Tetrahydronaphthol-phosphine non-metallocene vanadium 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-phosphine non-vanadium-locene metal complex as well as a preparation method and application thereof. The structural formula of the tetrahydronaphthol-phosphine non-vanadocene metal complex is shown as a formula (I), and R1-R5 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-phosphine non-metallocene vanadium metal complex disclosed by the invention is used as a main catalyst, under similar polymerization conditions, the tetrahydronaphthol-phosphine non-metallocene vanadium metal complex has higher homopolymerization / copolymerization activity, the molecular weight of an obtained polymer is higher and narrower in distribution, and meanwhile, the tetrahydronaphthol-phosphine non-metallocene vanadium metal complex also has more excellent ethylene homopolymerization performance and copolymerization performance. # 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-phosphine non-vanadiumocene 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 potential rubber substitutes. However, its non-polar characteristics limit its scope of application. Introducing a small amount of polar functional groups into polyolefins can greatly improve its properties, thereby broadening its uses and increasing its commercial value. Polar polyolefins, its main application areas include high-end pipes, automotive parts, medical equipment, prosthetic implants, etc. 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. At present, the central metals of catalysts used in olefin coordination polymerization are mainly early transition metals and late transition metals. Among them, vanadium-based catalysts have excellent performance and are widely used. They are still the main catalysts for the industrial production of EPR and COC. By regulating the electronic effect and steric effect of the ligand, the catalytic performance of vanadium-based catalysts can be effectively improved. At present, vanadium-based catalysts used for catalytic olefin copolymerization mainly include various systems such as nitrogen-containing heterocyclic carbene monodentate ligands, N^N or N^O bidentate ligands, and multidentate chelate ligands. However, the various parameters of vanadium-based catalysts in these catalytic systems (copolymerization activity, molecular weight, polar monomer insertion ratio, etc.) are difficult to meet industrial standards, and they cannot maintain high catalytic activity and high polymerization performance at high temperatures. Summary of the invention

[0003] The purpose of the present invention is to provide a tetrahydronaphthol-phosphine non-vanadium cyclopentadienyl metal complex and a preparation method and application thereof. The tetrahydronaphthol-phosphine non-vanadium cyclopentadienyl metal complex has good thermal stability. In particular, the tetrahydronaphthol-phosphine monochromocene metal complex can still maintain a high ethylene polymerization activity at a relatively high temperature, and the molecular weight distribution of the obtained polymer is relatively narrow.

[0004] In order to achieve the above object, the present invention provides a tetrahydronaphthol-phosphine non-vanadiumocene metal complex, the structural formula of which is shown in formula (I):

[0005]

[0006] Wherein, R1-R5 are each independently selected from hydrogen, halogen, hydroxyl and substituted or unsubstituted C1-C15 hydrocarbon group; X is selected from halogen or C1-C10 hydrocarbon group.

[0007] Preferably, R1-R5 are each independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C15 aryl.

[0008] Preferably, X is selected from halogen or C1-C8 hydrocarbon group.

[0009] Preferably, the substituent is selected from halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy or halogenated C1-C10 alkoxy.

[0010] Preferably, the substituents are selected from halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy.

[0011] 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.

[0012] 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.

[0013] Preferably, the halogen is selected from fluorine, chlorine, bromine or iodine.

[0014] Preferably, the tetrahydronaphthol-phosphine non-vanadiumocene metal complex is selected from the group consisting of the following complexes:

[0015] Complex 1: a complex represented by formula (I), wherein R1-R5 are H, and X is Cl;

[0016] Complex 2: a complex represented by formula (I), wherein R1-R5 are H, and X is Br;

[0017] Complex 3: a complex represented by formula (I), wherein R1-R5 are H, and X is I;

[0018] Complex 4: a complex represented by formula (I), wherein R2 is methyl, R5 is isopropyl, R1, R3 and R4 are H, and X is Cl;

[0019] Complex 5: a complex represented by formula (I), wherein R2 is methyl, R5 is isopropyl, R1, R3 and R4 are H, and X is Br;

[0020] Complex 6: A complex represented by formula (I), wherein R2 is methyl, R5 is isopropyl, R1, R3 and R4 are H, and X is I.

[0021] The second aspect of the present invention provides a method for preparing the above-mentioned tetrahydronaphthol-phosphine non-metallocene vanadium metal complex, and the method comprises the following steps:

[0022] (1) React the compound shown in formula (II) with the compound shown in formula (III) to generate a ligand;

[0023] (2) React the ligand with a vanadium metal compound;

[0024]

[0025] Wherein, the definitions of R1-R5 are the same as those described above.

[0026] Preferably, the vanadium metal compound is selected from one or more of VCl3, VCl3(THF)3, VCl3(THF), VCl3O(Et)2, VBr3(THF)3 and VI3(THF)3.

[0027] The third aspect of the present invention provides the application of the above-mentioned tetrahydronaphthol-phosphine non-metallocene vanadium metal complex in olefin polymerization.

[0028] The fourth aspect of the present invention provides a catalyst for olefin polymerization, and the catalyst for olefin polymerization comprises a main catalyst and a cocatalyst;

[0029] The main catalyst is the above-mentioned tetrahydronaphthol-phosphine non-metallocene vanadium metal complex.

[0030] Preferably, the cocatalyst is an organoaluminum compound and / or ethyl trichloroacetate.

[0031] Preferably, 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 hydrocarbyloxy group, Z is selected from a halogen, 0 < n ≤ 3, and n is an integer.

[0032] Preferably, 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.

[0033] Preferably, Z is selected from chlorine or bromine.

[0034] The fifth aspect of the present invention provides the application of the above-mentioned catalyst for olefin polymerization in olefin polymerization.

[0035] The sixth aspect of the present invention provides an olefin polymerization method, which comprises carrying out an olefin polymerization reaction in the presence of the above-mentioned catalyst for olefin polymerization.

[0036] 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.

[0037] Compared with the prior art, the present invention has the following advantages:

[0038] 1. The synthesis method of the tetrahydronaphthol-phosphine non-vanadiumocene metal complex of the present invention is simple, has high yield and low cost;

[0039] 2. The tetrahydronaphthol-phosphine non-vanadiumocene metal complex of the present invention can catalyze ethylene polymerization with high activity, and can maintain high polymerization activity at a relatively high polymerization temperature;

[0040] 3. The olefin polymerization catalyst of the present invention has higher copolymerization performance with α-olefins or cycloolefins. DETAILED DESCRIPTION

[0041] 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.

[0042] 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.

[0043] In one aspect, the present invention provides a tetralinol-phosphine non-vanadiumocene metal complex, the structural formula of which is shown in formula (I):

[0044]

[0045] Wherein, R1-R5 are each independently selected from hydrogen, halogen, hydroxyl and substituted or unsubstituted C1-C15 hydrocarbon group; X is selected from halogen or C1-C10 hydrocarbon group.

[0046] In a preferred embodiment, R1-R5 are each independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C10 alkyl, and substituted or unsubstituted C6-C15 aryl.

[0047] In a more preferred embodiment, R1-R5 are each independently selected from hydrogen or unsubstituted C1-C10 alkyl.

[0048] In a preferred embodiment, X is selected from halogen or C1-C8 hydrocarbon group.

[0049] According to some embodiments of the invention, X is selected from chlorine, bromine or iodine.

[0050] 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-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy or halogenated C1-C10 alkoxy.

[0051] In a preferred embodiment, the substituent is 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-phosphine non-vanadiumocene metal complex is selected from the group consisting of the following complexes:

[0057] Complex 1: a complex represented by formula (I), wherein R1-R5 are H, and X is Cl;

[0058] Complex 2: a complex represented by formula (I), wherein R1-R5 are H, and X is Br;

[0059] Complex 3: a complex represented by formula (I), wherein R1-R5 are H, and X is I;

[0060] Complex 4: a complex represented by formula (I), wherein R2 is methyl, R5 is isopropyl, R1, R3 and R4 are H, and X is Cl;

[0061] Complex 5: a complex represented by formula (I), wherein R2 is methyl, R5 is isopropyl, R1, R3 and R4 are H, and X is Br;

[0062] Complex 6: A complex represented by formula (I), wherein R2 is methyl, R5 is isopropyl, R1, R3 and R4 are H, and X is I.

[0063] The second aspect of the present invention provides a method for preparing the above-mentioned tetrahydronaphthol-phosphine non-vanadiumocene metal complex, which comprises the following steps:

[0064] (1) reacting the compound represented by formula (II) with the compound represented by formula (III) to generate a ligand;

[0065] (2) reacting the ligand with a vanadium metal compound;

[0066]

[0067] Wherein, the definitions of R1-R5 are the same as described above.

[0068] In the method described in the present invention, the vanadium metal compound is selected from one or more of VCl3, VCl3(THF)3, VCl3(THF), VCl3O(Et)2, VBr3(THF)3 and VI3(THF)3.

[0069] In the present invention, "THF" means "tetrahydrofuran" and "Et" means "ethyl".

[0070] In the present invention, the reaction process of step (1) and step (2) is shown in the following reaction formula.

[0071]

[0072] Wherein, the definitions of R1-R5 and X are the same as described above.

[0073] 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.

[0074] 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 is tetrahydrofuran.

[0075] In a specific embodiment, the preparation process of step (1) includes: dissolving the compound shown in formula (II) in anhydrous diethyl ether under an atmosphere of a protective gas (such as nitrogen), dropping an n-BuLi (n-butyllithium) solution at -78 °C, and gradually restoring to room temperature after the reaction; then, dropping an anhydrous diethyl ether solution of the compound shown in formula (III) (in an ice-water bath), slowly rising to room temperature, and stirring the reaction overnight. Quench with water, extract the organic phase with anhydrous diethyl ether, concentrate the obtained organic phase, deoxygenate by freeze cycling, add 5 mL of concentrated hydrochloric acid to react under a nitrogen atmosphere, monitor the completion of the reaction by TLC, then add an aqueous NaHCO3 solution for neutralization, quench with water, extract the organic phase with anhydrous diethyl ether, dry over anhydrous MgSO4, filter, concentrate, and perform column chromatography to obtain the ligand shown in formula (IV).

[0076] In a specific embodiment, the preparation process of step (2) includes: dissolving the ligand obtained in step (1) in tetrahydrofuran under an atmosphere of a protective gas (such as nitrogen), adding a tetrahydrofuran solution of a vanadium metal compound, stirring at room temperature, adding Et3N, stirring at room temperature, filtering to remove NH4Cl, concentrating the filtrate, adding heptane for recrystallization to obtain the tetrahydronaphthol-phosphine non-metallocene vanadium metal complex of the present invention.

[0077] The third aspect of the present invention provides the application of the above-mentioned tetrahydronaphthol-phosphine non-metallocene vanadium metal complex in olefin polymerization.

[0078] Preferably, the olefins include ethylene, α-olefins containing polar groups, and cycloolefins.

[0079] 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;

[0080] The main catalyst is the above-mentioned tetrahydronaphthol-phosphine non-metallocene vanadium metal complex.

[0081] Preferably, the cocatalyst is an organoaluminum compound and / or ethyl trichloroacetate (Cl3CCO2Et).

[0082] In a preferred embodiment, 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 alkoxy groups, Z is selected from halogens, 0 < n ≤ 3, and n is an integer.

[0083] In a more preferred embodiment, Y is selected from C1-C20 alkyl groups, C1-C20 alkoxy groups, C7-C20 aralkyl groups, or C6-C20 aryl groups.

[0084] In a more preferred embodiment, Z is selected from chlorine or bromine.

[0085] Further preferably, the organoaluminum compound is selected from one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride, ethylaluminum dichloride, methylaluminumoxane (MAO), modified methylaluminumoxane (MMAO) and diethylaluminum chloride (Et2AlCl).

[0086] In a specific embodiment, the organoaluminum compound is diethylaluminum chloride (Et2AlCl).

[0087] According to some embodiments of the present invention, the co-catalyst is an organoaluminum compound and ethyl trichloroacetate.

[0088] In a preferred embodiment, the molar ratio of aluminum in the co-catalyst to vanadium 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.

[0089] In a preferred embodiment, the molar ratio of the ethyl trichloroacetate to the vanadium in the main catalyst is 1-1000:1, preferably 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.

[0090] 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.

[0091] A fifth aspect of the present invention provides use of the above-mentioned olefin polymerization catalyst in olefin polymerization.

[0092] Preferably, the olefins include ethylene, α-olefins containing polar groups and cyclic olefins.

[0093] 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.

[0094] 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.

[0095] According to some embodiments of the present invention, the polymerization reaction temperature may be -20°C, 50°C, 100°C or 150°C.

[0096] 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.

[0097] As used herein, "polymerization pressure" refers to the ethylene pressure in the polymerization system and is expressed as an absolute pressure.

[0098] According to some embodiments of the present invention, the olefin comprises a C2-C16 olefin.

[0099] According to some embodiments of the present invention, the olefin comprises a C2-C16 α-olefin or a cyclic olefin.

[0100] According to some embodiments of the invention, the olefin comprises ethylene.

[0101] According to some embodiments of the present invention, the olefin includes ethylene and an α-olefin or a cyclic olefin containing a polar group.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] In the present invention, examples of the aryl group include, but are not limited to, phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl and vinylphenyl.

[0106] In the present invention, alkenyl refers to straight-chain alkenyl, branched-chain alkenyl or cycloalkenyl, including but not limited to vinyl, allyl and butenyl.

[0107] 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.

[0108] 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.

[0109] The tetrahydronaphthol-phosphine non-vanadiumocene metal complex and its preparation method and application described in the present invention are further illustrated by examples. 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.

[0110] 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.

[0111] The analytical characterization instruments and test methods used in the following examples and comparative examples are as follows:

[0112] (1) Nuclear magnetic resonance instrument: Bruker DMX 300 (300 MHz), with tetramethylsilane (TMS) as the internal standard.

[0113] (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).

[0114] (3) Activity measurement method: The polymer was washed with hydrochloric acid ethanol solution, vacuum dried, and the weight of the polymer was measured. The calculation method of polymerization activity is: polymer weight (g) / vanadium (mol) × 60 / polymerization time (min).

[0115] (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.

[0116] Example 1

[0117] Complex 1: a complex represented by formula (I), wherein R1-R5 are H, and X=Cl;

[0118] 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 complete. Then, NaHCO3 aqueous solution was added for neutralization, quenched with water, and the organic phase was extracted with ether. The mixture was dried over anhydrous MgSO4, filtered, concentrated, and column chromatography was performed to obtain ligand L1 with a yield of 31%; 1 H NMR (500MHz, CDCl3, 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 (126MHz, CDCl3) 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 (202MHz, CDCl3) δ 60.52;

[0119] In a nitrogen atmosphere, ligand L1 (0.52 g, 1.5 mmol) was dissolved in tetrahydrofuran, and VCl3(THF)3 (0.56 g, 1.5 mmol) tetrahydrofuran solution was added dropwise, stirred at room temperature for 10 min, Et3N (0.2 mL, 1.6 mmol) was added, stirred at room temperature for 4 h, NH4Cl was removed by filtration, the filtrate was concentrated, and heptane was added for recrystallization to obtain complex 1 with a yield of 76%. The elemental analysis test showed that C 30 H48 Cl2O3PV (609.53): Theoretical calculated values ​​are: C, 59.12; H, 7.94; Test values ​​are: C, 59.35; H, 7.51;

[0120] A 1L stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130°C for 6h, evacuated while hot and replaced with N2 gas three times, 500mL of toluene was injected into the polymerization kettle, Cl3CCO2Et (0.20mL, 1.5mmol), Et2AlCl (20mmol), and 3.0mg (5μmol) of complex 1 were added, and the ethylene pressure was maintained at 1.0atm at 25°C. The reaction was stirred vigorously for 5min, and the reaction was neutralized with 10wt% hydrochloric acid-acidified ethanol solution 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 and polymerization activity of the obtained polymer are shown in Table 1.

[0121] Example 2

[0122] Complex 1: a complex represented by formula (I), wherein R1-R5 are H, and X=Cl;

[0123] A 1L stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130°C for 6h, evacuated while hot and replaced with N2 gas three times, 500mL of toluene was injected into the polymerization kettle, Cl3CCO2Et (0.20mL, 1.5mmol), Et2AlCl (20mmol), and 3.0mg (5μmol) of complex 1 were added, and the reaction was stirred vigorously at 70°C while maintaining an ethylene pressure of 1.0atm for 10min. 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 test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0124] Example 3

[0125] Complex 1: a complex represented by formula (I), wherein R1-R5 are H, and X=Cl;

[0126] A 100mL stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130°C for 6h, evacuated while hot and replaced with N2 gas three times, 50mL of toluene was injected into the polymerization kettle, Cl3CCO2Et (0.6mmol), Et2AlCl (8mmol), 1.0mL1-hexene, 1.2mg (2μmol) of complex 1 were added, and the ethylene pressure was maintained at 1.0atm at 25°C. The reaction was stirred vigorously for 10min, and the copolymer was neutralized with 10wt% hydrochloric acid-acidified ethanol solution to obtain the copolymer. The polymer was dried and weighed to test the polymerization activity. The test data of weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0127] Example 4

[0128] Complex 1: a complex represented by formula (I), wherein R1-R5 are H, and X=Cl;

[0129] A 100mL stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130°C for 6h, evacuated while hot and replaced with N2 gas three times, 50mL of toluene was injected into the polymerization kettle, Cl3CCO2Et (0.6mmol), Et2AlCl (8mmol), 1.0mol / L norbornene, 1.2mg (2μmol) of complex 1 were added, and the reaction was stirred vigorously for 10min at 25°C while maintaining an ethylene pressure of 1.0atm. The copolymer was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain the copolymer. The polymer was dried and weighed to test the polymerization activity. The test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0130] Example 5

[0131] Complex 4: a complex represented by formula (I), wherein R2 is methyl, R5 is isopropyl, R1, R3 and R4 are H, and X is Cl;

[0132] 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 a NaHCO3 aqueous solution was added for neutralization, quenched with water, and the organic phase was extracted with ether. The ligand L2 was dried over anhydrous MgSO4, filtered, concentrated, and column chromatography was performed to obtain the ligand L2 with a yield of 29%.

[0133] In a nitrogen atmosphere, ligand L2 (0.91 g, 2 mmol) was dissolved in tetrahydrofuran, and a tetrahydrofuran solution of VCl3(THF)3 (0.75 g, 2 mmol) was added dropwise, and stirred at room temperature for 10 min. Et3N (0.3 mL, 2.1 mmol) was added, and stirred at room temperature for 4 h. NH4Cl was removed by filtration, and the filtrate was concentrated. Heptane was added for recrystallization to obtain complex 4 with a yield of 78%. Elemental analysis test C 38 H 64Cl2O3PV (721.74): Theoretical calculated values ​​are: C, 63.23; H, 8.94; Test values ​​are: C, 61.11; H, 8.75;

[0134] A 1L stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130°C for 6h, evacuated while hot and replaced with N2 gas three times, 500mL of toluene was injected into the polymerization kettle, Cl3CCO2Et (0.20mL, 1.5mmol), Et2AlCl (20mmol), and 3.6mg (5μmol) of complex 4 were added, and the ethylene pressure was maintained at 1.0atm at 25°C. The reaction was stirred vigorously for 5min, and the mixture was neutralized with 10wt% hydrochloric acid-acidified ethanol solution 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 and polymerization activity of the obtained polymer are shown in Table 1.

[0135] Example 6

[0136] Complex 4: a complex represented by formula (I), wherein R2 is methyl, R5 is isopropyl, R1, R3 and R4 are H, and X is Cl;

[0137] A 100mL stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130°C for 6h, evacuated while hot and replaced with N2 gas three times, 50mL of toluene was injected into the polymerization kettle, Cl3CCO2Et (0.6mmol), Et2AlCl (8mmol), 1.0mL1-octene, 1.4mg (2μmol) of complex 4 were added, and the ethylene pressure was maintained at 1.0atm at 25°C. The reaction was stirred vigorously for 10min, and the copolymer was neutralized with 10wt% hydrochloric acid-acidified ethanol solution to obtain the copolymer. The polymer was dried and weighed to test the polymerization activity. The test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0138] Comparative Example 1

[0139] A 1L stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130°C for 6h, evacuated while hot and replaced with N2 gas three times, 500mL of toluene was injected into the polymerization kettle, Cl3CCO2Et (0.20mL, 1.5mmol), Et2AlCl (20mmol), 3.1mg (5μmol) of complex A (synthesis reference JOURNAL OF POLYMER SCIENCE PART A: POLYMERCHEMISTRY 2012, 50, 4721–4731) were added, and the ethylene pressure was maintained at 1.0atm at 25°C. The reaction was stirred vigorously for 5min, and the mixture was neutralized with 10wt% hydrochloric acid-acidified ethanol solution 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 and polymerization activity of the obtained polymer are shown in Table 1.

[0140]

[0141] Comparative Example 2

[0142] A 100mL stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130°C for 6h, evacuated while hot and replaced with N2 gas three times, 50mL of toluene was injected into the polymerization kettle, Cl3CCO2Et (0.6mmol), Et2AlCl (8mmol), 1.0mL1-hexene, 1.2mg (2μmol) of complex A were added, and the ethylene pressure was maintained at 1.0atm at 25°C. The reaction was stirred vigorously for 10min, and the copolymer was neutralized with 10wt% hydrochloric acid-acidified ethanol solution to obtain the copolymer. The polymer was dried and weighed to test the polymerization activity. The test data of weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0143] Table 1

[0144]

[0145] It can be seen from Table 1 that when the tetralinol-phosphine non-vanadiumocene 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 higher, and the molecular weight distribution of the obtained polymer is narrower, and it also has more excellent ethylene homopolymerization performance and copolymerization performance.

[0146] 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 tetralinol-phosphine non-vanadiumocene metal complex, characterized in that: Its structural formula is shown in formula (I), Wherein, R1-R5 are each 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-phosphine non-vanadiumocene metal complex according to claim 1, characterized in that: R1-R5 are each independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C15 aryl; Preferably, X is selected from halogen or C1-C8 hydrocarbon group.

3. The tetralin-phosphine non-vanadiumocene metal complex according to claim 2, characterized in that: The substituent is selected from halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy or halogenated C1-C10 alkoxy; 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.

4. The tetrahydronaphthol-phosphine non-vanadiumocene metal complex according to any one of claims 1 to 3, characterized in that: It is selected from the group consisting of the following complexes: Complex 1: a complex represented by formula (I), wherein R1-R5 are H, and X is Cl; Complex 2: a complex represented by formula (I), wherein R1-R5 are H, and X is Br; Complex 3: a complex represented by formula (I), wherein R1-R5 are H, and X is I; Complex 4: a complex represented by formula (I), wherein R2 is methyl, R5 is isopropyl, R1, R3 and R4 are H, and X is Cl; Complex 5: a complex represented by formula (I), wherein R2 is methyl, R5 is isopropyl, R1, R3 and R4 are H, and X is Br; Complex 6: A complex represented by formula (I), wherein R2 is methyl, R5 is isopropyl, R1, R3 and R4 are H, and X is I.

5. A method for preparing the tetrahydronaphthol-phosphine non-vanadiumocene metal complex as claimed in any one of claims 1 to 4, 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 vanadium metal compound; Wherein, the definitions of R1-R5 are the same as those in claim 1.

6. The method according to claim 5, characterized in that The vanadium metal compound is selected from one or more of VCl3, VCl3(THF)3, VCl3(THF), VCl3O(Et)2, VBr3(THF)3 and VI3(THF)3.

7. Use of the tetrahydronaphthol-phosphine non-vanadiumocene metal complex according to any one of claims 1 to 4 in olefin polymerization.

8. A catalyst for olefin polymerization, characterized in that The olefin polymerization catalyst comprises a main catalyst and a co-catalyst; The main catalyst is the tetralin-phosphine non-vanadiumocene metal complex as described in any one of claims 1 to 4.

9. The catalyst for olefin polymerization according to claim 8, characterized in that The co-catalyst is an organoaluminum compound and / or ethyl trichloroacetate; 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 alkoxy 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.

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

11. An olefin polymerization method, characterized in that: The method comprises carrying out an olefin polymerization reaction in the presence of the olefin polymerization catalyst according to claim 8 or 9; 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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