

[0154] A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While still hot, the mixture was evacuated and replaced with N2 three times. 500mL of toluene was injected into the polymerization kettle, and methylaluminoxane (6.5mL, 10mmol) and 7.7mg (5μmol) of complex 2 were added. The reaction was stirred vigorously at 80°C for 30 minutes while maintaining an ethylene pressure of 10atm. The mixture was neutralized with ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried, weighed, and tested for polymerization activity. The weight-average molecular weight, molecular weight distribution, and polymerization activity of the resulting polymer are shown in Table 1.

[0155] Example 4

[0156] Complex 2: Complex represented by formula (II), wherein M is Ti, R 11 -R 15 is H, X is Cl, and n=2.

[0157] A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While hot, the mixture was evacuated and replaced with N2 three times. 500mL of toluene was injected into the polymerization kettle, and 6.5mL of methylaluminoxane (10mmol), 10mL of 1-octene, and 7.7mg (5μmol) of complex 2 were added. The reaction was stirred vigorously at 30°C for 30 minutes while maintaining an ethylene pressure of 1.0atm. The reaction was neutralized with ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer, which was then dried, weighed, and tested for polymerization activity. The weight-average molecular weight, molecular weight distribution, polymerization activity, and comonomer content of the resulting polymer are shown in Table 1.

[0158] Example 5

[0159] Complex 2: Complex represented by formula (II), wherein M is Ti, R 11 -R15 is H, X is Cl, and n=2.

[0160] A 100 mL glass polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 h. While hot, the mixture was evacuated and replaced with N2 gas three times. 50 mL of toluene was injected into the polymerization kettle, and methylaluminoxane (6.5 mL, 10 mmol), 0.5 g of norbornene, and 3.1 mg (2 μmol) of complex 2 were added. The mixture was stirred vigorously at 30°C for 10 min while maintaining an ethylene pressure of 1.0 atm. The reaction was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The polymer was dried, weighed, and tested for polymerization activity. The weight-average molecular weight, molecular weight distribution, polymerization activity, and comonomer content of the obtained polymer are shown in Table 1.

[0161] Example 6

[0162] Complex 2: Complex represented by formula (II), wherein M is Ti, R 11 -R 15 is H, X is Cl, and n=2.

[0163] A 100 mL glass polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 h. While hot, the mixture was evacuated and replaced with N2 gas three times. 50 mL of toluene was injected into the polymerization kettle, and methylaluminoxane (6.5 mL, 10 mmol), 0.5 g of norbornene, and 3.1 mg (2 μmol) of complex 2 were added. The mixture was stirred vigorously at 50°C for 10 min while maintaining an ethylene pressure of 1.0 atm. The reaction was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The polymer was dried, weighed, and tested for polymerization activity. The test data for the weight-average molecular weight, molecular weight distribution, polymerization activity, and comonomer content of the obtained polymer are shown in Table 1.

[0164] Example 7

[0165] Complex 2: Complex represented by formula (II), wherein M is Ti, R 11 -R 15 is H, X is Cl, and n=2.

[0166] A 100 mL glass polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 h. While hot, the mixture was evacuated and replaced with N2 gas three times. 50 mL of toluene was injected into the polymerization kettle, and methylaluminoxane (6.5 mL, 10 mmol), 0.5 g of norbornene, and 3.1 mg (2 μmol) of complex 2 were added. The reaction was stirred vigorously at 70°C for 10 min while maintaining an ethylene pressure of 1.0 atm. The polymer was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The polymer was dried, weighed, and tested for polymerization activity. The test data for the weight-average molecular weight, molecular weight distribution, polymerization activity, and comonomer content of the obtained polymer are shown in Table 1.

[0167] Example 8

[0168] Complex 2: Complex represented by formula (II), wherein M is Ti, R 11 -R 15 is H, X is Cl, and n=2.

[0169] A 100 mL glass polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 h. While hot, the mixture was evacuated and replaced with N2 gas three times. 50 mL of toluene was injected into the polymerization kettle, and methylaluminoxane (6.5 mL, 10 mmol), 5.0 g of norbornene, and 3.1 mg (2 μmol) of complex 2 were added. The mixture was stirred vigorously at 75°C for 10 min while maintaining an ethylene pressure of 1.0 atm. The reaction was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The polymer was dried, weighed, and tested for polymerization activity. The weight-average molecular weight, molecular weight distribution, polymerization activity, and comonomer content of the obtained polymer are shown in Table 1.

[0170] Example 9

[0171] Complex 25: Complex represented by formula (II), wherein M is Zr, R 11 -R 15 is H, X is Cl, and n=2.

[0172] Ligand L1 was prepared according to the method of Example 1.

[0173] 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 mixture was stirred at room temperature for 10 h. The NaH was removed by filtration. A solution of (THF)ZrCl2 (0.377 g, 1 mmol) in tetrahydrofuran (-78°C) was added dropwise. The mixture was allowed to react overnight at room temperature. The solvent was drained, and dichloromethane (40 mL) was added to dissolve the mixture. The filter cake was removed by filtration, and the filtrate was concentrated and recrystallized from heptane to obtain white complex 25 in a 72% yield. 1 HNMR (300MHz, CDCl3): δ: 6.81-6.92(m,4H),7.04-7.10(m,4H),7.13-7.20(m,4H),7.27-7 .29(m,16H),7.38-7.45(m,20H),7.57-7.72(m,8H),7.78-7.87(m,2H),7.95-8.00(m,2H). 31 P NMR (162MHz, CDCl3): δ=-1.96(s). Elemental analysis test C 88 H 60Cl4O4P4Zr2: Theoretical calculated values ​​are: C, 64.86; H, 3.71; tested values ​​are: C, 64.69; H, 3.93.

[0174] A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While still hot, the mixture was evacuated and replaced with N2 three times. 500mL of toluene was injected into the polymerization kettle, and methylaluminoxane (6.5mL, 10mmol) and 8.1mg (5μmol) of complex 25 were added. The reaction was stirred vigorously for 30 minutes at 30°C, maintaining an ethylene pressure of 1.0atm. The mixture was neutralized with ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried, weighed, and tested for polymerization activity. The weight-average molecular weight, molecular weight distribution, and polymerization activity of the resulting polymer are shown in Table 1.

[0175] Example 10

[0176] Complex 25: Complex represented by formula (II), wherein M is Zr, R 11 -R 15 is H, X is Cl, and n=2.

[0177] A 1L stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130°C for 6 hours, evacuated while hot and replaced with N2 gas three times. 500mL of toluene was injected into the polymerization kettle, and methylaluminoxane (6.5mL, 10mmol) and 8.1mg (5μmol) of complex 25 were added. The mixture was stirred vigorously at 30°C, maintaining a propylene pressure of 2.0atm, and reacted for 30 minutes. The mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polypropylene. According to nuclear magnetic resonance carbon spectroscopy analysis, the syndiotacticity of the obtained polypropylene was 41.2%. The polymer was dried and weighed to test the polymerization activity. The weight average molecular weight, molecular weight distribution, and polymerization activity test data of the obtained polymer are shown in Table 1.

[0178] Example 11

[0179] Complex 43: A complex represented by formula (II), wherein M is Hf, R 11 -R 15 is H, X is Cl, and n=2.

[0180] Ligand L1 was prepared according to the method of Example 1.

[0181] 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 filtered to remove the NaH. A solution of (THF)2HfCl4 (0.464 g, 1 mmol) in tetrahydrofuran (-78°C) was added dropwise. The mixture was allowed to react overnight at room temperature. The solvent was drained and dissolved in dichloromethane (40 mL). The filter cake was removed by filtration, and the filtrate was concentrated and recrystallized from heptane to obtain a white complex 43 with a yield of 78%. Elemental analysis test C 88 H 60 Cl4Hf2O4P4: Theoretical calculated values ​​are: C, 58.59; H, 3.35; tested values ​​are: C, 58.71; H, 3.52.

[0182] A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While hot, the mixture was evacuated and replaced with N2 three times. 500mL of toluene was injected into the polymerization kettle, and methylaluminoxane (6.5mL, 10mmol) and 9.0mg (5μmol) of complex 43 were added. The reaction was stirred vigorously for 30 minutes at 30°C, maintaining an ethylene pressure of 1.0atm. The mixture was neutralized with ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried, weighed, and tested for polymerization activity. The weight-average molecular weight, molecular weight distribution, and polymerization activity of the resulting polymer are shown in Table 1.

[0183] Example 12

[0184] Complex 43: A complex represented by formula (II), wherein M is Hf, R 11 -R 15 is H, X is Cl, and n=2.

[0185] A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While hot, the mixture was evacuated and replaced with N2 three times. 500mL of toluene was injected into the polymerization kettle, and methylaluminoxane (6.5mL, 10mmol) and 9.0mg (5μmol) of complex 43 were added. The reaction was stirred vigorously at 50°C for 30 minutes while maintaining an ethylene pressure of 1.0atm. The mixture was neutralized with ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried, weighed, and tested for polymerization activity. The weight-average molecular weight, molecular weight distribution, and polymerization activity of the resulting polymer are shown in Table 1.

[0186] Example 13

[0187] Complex 43: A complex represented by formula (II), wherein M is Hf, R 11 -R 15 is H, X is Cl, and n=2.

[0188] A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While hot, the mixture was evacuated and replaced with N2 three times. 500mL of toluene was injected into the polymerization kettle, and methylaluminoxane (6.5mL, 10mmol) and 9.0mg (5μmol) of complex 43 were added. The reaction was stirred vigorously for 30 minutes at 30°C, maintaining a propylene pressure of 2.0atm. Polypropylene was neutralized with 10wt% hydrochloric acid in ethanol to obtain polypropylene. The polymer was dried, weighed, and tested for polymerization activity. The weight-average molecular weight, molecular weight distribution, and polymerization activity of the resulting polymer are shown in Table 1.

[0189] Example 14

[0190] Complex 18: Complex represented by formula (II), wherein M is Ti, R 11 、R 13 and R 15 H, R 12 and R 14 It is -CF3, X is Cl, and n=2.

[0191] The synthesis steps are similar to those of complex 2 in Example 1, except that diphenylphosphine chloride is replaced by bis(3,5-bis(trifluoromethyl)phenyl)phosphine chloride.

[0192] Under a nitrogen atmosphere, the compound represented by formula (III) (3.74 g, 10 mmol, R-type) was dissolved in anhydrous ether (120 mL). A solution of n-butyllithium (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, and the resulting black solution containing a precipitate was further stirred for 1 h. 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, the mixture was quenched by the addition of aqueous NH4Cl solution (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 were added, and the reaction was refluxed for 16 h. The reaction was monitored by TLC after completion. The organic solvent was removed, and the product was dissolved in ethyl acetate and neutralized by adding aqueous NaHCO 3 . The organic phase was extracted, dried over anhydrous MgSO 4 , filtered, concentrated, and purified by column chromatography (dichloromethane as solvent) to obtain 4.78 g of ligand L2 with a yield of 40%. 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).1 H NMR (400 MHz, DMSO) δ9.10 (s, 2H), 8.17 (s, 2H), 8.13 (s, 2H), 8.08 (dd, J = 13.3, 6.5 Hz, 8H), 7.81 (d, J = 7.6 Hz, 2H), 7.56 (d, J = 8.4 Hz, 2H), 7.27 (d, 4H), 6.90 (d, J = 8.2 Hz, 2H). High-resolution mass spectrometry: Theoretical calculation value: 1198.09; measured value: 1198.95. 31 P NMR (162MHz, DMSO): δ = -8.37 (s).

[0193] 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 mixture was stirred at room temperature for 10 h. The NaH was then removed by filtration. A solution of TiCl4(THF)2 (0.334 g, 1 mmol) in tetrahydrofuran was added dropwise. The reaction was allowed to proceed overnight at room temperature. The solvent was then drained, and dichloromethane (40 mL) was added to dissolve the mixture. The filter cake was removed by filtration, and the filtrate was concentrated and recrystallized from heptane to obtain the red complex 18 in a 72% yield. 1 H NMR (400MHz, CDCl3) δ6.78-7.04(m,4H),7.08-7.10(d,4H),7.14-7.18(m,2H),7.24-7.31(m,6H),7.41- 7.48(m,6H),7.64(d,4H),7.78-7.81(m,4H),7.83(d,4H),7.86(d,4H),7.92(d,4H),7.99-8.11(m,2H). 31 P NMR (162 MHz, DMSO): δ = -9.22 (s). Elemental analysis test C 104 H 44 Cl4F 48 O4P4Ti2: Theoretical calculated values ​​are: C, 47.48; H, 1.69; tested values ​​are: C, 47.57; H, 1.83.

[0194] A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While hot, the mixture was evacuated and replaced with N2 three times. 500mL of toluene was injected into the polymerization kettle, and methylaluminoxane (3.3mL, 5mmol) and 6.6mg (2.5μmol) of complex 18 were added. The reaction was stirred vigorously at 30°C for 20 minutes while maintaining an ethylene pressure of 1.0atm. The mixture was neutralized with ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried, weighed, and tested for polymerization activity. The weight-average molecular weight, molecular weight distribution, and polymerization activity of the resulting polymer are shown in Table 1.

[0195] Example 15

[0196] Complex 37: Complex represented by formula (II), wherein M is Zr, R 11 、R 13 and R 15 H, R 12 and R 14 It is -CF3, X is Cl, and n=2.

[0197] Ligand L2 was prepared according to the method of Example 1.

[0198] 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 filtered to remove the NaH. A solution of (THF)ZrCl2 (0.377 g, 1 mmol) in tetrahydrofuran (-78°C) was added dropwise. The mixture was allowed to react overnight at room temperature. The solvent was drained and dissolved in dichloromethane (40 mL). The filter cake was removed by filtration, and the filtrate was concentrated and recrystallized from heptane to obtain a white complex 37 with a yield of 74%. Elemental analysis test C 104 H 44 Cl4F 48 O4P4Zr2: Theoretical calculated values ​​are: C, 45.97; H, 1.63; tested values ​​are: C, 45.76; H, 1.92.

[0199] A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While still hot, the mixture was evacuated and replaced with N2 three times. 500mL of toluene, 3.3mL of methylaluminoxane (5mmol), and 6.8mg (2.5μmol) of complex 37 were injected into the polymerization kettle. The mixture was stirred vigorously for 30 minutes at 30°C, maintaining an ethylene pressure of 1.0atm. The mixture was neutralized with 10wt% hydrochloric acid in ethanol to obtain polyethylene. The polymer was dried, weighed, and tested for polymerization activity. The weight-average molecular weight, molecular weight distribution, and polymerization activity of the resulting polymer are shown in Table 1.

[0200] Example 16

[0201] Complex 40: Complex represented by formula (II), wherein M is Zr, R 11 、R 13 and R 15 H, R 12 and R 14 is methyl, X is Cl, and n=2.

[0202] Under a nitrogen atmosphere, the compound represented by formula (III) (3.74 g, 10 mmol, R type) was dissolved in anhydrous ether (120 mL), and n-butyl lithium solution (2.5 M, 12 mL, 30 mmol) was added dropwise at room temperature. The mixture was stirred at room temperature for 4 h, tetrahydrofuran (120 mL) was added, and the resulting black solution containing the precipitate was further stirred for 1 h. Chlorodi(3,5-dimethylphenyl)phosphine (30 mmol, 8.30 g) was added at 0 ° C. After stirring at room temperature for 1 h, NH4Cl aqueous solution (5 mL) was added to quench the mixture. 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 were added, and the reaction was refluxed for 16 h. After completion of the reaction, TLC was used to track the reaction. The organic solvent was removed, and the product was dissolved in ethyl acetate and neutralized by adding aqueous NaHCO3. The organic phase was extracted, dried over anhydrous MgSO4, filtered, concentrated, and purified by column chromatography (dichloromethane as solvent) to obtain ligand L3 with a yield of 58%. 1 H NMR (400 MHz, 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: Theoretical calculation value: 766.31; measured value: 767.32. 31 P NMR (162MHz, CDCl3) δ = -15.4 (s).

[0203] 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 filtered to remove the NaH. A solution of (THF)ZrCl2 (0.377 g, 1 mmol) in tetrahydrofuran (-78°C) was added dropwise. The mixture was allowed to react overnight at room temperature. The solvent was drained and dissolved in dichloromethane (40 mL). The filter cake was removed by filtration, and the filtrate was concentrated and recrystallized from heptane to obtain a white complex 40 with a yield of 72%. Elemental analysis test C 104 H 92 Cl4O4P4Zr2: Theoretical calculated values ​​are: C, 67.37; H, 5.00; tested values ​​are: C, 67.46; H, 5.32.

[0204] A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While still hot, the mixture was evacuated and replaced with N2 three times. 500mL of toluene was injected into the polymerization kettle, and methylaluminoxane (3.3mL, 5mmol) and 4.6mg (2.5μmol) of complex 40 were added. The reaction was stirred vigorously for 30 minutes at 30°C, maintaining an ethylene pressure of 1.0atm. The mixture was neutralized with ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried, weighed, and tested for polymerization activity. The weight-average molecular weight, molecular weight distribution, and polymerization activity of the resulting polymer are shown in Table 1.

[0205] Example 17

[0206] Complex 34: Complex represented by formula (II), wherein M is Zr, R 11 、R 12 、R 14 and R 15 H, R 13 is a methoxy group, X is Cl, and n=2.

[0207] In a nitrogen atmosphere, the compound represented by formula (III) (3.74 g, 10 mmol, S type) was dissolved in anhydrous ether (120 mL), and a hexane solution of n-butyl lithium (2.7 M, 11.1 mL, 30 mmol) was added dropwise at room temperature. The mixture was stirred at room temperature for 4 h, and tetrahydrofuran (120 mL) was added. The resulting black solution containing a precipitate was further stirred for 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, NH4Cl aqueous solution (5 mL) was added to quench the mixture. 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 were added, and the reaction was refluxed for 16 h. After completion of the reaction, TLC was used to track the reaction. The organic solvent was removed, and the product was dissolved in ethyl acetate and neutralized by adding aqueous NaHCO3. The organic phase was extracted, dried over anhydrous MgSO4, filtered, concentrated, and purified by column chromatography (dichloromethane as solvent) to obtain ligand L4 with a yield of 56%.

[0208] Under nitrogen, 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 filtered to remove the NaH. A solution of (THF)ZrCl2 (0.377 g, 1 mmol) in tetrahydrofuran (-78°C) was added dropwise. The mixture was allowed to react overnight at room temperature. The solvent was drained and dissolved in dichloromethane (40 mL). The filter cake was removed by filtration, and the filtrate was concentrated and recrystallized from heptane to obtain a white complex 34 with a yield of 73%. Elemental analysis test C 96 H 76 Cl4O12 P4Zr2: Theoretical calculated values ​​are: C, 61.67; H, 4.10; tested values ​​are: C, 61.58; H, 4.33.

[0209] A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours. While still hot, the mixture was evacuated and replaced with N2 three times. 500mL of toluene was injected into the polymerization kettle, and methylaluminoxane (3.3mL, 5mmol) and 4.7mg (2.5μmol) of complex 34 were added. The reaction was stirred vigorously for 30 minutes at 30°C, maintaining an ethylene pressure of 1.0atm. The mixture was neutralized with ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried, weighed, and tested for polymerization activity. The weight-average molecular weight, molecular weight distribution, and polymerization activity of the resulting polymer are shown in Table 1.

[0210] Comparative Example 1

[0211] A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours, evacuated while hot and replaced with N2 gas three times. 500mL of toluene was injected into the polymerization kettle, and methylaluminoxane (6.5mL, 10mmol) and 8.3mg (10μmol) of complex A (synthesis reference Organometallics, 2008, 27(2), 235-245) were added. At 30°C, an ethylene pressure of 1.0atm was maintained and the reaction was stirred vigorously for 20min. The reaction was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed to test the polymerization activity. The weight average molecular weight, molecular weight distribution and polymerization activity test data of the obtained polymer are shown in Table 1.

[0212]

[0213] Comparative Example 2

[0214] A 100 mL glass polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 h. While still hot, the mixture was evacuated and replaced with N2 three times. 50 mL of toluene was added to the polymerization kettle, followed by the addition of methylaluminoxane (6.5 mL, 10 mmol), 0.5 g of norbornene, and 3.3 mg (4.0 μmol) of complex A. The reaction was stirred vigorously at 30°C for 10 min while maintaining an ethylene pressure of 1.0 atm. The polymer was neutralized with 10 wt% hydrochloric acid in ethanol to obtain a polymer. The polymer was dried, weighed, and tested for polymerization activity. The weight-average molecular weight, molecular weight distribution, and polymerization activity of the resulting polymer are shown in Table 1.

[0215] Comparative Example 3

[0216] A 1L stainless steel polymerization kettle equipped with a mechanical stirrer was dried continuously at 130°C for 6 hours, evacuated while hot and replaced with N2 gas three times. 500mL of hexane was injected into the polymerization kettle, followed by the addition of methylaluminoxane (6.5mL, 10mmol) and 8.3mg (10μmol) of complex B (synthesis reference Organometallics, 2008, 27(2), 235-245). The mixture was stirred vigorously at 30°C for 30 minutes while maintaining an ethylene pressure of 1.0atm. The mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed to test the polymerization activity. The weight-average molecular weight, molecular weight distribution and polymerization activity test data of the obtained polymer are shown in Table 1.

[0217] Table 1

[0218]

[0219] It can be seen from the data in Table 1 that, compared with the complex of the comparative example, when the metal complex of the present invention is used as the main catalyst, the olefin polymerization activity of the complex of the same metal is higher, and the molecular weight of the obtained polymer is significantly higher than that of the polymer obtained in the comparative example.

[0220] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A phosphine-phenol transition metal complex, characterized in that: Its structural formula is shown in formula (II), Formula (II) wherein M is selected from Group IVB metals; R 11 -R 15 Each is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C20 hydrocarbon group; X is selected from halogen, C1-C10 hydrocarbon group, n is 1 or 2; the substituted in substituted or unsubstituted means containing substituents, and the substituents are selected from halogen, hydroxyl, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkoxy.

2. The phosphine-phenol transition metal complex according to claim 1, characterized in that M is selected from titanium, zirconium and hafnium.

3. The phosphine-phenol transition metal complex according to claim 1, 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; X is selected from halogen, C1-C8 hydrocarbon group; The term "substituted" in "substituted or unsubstituted" means containing a substituent selected from halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkoxy; The C1-C6 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl and 3,3-dimethylbutyl; The C1-C6 alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy and 3,3-dimethylbutoxy; The halogen is selected from fluorine, chlorine, bromine and iodine.

4. A phosphine-phenol transition metal complex, characterized in that: Its structural formula is shown in formula (II), Formula (II) It is selected from the group consisting of the following complexes, Complex 1: Complex represented by formula (II), wherein M is Ti, R 11 -R 15 is H, X is Cl, n=1; Complex 2: Complex represented by formula (II), where M is Ti, R 11 -R 15 is H, X is Cl, n=2; Complex 3: Complex represented by formula (II), where M is Ti, R 11 -R 15 is H, X is methyl, n=1; Complex 4: Complex represented by formula (II), where M is Ti, R 11 -R 15 is H, X is -CH2C6H5, n=2; Complex 5: Complex represented by formula (II), wherein M is Ti, R 11 、R 12 、R 14 and R 15 H, R 13 is -CF3, X is Cl, n=1; Complex 6: Complex represented by formula (II), where M is Ti, R 11 、R 12 、R 14 and R 15 H, R 13 is -CF3, X is Cl, n=2; Complex 7: Complex represented by formula (II), wherein M is Ti, R 11 、R 12 、R 14 and R 15 H, R 13 -CF3, X is methyl, n=2; Complex 8: Complex represented by formula (II), wherein M is Ti, R 11 、R 12 、R 14 and R 15 H, R 13 is -CF3, X is -CH2C6H5, n=2; Complex 9: Complex represented by formula (II), wherein M is Ti, R 12 -R 15 H, R 11 is methoxy, X is Cl, n=1; Complex 10: Complex represented by formula (II), wherein M is Ti, R 12 -R 15 H, R 11 is methoxy, X is Cl, n=2; Complex 11: Complex represented by formula (II), wherein M is Ti, R 12 -R 15 H, R 11 is methoxy, X is methyl, n=2; Complex 12: Complex represented by formula (II), wherein M is Ti, R 12 -R 15 H, R 11 is methoxy, X is -CH2C6H5, n=2; Complex 13: Complex represented by formula (II), wherein M is Ti, R 11 、R 12 、R 14 and R 15 H, R 13 is methoxy, X is Cl, n=1; Complex 14: Complex represented by formula (II), wherein M is Ti, R 11 、R 12 、R 14 and R 15 H, R 13 is methoxy, X is Cl, n=2; Complex 15: Complex represented by formula (II), wherein M is Ti, R 11 、R 12 、R 14 and R 15 H, R 13 is methoxy, X is methyl, n=2; Complex 16: The complex represented by formula (II), wherein M is Ti, R 11 、R 12 、R 14 and R 15 H, R 13 is methoxy, X is -CH2C6H5, n=2; Complex 17: Complex represented by formula (II), wherein M is Ti, R 11 、R 13 and R 15 H, R 12 and R 14 is -CF3, X is Cl, n=1; Complex 18: Complex represented by formula (II), wherein M is Ti, R 11 、R 13 and R 15 H, R 12 and R 14 is -CF3, X is Cl, n=2; Complex 19: The complex represented by formula (II), wherein M is Ti, R 11 、R 13 and R 15 H, R 12 and R 14 -CF3, X is methyl, n=2; Complex 20: Complex represented by formula (II), wherein M is Ti, R 11 、R 13 and R 15 H, R 12 and R 14 is -CF3, X is -CH2C6H5, n=2; Complex 21: Complex represented by formula (II), wherein M is Ti, R 11 、R 13 and R 15 H, R 12 and R 14 is methyl, X is Cl, n=1; Complex 22: The complex represented by formula (II), wherein M is Ti, R 11 、R 13 and R 15 H, R 12 and R 14 is methyl, X is Cl, n=2; Complex 23: Complex represented by formula (II), wherein M is Ti, R 11 、R 13 and R 15 H, R 12 and R 14 is a methyl group, X is a methyl group, and n=2; Complex 24: The complex represented by formula (II), wherein M is Ti, R 11 、R 13 and R 15 H, R 12 and R 14 is methyl, X is -CH2C6H5, n=2; Complex 25: The complex represented by formula (II), wherein M is Zr, R 11 -R 15 is H, X is Cl, n=2; Complex 26: Complex represented by formula (II), wherein M is Zr, R 11 -R 15 is H, X is methyl, n=2; Complex 27: The complex represented by formula (II), wherein M is Zr, R 11 -R 15 is H, X is -CH2C6H5, n=2; Complex 28: The complex represented by formula (II), wherein M is Zr, R 11 、R 12 、R 14 and R 15 H, R 13 is -CF3, X is Cl, n=2; Complex 29: The complex represented by formula (II), wherein M is Zr, R 11 、R 12 、R 14 and R 15 H, R 13 -CF3, X is methyl, n=2; Complex 30: Complex represented by formula (II), wherein M is Zr, R 11 、R 12 、R 14 and R 15 H, R 13 is -CF3, X is -CH2C6H5, n=2; Complex 31: The complex represented by formula (II), wherein M is Zr, R 12 -R 15 H, R 11 is methoxy, X is Cl, n=2; Complex 32: The complex represented by formula (II), wherein M is Zr, R 12 -R 15 For R 11 is methoxy, X is methyl, n=2; Complex 33: Complex represented by formula (II), wherein M is Zr, R 12 -R 15 For R 11 is methoxy, X is -CH2C6H5, n=2; Complex 34: The complex represented by formula (II), wherein M is Zr, R 11 、R 12 、R 14 and R 15 H, R 13 is methoxy, X is Cl, n=2; Complex 35: The complex represented by formula (II), wherein M is Zr, R 11 、R 12 、R 14 and R 15 H, R 13 is methoxy, X is methyl, n=2; Complex 36: The complex represented by formula (II), wherein M is Zr, R 11 、R 12 、R 14 and R 15 H, R 13 is methoxy, X is -CH2C6H5, n=2; Complex 37: The complex represented by formula (II), wherein M is Zr, R 11 、R 13 and R 15 H, R 12 and R 14 is -CF3, X is Cl, n=2; Complex 38: The complex represented by formula (II), wherein M is Zr, R 11 、R 13 and R 15 H, R 12 and R 14 -CF3, X is methyl, n=2; Complex 39: The complex represented by formula (II), wherein M is Zr, R 11 、R 13 and R 15 H, R 12 and R 14 is -CF3, X is -CH2C6H5, n=2; Complex 40: The complex represented by formula (II), wherein M is Zr, R 11 、R 13 and R 15 H, R 12 and R 14 is methyl, X is Cl, n=2; Complex 41: The complex represented by formula (II), wherein M is Zr, R 11 、R 13 and R 15 H, R 12 and R 14 is a methyl group, X is a methyl group, and n=2; Complex 42: The complex represented by formula (II), wherein M is Zr, R 11 、R 13 and R 15 H, R 12 and R 14 is methyl, X is -CH2C6H5, n=2; Complex 43: The complex represented by formula (II), wherein M is Hf, R 11 -R 15 is H, X is Cl, n=2; Complex 44: A complex represented by formula (II), wherein M is Hf, R 11 -R 15 is H, X is methyl, n=2; Complex 45: The complex represented by formula (II), wherein M is Hf, R 11 -R 15 is H, X is -CH2C6H5, n=2; Complex 46: The complex represented by formula (II), wherein M is Hf, R 11 、R 12 、R 14 and R 15 H, R 13 is -CF3, X is Cl, n=2; Complex 47: The complex represented by formula (II), wherein M is Hf, R 11 、R 12 、R 14 and R 15 H, R 13 is methoxy, X is Cl, n=2; Complex 48: The complex represented by formula (II), wherein M is Hf, R 11 、R 13 and R 15 H, R 12 and R 14 is -CF3, X is Cl, n=2; Complex 49: A complex represented by formula (II), wherein M is Hf, R 11 、R 13 and R 15 H, R 12 and R 14 is methyl, X is Cl, n=2; Complex 50: The complex represented by formula (II), wherein M is Hf, R 11 、R 13 and R 15 H, R 12 and R 14 is -CF3, X is -CH2C6H5, n=2; Complex 51: The complex represented by formula (II), wherein M is Hf, R 11 、R 12 、R 14 and R 15 H, R 13 is -CF3, X is -CH2C6H5, n=2; Complex 52: The complex represented by formula (II), wherein M is Hf, R 11 、R 12 、R 14 and R 15 H, R 13 is methoxy, X is -CH2C6H5, n=2; Complex 53: The complex represented by formula (II), wherein M is Hf, R 11 、R 13 and R 15 H, R 12 and R 14 is methyl, X is -CH2C6H5, n=2; Complex 54: A complex represented by formula (II), wherein M is Hf, R 11 、R 13 and R 15 H, R 12 and R 14 is -CF3, X is -CH2C6H5, and n=2.

5. A method for preparing the phosphine-phenol transition metal complex according to any one of claims 1 to 4, characterized in that: The method includes: (1) reacting the compound represented by formula (III) with the compound represented by formula (VI) to obtain the ligand represented by formula (VII); (2) reacting the ligand with a hydrogen extraction agent, and then reacting with an M metal compound, wherein the transition metal M in the M metal compound is selected from Group IVB metals; Formula (III) Formula (VI) Formula (VII) Among them, R 11 -R 15 The definition is the same as that of claim 1.

6. The method according to claim 5, characterized in that The M metal compound is at least one selected from titanium tetrachloride, bis(tetrahydrofuran)titanium tetrachloride, tris(tetrahydrofuran)titanium trichloride, zirconium tetrachloride, bis(tetrahydrofuran)zirconium tetrachloride, hafnium tetrachloride and bis(tetrahydrofuran)hafnium tetrachloride.

7. The method according to claim 5, characterized in that The hydrogen withdrawal agent is selected from at least one of NaH, KH, n-butyl lithium and methyl lithium.

8. Use of the phosphine-phenol transition metal complex according to any one of claims 1 to 4 in olefin polymerization.

9. An olefin polymerization catalyst, characterized in that Contains the phosphine-phenol transition metal complex according to any one of claims 1 to 4 and a co-catalyst.

10. The olefin polymerization catalyst according to claim 9, characterized in that The co-catalyst is an organoaluminum compound and / or an organoboron compound; The organoaluminum compound is one or more selected from alkylaluminoxane, alkylaluminum and alkylaluminum halide; The organic boron compound is one or more selected from organic boron and organic borate.

11. A method for olefin polymerization, characterized in that: The method comprises carrying out an olefin polymerization reaction in the presence of the olefin polymerization catalyst according to claim 9 or 10; The temperature of the olefin polymerization reaction is -78°C to 200°C, and the pressure is 0.01 to 10 MPa.

12. The olefin polymerization method according to claim 11, characterized in that The temperature of the olefin polymerization reaction is -20°C to 150°C, and the pressure is 0.01 to 5 MPa.

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