Tetrahydronaphthol-phosphorus mono-chromium metallocene metal complex as well as preparation method and application thereof

Abstract

The invention relates to the fields of olefin polymerization organic metal catalysts and olefin coordination polymerization, and discloses a tetrahydronaphthol-phosphorus mono-chromium metallocene metal complex as well as a preparation method and application of the tetrahydronaphthol-phosphorus mono-chromium metallocene metal complex. The structure of the tetrahydronaphthol-phosphorus mono-chromium metallocene metal complex is shown as a formula (I), and in the formula (I), R1-R5 are independently selected from C1-C20 alkyl substituted or unsubstituted by hydrogen, or R1-R5 are optionally and mutually cyclized; r6-R10 are respectively and independently selected from hydrogen, halogen, hydroxyl and substituted or unsubstituted C1-C15 alkyl; x is selected from halogen or C1-C10 alkyl. When the tetrahydronaphthol-phosphorus mono-metallocene chromium metal complex is used as a main catalyst, the tetrahydronaphthol-phosphorus mono-metallocene chromium metal complex has higher homopolymerization / copolymerization activity under similar polymerization conditions, and an obtained polymer is higher in molecular weight and narrower in distribution. # imgabs0 #

Description

Technical Field

[0001] The invention relates to the field of olefin polymerization organic metal catalysts and olefin coordination polymerization, and in particular to a tetralinol-phosphomonochromocene metal complex and a preparation method and application thereof. Background Art

[0002] Since Ziegler and Natta made pioneering work in the field of olefin polymerization, the polyolefin industry has experienced rapid development. Among them, polyethylene materials have the characteristics of good chemical resistance, low price, simple preparation, low density, good mechanical properties, etc., and can also be used as a potential rubber substitute. Introducing a small amount of polar functional groups into polyethylene can greatly improve its properties, broaden its uses, and increase its commercial value. Ethylene homopolymers and copolymers are widely used in films, pipes, automotive parts, medical equipment, prosthetic implants and other fields. The innovation of catalysts determines the progress of the polyolefin industry chain. Coordination catalytic copolymerization plays an irreplaceable role as a polymerization technology at room temperature and pressure. Chromium-based catalysts, as an important variety of ethylene polymerization catalysts, have attracted much attention due to their high polymerization activity and easy availability of complex raw materials. Among them, heterogeneous chromium-based catalysts can be used to prepare high-density polyethylene and linear low-density polyethylene products, but their catalytic mechanism is still unclear. In recent years, homogeneous chromium-based catalysts have developed rapidly. By changing the types of their active centers and ligands, polyethylene products with unique properties can be obtained. At present, the research on chromium homogeneous catalysts mainly focuses on the selection of ligands. Trivalent chromium complexes are the most widely used homogeneous chromium catalysts. At present, by changing the skeleton structure of the ligands of homogeneous chromium catalysts, a series of chromium catalysts for olefin polymerization have been developed. The developed systems mainly include N, N type catalytic systems; catalytic systems containing O, P, S atoms; catalytic systems substituted with cyclopentadienyl, etc. (Coordination Chemistry Reviews 2019, 385, 208–229; European Polymer Journal 2019, 121, 109339).

[0003] However, the above catalysts all have the problem of being unable to maintain high catalytic activity and high polymerization performance at high temperatures. Summary of the invention

[0004] The present invention aims to provide a tetralinol-phosphine chromium metal complex and a preparation method and application thereof. The tetralinol-phosphine chromium metal complex has good thermal stability. In particular, the tetralinol-phosphine chromium metal complex can still maintain high ethylene polymerization activity at a relatively high temperature, and the molecular weight distribution of the obtained polymer is relatively narrow.

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

[0006]

[0007] Among them, R 1 -R 5 are each independently selected from hydrogen and substituted or unsubstituted C1-C20 hydrocarbon groups, or R 1 -R 5 Optionally, they are cyclic to each other; R 6 -R 10 Each is independently selected from hydrogen, halogen, hydroxyl and substituted or unsubstituted C1-C15 hydrocarbon group; X is selected from halogen or C1-C10 hydrocarbon group.

[0008] Preferably, R 1 -R 5 Each is independently selected from hydrogen and a substituted or unsubstituted C1-C10 hydrocarbon group.

[0009] Preferably, R 6 -R 10 Each is independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C6 alkyl and substituted or unsubstituted C6-C15 aryl.

[0010] Preferably, X is selected from halogen or C1-C8 hydrocarbon group.

[0011] Preferably, the substituents are selected from halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy.

[0012] 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.

[0013] Preferably, the C1-C6 alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy or 3,3-dimethylbutoxy.

[0014] Preferably, the halogen is selected from fluorine, chlorine, bromine or iodine.

[0015] The second aspect of the present invention provides a method for preparing the above-mentioned tetrahydronaphthol-phosphocene chromium metal complex, which comprises the following steps:

[0016] (1) reacting the compound represented by formula (II) with the compound represented by formula (III) to generate a ligand;

[0017] (2) React the ligand with a chromium metal compound and a lithium compound, wherein the lithium compound contains a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted indenyl group, or a substituted or unsubstituted fluorenyl group;

[0018]

[0019] wherein R 6 -R 10 is defined as the same as described above.

[0020] Preferably, the chromium metal compound is selected from CrCl 3 (THF) 3 , CrCl 3 (H 2 O), CrCl 3 (H 2 O) 6 , CrCl 3 , CrBr 3 (H 2 O) 6 , CrBr 3 and CrI 3 or more than one of them.

[0021] Preferably, the lithium compound is selected from one or more of lithium cyclopentadienyl, lithium pentamethylcyclopentadienyl, lithium methyl-cyclopentadienyl, lithium n-butyl-cyclopentadienyl, lithium tert-butyl-cyclopentadienyl, lithium indenyl, lithium fluorenyl, lithium butyl-indenyl, lithium 1-methyl-indenyl, lithium 2-methyl-indenyl, and lithium 1-phenyl-indenyl.

[0022] The third aspect of the present invention provides the application of the above tetrahydronaphthol-phosphorus monocyclopentadienyl chromium metal complex in olefin polymerization.

[0023] The fourth aspect of the present invention provides a catalyst for olefin polymerization, and the catalyst for olefin polymerization includes a main catalyst and a cocatalyst;

[0024] The main catalyst is the above tetrahydronaphthol-phosphorus monocyclopentadienyl chromium metal complex.

[0025] Preferably, the cocatalyst is selected from an organoaluminum compound and / or an organoboron compound.

[0026] Preferably, the organoaluminum compound is selected from an alkylaluminoxane or an organoaluminum compound of the general formula AlY n Z 3-n , wherein Y is selected from hydrogen, a C1-C20 hydrocarbon group, or a C1-C20 hydrocarbon oxy group, Z is selected from a halogen, 0 < n ≤ 3, and n is an integer.

[0027] Preferably, Y is selected from C1-C20 alkyl, C1-C20 alkoxy, C7-C20 aralkyl or C6-C20 aryl.

[0028] Preferably, Z is selected from chlorine or bromine.

[0029] Preferably, the organic boron compound is selected from aromatic boron and / or organic borate.

[0030] A fifth aspect of the present invention provides use of the above-mentioned olefin polymerization catalyst in olefin polymerization.

[0031] A sixth 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.

[0032] Preferably, the polymerization reaction temperature is -78°C to 200°C, more preferably -20°C to 150°C; the polymerization pressure is 0.01 to 10 MPa, more preferably 0.01 to 5 MPa.

[0033] Compared with the prior art, the present invention has the following advantages:

[0034] 1. The synthesis method of the tetrahydronaphthol-phosphine monochromocene metal complex of the present invention is simple, has high yield and low cost;

[0035] 2. The tetrahydronaphthol-phosphine monochromocene metal complex of the present invention can catalyze ethylene oligomerization and polymerization with high activity, and can maintain high polymerization activity at a relatively high polymerization temperature;

[0036] 3. The olefin polymerization catalyst of the present invention has higher copolymerization performance with α-olefins or cycloolefins. DETAILED DESCRIPTION

[0037] The specific embodiments of the present invention are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0038] The endpoints and any values ​​of the ranges disclosed in this article 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 each range, the endpoint values ​​of each range and the 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 as specifically disclosed in this article.

[0039] The present invention provides a tetrahydronaphthol-phosphocene chromium metal complex, the structural formula of which is shown in formula (I):

[0040]

[0041] Among them, R 1 -R 5 are each independently selected from hydrogen and substituted or unsubstituted C1-C20 hydrocarbon groups, or R 1 -R 5 Optionally, they are cyclic to each other; R 6 -R 10 Each is independently selected from hydrogen, halogen, hydroxyl and substituted or unsubstituted C1-C15 hydrocarbon group; X is selected from halogen or C1-C10 hydrocarbon group.

[0042] In a preferred embodiment, R 1 -R 5 Each is independently selected from hydrogen and a substituted or unsubstituted C1-C10 hydrocarbon group.

[0043] In a more preferred embodiment, R 1 -R 5 Each is independently selected from hydrogen or unsubstituted C1-C10 alkyl.

[0044] According to some embodiments of the present invention, R 1 -R 5 It is an unsubstituted C1-C10 alkyl group.

[0045] According to some embodiments of the present invention, R 1 is an unsubstituted C1-C10 hydrocarbon group, R 2 -R 5 For hydrogen.

[0046] In formula (I), the ring structure connected to Cr is a cyclopentadiene ring structure, for example, cyclopentadienyl, pentamethylcyclopentadienyl, methyl-cyclopentadienyl, n-butyl-cyclopentadienyl, tert-butyl-cyclopentadienyl, indenyl, fluorenyl, butyl-indenyl, 1-methyl-indenyl, 2-methyl-indenyl or 1-phenyl-indenyl, etc.

[0047] In a preferred embodiment, R 6 -R 10 Each is independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C6 alkyl and substituted or unsubstituted C6-C15 aryl.

[0048] According to some embodiments of the present invention, R 6 , R 8 and R 9 is hydrogen, R 7 and R 10 is selected from substituted or unsubstituted C1-C6 alkyl groups.

[0049] In a preferred embodiment, X is selected from halogen or C1-C8 hydrocarbon group.

[0050] According to some embodiments of the invention, X is selected from chlorine or bromine.

[0051] 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 or halogenated C1-C6 alkoxy.

[0052] In the present invention, the alkyl group (such as C1-C6 alkyl group or C1-C10 alkyl group) can be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl and 3,3-dimethylbutyl.

[0053] 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.

[0054] In the present invention, the aryl group (eg, C6-C15 aryl group) may be selected from phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, and vinylphenyl.

[0055] In the present invention, the halogen is selected from fluorine, chlorine, bromine or iodine.

[0056] In a further preferred embodiment, the tetrahydronaphthol-phosphocene chromium metal complex is selected from the group consisting of the following complexes:

[0057] Complex 1: a complex represented by formula (I), wherein R 1 -R 5 For H, R 6 -R 10 is H, X is Cl;

[0058] Complex 2: Complex represented by formula (I), wherein R 1 -R 5 is methyl, R 6 -R 10 is H, X is Cl;

[0059] Complex 3: A complex represented by formula (I), wherein R 1 is methyl, R 2 -R 5 For H, R 6 -R 10 is H, X is Cl;

[0060] Complex 4: a complex represented by formula (I), wherein R 1 is n-butyl, R 2 -R 5 For H, R 6-R 10 is H, X is Cl;

[0061] Complex 5: A complex represented by formula (I), wherein R 1 is tert-butyl, R 2 -R 5 For H, R 6 -R 10 is H, X is Cl;

[0062] Complex 6: A complex represented by formula (I), wherein R 1 -R 5 For H, R 7 is methyl, R 10 is isopropyl, R 6 , R 8 and R 9 is H, X is Cl;

[0063] Complex 7: A complex represented by formula (I), wherein R 1 -R 5 is methyl, R 7 is methyl, R 10 is isopropyl, R 6 , R 8 and R 9 is H, X is Cl;

[0064] Complex 8: A complex represented by formula (I), wherein R 1 is methyl, R 2 -R 5 For H, R 7 is methyl, R 10 is isopropyl, R 6 , R 8 and R 9 is H, X is Cl;

[0065] Complex 9: A complex represented by formula (I), wherein R 1 is n-butyl, R 2 -R 5 For H, R 7 is methyl, R 10 is isopropyl, R 6 , R 8 and R 9 is H, X is Cl;

[0066] Complex 10: A complex represented by formula (I), wherein R 1 is tert-butyl, R 2 -R 5 For H, R 7 is methyl, R 10 is isopropyl, R 6 , R8 and R 9 is H, and X is Cl.

[0067] The second aspect of the present invention provides a method for preparing the above-mentioned tetrahydronaphthol-phosphocene chromium metal complex, which comprises the following steps:

[0068] (1) reacting the compound represented by formula (II) with the compound represented by formula (III) to generate a ligand, wherein the ligand is represented by formula (IV);

[0069] (2) reacting the ligand with a chromium metal compound and a lithium compound, wherein the lithium compound comprises a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted indenyl group, or a substituted or unsubstituted fluorenyl group;

[0070]

[0071] Among them, R 6 -R 10 The definition of is the same as described above.

[0072] In the method of the present invention, the chromium metal compound is selected from CrCl 3 (THF) 3 CrCl 3 (H 2 O), CrCl 3 (H 2 O) 6 CrCl 3 CrBr 3 (H 2 O) 6 CrBr 3 and CrI 3 One or more of the following.

[0073] In the present invention, "THF" means "tetrahydrofuran".

[0074] In the method described in the present invention, the lithium compound can be selected from at least one of cyclopentadienyl lithium, pentamethylcyclopentadienyl lithium, methyl-cyclopentadienyl lithium, n-butyl-cyclopentadienyl lithium, tert-butyl-cyclopentadienyl lithium, indenyl lithium, fluorenyl lithium, butyl-indenyl lithium, 1-methyl-indenyl lithium, 2-methyl-indenyl lithium and 1-phenyl-indenyl lithium.

[0075] In an optional embodiment, the lithium compound is a combination of at least one of cyclopentadienyl lithium, pentamethylcyclopentadienyl lithium, methyl-cyclopentadienyl lithium, n-butyl-cyclopentadienyl lithium, tert-butyl-cyclopentadienyl lithium, indenyl lithium, fluorenyl lithium, butyl-indenyl lithium, 1-methyl-indenyl lithium, 2-methyl-indenyl lithium and 1-phenyl-indenyl lithium and methyl lithium and / or butyl lithium.

[0076] In the present invention, the reaction process of step (1) is shown in the following reaction formula.

[0077]

[0078] Among them, R 6 -R 10 The definition of is the same as described above.

[0079] In the present invention, the reaction process of step (2) is shown in the following reaction formula.

[0080]

[0081] Among them, R 1 -R 5 , R 6 -R 10 The definitions of and X are the same as described above.

[0082] In a preferred embodiment, the reaction of step (1) is carried out in the presence of a solvent; in a specific embodiment, the solvent may be diethyl ether.

[0083] In a preferred embodiment, the reaction of step (2) is carried out in the presence of a reaction solvent; in a specific embodiment, the reaction solvent may be toluene or tetrahydrofuran.

[0084] In a specific embodiment, the preparation process of step (1) comprises: dissolving the compound represented by formula (II) in anhydrous ether in an atmosphere of protective gas (such as nitrogen), adding n-BuLi (n-butyl lithium) solution dropwise at -78°C, and gradually returning to room temperature after the reaction; then, adding anhydrous ether solution of the compound represented by formula (III) dropwise (ice-water bath), slowly warming to room temperature, stirring and reacting overnight. Quenching with water, extracting the organic phase with anhydrous ether, concentrating the obtained organic phase, deoxygenating by freezing cycle, adding 5 mL of concentrated hydrochloric acid to react under a nitrogen atmosphere, tracking the completion of the reaction by TLC, and then adding NaHCO 3 The aqueous solution was neutralized, quenched with water, and the organic phase was extracted with anhydrous ether and anhydrous MgSO 4 Dry, filter, concentrate and perform column chromatography to obtain the ligand represented by formula (IV).

[0085] In a specific embodiment, the preparation process of step (2) includes: in an atmosphere of a protective gas (such as nitrogen), at 0 °C, dissolving a chromium metal compound and a lithium compound in tetrahydrofuran respectively, and then slowly dropping the lithium compound tetrahydrofuran solution into the chromium metal compound tetrahydrofuran solution, reacting at room temperature overnight to obtain a blue solution; then dissolving the ligand obtained in step (1) in a reaction solvent (such as toluene, tetrahydrofuran, etc.), adding an excessive dehydrogent (such as sodium hydride), reacting at room temperature, filtering to remove the dehydrogent, dropping into the blue solution, reacting at normal temperature overnight, drying the solvent by evaporation, adding dichloromethane to dissolve and filter, removing the filter cake, concentrating the filtrate, adding heptane for recrystallization to obtain the tetrahydronaphthol-phosphorus mono-cyclopentadienyl chromium metal complex of the present invention.

[0086] The third aspect of the present invention provides the application of the above-mentioned tetrahydronaphthol-phosphorus mono-cyclopentadienyl chromium metal complex in olefin polymerization.

[0087] Preferably, the olefin includes ethylene, α-olefin and cycloolefin.

[0088] The fourth aspect of the present invention provides a catalyst for olefin polymerization, and the catalyst for olefin polymerization includes a main catalyst and a cocatalyst;

[0089] The main catalyst is the above-mentioned tetrahydronaphthol-phosphorus mono-cyclopentadienyl chromium metal complex.

[0090] Preferably, the cocatalyst is selected from organoaluminum compounds and / or organoboron compounds.

[0091] In a preferred embodiment, the organoaluminum compound is selected from alkylaluminoxane or an organoaluminum compound of the general formula AlY n Z 3-n wherein Y is selected from hydrogen, a C1-C20 hydrocarbon group or a C1-C20 alkoxy group, Z is selected from a halogen, 0 < n ≤ 3, and n is an integer.

[0092] In a more preferred embodiment, Y is selected from a C1-C20 alkyl group, a C1-C20 alkoxy group, a C7-C20 aralkyl group or a C6-C20 aryl group.

[0093] In a more preferred embodiment, Z is selected from chlorine or bromine.

[0094] Further preferably, the organoaluminum compound is selected from one or more of 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).

[0095] In a specific embodiment, the organoaluminum compound is methylaluminoxane (MAO).

[0096] In a preferred embodiment, the organic boron compound is selected from aromatic boron and / or organic borate.

[0097] In a more preferred embodiment, the arene boron is selected from substituted or unsubstituted phenyl boron.

[0098] In a specific embodiment, the arene boron is tris(pentafluorophenyl)boron.

[0099] In a more preferred embodiment, the organic borate is selected from N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and / or triphenylmethyl tetrakis(pentafluorophenyl)borate.

[0100] In a preferred embodiment, when the co-catalyst is an organoaluminum compound, the molar ratio of aluminum in the co-catalyst to chromium in the main catalyst is 10-10. 7 :1, preferably 10-100000:1, more preferably 100-10000:1; specifically, the molar ratio can be 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, 1000000:1, 10000000:1 or any value therebetween.

[0101] In a preferred embodiment, when the co-catalyst is an organic boron compound, the molar ratio of boron in the co-catalyst to chromium in the main catalyst is 0.1-1000:1, preferably 0.1-500:1; specifically, the molar ratio can be 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 or any value therebetween.

[0102] 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.

[0103] A fifth aspect of the present invention provides use of the above-mentioned olefin polymerization catalyst in olefin polymerization.

[0104] Preferably, the olefins include ethylene, α-olefins and cycloolefins.

[0105] A sixth 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.

[0106] In a preferred embodiment, the polymerization reaction temperature is -78°C to 200°C, more preferably -20°C to 150°C; the polymerization pressure is 0.01 to 10 MPa, more preferably 0.01 to 5 MPa.

[0107] According to some embodiments of the present invention, the polymerization reaction temperature may be -20°C, 50°C, 100°C or 150°C.

[0108] According to some embodiments of the present invention, the polymerization pressure may be 0.01 MPa, 0.1 MPa, 0.2 MPa, 0.5 MPa, 1 MPa or 2 MPa.

[0109] As used herein, "polymerization pressure" refers to the ethylene pressure in the polymerization system and is expressed as an absolute pressure.

[0110] According to some embodiments of the present invention, the olefin comprises a C2-C16 olefin.

[0111] According to some embodiments of the present invention, the olefin comprises a C2-C16 α-olefin or a cycloolefin.

[0112] According to some embodiments of the invention, the olefin comprises ethylene.

[0113] According to some embodiments of the present invention, the olefin includes ethylene and an α-olefin or a cyclic olefin containing a polar group.

[0114] According to some embodiments of the present invention, the polymerization reaction is carried out by olefin monomers in a solvent, and the polymerization solvent is independently selected from one or more of alkanes, aromatic hydrocarbons and halogenated hydrocarbons.

[0115] 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 one or more of hexane, toluene and heptane.

[0116] In the present invention, alkyl refers to a straight chain alkyl, a branched 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.

[0117] In the present invention, examples of the aryl group include, but are not limited to, phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl and vinylphenyl.

[0118] In the present invention, alkenyl refers to straight-chain alkenyl, branched-chain alkenyl or cycloalkenyl, including but not limited to vinyl, allyl and butenyl.

[0119] 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.

[0120] In the present invention, examples of the alkylaryl group include, but are not limited to, tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl and tert-butylphenyl.

[0121] The tetrahydronaphthol-phosphocene chromium metal complex and its preparation method and application described in the present invention are further illustrated by examples below. The examples are implemented on the premise of the technical solution of the present invention, and detailed implementation methods and specific operation processes are given, but the protection scope of the present invention is not limited to the following examples.

[0122] 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.

[0123] The analytical characterization instruments and test methods used in the following examples and comparative examples are as follows:

[0124] (1) Nuclear magnetic resonance instrument: Bruker DMX 300 (300 MHz), with tetramethylsilane (TMS) as internal standard;

[0125] (2) Molecular weight and molecular weight distribution PDI of polymer (PDI = Mw / Mn): measured at 150°C using PL-GPC220 chromatograph with trichlorobenzene as solvent (standard sample: PS, flow rate: 1.0 mL / min, chromatographic column: 3×PLgel 10um M1×ED-B, 300×7.5 nm);

[0126] (3) Activity measurement method: The polymer was washed with hydrochloric acid ethanol solution, vacuum dried, and the weight of the polymer was measured; the polymerization activity was calculated as follows: polymer weight (g) / chromium (mol) × 60 / polymerization time (min);

[0127] (4) Analysis of the comonomer content of polymers: 1 H NMR, 13 C NMR spectrum was determined on a 400 MHz Bruker Avance 400 NMR spectrometer using a 10 mm PASEX 13 probe. The polymer sample was dissolved in 1,2,4-trichlorobenzene at 120°C for analysis and testing.

[0128] Example 1

[0129] Complex 2: Complex represented by formula (I), wherein R 1 -R 5 is methyl, R 6 -R 10 is H, X is Cl;

[0130] In a nitrogen atmosphere, the compound represented by formula (II) (2.32 g, 10 mmol) was dissolved in anhydrous ether (20 mL), and n-butyl lithium solution (2.7 M, 4.0 mL, 11 mmol) was added dropwise at -78 °C. The reaction was gradually restored to room temperature and stirred for 12 h to obtain a white precipitate. Dicyclohexylphosphine chloride (10 mmol, 2.32 g) was evenly dispersed in 10 mL of ether and added dropwise to the original reaction system under an ice-water bath. The temperature was slowly raised to room temperature and stirred overnight. The mixture was quenched with water, and the organic phase was extracted with ether. The obtained organic phase was concentrated, deoxygenated by freezing cycle, and 5 mL of concentrated hydrochloric acid was added under a nitrogen atmosphere to react for 5 h. The reaction was followed by TLC to completion, and then NaHCO was added. 3 The aqueous solution was neutralized, quenched with water, the organic phase was extracted with ether, and anhydrous MgSO 4 Dry, filter, concentrate, and column chromatograph to obtain ligand L 1 , the yield is 31%; 1 H NMR (500 MHz, CDCl 3 , TMS): δ11.65 (s, 0.9H), 6.72-6.68 (m, 1H), 6.58-6.56 (m, 1H), 2.74-2.72 (t, J=5.8Hz, 2H ), 2.65-2.63(t, J=6.3Hz, 2H), 2.06-1.96(m, 4H), 1.86-1.68(m, 12H), 1.45-1.13(m, 10H). 13 C NMR (126 MHz, CDCl 3 )δ163.26, 143.18, 143.16, 126.63, 126.58, 125.86, 125.79, 119.39, 119.30, 104.10, 103.39, 77.28, 77.03, 76 .77, 36.01, 35.49, 29.98, 26.41, 26.31, 26.27, 26.17, 25.76, 25.27, 25.25, 24.10, 24.08, 22.78, 22.59, 22.54; 31 P NMR (202 MHz, CDCl 3 )δ60.52;

[0131] In a nitrogen atmosphere, at 0°C, CrCl 3 (THF)3 (0.75 g, 2.0 mmol) was dissolved in 20 mL of tetrahydrofuran, pentamethylcyclopentadienyl lithium (0.28 g, 2.0 mmol) was dissolved in 10 mL of tetrahydrofuran, and then the pentamethylcyclopentadienyl lithium tetrahydrofuran solution was slowly dripped into CrCl 3 (THF) 3 In tetrahydrofuran solution, react at room temperature overnight to obtain a blue solution B;

[0132] In a nitrogen atmosphere, the ligand L 1 (0.69 g, 2.0 mmol) was dissolved in tetrahydrofuran, excess NaH (0.12 g, 5.0 mmol) was added, and the mixture was stirred at room temperature for 10 h. NaH was removed by filtration, and the blue solution B was added dropwise. The reaction was allowed to proceed at room temperature overnight, and the solvent was drained off. Dichloromethane (40 mL) was added to dissolve the mixture, and the filter cake was removed by filtration. The filtrate was concentrated, and heptane was added for recrystallization to obtain complex 2. The yield was 75%, and the elemental analysis detected C 33 H 50 ClCrOP (581.18): Theoretical values: C, 68.20; H, 8.67; Test values: C, 68.09; H, 8.91;

[0133] A 1L stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130 °C for 6 h, and then vacuumed and heated with N 2 The gas was replaced three times, 500 mL of toluene was injected into the polymerization kettle, methylaluminoxane (MAO) (6.5 mL, 10 mmol) and 5.8 mg (10 μmol) of complex 2 were added, and the ethylene pressure was maintained at 5 atm at 25°C. The reaction was stirred vigorously for 10 min, and the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed to test the polymerization activity. The test data of the weight average molecular weight, molecular weight distribution, polymerization activity and comonomer content of the obtained polymer are shown in Table 1.

[0134] Example 2

[0135] Complex 2: Complex represented by formula (I), wherein R 1 -R 5 is methyl, R 6 -R 10 is H, X is Cl;

[0136] A 1L stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130 °C for 6 h, and then vacuumed and heated with N 2The gas was replaced three times, 500 mL of toluene was injected into the polymerization kettle, methylaluminoxane (MAO) (6.5 mL, 10 mmol) and 5.8 mg (10 μmol) of complex 2 were added, and the reaction was carried out at 70°C with an ethylene pressure of 5 atm for 30 min with vigorous stirring. The mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed to test the polymerization activity. The test data of the weight average molecular weight, molecular weight distribution, polymerization activity and comonomer content of the obtained polymer are shown in Table 1.

[0137] Example 3

[0138] Complex 2: Complex represented by formula (I), wherein R 1 -R 5 is methyl, R 6 -R 10 is H, X is Cl;

[0139] A 100 mL stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130 °C for 6 h, and then vacuumed and heated with N 2 The gas was replaced three times, 50 mL of toluene was injected into the polymerization kettle, methylaluminoxane (MAO) (1.3 mL, 2 mmol), 2.5 mL of norbornene, and 1.1 mg (2 μmol) of complex 2 were added, and the ethylene pressure was maintained at 5 atm at 25°C. The reaction was stirred vigorously for 10 min, and the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a copolymer. The polymer was dried and weighed to test the polymerization activity. The test data of the weight average molecular weight, molecular weight distribution, polymerization activity and comonomer content of the obtained polymer are shown in Table 1.

[0140] Example 4

[0141] Complex 7: A complex represented by formula (I), wherein R 1 -R 5 is methyl, R 7 is methyl, R 10 is isopropyl, R 6 , R 8 and R 9 is H, X is Cl;

[0142] In a nitrogen atmosphere, the compound represented by formula (II) (2.32 g, 10 mmol) was dissolved in anhydrous ether (20 mL), and n-butyl lithium solution (2.7 M, 4.0 mL, 11 mmol) was added dropwise at -78 °C. The reaction was gradually restored to room temperature and stirred for 12 h to obtain a white precipitate. Bis[5-methyl-2-(1-methylethyl)cyclohexyl]-phosphine chloride (15 mmol, 5.18 g) was evenly dispersed in 8 mL of ether and added dropwise to the original reaction system under an ice-water bath. The temperature was slowly raised to room temperature and stirred overnight. The mixture was quenched with water, and the organic phase was extracted with ether. The obtained organic phase was concentrated, deoxygenated by freezing cycle, and 5 mL of concentrated hydrochloric acid was added under a nitrogen atmosphere to react for 5 h. The reaction was followed by TLC to complete, and then NaHCO was added. 3 The aqueous solution was neutralized, quenched with water, the organic phase was extracted with ether, and anhydrous MgSO 4 Dry, filter, concentrate, and column chromatograph to obtain ligand L 2 , the yield is 29%;

[0143] Prepare blue solution B in the manner of Example 1;

[0144] In a nitrogen atmosphere, the ligand L 2 (0.46 g, 1 mmol) was dissolved in tetrahydrofuran, excess NaH (0.072 g, 3 mmol) was added, stirred at room temperature for 10 h, filtered to remove NaH, blue solution B was added dropwise, reacted at room temperature overnight, the solvent was drained, dichloromethane (40 mL) was added to dissolve, the filter cake was removed by filtration, the filtrate was concentrated, heptane was added for recrystallization, and complex 7 was obtained with a yield of 79%. Elemental analysis test C 41 H 66 ClCrOP (693.40): Theoretical calculated values: C, 71.02; H, 9.59; Test values: C, 70.01; H, 9.27;

[0145] A 1L stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130 °C for 6 h, and then vacuumed and heated with N 2 The gas was replaced three times, 500 mL of toluene was injected into the polymerization kettle, methylaluminoxane (MAO) (6.5 mL, 10 mmol) and 6.9 mg (10 μmol) of complex 7 were added, and the ethylene pressure was maintained at 5 atm at 25°C. The reaction was stirred vigorously for 10 min, and the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed to test the polymerization activity. The test data of the weight average molecular weight, molecular weight distribution, polymerization activity and comonomer content of the obtained polymer are shown in Table 1.

[0146] Example 5

[0147] Complex 7: A complex represented by formula (I), wherein R 1 -R5 is methyl, R 7 is methyl, R 10 is isopropyl, R 6 , R 8 and R 9 is H, X is Cl;

[0148] A 100 mL stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130 °C for 6 h, and then vacuumed and heated with N 2 The gas was replaced three times, 50 mL of toluene was injected into the polymerization kettle, methylaluminoxane (MAO) (1.3 mL, 2 mmol), 2.5 mL of norbornene, and 1.4 mg (2 μmol) of complex 7 were added, and the ethylene pressure was maintained at 5 atm at 25°C. The reaction was stirred vigorously for 10 min, and the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a copolymer. The polymer was dried and weighed to test the polymerization activity. The test data of the weight average molecular weight, molecular weight distribution, polymerization activity and comonomer content of the obtained polymer are shown in Table 1.

[0149] Example 6

[0150] Complex 6: a complex represented by formula (I), wherein R 1 -R 5 is hydrogen, R 7 is methyl, R 10 is isopropyl, R 6 , R 8 and R 9 is H, X is Cl;

[0151] Ligand L was prepared in the same manner as in Example 4 2 ;

[0152] In a nitrogen atmosphere, at 0°C, CrCl 3 (THF) 3 (0.75 g, 2.0 mmol) was dissolved in 20 mL of tetrahydrofuran, cyclopentadienyl lithium (0.14 g, 2.0 mmol) was dissolved in 10 mL of tetrahydrofuran, and then the cyclopentadienyl lithium tetrahydrofuran solution was slowly dripped into CrCl 3 (THF) 3 In tetrahydrofuran solution, react at room temperature overnight to obtain a blue solution C;

[0153] In a nitrogen atmosphere, the ligand L 2(0.46 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. NaH was removed by filtration, and the blue solution C was added dropwise. The reaction was allowed to proceed overnight at room temperature, and the solvent was drained. Dichloromethane (40 mL) was added to dissolve the mixture, and the filter cake was removed by filtration. The filtrate was concentrated, and heptane was added for recrystallization to obtain complex 6. The yield was 75%. The elemental analysis test of C 27 H 36 ClCrOP (495.00): Theoretical calculation value: C, 65.51; H, 7.33; Test value: C, 65.23; H, 7.01;

[0154] A 1L stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130 °C for 6 h, and then vacuumed and heated with N 2 The gas was replaced three times, 500 mL of toluene was injected into the polymerization kettle, methylaluminoxane (MAO) (6.5 mL, 10 mmol) and 5.0 mg (10 μmol) of complex 6 were added, and the ethylene pressure was maintained at 5 atm at 25°C. The reaction was stirred vigorously for 10 min, and the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed to test the polymerization activity. The test data of the weight average molecular weight, molecular weight distribution, polymerization activity and comonomer content of the obtained polymer are shown in Table 1.

[0155] Example 7

[0156] Complex 8: A complex represented by formula (I), wherein R 1 is methyl, R 2 -R 5 For H, R 7 is methyl, R 10 is isopropyl, R 6 , R 8 and R 9 is H, X is Cl;

[0157] Ligand L was prepared in the same manner as in Example 4 2 ;

[0158] In a nitrogen atmosphere, at 0°C, CrCl 3 (THF) 3 (0.75 g, 2.0 mmol) was dissolved in 20 mL of tetrahydrofuran, methyl-cyclopentadienyl lithium (0.17 g, 2.0 mmol) was dissolved in 10 mL of tetrahydrofuran, and then the methyl-cyclopentadienyl lithium tetrahydrofuran solution was slowly dripped into CrCl 3 (THF) 3 In tetrahydrofuran solution, react at room temperature overnight to obtain a blue solution D;

[0159] In a nitrogen atmosphere, the ligand L 2(0.46 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. NaH was removed by filtration, and the blue solution D was added dropwise. The reaction was allowed to proceed overnight at room temperature, and the solvent was drained. Dichloromethane (40 mL) was added to dissolve the mixture, and the filter cake was removed by filtration. The filtrate was concentrated, and heptane was added for recrystallization to obtain complex 8 with a yield of 77%. The elemental analysis test was C 28 H 38 ClCrOP (509.03): Theoretical calculated values ​​are: C, 66.07; H, 7.52; Test values ​​are: C, 65.86; H, 7.28;

[0160] A 1L stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130 °C for 6 h, and then vacuumed and heated with N 2 The gas was replaced three times, 500 mL of toluene was injected into the polymerization kettle, methylaluminoxane (MAO) (6.5 mL, 10 mmol) and 5.1 mg (10 μmol) of complex 8 were added, and the ethylene pressure was maintained at 5 atm at 25°C. The reaction was stirred vigorously for 10 min, and the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The polymer was dried and weighed to test the polymerization activity. The test data of the weight average molecular weight, molecular weight distribution, polymerization activity and comonomer content of the obtained polymer are shown in Table 1.

[0161] Comparative Example 1

[0162] 10atm ethylene: Dry a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130℃ for 6h, evacuate while hot and use N 2 The reaction mixture was replaced with air three times, 500 mL of hexane was injected into the polymerization kettle, and then 6.5 ml of methylaluminoxane (MAO) (1.53 mol / L toluene solution) was added, and 5.1 mg (10 μmol) of complex A (reference Organometallics 2013, 32, 4805-4812) was added. The reaction mixture was stirred vigorously for 10 min at 25° C. while maintaining an ethylene pressure of 5 atm. The mixture was neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain polyethylene. The polymer was dried and weighed to test the polymerization activity. The test data of the weight average molecular weight, molecular weight distribution, polymerization activity and comonomer content of the obtained polymer are shown in Table 1.

[0163]

[0164] Comparative Example 2

[0165] A 100 mL stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130 °C for 6 h, and then vacuumed and heated with N 2The gas was replaced three times, 50 mL of toluene was injected into the polymerization kettle, methylaluminoxane (MAO) (1.3 mL, 2 mmol), 2.5 mL of norbornene, and 1.0 mg (2 μmol) of complex A were added, and the ethylene pressure was maintained at 5 atm at 25°C. The reaction was stirred vigorously for 10 min, and the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a copolymer. The polymer was dried and weighed to test the polymerization activity. The test data of the weight average molecular weight, molecular weight distribution, polymerization activity and comonomer content of the obtained polymer are shown in Table 1.

[0166] Table 1

[0167]

[0168] It can be seen from Table 1 that when the tetralinol-phosphocene chromium metal complex of the present invention is used as the main catalyst, under similar polymerization conditions, it has higher homopolymerization / copolymerization activity, the molecular weight of the obtained polymer is significantly higher than that of the polymer obtained in the comparative example, and the molecular weight distribution of the obtained polymer is narrower.

[0169] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A tetrahydronaphthol-phosphocene chromium metal complex, It is characterized in that Its structural formula is shown in formula (I): Among them, R 1 -R 5 are each independently selected from hydrogen and substituted or unsubstituted C1-C20 hydrocarbon groups, or R 1 -R 5 Optionally, they are cyclic to each other; R 6 -R 10 Each is independently selected from hydrogen, halogen, hydroxyl and substituted or unsubstituted C1-C15 hydrocarbon group; X is selected from halogen or C1-C10 hydrocarbon group.

2. The tetrahydronaphthol-phosphocene chromium metal complex according to claim 1, It is characterized in that R 1 -R 5 Each is independently selected from hydrogen and substituted or unsubstituted C1-C10 hydrocarbon groups; Preferably, R 6 -R 10 Each is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C6 alkyl and substituted or unsubstituted C6-C15 aryl; Preferably, X is selected from halogen or C1-C8 hydrocarbon group; 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-hexoxy, isohexoxy or 3,3-dimethylbutoxy; Preferably, the halogen is selected from fluorine, chlorine, bromine or iodine.

3. The tetrahydronaphthol-phosphocene chromium metal complex according to claim 1 or 2, It is characterized in that It is selected from the group consisting of the following complexes: Complex 1: a complex represented by formula (I), wherein R 1 -R 5 For H, R 6 -R 10 is H, X is Cl; Complex 2: Complex represented by formula (I), wherein R 1 -R 5 is methyl, R 6 -R 10 is H, X is Cl; Complex 3: A complex represented by formula (I), wherein R 1 is methyl, R 2 -R 5 For H, R 6 -R 10 is H, X is Cl; Complex 4: a complex represented by formula (I), wherein R 1 is n-butyl, R 2 -R 5 For H, R 6 -R 10 is H, X is Cl; Complex 5: A complex represented by formula (I), wherein R 1 is tert-butyl, R 2 -R 5 For H, R 6 -R 10 is H, X is Cl; Complex 6: A complex represented by formula (I), wherein R 1 -R 5 For H, R 7 is methyl, R 10 is isopropyl, R 6 , R 8 and R 9 is H, X is Cl; Complex 7: A complex represented by formula (I), wherein R 1 -R 5 is methyl, R 7 is methyl, R 10 is isopropyl, R 6 , R 8 and R 9 is H, X is Cl; Complex 8: A complex represented by formula (I), wherein R 1 is methyl, R 2 -R 5 For H, R 7 is methyl, R 10 is isopropyl, R 6 , R 8 and R 9 is H, X is Cl; Complex 9: A complex represented by formula (I), wherein R 1 is n-butyl, R 2 -R 5 For H, R 7 is methyl, R 10 is isopropyl, R 6 , R 8 and R 9 is H, X is Cl; Complex 10: A complex represented by formula (I), wherein R 1 is tert-butyl, R 2 -R 5 For H, R 7 is methyl, R 10 is isopropyl, R 6 , R 8 and R 9 is H, and X is Cl.

4. A method for preparing the tetrahydronaphthol-phosphomonochromocene metal complex as claimed in any one of claims 1 to 3, It is characterized in that The method comprises the following steps: (1) reacting the compound represented by formula (II) with the compound represented by formula (III) to generate a ligand; (2) reacting the ligand with a chromium metal compound and a lithium compound, wherein the lithium compound comprises a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted indenyl group, or a substituted or unsubstituted fluorenyl group; Among them, R 6 -R 10 The definition is the same as that of claim 1.

5. The method according to claim 4, It is characterized in that The chromium metal compound is selected from CrCl 3 (THF) 3 CrCl 3 (H 2 O), CrCl 3 (H 2 O) 6 CrCl 3 CrBr 3 (H 2 O) 6 CrBr 3 and CrI 3 One or more of the following. Preferably, the lithium compound is selected from one or more of cyclopentadienyl lithium, pentamethylcyclopentadienyl lithium, methyl-cyclopentadienyl lithium, n-butyl-cyclopentadienyl lithium, tert-butyl-cyclopentadienyl lithium, indenyl lithium, fluorenyl lithium, butyl-indenyl lithium, 1-methyl-indenyl lithium, 2-methyl-indenyl lithium and 1-phenyl-indenyl lithium.

6. Use of the tetralinol-phosphomonochromocene metal complex according to any one of claims 1 to 3 in olefin polymerization.

7. A catalyst for olefin polymerization, It is characterized in that The olefin polymerization catalyst comprises a main catalyst and a co-catalyst; The main catalyst is the tetralin-phosphomonochromocene metal complex as described in any one of claims 1 to 3.

8. The catalyst for olefin polymerization according to claim 7, It is characterized in that The co-catalyst is selected from organoaluminum compounds and / or organoboron compounds; Preferably, the organoaluminum compound is selected from alkylaluminoxanes or organoaluminum compounds of the general formula AlY n Z 3-n , wherein Y is selected from hydrogen, C1-C20 hydrocarbon groups or C1-C20 hydrocarbyloxy groups, Z is selected from halogens, 0 < n ≤ 3, and n is an integer; Preferably, Y is selected from C1-C20 alkyl, C1-C20 alkoxy, C7-C20 aralkyl or C6-C20 aryl; Preferably, Z is selected from chlorine or bromine; Preferably, the organic boron compound is selected from aromatic boron and / or organic borate.

9. Use of the catalyst for olefin polymerization according to claim 7 or 8 in olefin polymerization.

10. A method for the polymerization of olefins, It is characterized in that The method comprises carrying out an olefin polymerization reaction in the presence of the olefin polymerization catalyst according to claim 7 or 8; Preferably, the polymerization reaction temperature is -78°C to 200°C, more preferably -20°C to 150°C; the polymerization pressure is 0.01 to 10 MPa, more preferably 0.01 to 5 MPa.

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