Tetrahydro-naphthol-phosphine non-metallocene vanadium metal complexes, methods for their preparation and use

Abstract

The present application relates to the field of olefin polymerization organometallic catalyst and olefin coordination polymerization, and discloses a tetrahydronaphthol-phosphine non-metallocene vanadium metal complex and a preparation method and application thereof.The structural formula of the tetrahydronaphthol-phosphine non-metallocene vanadium metal complex is shown as 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.When the tetrahydronaphthol-phosphine non-metallocene vanadium metal complex is used as a main catalyst, under similar polymerization conditions, the tetrahydronaphthol-phosphine non-metallocene vanadium metal complex has higher homopolymerization / copolymerization activity, the obtained polymer has higher molecular weight and narrower distribution, and the tetrahydronaphthol-phosphine non-metallocene vanadium metal complex also has more excellent ethylene homopolymerization performance and copolymerization performance.

Description

Technical Field

[0001] This invention relates to the field of organometallic catalysts for olefin polymerization and olefin coordination polymerization, specifically to a tetrahydronaphthol-phosphine non-vanadium-ceramic metal complex, its preparation method, and its application. Background Technology

[0002] Since Ziegler and Natta's pioneering work in olefin polymerization, the polyolefin industry has experienced rapid development. Polyethylene, in particular, possesses advantages such as good chemical resistance, low cost, simple preparation, low density, and good mechanical properties, and can also serve as a potential rubber substitute. However, its non-polar nature limits its applications. Introducing a small number of polar functional groups into polyolefins can significantly improve their properties, thereby broadening their uses and increasing their commercial value. Polar polyolefins are mainly used in high-end pipes, automotive parts, medical devices, and prosthetic implants. Catalyst innovation determines the progress of the polyolefin industry chain, and coordination catalytic copolymerization, as a room-temperature and atmospheric-pressure polymerization technology, plays an irreplaceable role. Currently, the central metals of catalysts used in olefin coordination polymerization are mainly pre-transition metals and post-transition metals. Among them, vanadium-based catalysts have excellent performance and wide applications, and are still the main catalysts for the industrial production of EPR and COC. By controlling the electronic and steric effects of ligands, the catalytic performance of vanadium-based catalysts can be effectively improved. Currently, vanadium-based catalysts used for catalyzing 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 parameters of these vanadium-based catalysts (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 this invention is to provide a tetrahydronaphthol-phosphine non-vanadium metal complex, its preparation method and application. The tetrahydronaphthol-phosphine non-vanadium metal complex has good thermal stability. In particular, the tetrahydronaphthol-phosphine monochromium metal complex can maintain high ethylene polymerization activity at high temperatures, and the resulting polymer has a narrow molecular weight distribution.

[0004] To achieve the above objectives, the present invention provides a tetrahydronaphthol-phosphine non-vanadium-ceramic metal complex, the structural formula of which is shown in formula (I).

[0005]

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

[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 halogens or C1-C8 hydrocarbon groups.

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

[0010] Preferably, the substituent is selected from halogen, hydroxyl, 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-hexyloxy, isohexyloxy, or 3,3-dimethylbutoxy.

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

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

[0015] Complex 1: The complex shown in formula (I), wherein R1-R5 are H and X is Cl;

[0016] Complex 2: The complex shown in formula (I), wherein R1-R5 are H and X is Br;

[0017] Complex 3: The complex shown in formula (I), where R1-R5 are H and X is I;

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

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

[0020] Complex 6: The complex shown in 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 this 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 said 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 than two 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 this 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 with the general formula AlY n Z 3-n wherein, Y is selected from hydrogen, C1-C20 hydrocarbyl or C1-C20 hydrocarbyloxy, Z is selected from halogen, 0 < n ≤ 3, and n is an integer.

[0032] Preferably, Y is selected from C1-C20 alkyl, C1-C20 alkoxy, C7-C20 aralkyl or C6-C20 aryl.

[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 temperature is -78℃ to 200℃, more preferably -20℃ to 150℃; 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 method for synthesizing the tetrahydronaphthol-phosphine non-vanadium metal complex described in this invention is simple, has a high yield, and low cost;

[0039] 2. The tetrahydronaphthol-phosphine non-vanadium-ceramic metal complex of the present invention can catalyze ethylene polymerization with high activity, especially maintaining high polymerization activity at higher polymerization temperatures.

[0040] 3. The catalyst for olefin polymerization described in this invention has higher performance in copolymerizing with α-olefins or cycloolefins. Detailed Implementation

[0041] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0042] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0043] In one aspect, this invention provides a tetrahydronaphthol-phosphine non-vanadium-ceramic metal complex, the structural formula of which is shown in formula (I).

[0044]

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

[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 groups.

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

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

[0050] In this invention, "substituted or unsubstituted" means containing a substituent, which can be selected from halogens, hydroxyl groups, C1-C10 alkyl groups, halogenated C1-C10 alkyl groups, C1-C10 alkoxy groups, or halogenated C1-C10 alkoxy groups.

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

[0053] In this invention, the alkoxy group (such as C1-C6 alkoxy) may be selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexyloxy, isohexyloxy and 3,3-dimethylbutoxy.

[0054] In this invention, the aryl group (such as C6-C15 aryl) can be selected from phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl and vinylphenyl.

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

[0056] In a further preferred embodiment, the tetrahydronaphthol-phosphine non-vanadium-containing metal complex is selected from the group consisting of the following complexes:

[0057] Complex 1: The complex shown in formula (I), wherein R1-R5 are H and X is Cl;

[0058] Complex 2: The complex shown in formula (I), wherein R1-R5 are H and X is Br;

[0059] Complex 3: The complex shown in formula (I), where R1-R5 are H and X is I;

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

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

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

[0063] A second aspect of the present invention provides a method for preparing the above-mentioned tetrahydronaphthol-phosphine non-vanadium metal complex, the method comprising the following steps:

[0064] (1) React the compound shown in formula (II) with the compound shown in formula (III) to generate a ligand;

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

[0066]

[0067] The definitions of R1-R5 are the same as those described above.

[0068] In the method described in this 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 this invention, "THF" refers to "tetrahydrofuran" and "Et" refers to "ethyl".

[0070] In this invention, the reaction processes of steps (1) and (2) are shown in the following reaction formula.

[0071]

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

[0073] In a preferred embodiment, the reaction in 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 in 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 the atmosphere of a protective gas (such as nitrogen), dropping a solution of n-BuLi (n-butyl lithium) 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 raising the temperature to room temperature, and stirring the reaction overnight. Quench with water, extract the organic phase with anhydrous diethyl ether, concentrate the obtained organic phase, perform freeze-cycle deoxidation, add 5 mL of concentrated hydrochloric acid to react under the nitrogen atmosphere, track the completion of the reaction by TLC, then add an aqueous solution of NaHCO3 for neutralization, quench with water, extract the organic phase with anhydrous diethyl ether, dry with 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 the 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 olefin includes ethylene, an α-olefin containing a polar group, and a cycloolefin.

[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 alkylaluminoxane or an organoaluminum compound of the general formula AlY n Z 3-n where 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.

[0083] 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.

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

[0085] More preferably, the organoaluminum compound is selected from one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum hydrogen, diisobutylaluminum hydrogen, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, dichloroethylaluminum, methylaluminoxane (MAO), modified methylaluminoxane (MMAO), and diethylaluminum chloride (Et2AlCl).

[0086] In one 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 The molar ratio can be 1:1, 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, 100000:1, 1000000:1, 10000000:1 or any value between them.

[0089] In a preferred embodiment, the molar ratio of ethyl trichloroacetate to 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 between them.

[0090] In this invention, the olefin is a C2-C16 olefin. Preferably, the olefin is ethylene or an α-olefin having 3-16 carbon atoms.

[0091] The fifth aspect of the present invention provides the application of the above-mentioned catalyst for olefin polymerization in olefin polymerization.

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

[0093] The sixth aspect of the present invention provides a method for olefin polymerization, comprising carrying out an olefin polymerization reaction in the presence of the catalyst described above for olefin polymerization.

[0094] Preferably, the polymerization temperature is -78℃ to 200℃, more preferably -20℃ to 150℃; 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 temperature of the polymerization reaction can 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] In this paper, "polymerization pressure" refers to the ethylene pressure in the polymerization system, expressed as absolute pressure.

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

[0099] According to some embodiments of the present invention, the olefin includes C2-C16 α-olefins or cycloolefins.

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

[0101] According to some embodiments of the present invention, the olefin includes ethylene and α-olefins or cycloolefins containing polar groups.

[0102] According to some embodiments of the present invention, the polymerization reaction is carried out by olefin monomers in a solvent, wherein the solvent for polymerization 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 from one or more of hexane, toluene and heptane.

[0104] In this invention, alkyl refers to straight-chain alkyl, branched alkyl, or cycloalkyl, including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, and 4-n-butylcyclohexyl.

[0105] Examples of aryl groups in this invention include, but are not limited to, phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, and vinylphenyl.

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

[0107] In this invention, examples of aralkyl groups include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenylisopropyl, phenyl-n-butyl, and phenyl-tert-butyl.

[0108] In this invention, examples of alkylaryl groups include, but are not limited to: tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, and tert-butylphenyl.

[0109] The following examples further illustrate the tetrahydronaphthol-phosphine non-vanadium-ceramic metal complex, its preparation method, and its applications according to the present invention. The examples are implemented based on the technical solution of the present invention, providing detailed implementation methods and specific operating procedures; however, the scope of protection of the present invention is not limited to the following examples.

[0110] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods in the art. Unless otherwise specified, the experimental materials used in the following embodiments are commercially available.

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

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

[0113] (2) Molecular weight and molecular weight distribution of polymer PDI (PDI=Mw / Mn): The molecular weight and molecular weight distribution of polymer PDI (PDI=Mw / Mn) were determined by PL-GPC220 chromatograph with trichlorobenzene as solvent at 150℃ (wherein, standard sample: PS, flow rate: 1.0mL / min, chromatographic column: 3×PLgel 10um M1×ED-B, 300×7.5nm).

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

[0115] (4) Analysis of comonomer content in the polymer: using... 1 H NMR, 13 The polymer sample was dissolved in 1,2,4-trichlorobenzene and analyzed using a 10 mm PASEX 13 probe on a 400 MHz Bruker Avance 400 NMR spectrometer at 120 °C on a 400 MHz Bruker Avance 400 NMR spectrometer.

[0116] Example 1

[0117] Complex 1: The complex shown in formula (I), wherein R1-R5 are H and X = Cl;

[0118] In a nitrogen atmosphere, the compound (2.32 g, 10 mmol) of formula (II) was dissolved in anhydrous diethyl ether (20 mL). A solution of n-butyllithium (2.7 M, 4.0 mL, 11 mmol) was added dropwise at -78 °C. The reaction was gradually brought back to room temperature and stirred for 12 h to obtain a white precipitate. Dicyclohexylphosphine chloride (10 mmol, 2.32 g) was uniformly dispersed in 10 mL of diethyl 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 reaction was quenched with water, and the organic phase was extracted with diethyl ether. The obtained organic phase was concentrated, deoxygenated by refrigeration, and reacted with 5 mL of concentrated hydrochloric acid under a nitrogen atmosphere for 5 h. The reaction was monitored by TLC until it was completed. Then, NaHCO3 aqueous solution was added for neutralization, and the reaction was quenched with water. The organic phase was extracted with diethyl ether, dried over anhydrous MgSO4, filtered, concentrated, and column chromatography was used 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] Under a nitrogen atmosphere, ligand L1 (0.52 g, 1.5 mmol) was dissolved in tetrahydrofuran, and a solution of VCl3(THF)3 (0.56 g, 1.5 mmol) in tetrahydrofuran was added dropwise. The mixture was stirred at room temperature for 10 min, and then Et3N (0.2 mL, 1.6 mmol) was added. The mixture was stirred at room temperature for 4 h, and NH4Cl was removed by filtration. The filtrate was concentrated, and heptane was added for recrystallization to obtain complex 1 with a yield of 76%. Elemental analysis showed that C... 30 H48 Cl2O3PV(609.53): Theoretical values: C, 59.12; H, 7.94; Test values: C, 59.35; H, 7.51;

[0120] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 6 hours. While still hot, a vacuum was drawn and the reactor was purged with N2 gas three times. 500mL of toluene was injected into the polymerization reactor, followed by Cl3CCO2Et (0.20mL, 1.5mmol), Et2AlCl (20mmol), and 3.0mg (5μmol) of complex 1. The reaction was carried out at 25℃ with an ethylene pressure of 1.0atm and stirred vigorously for 5 minutes. The mixture was then neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried, weighed, and its polymerization activity was tested. The weight-average molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0121] Example 2

[0122] Complex 1: The complex shown in formula (I), wherein R1-R5 are H and X = Cl;

[0123] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 6 hours. While still hot, a vacuum was drawn and the reactor was purged with N2 gas three times. 500mL of toluene was injected into the polymerization reactor, followed by Cl3CCO2Et (0.20mL, 1.5mmol), Et2AlCl (20mmol), and 3.0mg (5μmol) of complex 1. The reaction was carried out at 70℃ with an ethylene pressure of 1.0atm and stirred vigorously for 10min. The mixture was then neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried, weighed, and its polymerization activity was tested. The weight-average molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0124] Example 3

[0125] Complex 1: The complex shown in formula (I), wherein R1-R5 are H and X = Cl;

[0126] A 100 mL stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130 °C for 6 h. While still hot, a vacuum was drawn and the reactor was purged with N2 gas three times. 50 mL of toluene was injected into the polymerization reactor, followed by Cl3CCO2Et (0.6 mmol), Et2AlCl (8 mmol), 1.0 mL of 1-hexene, and 1.2 mg (2 μmol) of complex 1. The reaction was carried out at 25 °C with an ethylene pressure of 1.0 atm and vigorously stirred for 10 min. The mixture was then neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the copolymer. The polymer was dried, weighed, and its polymerization activity was tested. The weight-average molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0127] Example 4

[0128] Complex 1: The complex shown in formula (I), wherein R1-R5 are H and X = Cl;

[0129] A 100 mL stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130 °C for 6 h. While still hot, a vacuum was drawn and the reactor was purged with N2 gas three times. 50 mL of toluene was injected into the polymerization reactor, followed by Cl3CCO2Et (0.6 mmol), Et2AlCl (8 mmol), 1.0 mol / L norbornene, and 1.2 mg (2 μmol) of complex 1. The reaction was carried out at 25 °C with an ethylene pressure of 1.0 atm and vigorously stirred for 10 min. The mixture was then neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the copolymer. The polymer was dried, weighed, and its polymerization activity was tested. The weight-average molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0130] Example 5

[0131] Complex 4: The complex shown in 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 (2.32 g, 10 mmol) of formula (II) was dissolved in anhydrous diethyl ether (20 mL). A solution of n-butyllithium (2.7 M, 4.0 mL, 11 mmol) was added dropwise at -78 °C. The reaction was gradually brought back 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 uniformly dispersed in 8 mL of diethyl 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 diethyl ether. The obtained organic phase was concentrated, deoxygenated by refrigeration, and reacted with 5 mL of concentrated hydrochloric acid under a nitrogen atmosphere for 5 h. The reaction was monitored by TLC until completion. Then, NaHCO3 aqueous solution was added for neutralization, and the mixture was quenched with water. The organic phase was extracted with diethyl ether, dried over anhydrous MgSO4, filtered, concentrated, and column chromatography was used to obtain ligand L2 in 29% yield.

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

[0134] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 6 hours. While still hot, a vacuum was drawn and the reactor was purged with N2 gas three times. 500mL of toluene was injected into the polymerization reactor, followed by Cl3CCO2Et (0.20mL, 1.5mmol), Et2AlCl (20mmol), and 3.6mg (5μmol) of complex 4. The reaction was carried out at 25℃ with an ethylene pressure of 1.0atm and stirred vigorously for 5 minutes. The mixture was then neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyethylene. The polymer was dried, weighed, and its polymerization activity was tested. The weight-average molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0135] Example 6

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

[0137] A 100 mL stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130 °C for 6 h. While still hot, a vacuum was drawn and the reactor was purged with N2 gas three times. 50 mL of toluene was injected into the polymerization reactor, followed by Cl3CCO2Et (0.6 mmol), Et2AlCl (8 mmol), 1.0 mL of 1-octene, and 1.4 mg (2 μmol) of complex 4. The reaction was carried out at 25 °C with an ethylene pressure of 1.0 atm and vigorously stirred for 10 min. The mixture was then neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the copolymer. The polymer was dried, weighed, and its polymerization activity was tested. The weight-average molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0138] Comparative Example 1

[0139] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 6 hours. While still hot, a vacuum was drawn and the reactor was purged with N2 gas three times. 500 mL of toluene was injected into the polymerization reactor, followed by Cl3CCO2Et (0.20 mL, 1.5 mmol), Et2AlCl (20 mmol), and 3.1 mg (5 μmol) of complex A (synthesis reference: JOURNAL OF POLYMER SCIENCE PART A: POLYMERCHEMISTRY 2012, 50, 4721–4731). The reaction was carried out at 25℃ with an ethylene pressure of 1.0 atm and the mixture was stirred vigorously for 5 minutes. The mixture was then neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The polymer was dried, weighed, and its polymerization activity was tested. The weight-average molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0140]

[0141] Comparative Example 2

[0142] A 100 mL stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130 °C for 6 h. While still hot, a vacuum was drawn and the reactor was purged with N2 gas three times. 50 mL of toluene was injected into the polymerization reactor, followed by Cl3CCO2Et (0.6 mmol), Et2AlCl (8 mmol), 1.0 mL of 1-hexene, and 1.2 mg (2 μmol) of complex A. The reaction was carried out at 25 °C with an ethylene pressure of 1.0 atm and vigorously stirred for 10 min. The mixture was then neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the copolymer. The polymer was dried, weighed, and its polymerization activity was tested. The weight-average molecular weight, molecular weight distribution, and polymerization activity data of the obtained polymer are shown in Table 1.

[0143] Table 1

[0144]

[0145] As can be seen from Table 1, when the tetrahydronaphthol-phosphine non-vanadium metal complex of the present invention is used as the main catalyst, it has higher homopolymerization / copolymerization activity under similar polymerization conditions, the resulting polymer has a higher molecular weight and a narrower molecular weight distribution, and also has better homopolymerization and copolymerization performance of ethylene.

[0146] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A tetrahydro naphthol-phosphine non-metallocene vanadium metal complex, characterized in that, The structural formula is shown as formula (I), Formula (I) wherein R1-R5 are each independently selected from hydrogen, halogen, hydroxyl, and substituted or unsubstituted C1-C15 hydrocarbyl; X is selected from halogen or C1-C10 hydrocarbyl; the substituent group in the substituted or unsubstituted is selected from halogen, hydroxyl, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy or halogenated C1-C10 alkoxy.

2. The tetrahydro naphthol-phosphine nonmetallocene vanadium metal complex of claim 1 wherein, R1-R5 are each independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C15 aryl.

3. The tetrahydro naphthol-phosphine nonmetallocene vanadium metal complex of claim 1 or 2, wherein, X is selected from halogen or C1-C8 hydrocarbyl.

4. The tetrahydro naphthol-phosphine nonmetallocene vanadium metal complex of claim 3, wherein, the substituent group in the substituted or unsubstituted is selected from halogen, hydroxyl, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy.

5. The tetrahydro naphthol-phosphine nonmetallocene vanadium metal complex of claim 4, wherein, the C1-C6 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl or 3,3-dimethylbutyl.

6. The tetrahydro naphthol-phosphine nonmetallocene vanadium metal complex of claim 4 or 5, wherein, the C1-C6 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy or 3,3-dimethylbutoxy.

7. The tetrahydro naphthol-phosphine nonmetallocene vanadium metal complex of claim 6, wherein, the halogen is selected from fluorine, chlorine, bromine or iodine.

8. The tetrahydro naphthol-phosphine nonmetallocene vanadium metal complex of claim 1 or 7, wherein, It is selected from the group consisting of the following complexes: Complex 1: the complex shown as formula (I), wherein R1-R5 are H, and X is Cl; Complex 2: the complex shown as formula (I), wherein R1-R5 are H, and X is Br; Complex 3: the complex shown as formula (I), wherein R1-R5 are H, and X is I; Complex 4: the complex shown as formula (I), wherein R2 is methyl, R5 is isopropyl, R1, R3 and R4 are H, and X is Cl; Complex 5: the complex shown as formula (I), wherein R2 is methyl, R5 is isopropyl, R1, R3 and R4 are H, and X is Br; Complex 6: the complex shown as formula (I), wherein R2 is methyl, R5 is isopropyl, R1, R3 and R4 are H, and X is I.

9. A process for the preparation of the tetrahydro- naphthol-phosphine non-metallocene vanadium complex according to any one of claims 1 to 8, characterized in that, The method comprises the following steps: (1) reacting the compound shown as formula (II) with the compound shown as formula (III) to generate a ligand; (2) reacting the ligand with a vanadium metal compound; Formula (II) Formula (III) wherein the definitions of R1-R5 are the same as those in claim 1.

10. The method of claim 9, wherein, 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.

11. Use of the tetrahydro-naphthol-phosphine non-metallocene vanadium metal complex of any one of claims 1-8 in olefin polymerization.

12. A catalyst for the polymerization of olefins, characterized in that, The catalyst for olefin polymerization comprises a main catalyst and a cocatalyst; The main catalyst is the tetrahydro-naphthol-phosphine non-metallocene vanadium metal complex of any one of claims 1-8.

13. The catalyst according to claim 12, wherein The cocatalyst is an organic aluminum compound and / or ethyl trichloroacetate.

14. The catalyst according to claim 13, wherein said organoaluminum compound is selected from the group consisting of alkylaluminoxane or an organoaluminum compound of the general formula AlY n Z 3-n wherein Y is selected from the group consisting of hydrogen, C1-C20 hydrocarbyl or C1-C20 hydrocarbyloxy, Z is selected from the group consisting of halogen, 0 < n < 3, and n is an integer.

15. The catalyst according to claim 14, wherein Y is selected from C1-C20 alkyl, C1-C20 alkoxy, C7-C20 aralkyl or C6-C20 aryl.

16. The catalyst for the polymerization of olefins according to claim 14 or 15, characterized by the fact that, Z is selected from chlorine or bromine.

17. Use of the catalyst for the polymerization of olefins according to any one of claims 12 to 16 for the polymerization of olefins.

18. A process for the polymerization of olefins, characterized in that, carrying out a polymerization reaction of olefins in the presence of the catalyst for the polymerization of olefins according to any one of claims 12 to 16.

19. The olefin polymerization process of claim 18, wherein, The temperature of the polymerization reaction is -78 o C ~ 200 o C, and the polymerization pressure is 0.01 ~ 10 MPa.

20. The olefin polymerization process of claim 19, wherein, The temperature of the polymerization reaction is -20 o C ~ 150 o C; and the polymerization pressure is 0.01 ~ 5 MPa.

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