Metal compound containing dihydronaphthalene structure and preparation method and application thereof

Abstract

The invention relates to a metal compound containing a dihydronaphthalene structure as well as a preparation method and application of the metal compound. The metal compound containing the dihydronaphthalene structure has a structure as shown in a formula (I). The metal compound containing the dihydronaphthalene structure provided by the invention takes dihydronaphthalene as a skeleton, has rigidity of an aromatic ring and flexibility of a naphthenic base, and is complexed with a fourth pair (IVB group) metal to form a stable complex. The metal compound has the advantages of being easy to prepare, high in activity, good in copolymerization performance and the like, a catalyst composition formed by the metal compound is suitable for preparing a polyolefin material through olefin slurry polymerization, and an obtained polymer has the advantages of being good in form, low in cost, high in molecular weight, low in extraction rate, high in bulk density and the like.

Description

Technical Field

[0001] The invention relates to the technical field of olefin polymer catalysts, and in particular to a metal compound containing a dihydronaphthalene structure, a preparation method and application thereof. Background Art

[0002] Polyolefin materials have become the leader in polymer materials due to their wide variety, large output and wide application. Polyolefin elastomer materials have excellent properties such as good compatibility, good processability and weather resistance. They have become the "star" materials among polyolefin materials and are deeply loved by people. They are widely used in national defense science and technology, agriculture, automobiles and other fields. For polyolefin materials, polyolefin catalysts are the core of their development. In recent years, catalysts for ethylene homopolymerization and copolymerization have been reported. Polyolefin catalysts with excellent thermal stability are crucial for the preparation of polyolefin elastomers (POE).

[0003] At present, the industry adopts the homogeneous high-temperature solution method to prepare polyolefin elastomer materials. This process has high energy consumption, poor polymer morphology, low polymer bulk density, and the process usually uses methylaluminoxane (MAO) as a catalyst, which increases the cost. In the 1990s, the Dow Chemical Company of the United States developed a constrained geometry catalyst (EP0416815A2), which has a structure of formula I. The polyolefin elastomer prepared by this structure catalyst has a low molecular weight and poor catalytic performance at low temperatures;

[0004]

[0005] Stephen, A, Miller, et al. Isotactic-Hemiisotactic Polypropylene from C 1 -Symmetric ansa-Metallocene Catalysts: A New Strategy for the Synthesis of Elastomeric Polypropylene [J]. Organometallics, 2002.) discloses a catalyst having a structure of Formula 2, which is used for catalyzing olefin polymerization, but has the disadvantages of low polymer molecular weight, poor polymer morphology, easy blockage of reactor in industrial production process, and increased cost caused by using a large amount of MAO in the polymerization process;

[0006]

[0007] Froese et al. (Froese RDJ, Jazdzewski BA, Klosin J, et al. Imino-Amido Hfand Zr Complexes: Synthesis, Isomerization, and Olefin Polymerization [J]. Organometallics, 2011, 30 (2): 251–262.) reported a catalyst having the structure of Formula 3 for catalyzing olefin polymerization. However, the catalyst had the disadvantages of low catalytic activity, low comonomer insertion rate, and wide molecular weight distribution, which resulted in a decrease in the mechanical properties of the material and limited its application.

[0008]

[0009] Therefore, it is of great significance to provide a catalyst with the advantages of high catalytic activity, high comonomer insertion rate, and narrow molecular weight distribution. Summary of the invention

[0010] In order to solve the above technical problems, the purpose of the present invention is to provide a metal compound containing a dihydronaphthalene structure and a preparation method and application thereof. The metal compound containing a dihydronaphthalene structure provided by the present invention uses dihydronaphthalene as a skeleton and is complexed with a fourth subgroup (IVB group) metal, as shown in the structure shown in formula (I). The metal compound with a dihydronaphthalene structure adopts a hydrogenated naphthalene skeleton, that is, it has the rigidity of an aromatic ring and the flexibility of a cycloalkyl group. The flexibility of the cycloalkyl group provides the possibility for the insertion of a comonomer. In addition, the nitrogen in the metal compound exists in the form of a covalent bond, which makes the formed metal compound more stable, achieves the purpose of catalyzing olefin polymerization at room temperature, and exhibits good catalytic performance. By modifying the benzene ring connected to the middle nitrogen atom, the position of the substituent, the size of the steric hindrance and the strength of the power supply capacity are changed, thereby playing a better modification role on the metal center. Heteroatoms are introduced on the benzene ring to form a unique "barrier effect"; by adjusting the size of the steric hindrance of the side arm and the electronic effect, the insertion of the comonomer is affected, thereby achieving precise regulation of the polymer structure, and preparing a polymer with a high molecular weight and a high comonomer insertion rate. Ultra-high molecular weight polyethylene can be prepared by catalyzing the homopolymerization of ethylene; it shows high activity in catalyzing the copolymerization of ethylene with α-olefins such as 1-hexene and 1-octene, and produces copolymers with high molecular weight, high comonomer insertion rate and narrow molecular weight distribution. The polymers have high bulk density and low extraction rate.

[0011] To achieve this object, the present invention adopts the following technical solutions:

[0012] In a first aspect, the present invention provides a metal compound containing a dihydronaphthalene structure, wherein the metal compound containing a dihydronaphthalene structure has a structure shown in formula (I):

[0013]

[0014] Among them, R 1 is selected from hydrogen, halogen, substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 3 -C 20 Cycloalkyl, substituted or unsubstituted C 6 -C 18 Aryl, substituted or unsubstituted C 4 -C 18 Heteroaryl; R 2 is selected from hydrogen, halogen, substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 1 -C 20 Cycloalkyl, substituted or unsubstituted C 1 -C 16 Alkoxy;

[0015] X is selected from halogen, substituted or unsubstituted C 1 -C 20 Alkyl, -NR 4 R 5 ; said R 4 and R 5 The same or different, each independently selected from C 1 -C 8 alkyl;

[0016] M is selected from Group IVB metals;

[0017] When the group contains heteroatoms, the heteroatoms are selected from one or a combination of at least two of O, S, N, P, and Si;

[0018] The substituted group is selected from halogen, C 1 -C 8 Alkyl, C 1 -C 8 Alkoxy, C 6 -C 10 Aryl, C 6 -C 10 Heteroaryl.

[0019] Among them, C 1 -C 20 Can be C 1 , C 2 , C 4 , C 6 , C 8 , C 10 , C 12 , C 15, C 18 or C 20 etc.; C 3 -C 20 Can be C 3 , C 4 , C 5 , C 8 , C 10 , C 12 , C 15 , C 18 or C 20 etc.; C 6 -C 18 Can be C 6 , C 10 , C 12 , C 14 or C 18 etc.; C 4 -C 18 Can be C 4 , C 5 , C 8 , C 9 , C 12 , C 13 , C 14 , C 15 , C 16 or C 18 etc.; C 1 -C 16 Can be C 1 , C 2 , C 4 , C 6 , C 8 , C 10 , C 12 , C 14 or C 16 etc.; C 1 -C 8 Can be C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 7 or C 8 ; C 6 -C 10 Can be C 6 , C 7 , C 8 , C 9 or C 10 .

[0020] Preferably, R 1 is selected from hydrogen, halogen, substituted or unsubstituted C 1 -C4 Alkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl, substituted or unsubstituted C 6 -C 14 Aryl, substituted or unsubstituted C 4 -C 12 Heteroaryl.

[0021] Among them, C 1 -C 4 Can be C 1 , C 2 , C 3 or C 4 ; C 3 -C 6 Can be C 3 , C 4 , C 5 or C 6 ; C 6 -C 14 Can be C 6 , C 9 , C 10 , C 12 or C 14 ; C 4 -C 12 Can be C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , C 11 or C 12 .

[0022] Preferably, R 1 is selected from hydrogen, chlorine, methyl, ethyl, isopropyl, tert-butyl, phenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-tert-butylphenyl, 2,6-diisopropylphenyl or 2,4,6-trimethylphenyl.

[0023] Preferably, R 2 is selected from hydrogen, halogen, substituted or unsubstituted C 1 -C 4 Alkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl, substituted or unsubstituted C 1 -C 8 Alkoxy.

[0024] Preferably, R 2 is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl or methoxy.

[0025] Preferably, X is selected from halogen, substituted or unsubstituted C 1 -C 4 Alkyl, -NR 4 R 5 , the R 4 and R 5 The same or different, each independently selected from C 1-8 alkyl.

[0026] Preferably, X is selected from chlorine, methyl, benzyl or dimethylamino.

[0027] Preferably, M is selected from titanium, zirconium or hafnium.

[0028] Preferably, the metal compound containing a dihydronaphthalene structure is selected from any one of the following compounds:

[0029]

[0030] In a second aspect, the present invention provides a method for preparing the metal compound containing a dihydronaphthalene structure according to the first aspect, the preparation method comprising the following steps:

[0031] (1) 1,4-dihydro-naphthalene-2,3-dione reacts with morpholine to obtain the intermediate 2-(4-morpholine)-1,4-dihydro-naphthalene-3-one;

[0032]

[0033] (2) mixing the intermediate 2-(4-morpholine)-1,4-dihydro-naphthalen-3-one described in step (1) with the compound represented by formula II, adding a catalyst, and reacting to obtain intermediate 2;

[0034]

[0035] (3) mixing the intermediate 2 described in step (2) with the compound represented by formula III, adding a desiccant and a catalyst, and reacting to obtain an intermediate 3;

[0036]

[0037] (4) mixing the compound represented by formula IV and the compound represented by formula V, and adding the intermediate 3 described in step (3) to carry out reaction a to obtain the metal compound containing a dihydronaphthalene structure;

[0038]

[0039] Alternatively, the compound represented by formula IV is directly added to the intermediate 3 described in step (3) to carry out reaction b to obtain the metal compound containing a dihydronaphthalene structure;

[0040]

[0041] Alternatively, the compound represented by formula VI is directly added to the intermediate 3 described in step (3) to carry out reaction c to obtain the metal compound containing a dihydronaphthalene structure;

[0042]

[0043] Preferably, the reactions in steps (1) to (4) are carried out in an anhydrous solvent, and the anhydrous solvent includes any one of benzene, toluene, xylene or n-hexane, or a combination of at least two thereof.

[0044] Preferably, the molar ratio of 1,4-dihydro-naphthalene-2,3-dione to morpholine in step (1) is 1:(0.9-1), for example, it can be 1:0.9, 1:0.91, 1:0.92, 1:0.93, 1:0.94, 1:0.95, 1:0.96, 1:0.97, 1:0.98, 1:0.99 or 1:1, etc.

[0045] Preferably, the reaction in step (1) is carried out under reflux.

[0046] Preferably, the reaction time of step (1) is 5 to 10 h, for example, it can be 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h, 8 h, 8.5 h, 9 h, 9.5 h or 10 h.

[0047] Preferably, after the reaction in step (1) is completed, the anhydrous solvent is removed by vortexing under reduced pressure.

[0048] Preferably, the molar ratio of the 2-(4-morpholine)-1,4-dihydro-naphthalen-3-one in step (2) to the compound represented by formula II is 1:(0.6-1.0), for example, it can be 1:0.6, 1:0.65, 1:0.7, 1:0.75, 1:0.8, 1:0.85, 1:0.9, 1:0.95 or 1:1.0, etc.

[0049] Preferably, the compound represented by formula II in step (2) is added in batches, more preferably in three batches.

[0050] Preferably, the mixing in step (2) is carried out under stirring.

[0051] Preferably, the molar ratio of the 2-(4-morpholine)-1,4-dihydro-naphthalene-3-one to the catalyst in step (2) is 1:(0.0058-0.029), for example, it can be 1:0.0058, 1:0.008, 1:0.01, 1:0.015, 1:0.02, 1:0.025 or 1:0.029, etc.

[0052] Preferably, the catalyst in step (2) comprises p-toluenesulfonic acid.

[0053] Preferably, the reaction in step (2) is carried out under reflux.

[0054] Preferably, the reaction time of step (2) is 10 to 18 h, for example, 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, 16 h, 17 h or 18 h.

[0055] Preferably, after the reaction in step (2) is completed, the reaction solution is cooled to room temperature, filtered, the anhydrous solvent is removed under reduced pressure, and column chromatography is performed to obtain intermediate 2.

[0056] Preferably, the eluents in the column chromatography are petroleum ether and ethyl acetate in a volume ratio of (1-20):1, for example, 1:1, 2:1, 5:1, 8:1, 10:1, 12:1, 15:1, 18:1 or 20:1, etc.

[0057] In the present invention, column chromatography can be performed using a gradient elution with an eluent of petroleum ether and ethyl acetate in a volume ratio of (1-20):1, or a fixed ratio of (1-20):1. If gradient elution is performed, the elution ratios are 1:1, 5:1, 10:1, 15:1, and 20:1, respectively.

[0058] Preferably, the molar ratio of the intermediate 2 in step (3) to the compound represented by formula III is 1:(1-5), for example, it can be 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5 or 1:5, etc.

[0059] Preferably, the mixing in step (3) is carried out under stirring.

[0060] Preferably, the desiccant in step (3) comprises molecular sieves.

[0061] Preferably, the catalyst in step (3) comprises formic acid.

[0062] Preferably, the molar ratio of the intermediate 2 to the catalyst in step (3) is 1:(0.1-0.5), for example, it can be 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45 or 1:0.5, etc.

[0063] Preferably, the reaction in step (3) is carried out under reflux.

[0064] Preferably, the reaction time of step (3) is 10 to 18 h, for example, it can be 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, 16 h, 17 h or 18 h.

[0065] Preferably, after the reaction in step (3) is completed, the reaction solution is filtered to remove the desiccant, the anhydrous solvent is removed under reduced pressure, and column chromatography is performed to obtain intermediate 3.

[0066] Preferably, the column used for column chromatography is treated with triethylamine.

[0067] Preferably, the eluent used for the column chromatography includes petroleum ether and ethyl acetate in a volume ratio of (1:50) to (100:1).

[0068] In the present invention, specific eluents of petroleum ether and ethyl acetate are used in the column chromatography process. The elution can be a fixed ratio or a gradient elution, such as eluting in a gradient of 1:50, 1:10, 1:1, 10:1, 20:1, 50:1, 80:1, and 100:1 in sequence, but the elution is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0069] Preferably, the eluent further comprises triethylamine.

[0070] Preferably, the added volume of the triethylamine is 1-5% of the sum of the added volumes of the petroleum ether and the ethyl acetate, for example, it can be 1%, 2%, 3%, 4% or 5%.

[0071] Preferably, the compound represented by formula IV in step (4) is first dissolved in an anhydrous solvent before being mixed and stirred with the compound represented by formula V.

[0072] Preferably, when the amount of the compound represented by formula IV added in step (4) is 1 mmol, the volume of the anhydrous solvent added is 15 to 50 mL, for example, 18 mL, 20 mL, 22 mL, 25 mL, 28 mL, 30 mL, 35 mL, 40 mL or 45 mL.

[0073] Preferably, the molar ratio of formula IV, formula V and intermediate 3 in reaction a of step (4) is 1:(4-6):1, for example, it can be 1:4:1, 1:4.2:1, 1:4.5:1, 1:4.8:1, 1:5:1, 1:5.2:1, 1:5.5:1, 1:5.8:1 or 1:6:1, etc.

[0074] Preferably, the mixing and stirring in step (4) is carried out at low temperature.

[0075] Preferably, the low temperature is -45°C to 10°C, for example, it can be -45°C, -40°C, -35°C, -30°C, -25°C, -20°C, -15°C, -10°C, -5°C, 0°C or 5°C.

[0076] Preferably, the stirring time in step (4) is 1.5 to 2.5 h, for example, it can be 1.6 h, 1.7 h, 1.8 h, 1.9 h, 2 h, 2.1 h, 2.2 h, 2.3 h, 2.4 h or 2.5 h.

[0077] Preferably, the reaction a in step (4) is first stirred at -45°C to 10°C for 1.5 to 2.5 hours, then heated to room temperature and stirred for 4 to 6 hours (for example, 4.2 hours, 4.5 hours, 4.8 hours, 5 hours, 5.2 hours, 5.5 hours or 5.8 hours, etc.).

[0078] Preferably, the molar ratio of formula IV to intermediate 3 in reaction b of step (4) is 1:(1-2), for example, it can be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8 or 1:1.9, etc.

[0079] Preferably, the reaction b in step (4) is first stirred at -45°C to 10°C (for example, -45°C, -40°C, -35°C, -30°C, -25°C, -20°C, -15°C, -10°C, -5°C, 0°C or 5°C, etc.) for 1.5 to 2.5 h (for example, 1.5 h, 1.8 h, 1.9 h, 2.0 h, 2.2 h, 2.4 h or 2.5 h, etc.), and then heated to room temperature and stirred for 4 to 6 h (for example, 4.2 h, 4.5 h, 4.8 h, 5 h, 5.2 h, 5.5 h or 5.8 h, etc.).

[0080] Preferably, the molar ratio of formula VI to intermediate 3 in reaction c of step (4) is 1:(1-2), for example, it can be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8 or 1:1.9, etc.

[0081] Preferably, the reaction c in step (4) is stirred at 50°C to 100°C (for example, 55°C, 60°C, 65°C, 70°C, 75°C or 80°C, etc.) for 4 to 10 h (for example, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h, 8 h, 8.5 h, 9 h or 9.5 h, etc.).

[0082] Preferably, in the synthesis method in which the compound represented by formula IV or the compound represented by formula VI directly reacts with the intermediate 3 described in step (3), the compound represented by formula IV or the compound represented by formula VI is first dissolved in an anhydrous solvent, and when the added amount of the compound represented by formula IV or the compound represented by formula VI is 1 mmol, the added volume of the anhydrous solvent is 15 to 50 mL.

[0083] Preferably, after the reaction a, b or c in step (4) is completed, the anhydrous solvent is removed under reduced pressure, and extraction is performed with a good solvent to obtain the metal compound containing a dihydronaphthalene structure.

[0084] Preferably, the reactions in steps (1), (3) and (4) are all carried out under a protective gas atmosphere, wherein the protective gas comprises any one of nitrogen, argon and helium, or a combination of at least two of them.

[0085] Preferably, the good solvent in step (4) includes any one of n-hexane, n-pentane, n-heptane, cyclohexane, methylcyclohexane or toluene, or a combination of at least two thereof.

[0086] In a third aspect, the present invention provides a catalyst composition for olefin polymerization, wherein the catalyst composition comprises the metal compound containing a dihydronaphthalene structure as described in the first aspect, a co-catalyst and an activator.

[0087] Preferably, the molar ratio of the co-catalyst to the metal compound containing a dihydronaphthalene structure according to claim 1 is (0.001-100000):1, for example, it can be 0.001:1, 0.01:1, 0.1:1, 0.2:1, 1:1, 10:1, 100:1, 500:1, 1000:1, 10000:1 or 100000:1, etc., preferably (0.2-500):1.

[0088] Preferably, the co-catalyst comprises an organometallic compound and / or an organoboron compound.

[0089] Preferably, the organometallic compound and / or organoboron compound comprises M 3 (X 10 ) n1 (X 11 ) 3-n1 、M 4 (X 10 ) n2 (X 11 ) 2-n2 or M 5 X 10 Any of the following:

[0090] Among them, M 3 is boron or aluminum, n1 is 1-3 (for example, 1, 2 or 3, etc.); M 4 is magnesium or zinc, n2 is 1-2 (for example, 1 or 2, etc.); M 5 For Li;

[0091] X 10 Selected from hydrogen, C 1 -C 20 Hydrocarbon; X 11 Selected from hydrogen, halogen, C1 -C 20 Hydrocarbon or C 1 -C 20 Alkyloxy;

[0092] Preferably, the M 3 (X 10 ) n1 (X 11 ) 3-n1 The invention includes any one of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide or diethylaluminum chloride, or a combination of at least two thereof.

[0093] Preferably, the M 4 (X 10 ) n2 (X 11 ) 2-n2 The invention comprises any one of dimethyl zinc, diethyl zinc, dipropyl zinc, dibutyl zinc or dineopentyl zinc or a combination of at least two thereof.

[0094] Preferably, the activator comprises any one or a combination of at least two of an organic boron compound, an organic borate compound, an ionizing ionic compound, an aluminoxane compound or a solid oxide (activator-support).

[0095] Preferably, the solid oxide comprises any one of silica, alumina, titania, zirconia, magnesia, boria, calcium oxide, zinc oxide, silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, silica-magnesia, silica-boria, alumina-titania, titania-zirconia, alumina-zirconia, alumina-boria, zinc aluminate, aluminum phosphate, aluminum phosphate, aluminum phosphate-silica, magnesium aluminate, boehmite or heteropolytungstate, or a combination of at least two thereof.

[0096] Preferably, the solid oxide needs to be calcined.

[0097] Preferably, the calcination is carried out under a protective gas atmosphere, and the protective gas includes any one of nitrogen, argon and helium, or a combination of at least two of them.

[0098] Preferably, the calcination includes low-temperature calcination and high-temperature calcination.

[0099] Preferably, the temperature of the low-temperature calcination is 200-500°C, for example, 220°C, 240°C, 260°C, 280°C, 300°C, 350°C, 400°C, 450°C or 500°C, etc., preferably 200-300°C.

[0100] Preferably, the low-temperature calcination time is 1 to 10 h, for example, it can be 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h or 10 h, etc., preferably 2 to 5 h.

[0101] Preferably, the high temperature calcination temperature is 600-900°C, for example, 600°C, 650°C, 700°C, 750°C, 800°C, 850°C or 900°C.

[0102] Preferably, the high temperature calcination time is 4 to 40 h, for example, it can be 4 h, 6 h, 8 h, 10 h, 15 h, 20 h, 25 h, 30 h, 35 h or 40 h, etc., preferably 4 to 10 h.

[0103] In a fourth aspect, the present invention provides a use of the metal compound containing a dihydronaphthalene structure described in the first aspect or the catalyst composition described in the third aspect in an olefin polymerization reaction.

[0104] The catalyst composition provided in the present invention can contact with olefin monomers under polymerization conditions to catalyze the monomers to quickly form olefin polymers.

[0105] The metal compound containing dihydronaphthalene structure provided by the present invention is pre-contacted with at least one organoaluminum compound and olefin monomer to form a pre-contact mixture, and then the pre-contact mixture is contacted with a solid oxide activator-support to form an active catalyst. When preparing the catalyst composition in this way, a portion of the organoaluminum compound can be added to the pre-contact mixture, and another portion of the organoaluminum compound can be added to the post-contact mixture prepared when the pre-contact mixture can be contacted with the solid oxide activator. All organoaluminum compounds are used to prepare catalysts in the pre-contact or post-contact steps. Alternatively, all catalyst components can be contacted in a single step.

[0106] Preferably, the olefin monomer includes any one of ethylene, propylene, butene, pentene, hexene, heptene, octene, styrene or 4-methyl-1-pentene, or a combination of at least two thereof.

[0107] Compared with the prior art, the present invention has at least the following beneficial effects:

[0108] (1) The metal compound containing a dihydronaphthalene structure provided by the present invention adopts a hydrogenated naphthalene skeleton, that is, it has the rigidity of an aromatic ring and the flexibility of a cycloalkyl group; the flexibility of the cycloalkyl group provides the possibility for the insertion of a comonomer; and the nitrogen in the metal compound exists in the form of a covalent bond, making the formed metal compound more stable, and can be used to catalyze olefin polymerization reactions at room temperature, and exhibits good catalytic performance;

[0109] (2) The metal compound containing a dihydronaphthalene structure provided by the present invention modifies the benzene ring connected to the middle nitrogen atom to change the position of the substituent, the size of the steric hindrance and the strength of the power supply capacity, thereby playing a better modification role on the metal center; introduces heteroatoms on the benzene ring to form a unique "barrier effect"; by adjusting the size of the steric hindrance and the electronic effect of the side arm, the insertion of the comonomer is affected in the olefin copolymerization reaction, thereby achieving precise control of the polymer structure and preparing a polymer with a high molecular weight and a high comonomer insertion rate. DETAILED DESCRIPTION

[0110] For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0111] The materials and reagents used in the following examples can be obtained from commercial sources. The specific information is as follows:

[0112] 1,4-Dihydro-2,3-naphthalenedione: AR, Innochem

[0113] Morpholine: AR, Innochem

[0114] 2-Amino-4,6-dimethylphenol: AR, Aladdin

[0115] 2-Amino-4,6-di-tert-butylphenol: AR, Aladdin

[0116] 2-Amino-4,6-diisobutylphenol: AR, Aladdin

[0117] 2-Amino-4,6-dicyclohexylphenol: AR, Aladdin

[0118] 2-Amino-4,6-difluorophenol: AR, Aladdin

[0119] 2-Aminophenol: AR, Aladdin

[0120] Aniline: AR, Innochem

[0121] n-Octylamine: AR, Innochem

[0122] Tert-butylamine: AR, Innochem

[0123] n-Hexylamine: AR, Innochem

[0124] n-Butylamine: AR, Innochem

[0125] n-Propylamine: AR, Innochem

[0126] Cyclohexylamine: AR, Innochem

[0127] Cyclooctylamine: AR, Innochem

[0128] 2,6-Diisopropylaniline: AR, Aladdin

[0129] 4-Methoxyaniline: AR, Innochem

[0130] Methylmagnesium bromide ether solution: 3M, AR, Aladdin

[0131] p-Toluenesulfonic acid: AR, Aladdin

[0132] Toluene: AR, Aladdin

[0133] Hexane: AR, Aladdin

[0134] Petroleum ether: 60-90℃, Sinopharm

[0135] Ethyl acetate: AR, Aladdin

[0136] Deuterated chloroform: AR, Acros

[0137] Industrial ethanol: 95%, Beijing Chemical Reagent Company

[0138] Triphenylcarbonium tetrakis(pentafluorophenyl)borate: AR, Aladdin

[0139] MAO (methylaluminoxane): AR, Aladdin

[0140] 1-Octene: AR, Acros

[0141] Silica gel: AR, 200-300 mesh, Shanghai Wusi Chemical Reagent Company

[0142] Titanium tetrachloride: AR, Aladdin

[0143] Zirconium tetrachloride: AR, Aladdin

[0144] Hafnium tetrachloride: AR, Aladdin

[0145] Tetrabenzylhafnium: AR, Aladdin

[0146] Other reagents or raw materials not otherwise specified were commercially available.

[0147] In the present invention, the compounds in the preparation examples, embodiments and comparative examples were all tested and characterized using a nuclear magnetic resonance spectrometer (Brucker ARX-400).

[0148] Preparation Example 1

[0149] This preparation example provides a preparation method of the compound 2-(4-morpholine)-1,4-dihydro-naphthalen-3-one, which comprises the following steps:

[0150] Under a nitrogen atmosphere, 1,4-dihydro-2,3-naphthalenedione (16.0 g, 100 mmol) was mixed with morpholine (7.84 g, 90 mmol), refluxed in 150 mL of toluene for 8 h, and the toluene was removed under reduced pressure to obtain compound 2-(4-morpholine)-1,4-dihydro-naphthalene-3-one (18.98 g, yield 92%).

[0151] The NMR characterization data of the compound 2-(4-morpholine)-1,4-dihydro-naphthalene-3-one are as follows:

[0152] 1 H NMR (400 MHz, C 6 D 6 ): δ7.35-7.20(m,4H),6.38(s,1H),4.20(s,2H),3.65(t,4H,J=7.1Hz),3.47(t,4H,J=7.3Hz).

[0153] Preparation Example 2

[0154] This preparation example provides a preparation method of the compound 3-((2-hydroxy-3,5-di-tert-butylphenyl)-amino)naphthalene-2-one, which comprises the following steps:

[0155] The compound 2-(4-morpholine)-1,4-dihydro-naphthalene-3-one (2.29 g, 10 mmol) shown in Preparation Example 1 was mixed with 2-hydroxy-3,5-di-tert-butylaniline (1.99 g, 9 mmol) three times, 50 mg of p-toluenesulfonic acid was added as a catalyst, and the mixture was refluxed in 50 mL of dry toluene solvent for 18 h; cooled to room temperature, the reaction system was filtered, toluene was removed under reduced pressure, and then purified by column chromatography, with petroleum ether and ethyl acetate as the eluent in a volume ratio of 10:1, to obtain compound 3-((2-hydroxy-3,5-di-tert-butylphenyl)-amino)naphthalene-2-one (2.40 g, yield 73.4%).

[0156] The NMR characterization data of the compound 3-((2-hydroxy-3,5-di-tert-butylphenyl)-amino)naphthalene-2-one are as follows:

[0157] 1 H NMR (400 MHz, C 6 D 6): δ7.34-7.32(m,1H),7.26(dd,1H),7.21(dd,2H,J=9.1,5.2Hz),7.11(s,1H),6.75(dd,1H, J=8.3Hz),5.98(dd,1H,J=8.5,4.4Hz),5.35(s,1H),4.20(s,2H),4.00(s,1H),1.35(s,18H).

[0158] Preparation Example 3

[0159] This preparation example provides a preparation method of the compound 3-((2-hydroxy-3,5-dimethylphenyl)-amino)naphthalene-2-one, which comprises the following steps:

[0160] The compound 2-(4-morpholine)-1,4-dihydro-naphthalene-3-one (2.29 g, 10 mmol) shown in Preparation Example 1 was mixed with 2-hydroxy-3,5-dimethylaniline (1.23 g, 9 mmol) three times, 50 mg of p-toluenesulfonic acid as a catalyst was added, and the mixture was refluxed in 50 mL of dry toluene solvent for 18 h; cooled to room temperature, the reaction system was filtered, toluene was removed under reduced pressure, and then purified by column chromatography, with petroleum ether and ethyl acetate as the eluent in a volume ratio of 10:1, to obtain compound 3-((2-hydroxy-3,5-dimethylphenyl)-amino)naphthalene-2-one (2.16 g, yield 85.8%).

[0161] The NMR characterization data of the compound 3-((2-hydroxy-3,5-dimethylphenyl)-amino)naphthalene-2-one are as follows:

[0162] 1 H NMR (400 MHz, C 6 D 6 ): δ7.34-7.32(m,1H),7.26(dd,1H),7.21(dd,2H,J=9.1,5.2Hz),7.11(s,1H),6.96(d,1H,J=8.3H z,),6.29(dd,1H,J=8.6,4.2Hz),5.33(s,1H),4.20(s,2H),4.00(s,1H),2.34(s,3H),2.15(s,3H).

[0163] Preparation Example 4

[0164] This preparation example provides a preparation method of the compound 3-((2-hydroxyphenyl)-amino)naphthalene-2-one, which comprises the following steps:

[0165] The compound 2-(4-morpholine)-1,4-dihydro-naphthalene-3-one (2.29 g, 10 mmol) shown in Preparation Example 1 was mixed with 2-hydroxyaniline (0.98 g, 9 mmol) three times, 50 mg of p-toluenesulfonic acid as a catalyst was added, and the mixture was refluxed in 50 mL of dry toluene solvent for 18 h; cooled to room temperature, the reaction system was filtered, and toluene was removed under reduced pressure, and then purified by column chromatography, with petroleum ether and ethyl acetate as eluents in a volume ratio of 8:1, to obtain compound 3-((2-hydroxyphenyl)-amino)naphthalene-2-one (1.66 g, yield 73.6%).

[0166] The NMR characterization data of the compound 3-((2-hydroxyphenyl)-amino)naphthalene-2-one are as follows:

[0167] 1 H NMR (400 MHz, C 6 D 6 ): δ7.34-7.32(m,1H),7.26(dd,1H),7.21(dd,2H,J=9.1,5.2Hz),7.11(s,1H),6.93(d,1H,J=8.3Hz),6.76(td,1H,J =8.3,7.6,5.2Hz),6.70(dd,1H,J=8.6,4.2Hz),6.61(dd,1H,J=8.6,4.2Hz,),5.35(s,1H),4.20(s,2H),4.01(s,1H).

[0168] Preparation Example 5

[0169] This preparation example provides a preparation method of the compound 3-((2-hydroxy-3,5-diisopropylphenyl)-amino)naphthalene-2-one, which comprises the following steps:

[0170] The compound 2-(4-morpholine)-1,4-dihydro-naphthalene-3-one (2.29 g, 10 mmol) shown in Preparation Example 1 was mixed with 2-hydroxy-3,5-diisopropylaniline (1.74 g, 9 mmol) three times, 50 mg of p-toluenesulfonic acid was added as a catalyst, and the mixture was refluxed in 50 mL of dry toluene solvent for 18 h; the mixture was cooled to room temperature, filtered, and toluene was removed under reduced pressure, and then purified by column chromatography, with petroleum ether and ethyl acetate as eluents in a volume ratio of 10:1, to obtain compound 3-((2-hydroxy-3,5-diisopropylphenyl)-amino)naphthalene-2-one (2.56 g, yield 84.7%).

[0171] The NMR characterization data of the compound 3-((2-hydroxy-3,5-diisopropylphenyl)-amino)naphthalene-2-one are as follows:

[0172] 1H NMR (400 MHz, C 6 D 6 ): δ7.34-7.32(m,1H),7.26(dd,1H),7.21(dd,2H,J=9.1,5.2Hz),7.11(s,1H),6.43(dd,1H,J=8.3Hz),6.27( dd,1H,J=8.5,4.4Hz),5.33(s,1H),4.20(s,2H),4.00(s,1H),3.05(hept,1H),2.87(hept,1H),1.02(s,12H).

[0173] Preparation Example 6

[0174] This preparation example provides a preparation method of the compound 2,4-di-tert-butyl-6-((3-(n-butylamino)naphthalene-2-imide))phenol, the preparation method comprising the following steps:

[0175] Under nitrogen atmosphere, the compound 3-((2-hydroxy-3,5-di-tert-butylphenyl)-amino)naphthalene-2-one (36.3 g, 100 mmol) shown in Preparation Example 2 was mixed with n-butylamine (7.46 g, 102 mmol) and added Molecular sieves, formic acid (474 ​​mg, 10.3 mmol) was added, and refluxed in 500 mL toluene solvent for 16 h; the molecular sieves were removed by filtration, and toluene was removed under reduced pressure to obtain a crude product. After column chromatography purification, the column was treated with triethylamine, and the eluent was triethylamine, petroleum ether and ethyl acetate, wherein the volume ratio of petroleum ether to ethyl acetate was 3:1, and triethylamine was 2% of the sum of the added volumes of petroleum ether and ethyl acetate; the compound 2,4-di-tert-butyl-6-((3-(n-butylamino)naphthalene-2-imine))phenol (30.8 g, yield 73.6%) was obtained.

[0176] The NMR characterization data of the compound 2,4-di-tert-butyl-6-((3-(n-butylamino)naphthalene-2-imide))phenol are as follows:

[0177] 1 H NMR (400 MHz, C 6 D 6 ): δ8.37(s,1H),7.37(d,1H,J=8.1Hz),7.34(d,2H,J=7.6Hz),7.26(dd,2H,J=7.7Hz),6.87(d,1H,J=7.6Hz),6.46(s,1 H), 6.03 (s, 1H), 3.39-3.35 (m, 4H), 1.47 (m, 2H), 1.41 (s, 9H), 1.38 (s, 9H), 1.27 (m, 2H), 0.88 (t, 3H, J = 7.6Hz, 8.3Hz).

[0178] Preparation Example 7

[0179] This preparation example provides a preparation method of the compound 2,4-dimethyl-6-(3-(n-butylamino)naphthalene-2-imide)phenol, the preparation method comprising the following steps:

[0180] Under nitrogen atmosphere, the compound 3-((2-hydroxy-3,5-dimethylphenyl)-amino)naphthalene-2-one (27.9 g, 100 mmol) shown in Preparation Example 3 was mixed with n-butylamine (7.46 g, 102 mmol) and added Molecular sieves, formic acid (474 ​​mg, 10.3 mmol) was added, and refluxed in 500 mL toluene solvent for 16 h; the molecular sieves were removed by filtration, and toluene was removed under reduced pressure to obtain a crude product. After column chromatography purification, the column was treated with triethylamine, and the eluent was triethylamine, petroleum ether and ethyl acetate, wherein the volume ratio of petroleum ether to ethyl acetate was 1:1, and triethylamine was 1% of the sum of the added volumes of petroleum ether and ethyl acetate, to obtain the compound 2,4-dimethyl-6-(3-(n-butylamino)naphthalene-2-imine)phenol (25.5 g, yield 76.2%).

[0181] The NMR characterization data of the compound 2,4-dimethyl-6-(3-(n-butylamino)naphthalene-2-imide)phenol are as follows:

[0182] 1 H NMR (400 MHz, C 6 D 6 ): δ8.35(s,1H),7.39(d,1H,J=8.1Hz),7.36(d,2H,J=7.6Hz),7.24(dd,2H,J=7.7Hz),6.87(d,1H,J=7.6Hz),6.48(s,1H), 6.03(s,1H),3.39(s,2H),3.35(t,2H),2.36(s,3H),2.32(s,3H),1.47(m,2H),1.27(m,2H),0.89(t,3H,J=7.6Hz,8.3Hz).

[0183] Preparation Example 8

[0184] This preparation example provides a preparation method of the compound 2,4-di-tert-butyl-6-(3-(aniline)naphthalene-2-imide)phenol, the preparation method comprising the following steps:

[0185] Under nitrogen atmosphere, 3-((2-hydroxy-3,5-di-tert-butylphenyl)-amino)naphthalen-2-one (36.3 g, 100 mmol) and aniline (9.49 g, 102 mmol) as shown in Preparation Example 2 were mixed and added. Molecular sieves, formic acid (474 ​​mg, 10.3 mmol) was added, and refluxed in 500 mL toluene solvent for 16 h; the molecular sieves were removed by filtration, and toluene was removed under reduced pressure to obtain a crude product. After column chromatography purification, the column was treated with triethylamine, and the eluent was triethylamine, petroleum ether and ethyl acetate, wherein the volume ratio of petroleum ether to ethyl acetate was 5:1, and triethylamine was 3% of the sum of the added volumes of petroleum ether and ethyl acetate; the compound 2,4-di-tert-butyl-6-(3-(aniline)naphthalene-2-imine)phenol (30.4 g, yield 69.2%) was obtained.

[0186] The NMR characterization data of the compound 2,4-di-tert-butyl-6-(3-(aniline)naphthalene-2-imide)phenol are as follows:

[0187] 1 H NMR (400 MHz, C 6 D 6 ): δ8.35(s,1H),7.38(d,1H),7.33(d,2H),7.24(dd,2H),7.03(d,2H),6.87(d ,2H),6.73-6.69(m,3H),4.74(s,1H),3.39(s,2H),1.51(s,9H),1.33(s,9H).

[0188] Preparation Example 9

[0189] This preparation example provides a preparation method of the compound 2-(3-(n-butylamino)naphthalene-2-imide)phenol, which comprises the following steps:

[0190] Under nitrogen atmosphere, 3-((2-hydroxyphenyl)-amino)naphthalen-2-one (25.1 g, 100 mmol) prepared in Preparation Example 4 was mixed with n-butylamine (7.46 g, 102 mmol) and added. Molecular sieves, formic acid (474 ​​mg, 10.3 mmol) was added, and refluxed in 500 mL toluene solvent for 16 h; the molecular sieves were removed by filtration, and toluene was removed under reduced pressure to obtain a crude product. Purification by column chromatography, the column was treated with triethylamine, and the eluent was triethylamine, petroleum ether and ethyl acetate, wherein the volume ratio of petroleum ether to ethyl acetate was 2:1, and triethylamine was 5% of the sum of the added volumes of petroleum ether and ethyl acetate; the final product 2-(3-(n-butylamino)naphthalene-2-imide)phenol (24.5 g, yield 80.1%) was obtained.

[0191] The NMR characterization data of the compound 2-(3-(n-butylamino)naphthalene-2-imide)phenol are as follows:

[0192] 1 H NMR (400 MHz, C 6 D 6): δ9.85(s,1H),8.37(s,1H),7.39(d,1H,J=8.1Hz),7.36(d,2H,J=7.6Hz),7.21(dd,2H,J=7.7Hz),6.97(m,2H ), 6.81 (m, 1H), 6.48 (s, 1H), 3.39 (s, 2H), 3.35 (t, 2H), 1.47 (m, 2H), 1.27 (m, 2H), 0.89 (t, 3H, J = 7.6Hz, 8.3Hz).

[0193] Preparation Example 10

[0194] This preparation example provides a preparation method of the compound 2,4-diisopropyl-6-(3-(n-butylamino)naphthalene-2-imide)phenol, the preparation method comprising the following steps:

[0195] Under nitrogen atmosphere, the compound 3-((2-hydroxy-3,5-diisopropylphenyl)-amino)naphthalene-2-one (33.5 g, 100 mmol) shown in Preparation Example 5 was mixed with n-butylamine (7.46 g, 102 mmol) and added Molecular sieves, formic acid (474 ​​mg, 10.3 mmol) was added, and refluxed in 500 mL toluene solvent for 16 h; the molecular sieves were removed by filtration, and toluene was removed under reduced pressure to obtain a crude product. After column chromatography purification, the column was treated with triethylamine, and the eluent was triethylamine, petroleum ether and ethyl acetate, wherein the volume ratio of petroleum ether to ethyl acetate was 3:1, and triethylamine was 3% of the sum of the added volumes of petroleum ether and ethyl acetate; the final product 2,4-diisopropyl-6-(3-(n-butylamino)naphthalene-2-imide)phenol (28.9 g, yield 73.8%) was obtained.

[0196] The NMR characterization data of the compound 2,4-diisopropyl-6-(3-(n-butylamino)naphthalene-2-imide)phenol are as follows:

[0197] 1 H NMR (400 MHz, C 6 D 6 ): δ8.39(s,1H),7.34(d,2H),7.33(m,2H,),7.27(dd,2H),7.04(d,1H),4.21(s,1H),3.39(s,2H ),3.27(m,1H),3.08(m,1H),1.44(m,2H),1.38(m,2H),1.34(m,2H),1.27(t,3H),1.18(dd,12H).

[0198] The compounds 2,4-di(trimethylphenyl)-6-(3-(isopropylamine)naphthalene-2-imine)phenol, 2,4-dichloro-6-(3-(methylamine)naphthalene-2-imine)phenol, 2,4-dimethyl-6-(3-(trimethylaniline)naphthalene-2-imine)phenol, 2,4-dimethoxy-6-(3-(chloroamine)naphthalene-2-imine)phenol and 6-(3-(n-ethylamine)naphthalene-2-imine)phenol were synthesized according to the following synthetic route. The specific equivalents of each raw material and the reaction conditions were all referenced to the synthesis of the compound 2,4-di-tert-butyl-6-(3-(n-butylamine)naphthalene-2-imine)phenol.

[0199]

[0200] Among them, in the synthetic route of the compound 2,4-di(trimethylphenyl)-6-(3-(isopropylamino)naphthalene-2-imide)phenol, R 1 is isopropyl, R 2 is 2,4,6-trimethylphenyl; in the synthetic route of the compound 2,4-dichloro-6-(3-(methylamino)naphthalene-2-imide)phenol, R 1 is methyl, R 2 is chlorine; in the synthetic route of the compound 2,4-dimethyl-6-(3-(trimethylaniline)naphthalene-2-imide)phenol, R 1 is 2,4,6-trimethylphenyl, R 2 is methyl; in the synthetic route of 2,4-dimethoxy-6-(3-(chloroamine)naphthalene-2-imide)phenol, R 1 is chlorine, R 2 is methoxy, formula III is ammonium chloride; in the synthetic route of compound 6-(3-(n-ethylamine)naphthalene-2-imide)phenol, R 1 Ethyl, R 2 For hydrogen.

[0201] Example 1

[0202] This embodiment provides a metal compound L1TiMe containing a dihydronaphthalene structure 2 A method for preparing (2,4-di-tert-butyl-6-(3-(n-butylamino)naphthalene-2-imide)phenol)-dimethyltitanium, the method comprising the following steps:

[0203] Weigh titanium tetrachloride (0.378 g, 2 mmol), add 40 mL of dry toluene, slowly add 3 M methylmagnesium bromide solution (4 mL, 12 mmol) at -40 °C, and stir for 2 h. Add 2,4-di-tert-butyl-6-((3-(n-butylamino)naphthalene-2-imide))phenol (0.837 g, 2 mmol) in Preparation Example 6, stir for 2 h at -40 °C, and continue stirring for 5 h after returning to room temperature. Protect from light. Remove the solvent by vortexing, extract with n-hexane, and filter to obtain compound L1TiMe 2 (0.80 g, 81% yield).

[0204] The compound L1TiMe 2 The NMR characterization data are as follows:

[0205] 1 H NMR (400 MHz, C 6 D 6 ): δ7.37(d,1H),7.34(d,2H),7.26(dd,2H),6.87(d,1H),6.46(s,1H),3.39(s,2H,),3.1 1(t,2H),1.47(m,2H),1.41(s,9H),1.30(m,2H),1.27(s,9H),0.88(t,3H,),0.76(s,6H).

[0206] Example 2

[0207] This embodiment provides a metal compound L1ZrMe containing a dihydronaphthalene structure 2 A method for preparing (2,4-di-tert-butyl-6-((3-(n-butylamino)naphthalene-2-imine))phenol)-dimethylzirconium, the difference between the preparation method and Example 1 is that titanium tetrachloride (0.378 g, 2 mmol) is replaced by zirconium tetrachloride (0.466 g, 2 mmol), and other raw materials, contents and preparation methods are the same as those in Example 1, to obtain compound L1ZrMe 2 (0.96 g, 89% yield).

[0208] The compound L1ZrMe 2 The NMR characterization data are as follows:

[0209] 1 H NMR (400 MHz, C 6 D 6): δ7.37(d,1H),7.33(d,2H,7.26(dd,2H),6.87(d,1H),6.46(s,1H),3.39(s,2H ),3.16(t,2H),1.45(m,4H),1.41(s,9H),1.27(s,9H),0.88(t,3H),0.66(s,6H).

[0210] Example 3

[0211] This embodiment provides a metal compound L1HfMe containing a dihydronaphthalene structure 2 A method for preparing (2,4-di-tert-butyl-6-((3-(n-butylamine)naphthalene-2-imine))phenol)-dimethylhafnium, the difference between the preparation method and Example 1 is that titanium tetrachloride (0.378 g, 2 mmol) is replaced by hafnium tetrachloride (0.466 g, 2 mmol), and other raw materials, contents and preparation methods are the same as those in Example 1, to obtain compound L1HfMe 2 (1.06 g, 85% yield).

[0212] The compound L1HfMe 2 The NMR characterization data are as follows:

[0213] 1 H NMR (400 MHz, C 6 D 6 ): δ7.41(d,1H),7.33(d,2H),7.26(dd,2H),6.87(d,1H),6.46(s,1H),3.39(s,2H,),3.1 1(t,2H),1.45(m,2H,),1.41(s,9H),1.30(m,2H),1.27(s,9H),0.88(t,3H),0.66(s,6H).

[0214] Example 4

[0215] This embodiment provides a metal compound L2HfMe containing a dihydronaphthalene structure 2 A method for preparing (2,4-dimethyl-6-(3-(n-butylamine)naphthalene-2-imine)phenol)-dimethylhafnium, the difference between the preparation method and Example 3 is that the compound 2,4-di-tert-butyl-6-((3-(n-butylamine)naphthalene-2-imine))phenol (0.837 g, 2 mmol) shown in Preparation Example 6 is replaced by the compound 2,4-dimethyl-6-(3-(n-butylamine)naphthalene-2-imine)phenol (0.668 g, 2 mmol) shown in Preparation Example 7, and the other raw materials, contents and preparation methods are the same as those in Example 3 to obtain the compound L2HfMe 2(0.94 g, 87% yield).

[0216] The compound L2HfMe 2 The NMR characterization data are as follows:

[0217] 1 H NMR (400 MHz, C 6 D 6 ): δ7.39(d,1H,J=8.1Hz,),7.36(d,2H,J=7.6Hz),7.24(dd,2H,J=7.7Hz),6.85(d,1H,J=7.6Hz),6.48(s,1H),3.39( s,2H),3.35(t,2H),2.36(s,3H),2.15(s,3H),1.47(m,2H),1.27(m,2H),0.89(t,3H,J=7.6Hz,8.3Hz),0.77(s,6H).

[0218] Example 5

[0219] This embodiment provides a metal compound L3HfMe containing a dihydronaphthalene structure 2 A method for preparing (2,4-di-tert-butyl-6-(3-(aniline)naphthalene-2-imine)phenol)-dimethylhafnium, the difference between the preparation method and Example 3 is that the compound 2,4-di-tert-butyl-6-((3-(n-butylamine)naphthalene-2-imine))phenol (0.837 g, 2 mmol) shown in Preparation Example 6 is replaced by the compound 2,4-di-tert-butyl-6-(3-(aniline)naphthalene-2-imine)phenol (0.877 g, 2 mmol) shown in Preparation Example 8, and other raw materials, contents and preparation methods are the same as those in Example 3 to obtain compound L3HfMe 2 (1.08 g, 83.6% yield).

[0220] The compound L3HfMe 2 The NMR characterization data are as follows:

[0221] 1 H NMR (400 MHz, C 6 D 6 ): δ7.38(d,2H),7.33(d,3H),7.24(dd,2H),7.18(d,2H),6.73-6.69(m,3H),3.39(s,2H),1.41(s,9H),1.27(s,9H),0.78(s,6H).

[0222] Example 6

[0223] This embodiment provides a metal compound L5HfMe containing a dihydronaphthalene structure 2 A method for preparing (2,4-diisopropyl-6-(3-(n-butylamine)naphthalene-2-imine)phenol)-dimethylhafnium, the difference between the preparation method and Example 3 is that the compound 2,4-di-tert-butyl-6-((3-(n-butylamine)naphthalene-2-imine))phenol (0.837 g, 2 mmol) shown in Preparation Example 6 is replaced by the compound 2,4-diisopropyl-6-(3-(n-butylamine)naphthalene-2-imine)phenol (0.78 g, 2 mmol) shown in Preparation Example 10, and other raw materials, contents and preparation methods are the same as those in Example 3 to obtain compound L5HfMe 2 (0.907 g, 76% yield).

[0224] The compound shown is L5HfMe 2 The NMR characterization data are as follows:

[0225] 1 H NMR (400 MHz, C 6 D 6 ): δ7.39(d,1H),7.36(d,2H),7.24(dd,2H),6.85(d,1H),6.48(s,1H),3.39(s,2H),3.35( t,2H),2.15(s,2H),1.47(m,2H),1.33(dd,12H),1.27(m,2H,),0.89(t,3H),0.77(s,6H).

[0226] Example 7

[0227] This embodiment provides a metal compound L6TiMe containing a dihydronaphthalene structure 2 A method for preparing (2,4-di(trimethylphenyl)-6-(3-(isopropylamine)naphthalene-2-imine)phenol)-dimethyltitanium, wherein the method is different from that in Example 1 in that the compound 2,4-di-tert-butyl-6-((3-(n-butylamine)naphthalene-2-imine))phenol (0.837 g, 2 mmol) shown in Preparation Example 6 is replaced with the compound 2,4-di(trimethylphenyl)-6-(3-(isopropylamine)naphthalene-2-imine)phenol (1.2 g, 2 mmol), and the other raw materials, contents and preparation methods are the same as those in Example 1, to obtain the compound L6TiMe 2 (1 g, yield 83.5%).

[0228] The compound L6TiMe 2 The NMR characterization data are as follows:

[0229] 1 H NMR (400 MHz, C6 D 6 ): δ7.39(d,1H),7.36(d,2H),7.24(m,6H),6.85(d,1H),6.48(s,1H),3.47(m,1H) ,3.41(t,2H),3.39(s,6H),3.35(t,6H),3.15(s,6H),1.27(d,6H,),0.77(s,6H).

[0230] Example 8

[0231] This embodiment provides a metal compound L7TiBn containing a dihydronaphthalene structure. 2 A method for preparing (2,4-dichloro-6-(3-(methylamine)naphthalene-2-imine)phenol)-dibenzyltitanium, wherein the method is different from that in Example 1 in that 3M methylmagnesium bromide solution (4mL, 12mmol) is replaced with 1M benzylmagnesium bromide solution (12mL, 12mmol), the compound 2,4-di-tert-butyl-6-((3-(n-butylamine)naphthalene-2-imine))phenol (0.837g, 2mmol) shown in Preparation Example 6 is replaced with the compound 2,4-dichloro-6-(3-(methylamine)naphthalene-2-imine)phenol (0.66g, 2mmol), and the other raw materials, contents and preparation methods are the same as those in Example 1 to obtain compound L7TiBn 2 (0.91 g, 81.2% yield).

[0232] The compound L7TiBn 2 The NMR characterization data are as follows:

[0233] 1 H NMR (400 MHz, C 6 D 6 ): δ7.39(m,3H),7.36(d,3H),7.24(m,3H),6.85(d,4H),6.48(s,4H),3.41(t,2H),3.39(s,3H),2.83(s,4H).

[0234] Example 9

[0235] This embodiment provides a metal compound L8ZrCl containing a dihydronaphthalene structure 2 A method for preparing (2,4-dimethyl-6-(3-(trimethylaniline)naphthalene-2-imine)phenol)-zirconium dichloride, the method comprising the following steps:

[0236] Weigh zirconium tetrachloride (0.466 g, 2 mmol), add 40 mL of dry toluene, and continue to add compound 2,4-dimethyl-6-(3-(trimethylaniline)naphthalene-2-imide)phenol (0.792 g, 2 mmol) at -40°C, stir for 2 hours, and continue stirring for 5 hours after returning to room temperature. Protect from light. Remove the solvent by vortexing, extract with n-hexane, and filter to obtain compound L8ZrCl 2 (0.94 g, 84.4% yield).

[0237] The compound L8ZrCl 2 The NMR characterization data are as follows:

[0238] 1 H NMR (400 MHz, C 6 D 6 ): δ7.39(d,1H),7.36(d,2H),7.24(dd,2H),6.85(d,2H),6.48(s,2H),3.39(s,2H),2.35(s,3H),2.15(s,12H).

[0239] Example 10

[0240] This embodiment provides a metal compound L9ZrMe containing a dihydronaphthalene structure 2 A method for preparing (2,4-dimethoxy-6-(3-(chloroamine)naphthalene-2-imine)phenol)-dimethylzirconium, wherein the method is different from that in Example 2 in that the compound 2,4-di-tert-butyl-6-((3-(n-butylamine)naphthalene-2-imine))phenol (0.837 g, 2 mmol) shown in Preparation Example 6 is replaced with the compound 2,4-dimethoxy-6-(3-(chloroamine)naphthalene-2-imine)phenol (0.688 g, 2 mmol), and the other raw materials, contents and preparation method are the same as those in Example 2 to obtain the compound L9ZrMe 2 (0.8 g, 86.6% yield).

[0241] The compound L9ZrMe 2 The NMR characterization data are as follows:

[0242] 1 H NMR (400 MHz, C 6 D 6 ): δ7.39(d,1H),7.36(d,2H),7.24(dd,2H),6.85(d,1H),6.48(s,1H),3.89(s,6H),3.35(t,2H),0.77(s,6H).

[0243] Embodiment 11

[0244] This embodiment provides a metal compound L10Ti(N(CH 3 ) 2 ) 2 A method for preparing (6-(3-(n-ethylamine)naphthalene-2-imide)phenol)-bis(dimethylamino)titanium, the method comprising the following steps:

[0245] Weigh tetra(N,N-dimethylamino)titanium (0.44 g, 2 mmol), add 40 mL of dry toluene, and continue to add compound 6-(3-(n-ethylamino)naphthalene-2-imide)phenol (0.456 g, 2 mmol) at 80°C, and stir for 6 hours. Protect from light. Remove the solvent by vortexing, extract with n-hexane, and filter to obtain compound L10Ti(N(CH 3 ) 2 ) 2 (0.64 g, yield 77.2%). 3 ) 2 ) 2 The NMR characterization data are as follows:

[0246] 1 H NMR (400 MHz, C 6 D 6 ): δ7.39(m,1H),7.36(d,2H),7.24(m,2H),6.85(d,2H),6.48(s,2H),4.41(t,2H),3.39(m,2H),2.63(s,12H),1.32(t,3H).

[0247] Application Example 1

[0248] This application example provides a L1TiMe 2 The use of a catalyst composition in catalyzing the copolymerization of ethylene and 1-octene, wherein the catalyst composition comprises L1TiMe 2 , activators silica gel and MAO and co-catalyst triisobutylaluminum.

[0249] Preparation of the main catalyst: 955 type silica gel produced by Grace was selected and calcined in a muffle furnace at 200°C for 2h, and then calcined at 600°C for 4h. 6g of the calcined silica gel was weighed, 100mL of 10wt% MAO toluene solution was added, stirred at 55°C for 4h, filtered and dried to obtain MAO-silica gel. Then 2g L1TiMe 2 , dissolved in 20 mL of toluene, added with 6 g of MAO-silica gel, stirred at 55° C. for 6 h, filtered and dried to obtain the main catalyst.

[0250] The 2L polymerization reactor was dried continuously at 120 °C for 6 h, and then vacuumed and heated with N 2 The mixture was replaced with ethylene three times, cooled to room temperature, and replaced with ethylene three times. Add 533 mL of n-hexane, 347 mL / 250 g of 1-octene, and 1.5 mL of 0.5 M triisobutylaluminum ether solution; the temperature was 25 ° C, 3 mg of the above main catalyst was added, and the ethylene pressure was adjusted to 4 MPa and kept constant; the reaction was stirred vigorously for 30 minutes. After the reaction was completed, the mixture was cooled to room temperature and the pressure was released; the reaction solution was neutralized with an ethanol solution acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed with ethanol and water, and vacuum dried to constant weight, and 73.2 g of copolymer was obtained by weighing.

[0251] Application Example 2

[0252] This application example provides a L1ZrMe 2 The application of the catalyst composition in catalyzing the copolymerization of ethylene and 1-octene is different from the application example 1 only in that L1TiMe 2 Replaced by L1ZrMe 2 The other reaction conditions and polymerization process were the same as those in Application Example 1, and 127.4 g of polymer was obtained.

[0253] Application Example 3

[0254] This application example provides a L1HfMe 2 The application of the catalyst composition in catalyzing the copolymerization of ethylene and 1-octene is different from the application example 1 only in that L1TiMe 2 Replaced by L1HfMe 2 The other reaction conditions and polymerization process were the same as those in Application Example 1, and 141.3 g of polymer was obtained.

[0255] Application Example 4

[0256] This application example provides a L2HfMe 2 The application of the catalyst composition in catalyzing the copolymerization of ethylene and 1-octene is different from the application example 1 only in that L1TiMe 2 Replaced by L2HfMe 2 The other reaction conditions and polymerization process were the same as those in Application Example 1, and 219.2 g of polymer was obtained.

[0257] Application Example 5

[0258] This application example provides a L3HfMe 2 The application of the catalyst composition in catalyzing the copolymerization of ethylene and 1-octene is different from the application example 1 only in that L1TiMe 2Replaced by L3HfMe 2 The other reaction conditions and polymerization process were the same as those in Application Example 1, and 104.7 g of polymer was obtained.

[0259] Application Example 6

[0260] This application example provides a L5HfMe 2 The use of a catalyst composition in catalyzing ethylene homopolymerization, wherein the catalyst composition comprises L5HfMe 2 , activators silica gel and MAO and co-catalyst triisobutylaluminum.

[0261] Preparation of the main catalyst: 955 type silica gel produced by Grace was selected and calcined in a muffle furnace at 200°C for 2h, and then calcined at 600°C for 4h. 6g of the calcined silica gel was weighed, 100mL of 10wt% MAO toluene solution was added, stirred at 55°C for 4h, filtered and dried to obtain MAO-silica gel. Then 2g L5HfMe 2 , dissolved in 20 mL of toluene, added with 6 g of MAO-silica gel, stirred at 55° C. for 6 h, filtered and dried to obtain the main catalyst.

[0262] The 2L polymerization reactor was dried continuously at 120 °C for 6 h, and then vacuumed and heated with N 2 The mixture was replaced with gas three times, cooled to room temperature, and replaced with ethylene three times. Add 500 mL of n-hexane, add 1.5 mL of 0.5 M triisobutylaluminum ether solution; the temperature was 25 ° C, 3 mg of the main catalyst was added, and the ethylene pressure was adjusted to 4 MPa and kept constant; the reaction was stirred vigorously for 30 minutes. After the reaction was completed, the mixture was cooled to room temperature and the pressure was released; the reaction solution was neutralized with 5% hydrochloric acid acidified ethanol solution to obtain a polymer precipitate, washed with ethanol and water, and vacuum dried to constant weight, and 66.7 g of copolymer was obtained by weighing.

[0263] Application Example 7

[0264] This application example provides a L6TiMe 2 The application of the catalyst composition in catalyzing ethylene homopolymerization reaction is different from Application Example 6 only in that L5HfMe 2 Replaced by L6TiMe 2 The other reaction conditions and polymerization process were the same as those in Application Example 6, and 133.5 g of polymer was obtained.

[0265] Application Example 8

[0266] This application example provides a L7TiBn 2 The application of the catalyst composition in catalyzing ethylene homopolymerization reaction is different from Application Example 6 only in that L5HfMe2 Replaced by L7TiBn 2 The other reaction conditions and polymerization process were the same as those in Application Example 6, and 143.2 g of polymer was obtained.

[0267] Application Example 9

[0268] This application example provides a L8ZrCl 2 The use of a catalyst composition in catalyzing the copolymerization of 4-methyl-1-pentene and 1-hexene, wherein the catalyst composition comprises L8ZrCl 2 , activators silica gel and MAO and co-catalyst triisobutylaluminum.

[0269] Preparation of the main catalyst: 955 type silica gel produced by Grace was selected and calcined in a muffle furnace at 200°C for 2h, and then calcined at 600°C for 4h. 6g of the calcined silica gel was weighed, 100mL of 10wt% MAO toluene solution was added, stirred at 55°C for 4h, filtered and dried to obtain MAO-silica gel. Then 2g L8ZrCl 2 , dissolved in 20 mL of toluene, added with 6 g of MAO-silica gel, stirred at 55° C. for 6 h, filtered and dried to obtain the main catalyst.

[0270] The 2L polymerization reactor was dried continuously at 120 °C for 6 h, and then vacuumed and heated with N 2 The gas was replaced 3 times and cooled to room temperature. Add 500mL of n-hexane, 300mL / 198g of 4-methyl-1-pentene, 6mL of 1-hexene, and 1.5mL of 0.5M triisobutylaluminum ether solution; the temperature was 25°C, 3mg of the main catalyst was added, and it was kept constant; the reaction was stirred vigorously for 30min. After the reaction was completed, it was cooled to room temperature and the pressure was released; the reaction solution was neutralized with an ethanol solution acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed with ethanol and water, and vacuum dried to constant weight, and 73.1g of copolymer was weighed.

[0271] Application Example 10

[0272] This application example provides a L9ZrMe 2 The use of the catalyst composition in catalyzing the copolymerization of 4-methyl-1-pentene and 1-hexene is different from Application Example 9 only in that L8ZrCl 2 Replaced by L9ZrMe 2 The other reaction conditions and polymerization process were the same as those in Application Example 9, and 113.6 g of polymer was obtained.

[0273] Application Example 11

[0274] This application example provides a L10Ti(N(CH 3) 2 ) 2 The use of the catalyst composition in catalyzing the copolymerization of 4-methyl-1-pentene and 1-hexene is different from Application Example 9 only in that L8ZrCl 2 Replaced by L10Ti(N(CH 3 ) 2 ) 2 The other reaction conditions and polymerization process were the same as those in Application Example 9, and 128.2 g of polymer was obtained.

[0275] Comparative application example 1

[0276] This application example provides an application of a catalyst composition in catalyzing the copolymerization of ethylene and 1-octene. The difference between this application example and application example 1 is that L1TiMe 2 M1 (its synthesis reference patent CN1461756A, Example 2) was used as the replacement, and other reaction conditions and polymerization process were the same as those in Application Example 1, to obtain 1.4 g of polymer.

[0277]

[0278] Comparative Application Example 2

[0279] This application example provides an application of a catalyst composition in catalyzing the copolymerization of ethylene and 1-octene. The difference between this application example and application example 1 is that L1TiMe 2 It was replaced by M2 (its synthesis reference patent CN1472230A, Synthesis Example 13), and other reaction conditions and polymerization process were the same as those in Application Example 1, and 0.42 g of polymer was obtained.

[0280]

[0281] Comparative Application Example 3

[0282] This application example provides an application of a catalyst composition in catalyzing the copolymerization of ethylene and 1-octene. The difference between this application example and application example 1 is that the catalyst composition does not contain L1TiMe 2 , other reaction conditions and polymerization process were the same as those in Application Example 1, no polymer was obtained, and the reaction system was inactive.

[0283] The aggregation results of use case 1-11 and comparison application case 1-2 are tested. The test method is as follows:

[0284] Polymerization activity test: calculated according to the formula "polymerization activity = polymer mass / (catalyst mass)";

[0285] Polymer weight average molecular weight and molecular weight distribution test: obtained by PL-GPC220 test at 150°C, using three PLgel 10μm MIXED-B separation columns in series and 1,2,4-trichlorobenzene as solvent;

[0286] Melting point test: measured by conventional DSC (2000) method;

[0287] Comonomer insertion rate: According to reference (Liu W, Ray DG, Rinaldi P L. Resolution of Signals from Long-Chain Branching in Polyethylene by 13 C NMR at 188.6MHz[J].Macromolecules,1999,32(11).) was tested at high temperature and calculated; high temperature 13C NMR was obtained by Brucker DMX 300MHz test at 120℃ with 1,1,2,2-tetrachloroethane as solvent;

[0288] Extraction rate test: weigh 5g of polymer and place it on the top of the Soxhlet extractor, add n-hexane into the flask and reflux at 70℃;

[0289] Extraction rate = mass of extracted substance / total mass of substance*100%;

[0290] Bulk density test: Use the weighing method to test, weigh 10g (accurate to 0.1%) of the sample and place it in a 100mL measuring cylinder, level the sample powder without compacting it, and read the apparent volume V.

[0291]

[0292] The test results of application examples 1-5 and comparative application examples 1-2 are shown in Table 1:

[0293] Table 1

[0294]

[0295] The test results of application examples 6-8 are shown in Table 2:

[0296] Table 2

[0297]

[0298] The test results of application examples 9-11 are shown in Table 3:

[0299] Table 3

[0300]

[0301]

[0302] The test results show that:

[0303] It can be seen from Tables 1-3 above that the catalyst composition prepared from the metal compound containing a dihydronaphthalene structure provided by the present invention shows high activity in the copolymerization reaction of ethylene with α-olefins such as 1-hexene and 1-octene, and prepares copolymers with high molecular weight, high comonomer insertion rate and narrow molecular weight distribution, and the polymer has a high bulk density.

[0304] As shown in Table 1, when catalyzing the copolymerization of ethylene and 1-octene at 25°C, the activity can reach 73.1 kg / g (catalyst) and the weight average molecular weight can reach 1364×10 3 g / mol, molecular weight distribution is not higher than 2.3, the insertion rate of 1-octene can reach 61.8wt%, the bulk density can reach 0.71g / mL, and the extraction rate is only 0.02-0.07wt%; by comparing Application Example 1 with Comparative Application Example 1 and Comparative Application Example 2, it can be seen that the catalyst composition prepared by using the metal compound containing a dihydronaphthalene structure that is not specific to the present invention has poor catalytic activity in catalyzing olefin copolymerization reactions, the molecular weight of the prepared polymer is not high, and its molecular weight distribution is much higher than 2.3. At the same time, the polymer has a low bulk density and an extraction rate much higher than 0.07%, which cannot meet the actual production requirements for high activity, high insertion rate and narrow molecular weight distribution of the catalyst, and is also not conducive to the preparation of a polymer with high bulk density and low extraction.

[0305] From Table 2, it can be seen that when catalyzing ethylene homopolymerization at 25°C, the activity is as high as 95.5 kg / g (catalyst), and the weight average molecular weight can reach 1027×10 3 g / mol, the molecular weight distribution is not higher than 3, the bulk density can reach 0.89g / mL, and the extraction rate is only 0.03-0.05wt%.

[0306] It can be seen from Table 3 that when catalyzing the copolymerization of 4-methyl-1-pentene and 1-hexene at 25°C, the activity can reach 85.7 kg / g (catalyst) and the weight average molecular weight can reach 1247×10 3 g / mol, the molecular weight distribution is not higher than 2.5, the melting point of poly 4-methyl-1-pentene can reach 236°C, the bulk density can reach 0.83g / mL, and the extraction rate is only 0.02-0.06wt%.

[0307] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A metal compound containing a dihydronaphthalene structure, characterized in that: The metal compound containing a dihydronaphthalene structure has a structure shown in formula (I): wherein R1 is selected from hydrogen, halogen, substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl, substituted or unsubstituted C6-C 18 Aryl, substituted or unsubstituted C4-C 18 Heteroaryl; R2 is selected from hydrogen, halogen, substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C1-C 20 Cycloalkyl, substituted or unsubstituted C1-C 16 Alkoxy; X is selected from halogen, substituted or unsubstituted C1-C 20 Alkyl, -NR4R5; said R4 and R5 are the same or different, each independently selected from C 1-8 alkyl; M is selected from Group IVB metals; When the group contains heteroatoms, the heteroatoms are selected from one or a combination of at least two of O, S, N, P, and Si; The substituted groups are selected from halogen, C1-C8 alkyl, C1-C8 alkoxy, C6-C 10 Aryl, C6-C 10 Heteroaryl.

2. The metal compound containing a dihydronaphthalene structure according to claim 1, characterized in that: R1 is selected from hydrogen, halogen, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 14 Aryl, substituted or unsubstituted C4-C 12 heteroaryl; Preferably, R1 is selected from hydrogen, chlorine, methyl, ethyl, isopropyl, tert-butyl, phenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-tert-butylphenyl, 2,6-diisopropylphenyl or 2,4,6-trimethylphenyl; Preferably, R2 is selected from hydrogen, halogen, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C1-C8 alkoxy; Preferably, R2 is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl or methoxy; Preferably, X is selected from halogen, substituted or unsubstituted C1-C4 alkyl, -NR4R5, wherein R4 and R5 are the same or different and are independently selected from C 1-8 alkyl; Preferably, X is selected from chlorine, methyl, benzyl or dimethylamino; Preferably, M is selected from titanium, zirconium or hafnium.

3. The metal compound containing a dihydronaphthalene structure according to claim 1 or 2, characterized in that: The metal compound containing a dihydronaphthalene structure is selected from any one of the following compounds:

4. A method for preparing a metal compound containing a dihydronaphthalene structure as claimed in any one of claims 1 to 3, characterized in that: The preparation method comprises the following steps: (1) 1,4-dihydro-naphthalene-2,3-dione reacts with morpholine to obtain the intermediate 2-(4-morpholine)-1,4-dihydro-naphthalene-3-one; (2) mixing the intermediate 2-(4-morpholine)-1,4-dihydro-naphthalen-3-one described in step (1) with the compound represented by formula II, adding a catalyst, and reacting to obtain intermediate 2; (3) mixing the intermediate 2 described in step (2) with the compound represented by formula III, adding a desiccant and a catalyst, and reacting to obtain an intermediate 3; (4) mixing the compound represented by formula IV and the compound represented by formula V, and adding the intermediate 3 described in step (3) to carry out reaction a to obtain the metal compound containing a dihydronaphthalene structure; Alternatively, the compound represented by formula IV is directly added to the intermediate 3 described in step (3) to carry out reaction b to obtain the metal compound containing a dihydronaphthalene structure; Alternatively, the compound represented by formula VI is directly added to the intermediate 3 described in step (3) to carry out reaction c to obtain the metal compound containing a dihydronaphthalene structure; Preferably, the reaction in steps (1) to (4) is carried out in an anhydrous solvent, and the anhydrous solvent includes any one of benzene, toluene, xylene or n-hexane, or a combination of at least two thereof; Preferably, the molar ratio of 1,4-dihydro-naphthalene-2,3-dione to morpholine in step (1) is 1:(0.9-1); Preferably, the reaction in step (1) is carried out under reflux; Preferably, the reaction time in step (1) is 5 to 10 hours; Preferably, after the reaction in step (1) is completed, the anhydrous solvent is removed by vortexing under reduced pressure; Preferably, the molar ratio of the 2-(4-morpholine)-1,4-dihydro-naphthalen-3-one in step (2) to the compound represented by formula II is 1:(0.6-1.0); Preferably, the compound represented by formula II in step (2) is added in batches, more preferably in three batches; Preferably, the mixing in step (2) is carried out under stirring; Preferably, the molar ratio of the 2-(4-morpholine)-1,4-dihydro-naphthalene-3-one to the catalyst in step (2) is 1:(0.0058-0.029); Preferably, the catalyst in step (2) comprises p-toluenesulfonic acid; Preferably, the reaction in step (2) is carried out under reflux; Preferably, the reaction time in step (2) is 10 to 18 hours; Preferably, after the reaction in step (2) is completed, the reaction solution is cooled to room temperature, filtered, the anhydrous solvent is removed by vortexing under reduced pressure, and intermediate 2 is obtained by column chromatography; Preferably, the eluent in the column chromatography is petroleum ether and ethyl acetate, and the volume ratio thereof is (1-20):1; Preferably, the molar ratio of the intermediate 2 in step (3) to the compound represented by formula III is 1:(1-5); Preferably, the mixing in step (3) is carried out under stirring; Preferably, the desiccant in step (3) comprises a molecular sieve; Preferably, the catalyst in step (3) comprises formic acid; Preferably, the molar ratio of the intermediate 2 to the catalyst in step (3) is 1:(0.1-0.5); Preferably, the reaction in step (3) is carried out under reflux; Preferably, the reaction time in step (3) is 10 to 18 hours; Preferably, after the reaction in step (3) is completed, the reaction solution is filtered to remove the desiccant, the anhydrous solvent is removed by vortexing under reduced pressure, and the intermediate 3 is obtained by column chromatography; Preferably, the column used for column chromatography is treated with triethylamine; Preferably, the eluent used in the column chromatography comprises petroleum ether and ethyl acetate in a volume ratio of (1:50) to (100:1); Preferably, the eluent further comprises triethylamine; Preferably, the added volume of the triethylamine is 1 to 5% of the sum of the added volumes of the petroleum ether and ethyl acetate; Preferably, the compound represented by Formula IV in step (4) is dissolved in an anhydrous solvent before being mixed and stirred with the compound represented by Formula V; Preferably, when the amount of the compound represented by formula IV added in step (4) is 1 mmol, the volume of the anhydrous solvent added is 15 to 50 mL; Preferably, the molar ratio of formula IV, formula V and intermediate 3 in the reaction a of step (4) is 1:(4-6):1; Preferably, the mixing and stirring in step (4) is carried out at low temperature; Preferably, the low temperature is -45°C to 10°C; Preferably, the stirring time in step (4) is 1.5 to 2.5 hours; Preferably, the reaction a in step (4) is first stirred at -45°C to 10°C for 1.5 to 2.5 hours, then heated to room temperature and stirred for 4 to 6 hours; Preferably, the molar ratio of formula IV to intermediate 3 in reaction b of step (4) is 1:(1-2); Preferably, the reaction b in step (4) is first stirred at -45°C to 10°C for 1.5 to 2.5 hours, then heated to room temperature and stirred for 4 to 6 hours; Preferably, the molar ratio of Formula VI to Intermediate 3 in the reaction c of step (4) is 1:(1-2); Preferably, the reaction c in step (4) is stirred at 50°C to 100°C for 4 to 10 hours; Preferably, after the reaction a, b or c in step (4) is completed, the anhydrous solvent is removed under reduced pressure, and extraction is performed with a good solvent to obtain the metal compound containing a dihydronaphthalene structure; Preferably, the reactions in steps (1), (3) and (4) are all carried out under a protective gas atmosphere, wherein the protective gas comprises any one of nitrogen, argon and helium, or a combination of at least two of them.

5. The method for preparing a metal compound containing a dihydronaphthalene structure according to claim 4, characterized in that: The good solvent in step (4) includes any one of n-hexane, n-pentane, n-heptane, cyclohexane, methylcyclohexane or toluene, or a combination of at least two thereof.

6. A catalyst composition for polymerizing olefins, characterized in that: The catalyst composition comprises the metal compound containing a dihydronaphthalene structure according to any one of claims 1 to 3, a co-catalyst and an activator; Preferably, the molar ratio of the co-catalyst to the metal compound containing a dihydronaphthalene structure according to any one of claims 1 to 3 is (0.001 to 100,000):1, preferably (0.2 to 500):

1.

7. The catalyst composition according to claim 6, characterized in that The co-catalyst comprises an organometallic compound and / or an organoboron compound; Preferably, the organometallic compound and / or organoboron compound comprises M 3 (X 10 ) n1 (X 11 ) 3-n1 、M 4 (X 10 ) n2 (X 11 ) 2-n2 or M 5 X 10 Any of the following: Among them, M 3 is boron or aluminum, n1 is 1-3; M 4 is magnesium or zinc, n2 is 1-2; M 5 For Li; X 10 Selected from hydrogen, C1-C 20 Hydrocarbon; X 11 Selected from hydrogen, halogen, C1-C 20 Hydrocarbon or C1-C 20 Alkyloxy; Preferably, the M 3 (X 10 ) n1 (X 11 ) 3-n1 Including any one of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide or diethylaluminum chloride, or a combination of at least two thereof; Preferably, the M 4 (X 10 ) n2 (X 11 ) 2-n2 The invention comprises any one of dimethyl zinc, diethyl zinc, dipropyl zinc, dibutyl zinc or dineopentyl zinc or a combination of at least two thereof.

8. The catalyst composition according to claim 6 or 7, characterized in that The activator comprises any one or a combination of at least two of an organic boron compound, an organic borate compound, an ionized ionic compound, an aluminoxane compound or a solid oxide; Preferably, the solid oxide comprises any one of silica, alumina, titania, zirconia, magnesia, boria, calcium oxide, zinc oxide, silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, silica-magnesia, silica-boria, alumina-titania, titania-zirconia, alumina-zirconia, alumina-boria, zinc aluminate, aluminum phosphate, aluminum phosphate, aluminum phosphate-silica, magnesium aluminate, boehmite or heteropolytungstate, or a combination of at least two thereof.

9. The catalyst composition according to claim 8, characterized in that The solid oxide has a particle size of 20-100 μm and a specific surface area of ​​170-570 m 2 / g, pore volume 0.36-2.6mL / g, pore diameter 6-54nm, density 0.3g / cm 3 ; Preferably, the solid oxide needs to be calcined; Preferably, the roasting and calcining includes low-temperature roasting and high-temperature roasting; Preferably, the temperature of the low-temperature calcination is 200-500°C, preferably 200-300°C; Preferably, the low-temperature calcination time is 1 to 10 hours, preferably 2 to 5 hours; Preferably, the high temperature calcination temperature is 600-900°C; Preferably, the high temperature calcination time is 4 to 40 hours, preferably 4 to 10 hours.

10. Use of the metal compound containing a dihydronaphthalene structure according to any one of claims 1 to 3 or the catalyst composition according to any one of claims 6 to 9 in olefin polymerization; Preferably, the olefin monomer includes any one of ethylene, propylene, butene, pentene, hexene, heptene, octene, styrene or 4-methyl-1-pentene, or a combination of at least two thereof.

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