Method for preparing supported olefin polymerization catalyst, obtained catalyst and its application

Abstract

A method for preparing a supported olefin polymerization catalyst, comprising: Step 1, under an inert atmosphere or vacuum protection, activating COF at 0 °C to 800 °C for 0.1 to 48 hours; Optionally, Step 2, under an inert atmosphere or vacuum protection, reacting the activated COF with an auxiliary agent in a reaction medium at 5 °C to 120 °C, performing solid-liquid separation to obtain a solid phase, wherein the auxiliary agent is selected from metal alkyl compounds, boron fluorides, alkylaluminum oxides, modified methylaluminoxanes, Lewis acids, and Grignard reagents; and Step 3, under an inert atmosphere or vacuum protection, reacting the solid phase with an olefin polymerization catalyst in a reaction medium at -30 °C to 150 °C, performing solid-liquid separation, and collecting the solid phase as the supported olefin polymerization catalyst. A supported olefin polymerization catalyst and its application. The supported catalyst can maintain a high catalytic activity for a long time in olefin polymerization.

Description

Technical Field

[0001] The present invention belongs to the field of olefin polymerization, and particularly relates to a method for preparing a supported olefin polymerization catalyst, and also relates to the obtained catalyst and its application in olefin polymerization. Background Art

[0002] Polyolefins are one of the most important synthetic materials, and the output of polyolefins accounts for 60% of the total output of synthetic resins. Therefore, the development of the polyolefin industry directly affects the national economy. The development of catalysts has promoted the progress of the polyolefin industry. The discovery of Ziegler-Natta catalysts in the 1950s and the discovery of Sinn-Kaminsky metallocene catalysts in the 1980s have opened a new era for the development of the polyolefin industry. Subsequently, various high-performance post-metallocene catalysts discovered have further enriched the types of catalysts and improved the performance of polyolefin products.

[0003] Olefin polymerization catalysts include homogeneous catalysts and heterogeneous catalysts. Among them, homogeneous catalysts can effectively regulate the structure of polymer chains, and heterogeneous catalysts make the product morphology easy to control, the apparent density of the product higher, the reaction product not easy to stick to the kettle, and are suitable for most polymerization devices. In order to make homogeneous catalysts have the advantages of heterogeneous catalysts at the same time, it is necessary to heterogenize homogeneous catalysts. The common method is to anchor homogeneous catalysts on carriers. Currently, the disclosed carriers are generally inorganic materials such as silica, magnesium chloride, and alumina. There are a few studies on loading olefin polymerization catalysts on porous materials such as molecular sieves. For example, metallocene catalysts, Ziegler-Natta catalysts, post-metallocene catalysts, etc. are loaded on silica carriers, and for another example, metallocene catalysts are loaded on molecular sieves. Loading catalysts on inorganic materials generally leads to a decrease in catalytic activity, a rapid decrease in activity at high temperatures, and a decrease in selectivity. Therefore, there is an urgent need for a supported olefin polymerization catalyst that combines the advantages of homogeneous catalysts and heterogeneous catalysts, has high catalytic activity, and high selectivity.

[0004] Covalent organic frameworks (COF) have the advantages of highly ordered pore structures, adjustable pore sizes, large specific surface areas, high thermal stabilities, diverse synthesis methods, and easy functionalization modification, and are a class of emerging materials. Summary of the Invention

[0005] One object of the present invention is to provide a method for preparing a supported olefin polymerization catalyst, and the prepared supported catalyst can maintain high catalytic activity for a long time to catalyze the homopolymerization reaction or copolymerization reaction of olefins. Another object of the present invention is to provide a supported olefin polymerization catalyst. Another object of the present invention is to provide the application of the supported catalyst in olefin polymerization.

[0006] To achieve the above object, the first aspect of the present invention relates to a method for preparing a supported olefin polymerization catalyst, which is Method 1 or Method 2, wherein,

[0007] Method 1 includes the following steps:

[0008] (1) Under the protection of an inert atmosphere or vacuum, activate the COF at 0 °C to 800 °C (preferably 40 °C to 800 °C or 50 °C to 500 °C or 100 °C to 400 °C, such as 50 °C, 80 °C, 100 °C, 120 °C, 150 °C, 180 °C, 200 °C, 230 °C, 250 °C, 280 °C, 300 °C, 350 °C, 370 °C, 400 °C, 450 °C, 500 °C, 600 °C, 700 °C, 750 °C) for 0.1 to 48 hours (preferably 2 to 50 hours or 3 to 48 hours, such as 1 hour, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 10 hours, 12 hours, 15 hours, 20 hours, 24 hours, 28 hours, 30 hours, 35 hours, 40 hours, 43 hours, 45 hours, 48 hours);

[0009] (2) Under the protection of an inert atmosphere or vacuum, react the activated COF with the olefin polymerization catalyst at -30 °C to 150 °C (preferably -30 °C to 100 °C or -20 °C to 90 °C, such as -20 °C, -10 °C, 0 °C, 2 °C, 5 °C, 10 °C, 20 °C, 25 °C, 30 °C, 35 °C, 40 °C, 45 °C, 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 100 °C, 105 °C, 120 °C, 130 °C, 140 °C) in a reaction medium, perform solid-liquid separation, collect the solid phase, and optionally wash and dry the solid phase in sequence to obtain the supported olefin polymerization catalyst;

[0010] Method 2 includes the following steps:

[0011] 1) Under the protection of an inert atmosphere or vacuum, activate the COF at 0 °C to 800 °C (preferably 40 °C to 800 °C or 50 °C to 500 °C or 100 °C to 400 °C, such as 50 °C, 80 °C, 100 °C, 120 °C, 150 °C, 180 °C, 200 °C, 230 °C, 250 °C, 280 °C, 300 °C, 350 °C, 370 °C, 400 °C, 450 °C, 500 °C, 600 °C, 700 °C, 750 °C) for 0.1 to 48 hours (preferably 2 to 50 hours or 3 to 48 hours, such as 1 hour, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 10 hours, 12 hours, 15 hours, 20 hours, 24 hours, 28 hours, 30 hours, 35 hours, 40 hours, 43 hours, 45 hours, 48 hours);

[0012] 2) Under an inert atmosphere or vacuum protection, react the activated COF with an auxiliary agent at 5°C to 120°C (preferably 10°C to 100°C or 15°C to 90°C, such as 10°C, 15°C, 20°C, 25°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C) in a reaction medium, perform solid-liquid separation, and collect the solid phase; wherein, the auxiliary agent is selected from metal alkyl compounds (preferably metal trialkyl compounds, more preferably metal tri-C 1-6 alkyl compounds), borofluoroalkanes [such as tris(pentafluorophenyl)boron], alkylaluminum oxides (preferably C 1-6 alkylaluminum oxides, more preferably methylaluminoxane), modified methylaluminoxane, Lewis acids, and Grignard reagents; Optionally, wash the solid phase and dry it to obtain a dried product;

[0013] 3) Under an inert atmosphere or vacuum protection, react the solid phase or the optionally obtained dried product with an olefin polymerization catalyst at -30°C to 150°C (preferably -30°C to 100°C or -20°C to 90°C, such as -20°C, -10°C, 0°C, 2°C, 5°C, 10°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 100°C, 105°C, 120°C, 130°C, 140°C) in a reaction medium, perform solid-liquid separation, collect the solid phase, and optionally wash and dry the solid phase in sequence to obtain a supported olefin polymerization catalyst.

[0014] In some embodiments of the first aspect of the present invention, in step 2), the auxiliary agent is selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, trimethylaluminum, triethylaluminum, tris(pentafluorophenyl)borane, and triisobutylaluminum.

[0015] In some embodiments of the first aspect of the present invention, in step 2), the auxiliary agent is selected from methylaluminoxane, ethylaluminoxane, trimethylaluminum, triethylaluminum, and triisobutylaluminum.

[0016] In some embodiments of the first aspect of the present invention, in step 2), the weight ratio of the activated COF to the auxiliary agent is (0.05 to 30):1, preferably (0.05 to 25):1 or (0.1 to 20):1, such as 0.1:1, 0.2:1, 0.4:1, 0.5:1, 0.7:1, 1:1, 2:1, 3:1, 4:1, 5:1, 7:1, 10:1, 15:1, 20:1, 25:1.

[0017] In some embodiments of the first aspect of the present invention, in step 2), the ratio of the activated COF to the reaction medium is 1:(100 - 1000) g / mL, preferably 1:(300 - 700) g / mL, such as 1:200 g / mL, 1:300 g / mL, 1:500 g / mL, 1:700 g / mL, 1:800 g / mL.

[0018] In some embodiments of the first aspect of the present invention, in step (2), the weight ratio of the activated COF to the olefin polymerization catalyst is (0.05 - 120):1, or in step 3), the weight ratio of the solid phase or the optionally obtained dried product to the olefin polymerization catalyst is (0.05 - 120):1, preferably (0.1 - 100):1, such as 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 4:1, 5:1, 10:1, 12.5:1, 20:1, 30:1, 100:3, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, 110:1, 120:1.

[0019] In some embodiments of the first aspect of the present invention, in step (2) and / or step 3), the ratio of the olefin polymerization catalyst to the reaction medium is (0.001 - 1000):1 mg / mL, preferably (0.009 - 10):1 mg / mL, such as 0.005:1 mg / mL, 0.01:1 mg / mL, 0.02:1 mg / mL, 0.03:1 mg / mL, 0.04:1 mg / mL, 0.05:1 mg / mL, 0.06:1 mg / mL, 0.08:1 mg / mL, 0.09:1 mg / mL, 0.1:1 mg / mL, 0.2:1 mg / mL, 0.3:1 mg / mL, 1:3 mg / mL, 0.4:1 mg / mL, 0.6:1 mg / mL, 1:1 mg / mL, 1.5:1 mg / mL, 2:1 mg / mL, 3:1 mg / mL, 4:1 mg / mL, 5:1 mg / mL, 6:1 mg / mL, 8:1 mg / mL, 20:1 mg / mL, 50:1 mg / mL, 100:1 mg / mL, 140:1 mg / mL, 200:1 mg / mL, 400:1 mg / mL, 500:1 mg / mL.

[0020] In some embodiments of the first aspect of the present invention, in step (1) and / or step 1), the COF is selected from imine-based COFs (such as COF-LZU1, COF300, COF303), imide-based COFs, borate-based COFs (such as COF5), sp 2Imine-based COFs, hydrazone-based COFs, boroxine-based COFs (such as COF1), borazine-based COFs, triazine-based COFs (such as CTF1), and phenazine-based COFs.

[0021] In some embodiments of the first aspect of the present invention, in step (1) and / or step 1), the COF is selected from COF1, COF300, COF303, CTF1, COF5, and COF-LZU1, more preferably selected from COF1, COF300, COF303, and COF5.

[0022] Without being bound by theory, in step 2), the role of the reaction between the activated COF and the auxiliary agent is to remove impurities in the activated COF, which helps to load the olefin polymerization catalyst subsequently.

[0023] In the present invention, imine-based COFs, acylimide-based COFs, borate ester-based COFs, sp 2 -based COFs, hydrazone-based COFs, boroxine-based COFs, borazine-based COFs, triazine-based COFs, and phenazine-based COFs respectively refer to covalent organic framework materials bonded by imine, acylimide, borate ester, sp 2 , hydrazone, boroxine, borazine, triazine, phenazine and other structures. Among them, the bonding modes of imine-based COFs, acylimide-based COFs, borate ester-based COFs, sp 2 -based COFs, hydrazone-based COFs, boroxine-based COFs, borazine-based COFs, triazine-based COFs, and phenazine-based COFs include but are not limited to the following several:

[0024]

[0025] In the present invention, the structures of COF1, COF300, COF303, CTF1, COF5, and COF-LZU1 are shown as follows:

[0026]

[0027] In the present invention, COF1, COF300, COF303, CTF1, COF5, and COF-LZU1 are prepared by conventional methods.

[0028] In some embodiments of the first aspect of the present invention, COF1 is prepared by the following steps:

[0029] Mix the mixed solution of 1,4-benzenediboronic acid and mesitylene-dioxane, and react at 100 °C to 150 °C for 50 to 90 hours to obtain COF1;

[0030] Preferably, the volume ratio of 1,4-benzenediboronic acid to the mixed solution is 1:(10 - 20);

[0031] Preferably, the volume ratio of mesitylene to dioxane in the mixed solution is 1:1.

[0032] In some embodiments of the first aspect of the present invention, COF5 is prepared by the following steps:

[0033] Mix 2,3,6,7,10,11 - hexahydroxytriphenylene, 1,4 - phenylenediboronic acid, and the mesitylene - dioxane mixed solution, and react at 100 °C to 150 °C for 50 to 90 hours to obtain COF5;

[0034] Preferably, the weight ratio of 2,3,6,7,10,11 - hexahydroxytriphenylene to 1,4 - phenylenediboronic acid is (1 - 3):1;

[0035] Preferably, the volume ratio of mesitylene to dioxane in the mixed solution is 1:1;

[0036] Preferably, the ratio of 1,4 - phenylenediboronic acid to the mixed solution is 0.001 - 0.01 g / ml.

[0037] In some embodiments of the first aspect of the present invention, COF300 is prepared by the following steps:

[0038] Mix tetrakis(4 - aminophenyl)methane, 1,4 - phthalaldehyde, and the acetic acid - dioxane mixed solution, and react at 100 °C to 150 °C for 50 to 90 hours to obtain COF300;

[0039] Preferably, the weight ratio of tetrakis(4 - aminophenyl)methane to 1,4 - phthalaldehyde is (0.1 - 1):1;

[0040] Preferably, the volume ratio of acetic acid to dioxane in the mixed solution is (1 - 3):1;

[0041] Preferably, the ratio of tetrakis(4 - aminophenyl)methane to the mixed solution is 0.005 - 0.02 g / ml.

[0042] In some embodiments of the first aspect of the present invention, COF303 is prepared by the following steps:

[0043] Mix tetrakis(4 - formylphenyl)methane, 1,4 - phenylenediamine, and the mesitylene - dioxane mixed solution, and react at room temperature for 100 to 150 hours to obtain COF303;

[0044] Preferably, the weight ratio of tetrakis(4 - formylphenyl)methane to 1,4 - phenylenediamine is 1:(1 - 3);

[0045] Preferably, the volume ratio of mesitylene to dioxane in the mixed solution is (1 - 3):1;

[0046] Preferably, the ratio of tetrakis(4-formylphenyl)methane to the mixed solution is 0.005 - 0.02 g / ml.

[0047] In some embodiments of the first aspect of the present invention, the olefin polymerization catalyst is selected from Ziegler-Natta catalysts, metallocene catalysts, and post-metallocene catalysts.

[0048] In some embodiments of the first aspect of the present invention, the Ziegler-Natta catalysts are selected from (including but not limited to) titanium tetrachloride, titanium trichloride, zirconium trichloride, and vanadium trichloride.

[0049] In some embodiments of the first aspect of the present invention, the metallocene catalysts are selected from (including but not limited to) zirconocene dichloride, bis(cyclopentadienyl)dimethylhafnium, bis(indenyl)dimethylzirconium, rac-ethylenebis(indenyl)zirconium dichloride, dimethylsilylene-bis(indenyl), diphenylmethylene-cyclopentadienyl-fluorenyl zirconium dichloride, dimethylsilylene-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium, bis(indenyl)zirconium dichloride, bis[2-(3',5'-di-tert-butylphenyl)-indenyl]zirconium dichloride, bis(2-methyl-4,5-phenyl-indenyl)zirconium dichloride, bis(cyclopentadienyl)-bis(phenoxy)zirconium, dimethylsilylene-bis(indenyl)zirconium dichloride, diphenylmethylene-cyclopentadienyl-fluorenyl zirconium dichloride, diphenylmethylene-cyclopentadienyl-(2-dimethylamino-fluorenyl)zirconium dichloride, dimethylsilylene-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium, dimethylsilylene-3-pyrrolylindenyl-tert-butylamino-dimethyltitanium, rac-dimethylsilylene-bis(2-methylindenyl)zirconium dichloride, and dimethylsilylene-fluorenyl-tert-butylamino-dimethyltitanium.

[0050] In some embodiments of the first aspect of the present invention, the post-metallocene catalysts are selected from (including but not limited to) imine-amine type catalysts, ketimine type catalysts, amidine type catalysts, diimine palladium nickel type catalysts, and phenoxyimine type catalysts.

[0051] In some embodiments of the first aspect of the present invention, the imine-amine type catalysts are selected from (including but not limited to) compounds 26, 27, 28, 29a, 29b, 30a, 30b, 31a, 31b, 32, 33a, 33b shown in the following structural formulas:

[0052]

[0053] In some embodiments of the first aspect of the present invention, the ketimine type catalysts are selected from (including but not limited to) compound 40 shown in the following structural formula:

[0054]

[0055] In some embodiments of the first aspect of the present invention, the amidine-based catalyst is selected from (including but not limited to) Compound 41 and Compound 42 represented by the following structural formulas:

[0056]

[0057] In some embodiments of the first aspect of the present invention, the diimine palladium nickel-based catalyst is selected from (including but not limited to) Compound 43 and Compound 44 represented by the following structural formulas:

[0058]

[0059] In some embodiments of the first aspect of the present invention, the phenoxyimine-based catalyst is selected from (including but not limited to) Compounds 45 - 48 represented by the following structural formulas:

[0060]

[0061] In some embodiments of the first aspect of the present invention, in step (2) and / or step (3), the olefin polymerization catalyst is selected from titanium tetrachloride, titanium trichloride, zirconium trichloride, vanadium trichloride, dichlorodicyclopentadienyl zirconium, bis(cyclopentadienyl)dimethyl hafnium, bis(indenyl)dimethyl zirconium, rac-ethylenebis(indenyl)zirconium dichloride, dimethylsilylene-bis(indenyl), diphenylmethylenecyclopentadienylfluorenyl zirconium dichloride, dimethylsilylene-tetramethylcyclopentadienyl-tert-butylamino-dimethyl titanium, bis(indenyl)zirconium dichloride, bis[2-(3',5'-di-tert-butylphenyl)-indenyl]zirconium dichloride, bis(2-methyl-4,5-phenyl-indenyl)zirconium dichloride, dicyclopentadienyl-bis(phenoxy)zirconium, dimethylsilylene bis(indenyl)zirconium dichloride, diphenylmethylenecyclopentadienylfluorenyl zirconium dichloride, diphenylmethylenecyclopentadienyl-(2-dimethylamino-fluorenyl)zirconium dichloride, dimethylsilylene-tetramethylcyclopentadienyl-tert-butylamino-dimethyl titanium, dimethylsilylene-3-pyrrolylindenyl-tert-butylamino-dimethyl titanium, rac-dimethylsilylene-bis(2-methylindenyl)zirconium dichloride, and dimethylsilylene-fluorenyl-tert-butylamino-dimethyl titanium, imine-amine type catalysts, ketoimine type catalysts, amidine-based catalysts, diimine palladium nickel-based catalysts, and phenoxyimine-based catalysts.

[0062] In some embodiments of the first aspect of the present invention, in step (2) and / or step (3), the olefin polymerization catalyst is selected from titanium tetrachloride, titanium trichloride, zirconium trichloride, vanadium trichloride, dichlorobis(cyclopentadienyl)zirconium, bis(cyclopentadienyl)dimethylhafnium, bis(indenyl)dimethylzirconium, rac-ethylenebis(indenyl)zirconium dichloride, dimethylsilyl-bis(indenyl), diphenylmethylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamido)dimethyltitanium, bis(indenyl)zirconium dichloride, bis[2-(3',5'-di-tert-butylphenyl)-indenyl]zirconium dichloride, bis(2-methyl-4,5-phenyl-indenyl)zirconium dichloride, bis(cyclopentadienyl)bis(phenoxy)zirconium, dimethylsilylbis(indenyl)zirconium dichloride, diphenylmethylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, diphenylmethylidene(cyclopentadienyl)(2-dimethylamino-fluorenyl)zirconium dichloride, dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamido)dimethyltitanium, dimethylsilyl(3-pyrrolylindenyl)(tert-butylamido)dimethyltitanium, rac-dimethylsilyl-bis(2-methylindenyl)zirconium dichloride, dimethylsilyl(fluorenyl)(tert-butylamido)dimethyltitanium, compound 26, compound 27, compound 28, compound 29a, compound 29b, compound 30a, compound 30b, compound 31a, compound 31b, compound 32, compound 33a, compound 33b, and compounds 40-48; wherein the structures of compound 26, compound 27, compound 28, compound 29a, compound 29b, compound 30a, compound 30b, compound 31a, compound 31b, compound 32, compound 33a, compound 33b, and compounds 40-48 are as shown in the previous structural formulas.

[0063] In some embodiments of the first aspect of the present invention, in step (2) and / or step (3), the olefin polymerization catalyst is selected from titanium tetrachloride, titanium trichloride, dichlorobis(cyclopentadienyl)zirconium, silyl(N-tert-butylamido)(tetramethylcyclopentadienyl)titanium dichloride, phenoxyimine zirconium, rac-dimethylsilyl-bis(2-methylindenyl)zirconium dichloride, dimethylsilyl(fluorenyl)(tert-butylamido)dimethyltitanium, rac-ethylenebis(indenyl)zirconium dichloride, diimine palladium, phenoxyimine titanium, and diimine nickel.

[0064] In some embodiments of the first aspect of the present invention, in step (2) and / or step (3), the olefin polymerization catalyst is selected from titanium tetrachloride, titanium trichloride, dichlorobis(cyclopentadienyl)zirconium, silyl(N-tert-butylamido)(tetramethylcyclopentadienyl)titanium dichloride, phenoxyimine zirconium, diimine palladium, phenoxyimine titanium, and diimine nickel.

[0065] In some embodiments of the first aspect of the present invention, the reaction medium in step (2) and in steps (2)-(3) is a non-polar organic solvent.

[0066] In some embodiments of the first aspect of the present invention, the reaction media in step (2) and steps 2)-3) are independently selected from one or more mixtures of aliphatic compounds containing 5-12 carbon atoms, cycloaliphatic compounds containing 6-12 carbon atoms, aromatic compounds containing 6-12 carbon atoms and their halogenated derivatives, and ether compounds containing 4-12 carbon atoms.

[0067] In some embodiments of the first aspect of the present invention, the reaction media in step (2) and steps 2)-3) are independently selected from one or more mixtures of n-hexane, n-heptane, n-octane, n-dodecane, cyclohexane, toluene, xylene, mesitylene, chlorobenzene, 1,2,4-trichlorobenzene, and diethyl ether. Preferably, the reaction media in steps (1-2) and (2) are independently selected from one or more mixtures of chlorobenzene, n-hexane, cyclohexane, n-heptane, and isooctane.

[0068] In some embodiments of the first aspect of the present invention, the reaction medium in step 2) is selected from chlorobenzene, n-hexane, and isooctane.

[0069] In some embodiments of the first aspect of the present invention, the reaction media in step (2) and / or step 3) are selected from chlorobenzene, n-hexane, cyclohexane, and n-heptane.

[0070] In some embodiments of the first aspect of the present invention, the inert atmospheres in step (2) and steps 2)-3) are independently selected from nitrogen, argon, and helium, and preferably nitrogen.

[0071] In some embodiments of the first aspect of the present invention, the inert atmospheres in step (1) and steps 1) are independently selected from nitrogen, argon, helium, and supercritical carbon dioxide, and preferably nitrogen.

[0072] In some embodiments of the first aspect of the present invention, it is characterized by one or more of the following 1) to 8):

[0073] 1) In step 2), the reaction time is 0.5 to 90 hours, preferably 2 to 80 hours or 4 to 72 hours, for example, 1 hour, 4 hours, 10 hours, 12 hours, 20 hours, 25 hours, 30 hours, 35 hours, 40 hours, 48 hours, 50 hours, 55 hours, 60 hours, 65 hours, 70 hours, 72 hours, 80 hours, 90 hours;

[0074] 2) In step 2), toluene washing is used;

[0075] 3) In step 2), the drying temperature is 40°C to 70°C, preferably 50°C;

[0076] 4) In step (2) and / or step (3), the reaction time is 0.1 to 110 hours, preferably 1 to 110 hours or 4 to 100 hours, such as 0.5 hour, 1 hour, 4 hours, 10 hours, 12 hours, 20 hours, 24 hours, 30 hours, 40 hours, 48 hours, 50 hours, 60 hours, 65 hours, 70 hours, 72 hours, 80 hours, 85 hours, 90 hours, 96 hours, 100 hours, 110 hours;

[0077] 5) In step (2) and / or step (3), toluene is used for washing;

[0078] 6) In step (2) and / or step (3), the drying is carried out under vacuum conditions;

[0079] 7) In step (2) and / or step (3), the drying temperature is 40°C to 70°C, preferably 50°C;

[0080] 8) In step (2) and in steps (2)-(3), solid-liquid separation is carried out by filtration.

[0081] The second aspect of the present invention relates to a supported olefin polymerization catalyst prepared by the preparation method described in the first aspect of the present invention.

[0082] In some embodiments of the second aspect of the present invention, the polymerization activity of the supported olefin polymerization catalyst at 0°C to 200°C (preferably 20°C to 200°C, such as 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 120°C, 140°C, 150°C, 160°C, 180°C) is 10 3 ~10 10 g polymer / g cat·bar·h, preferably 10 3 ~10 9 gpolymer / g cat·bar·h, such as 3.1×10 3 g polymer / g cat·bar·h, 1.3×10 4 g polymer / gcat·bar·h, 1.46×10 4 g polymer / g cat·bar·h, 3.83×10 4 g polymer / g cat·bar·h, 4.4×10 4 g polymer / gcat·bar·h, 5.3×10 4 g polymer / g cat·bar·h, 5.92×10 4 gpolymer / g cat·bar·h, 6×10 4g polymer / g cat·bar·h, 6.8×10 4 g polymer / g cat·bar·h, 3.25×10 5 g polymer / g cat·bar·h, 4.4×10 5 gpolymer / g cat·bar·h, 4.7×10 5 g polymer / g cat·bar·h, 5.2×10 5 g polymer / g cat·bar·h, 5.92×10 5 g polymer / g cat·bar·h, 6.6×10 5 g polymer / g cat·bar·h, 7.4×10 5 g polymer / gcat·bar·h, 9.1×10 5 g polymer / g cat·bar·h, 1.3×10 6 g polymer / g cat·bar·h, 2×10 6 gpolymer / g cat·bar·h, 2.3×10 6 g polymer / g cat·bar·h, 4.1×10 6 g polymer / gcat·bar·h, 6.2×10 6 gpolymer / g cat·bar·h, 4.25×10 7 g polymer / g cat·bar·h, 6.1×10 7 g polymer / g cat·bar·h, 7.9×10 8 g polymer / g cat·bar·h.

[0083] In some embodiments of the second aspect of the present invention, the olefin is selected from ethylene, propylene, linear or branched α-olefins having 4 to 20 carbon atoms, conjugated dienes having 4 to 20 carbon atoms, non-conjugated polyenes having 5 to 20 carbon atoms, cycloolefins having 5 to 20 carbon atoms, and aryl vinyls having 5 to 20 carbon atoms.

[0084] In some embodiments of the second aspect of the present invention, the olefin is selected from ethylene, propylene, 1-butene, butadiene, 1-hexene, 1-octene, and styrene.

[0085] The third aspect of the present invention relates to a catalyst product for olefin polymerization, comprising the supported olefin polymerization catalyst described in the second aspect of the present invention and an optional cocatalyst.

[0086] In some embodiments of the third aspect of the present invention, the cocatalyst is selected from triethylaluminum, methylaluminoxane, triisobutylaluminum, and modified methylaluminoxane.

[0087] In some embodiments of the third aspect of the present invention, the weight ratio of the supported olefin polymerization catalyst to the cocatalyst is 1:(1 - 125), such as 1:25, 3:100, etc.

[0088] The fourth aspect of the present invention relates to a method for olefin polymerization, comprising polymerizing olefins by using the supported olefin polymerization catalyst described in the second aspect of the present invention or the catalyst product described in the third aspect of the present invention.

[0089] In some embodiments of the fourth aspect of the present invention, the olefins are selected from ethylene, propylene, linear or branched α-olefins containing 4 - 20 carbon atoms, conjugated dienes containing 4 - 20 carbon atoms, non-conjugated polyenes containing 5 - 20 carbon atoms, cycloolefins containing 5 - 20 carbon atoms, and aryl vinyls containing 5 - 20 carbon atoms.

[0090] In some embodiments of the fourth aspect of the present invention, the olefins are selected from ethylene, propylene, 1-butene, butadiene, 1-hexene, 1-octene, and styrene.

[0091] In some embodiments of the fourth aspect of the present invention, the olefin polymerization is selected from gas-phase olefin polymerization, solution olefin polymerization, bulk olefin polymerization, and slurry olefin polymerization.

[0092] The fifth aspect of the present invention relates to the use of the supported olefin polymerization catalyst described in the second aspect of the present invention or the catalyst product described in the third aspect of the present invention in catalyzing olefin polymerization.

[0093] In some embodiments of the fifth aspect of the present invention, the olefin polymerization is selected from gas-phase olefin polymerization, solution olefin polymerization, bulk olefin polymerization, and slurry olefin polymerization.

[0094] In some embodiments of the fifth aspect of the present invention, the olefins are selected from ethylene, propylene, linear or branched α-olefins containing 4 - 20 carbon atoms, conjugated dienes containing 4 - 20 carbon atoms, non-conjugated polyenes containing 5 - 20 carbon atoms, cycloolefins containing 5 - 20 carbon atoms, and aryl vinyls containing 5 - 20 carbon atoms.

[0095] In some embodiments of the fifth aspect of the present invention, the olefins are selected from ethylene, propylene, 1-butene, butadiene, 1-hexene, 1-octene, and styrene.

[0096] Another aspect of the present invention relates to the supported olefin polymerization catalyst described in the second aspect of the present invention or the catalyst product described in the third aspect of the present invention, which is used for catalyzing olefin polymerization.

[0097] In some embodiments of the present invention, the olefin polymerization is selected from gas-phase olefin polymerization, solution-phase olefin polymerization, bulk olefin polymerization, and slurry-phase olefin polymerization.

[0098] In some embodiments of the present invention, the olefins are selected from ethylene, propylene, linear or branched α-olefins containing 4-20 carbon atoms, conjugated dienes containing 4-20 carbon atoms, non-conjugated polyenes containing 5-20 carbon atoms, cycloolefins containing 5-20 carbon atoms, and aryl vinyls containing 5-20 carbon atoms.

[0099] In some embodiments of the present invention, the olefins are selected from ethylene, propylene, 1-butene, butadiene, 1-hexene, 1-octene, and styrene.

[0100] In the present invention, the CAS number of the modified methylaluminoxane is 206451-54-9.

[0101] In the present invention, "rac" represents a racemate.

[0102] The present invention has achieved the following beneficial technical effects:

[0103] The supported olefin polymerization catalyst prepared by the method of the present invention can maintain high catalytic activity for a long time to catalyze olefin polymerization reactions, which promotes the development of the olefin polymerization industry. Specific Embodiments

[0104] The following will clearly and completely describe the embodiments of the present invention in conjunction with the examples. Obviously, the described examples are only a part of the embodiments of the present invention, rather than all of the embodiments. The description of at least one exemplary embodiment below is actually only illustrative and in no way restricts the present invention and its application or use. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention.

[0105] Example 1

[0106] (1) Preparation of COF1-supported titanium tetrachloride catalyst:

[0107] 5 mL of 1,4-benzenediboronic acid was added to a mixed solution of 40 mL of mesitylene and 40 mL of dioxane, and the reaction was carried out at 120 °C for 72 h to obtain COF1; COF1 was activated at 300 °C under vacuum conditions for 6 h; under the protection of a nitrogen atmosphere, 1 g of the activated COF1 and 500 mg of trimethylaluminum were dispersed into 500 mL of n-hexane, and the reaction was stirred at 25 °C for 48 h, filtered, washed with toluene, and dried at 50 °C to obtain pretreated COF1; in a glove box filled with nitrogen, 500 mg of the pretreated COF1, 50 mg of titanium tetrachloride and 500 mL of chlorobenzene were mixed, and the reaction was stirred at 0 °C for 72 h, filtered, washed with toluene, and vacuum dried at 50 °C to obtain a COF1-supported titanium tetrachloride catalyst.

[0108] (2) Application of the catalyst in the slurry homopolymerization of ethylene:

[0109] A 2-L autoclave was evacuated at 140 °C for 3 h, 1.5 L of n-hexane was added to the autoclave, the ethylene pressure in the autoclave was adjusted to 40 bar, the temperature in the autoclave was adjusted to 50 °C, then 20 mg of the prepared COF1-supported titanium tetrachloride catalyst and 500 mg of triethylaluminum were added, and the reaction was carried out for 0.5 h to obtain a polyethylene product, and the polymerization activity was 6.3×10 6 g polymer / gcat·bar·h.

[0110] Example 2

[0111] (1) Preparation of COF1-supported titanium trichloride catalyst:

[0112] COF1 [prepared according to the method in step (1) of Example 1] was activated at 400 °C under nitrogen conditions for 6 h. In a glove box filled with nitrogen, 100 mg of the activated COF1 and 5 mg of titanium trichloride were dispersed into 500 mL of n-hexane, and the reaction was stirred at 60 °C for 72 h, filtered, washed with toluene, and vacuum dried at 50 °C to obtain a COF1-supported titanium trichloride catalyst.

[0113] (2) Application of the catalyst in the slurry homopolymerization of propylene:

[0114] A 2-L autoclave was evacuated at 140 °C for 3 h, 1.5 L of n-hexane was added to the autoclave, the propylene pressure in the autoclave was adjusted to 15 bar, the temperature in the autoclave was adjusted to 60 °C, then 15 mg of the prepared COF1-supported titanium trichloride catalyst and 500 mg of triethylaluminum were added, and the reaction was carried out for 0.5 h to obtain a polypropylene product, and the polymerization activity was 4.3×10 5 g polymer / gcat·bar·h.

[0115] Example 3

[0116] (1) Preparation of COF1-supported dimethylsilyl-bridged-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium catalyst:

[0117] Activate COF1 [prepared by the method in step (1) of Example 1] at 250 °C under vacuum for 12 h; under the protection of nitrogen atmosphere, disperse 1 g of the activated COF1 and 1 g of triisobutylaluminum into 500 ml of chlorobenzene, stir and react at 90 °C for 12 h, filter, wash with toluene, and dry at 50 °C to obtain pretreated COF1; in a glove box filled with nitrogen, take 500 mg of the pretreated COF1 and 5 mg of dimethylsilyl-bridged-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium and disperse them into 500 ml of cyclohexane, stir and react at 0 °C for 72 h, filter, wash with toluene, and dry under vacuum at 50 °C to obtain the COF1-supported dimethylsilyl-bridged-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium catalyst.

[0118] (2) Application of the catalyst in ethylene slurry homopolymerization:

[0119] Vacuum treat a 2-liter autoclave at 140 °C for 3 h, add 1.5 L of n-hexane to the autoclave, adjust the ethylene pressure in the autoclave to 40 bar, adjust the temperature in the autoclave to 50 °C, then add 100 mg of the prepared COF1-supported dimethylsilyl-bridged-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium catalyst, react for 0.5 h to obtain a polyethylene product, and the polymerization activity is 8.2×10 6 g polymer / g cat·bar·h.

[0120] Example 4

[0121] (1) Preparation of COF1-supported dimethylsilyl-bridged-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium catalyst:

[0122] Activate COF1 [prepared by the method in step (1) of Example 1] at 300 °C under vacuum for 8 h; under the protection of nitrogen atmosphere, disperse 1 g of the activated COF1 and 500 mg of trimethylaluminum into 500 ml of isooctane, stir and react at 40 °C for 72 h, filter, wash with toluene, and dry at 50 °C to obtain pretreated COF1. In a glove box filled with nitrogen, take 500 mg of the pretreated COF1 and 1 g of dimethylsilyl-bridged-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium and disperse them into 500 ml of cyclohexane, stir and react at 50 °C for 12 h, filter, wash with toluene, and dry at 50 °C to obtain the COF1-supported dimethylsilyl-bridged-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium catalyst.

[0123] (2) Application of the catalyst in the homogeneous polymerization of propylene in solution:

[0124] A 2-L autoclave was evacuated at 140 °C for 3 h. Then, 1.5 L of n-hexane was added to the autoclave. The propylene pressure in the autoclave was adjusted to 15 bar, and the temperature in the autoclave was adjusted to 50 °C. Then, 5 mg of the prepared COF1-supported dimethylsilyl-bridged-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium catalyst was added, and the reaction was carried out for 0.5 h to obtain a polypropylene product. The polymerization activity was 3.25×10 6 g polymer / g cat·bar·h.

[0125] Example 5

[0126] (1) Preparation of the COF1-supported dimethylsilyl-bridged-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium catalyst:

[0127] COF1 [prepared by the method in step (1) of Example 1] was activated at 300 °C under vacuum for 6 h. Under the protection of a nitrogen atmosphere, 1 g of the activated COF1 and 50 mg of methylaluminoxane were dispersed in 500 ml of n-hexane, and the reaction was stirred at 25 °C for 48 h. After filtration, it was washed with toluene and dried at 50 °C to obtain the pretreated COF1. In a glove box filled with nitrogen, 500 mg of the pretreated COF1 and 15 mg of dimethylsilyl-bridged-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium were dispersed in 500 ml of cyclohexane, and the reaction was stirred at 25 °C for 96 h. After filtration, it was washed with toluene and dried at 50 °C to obtain the COF1-supported dimethylsilyl-bridged-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium catalyst.

[0128] (2) Application of the catalyst in the copolymerization of ethylene / 1-octene in solution:

[0129] A 2-L autoclave was evacuated at 140 °C for 3 h. Then, 1.5 L of n-hexane was added to the autoclave. The ethylene pressure in the autoclave was adjusted to 35 bar, and the temperature in the autoclave was adjusted to 60 °C. Then, 15 mg of the prepared COF1-supported dimethylsilyl-bridged-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium catalyst, 100 mg of methylaluminoxane and 50 ml of octene were added, and the reaction was carried out for 1 h to obtain an ethylene-octene copolymer. The polymerization activity was 5.2×10 6 g polymer / g cat·bar·h.

[0130] Example 6

[0131] (1) Preparation of the COF1-supported zirconocene dichloride catalyst:

[0132] Activate COF1 [prepared according to the method in step (1) of Example 1] at 100 °C under argon for 3 h. In a glove box filled with nitrogen, disperse 100 mg of the activated COF1 and 500 mg of zirconocene dichloride into 500 ml of n - hexane, stir and react at 40 °C for 72 h, filter, wash with toluene, and dry at 50 °C to obtain the COF1 - supported zirconocene dichloride catalyst.

[0133] (2) Application of the catalyst in ethylene slurry polymerization:

[0134] Vacuum - treat a 2 - liter autoclave at 140 °C for 3 h, add 1.5 L of n - hexane to the autoclave, adjust the ethylene pressure in the autoclave to 15 bar, adjust the temperature in the autoclave to 60 °C, then add 5 mg of the prepared COF1 - supported zirconocene dichloride catalyst and 300 mg of triethylaluminum, react for 1 h to obtain a polyethylene product, and the polymerization activity is 9.1×10 6 g polymer / gcat·bar·h.

[0135] Example 7

[0136] (1) Preparation of the COF1 - supported zirconocene dichloride catalyst:

[0137] Activate COF1 [prepared according to the method in step (1) of Example 1] at 300 °C under vacuum for 6 h; under the protection of a nitrogen atmosphere, disperse 1 g of the activated COF1 and 5 g of trimethylaluminum into 500 ml of n - hexane, stir and react at 40 °C for 4 h, filter, wash with toluene, and dry at 50 °C to obtain the pretreated COF1; in a glove box filled with nitrogen, take 500 mg of the pretreated COF1 and 10 mg of zirconocene dichloride, disperse them into 500 ml of chlorobenzene, stir and react at - 20 °C for 24 h, filter, wash with toluene, and dry at 50 °C to obtain the COF1 - supported zirconocene dichloride catalyst.

[0138] (2) Application of the catalyst in propylene slurry polymerization:

[0139] Vacuum - treat a 2 - liter autoclave at 140 °C for 3 h, add 1.5 L of cyclohexane to the autoclave, adjust the propylene pressure in the autoclave to 35 bar, adjust the temperature in the autoclave to 50 °C, then add 200 mg of the prepared COF1 - supported zirconocene dichloride catalyst and 800 mg of methylaluminoxane, react for 0.5 h to obtain a polypropylene product, and the polymerization activity is 7.4×10 6 g polymer / g cat·bar·h.

[0140] Example 8

[0141] (1) Preparation of zirconocene dichloride supported on COF1:

[0142] Activate COF1 [prepared by the method in step (1) of Example 1] at 200 °C under vacuum for 48 h; under the protection of nitrogen atmosphere, disperse 1 g of the activated COF1 and 10 g of ethylaluminoxane into 500 ml of n - hexane, stir and react at 15 °C for 12 h, filter, wash with toluene, and dry at 50 °C to obtain pretreated COF1; in a glove box filled with nitrogen, take 500 mg of the pretreated COF1 and 100 mg of zirconocene dichloride, disperse them into 500 ml of n - heptane, stir and react at 80 °C for 4 h, filter, wash with toluene, and dry at 50 °C to obtain zirconocene dichloride supported on COF1 catalyst.

[0143] (2) Application of the catalyst in the solution polymerization of ethylene / 1 - octene:

[0144] Vacuum - treat a 2 - liter autoclave at 140 °C for 3 h, add 1.5 L of toluene into the autoclave, adjust the ethylene pressure in the autoclave to 20 bar, adjust the temperature in the autoclave to 50 °C, then add 10 mg of the prepared zirconocene dichloride supported on COF1 catalyst, 500 mg of triethylaluminum and 50 ml of octene, react for 0.5 h to obtain ethylene - octene copolymer, and the polymerization activity is 9.46×10 5 g polymer / g cat·bar·h.

[0145] Example 9

[0146] (1) Preparation of zirconocene dichloride supported on COF5:

[0147] Add 2,3,6,7,10,11 - hexahydroxytriphenylene and 1,4 - phenylenediboronic acid in a weight ratio of 3:2, with a total of 1 g, into a mixed solution of 40 ml of mesitylene and 40 ml of dioxane, react at 120 °C for 72 h, wash the product three times with acetone to obtain COF5; activate COF5 at 300 °C under nitrogen atmosphere for 6 h; in a glove box filled with nitrogen, take 100 mg of the activated COF5 and 50 mg of zirconocene dichloride, disperse them into 500 ml of n - hexane, stir and react at 60 °C for 24 h, filter, wash with toluene, and dry at 50 °C to obtain zirconocene dichloride supported on COF5 catalyst.

[0148] (2) Application of the catalyst in the slurry polymerization of ethylene:

[0149] A 2-L autoclave was evacuated at 140 °C for 3 h. 1.5 L of n-heptane was added to the autoclave. The ethylene pressure in the autoclave was adjusted to 45 bar, and the temperature in the autoclave was adjusted to 50 °C. Then, 10 mg of the prepared COF5-supported zirconocene dichloride catalyst and 500 mg of methylaluminoxane were added, and the reaction was carried out for 0.5 h to obtain a polyethylene product, and the polymerization activity was 2.3×10 7 g polymer / gcat·bar·h.

[0150] Example 10

[0151] (1) Preparation of COF5-supported zirconocene dichloride catalyst:

[0152] COF5 [prepared according to the method in step (1) of Example 9] was activated at 150 °C under a nitrogen atmosphere for 3 h; in a glove box filled with nitrogen, 300 mg of the activated COF5 and 3 g of zirconocene dichloride were dispersed in 500 ml of n-hexane, and the mixture was stirred and reacted at 60 °C for 72 h, filtered, washed with toluene, and dried under vacuum at 50 °C to obtain the COF5-supported zirconocene dichloride catalyst.

[0153] (2) Application of the catalyst in propylene slurry polymerization:

[0154] A 2-L autoclave was evacuated at 140 °C for 3 h. 1.5 L of n-hexane was added to the autoclave. The propylene pressure in the autoclave was adjusted to 35 bar, and the temperature in the autoclave was adjusted to 60 °C. Then, 5 mg of the prepared COF5-supported zirconocene dichloride catalyst and 500 mg of triisobutylaluminum were added, and the reaction was carried out for 0.5 h to obtain a polypropylene product, and the polymerization activity was 3.83×10 6 g polymer / gcat·bar·h.

[0155] Example 11

[0156] (1) Preparation of COF5-supported zirconocene dichloride catalyst:

[0157] COF5 [prepared according to the method in step (1) of Example 9] was activated at 100 °C under a nitrogen atmosphere for 12 h; in a glove box filled with nitrogen, 100 mg of the activated COF5 and 500 mg of zirconocene dichloride were dispersed in 500 ml of n-hexane, and the mixture was stirred and reacted at 50 °C for 48 h, filtered, washed with toluene, and dried under vacuum at 50 °C to obtain the COF5-supported zirconocene dichloride catalyst.

[0158] (2) Application of the catalyst in ethylene / 1-octene solution polymerization:

[0159] The 2-L autoclave was evacuated at 140 °C for 3 h. 1.5 L of n-hexane was added to the autoclave. The ethylene pressure in the autoclave was adjusted to 15 bar, and the temperature in the autoclave was adjusted to 40 °C. Then, 5 mg of COF5-supported zirconocene dichloride catalyst, 500 mg of triethylaluminum, and 50 ml of octene were added, and the reaction was carried out for 0.5 h to obtain an ethylene-octene copolymer with a polymerization activity of 5.3×10 6 g polymer / g cat·bar·h.

[0160] Example 12

[0161] (1) Preparation of COF5-supported phenoxyimine titanium catalyst:

[0162] COF5 [prepared by the method in step (1) of Example 9] was activated at 300 °C under vacuum for 6 h. Under the protection of a nitrogen atmosphere, 1 g of the activated COF5 and 100 mg of triethylaluminum were dispersed in 500 ml of n-hexane, and the reaction was stirred at 15 °C for 48 h. After filtration, it was washed with toluene and dried under vacuum at 50 °C to obtain pretreated COF5. In a glove box filled with nitrogen, 500 mg of the pretreated COF5 and 100 mg of phenoxyimine titanium (structural formula 1) were dispersed in 500 ml of chlorobenzene, and the reaction was stirred at 0 °C for 72 h. After filtration and washing with toluene, it was dried under vacuum at 50 °C to obtain the COF5-supported phenoxyimine titanium catalyst.

[0163]

[0164] (2) Application of the catalyst in ethylene slurry polymerization:

[0165] The 2-L autoclave was evacuated at 140 °C for 3 h. 1.5 L of n-hexane was added to the autoclave. The ethylene pressure in the autoclave was adjusted to 35 bar, and the temperature in the autoclave was adjusted to 50 °C. Then, 5 mg of COF5-supported phenoxyimine titanium catalyst and 500 mg of methylaluminoxane were added, and the reaction was carried out for 0.5 h to obtain a polyethylene product with a polymerization activity of 6.1×10 7 g polymer / g cat·bar·h.

[0166] Example 13

[0167] (1) Preparation of COF5-supported phenoxyimine zirconium catalyst:

[0168] Activate COF5 [prepared by the method in step (1) of Example 9] at 400 °C under a nitrogen atmosphere for 12 h; in a glove box filled with nitrogen, take 500 mg of the activated COF5 and 50 mg of zirconium phenoxyimine and disperse them in 500 ml of n-hexane, stir and react at 60 °C for 48 h, filter, wash with toluene, and dry in vacuo at 50 °C to obtain a COF5-supported zirconium phenoxyimine catalyst.

[0169] (2) Application of the catalyst in the solution copolymerization of ethylene / 1-butene:

[0170] Vacuum-treat a 2-liter autoclave at 140 °C for 3 h, add 1.5 L of n-hexane to the autoclave, adjust the ethylene pressure in the autoclave to 20 bar, adjust the temperature in the autoclave to 50 °C, then add 5 mg of the prepared COF5-supported zirconium phenoxyimine catalyst and 500 mg of triethylaluminum, introduce 1-butene into the autoclave until the reaction pressure reaches 30 bar, and react for 0.5 h to obtain an ethylene / 1-butene copolymer, and the polymerization activity is 6.2×10 6 g polymer / g cat·bar·h.

[0171] Example 14

[0172] (1) Preparation of a COF5-supported diimine nickel catalyst:

[0173] Activate COF5 [prepared by the method in step (1) of Example 9] at 200 °C under a nitrogen atmosphere for 4 h; in a glove box filled with nitrogen, take 200 mg of the activated COF5 and 50 mg of diimine nickel (structural formula 2) and disperse them in 500 ml of n-hexane, stir and react at 60 °C for 48 h, filter, wash with toluene, and dry in vacuo at 50 °C to obtain a COF5-supported diimine nickel catalyst.

[0174]

[0175] (2) Application of the catalyst in the solution polymerization of ethylene:

[0176] Vacuum-treat a 2-liter autoclave at 140 °C for 3 h, add 1.5 L of n-hexane to the autoclave, adjust the ethylene pressure in the autoclave to 35 bar, adjust the temperature in the autoclave to 50 °C, then add 15 mg of the prepared COF5-supported diimine nickel catalyst and 500 mg of modified methylaluminoxane, and react for 0.5 h to obtain a polyethylene product, and the polymerization activity is 4.4×10 6 g polymer / gcat·bar·h.

[0177] Example 15

[0178] (1) Preparation of COF5-supported diimine palladium catalyst:

[0179] Activate COF5 [prepared according to the method in step (1) of Example 9] at 300 °C under vacuum for 8 h; under the protection of nitrogen atmosphere, disperse 1 g of activated COF5 and 2 g of trimethylaluminum into 500 ml of n-hexane, stir and react at 25 °C for 48 h, filter, wash with toluene, and dry under vacuum at 50 °C to obtain pretreated COF5. In a glove box filled with nitrogen, take 500 mg of pretreated COF5 and 500 mg of diimine palladium, disperse them into 500 ml of chlorobenzene, stir and react at 50 °C for 4 h, filter, wash with toluene, and dry under vacuum at 50 °C to obtain COF5-supported diimine palladium catalyst.

[0180] (2) Application of the catalyst in the solution polymerization of ethylene:

[0181] Vacuum-treat a 2-liter autoclave at 140 °C for 3 h, add 1.5 L of n-hexane to the autoclave, adjust the ethylene pressure in the autoclave to 40 bar, adjust the temperature in the autoclave to 50 °C, then add 10 mg of COF5-supported diimine palladium catalyst and 500 mg of methylaluminoxane, and react for 0.5 h to obtain a polyethylene product, and the polymerization activity is 6×10 6 g polymer / g cat·bar·h.

[0182] Example 16

[0183] (1) Preparation of COF300-supported zirconocene dichloride catalyst:

[0184] Add 0.8 g of tetrakis(4-aminophenyl)methane and 1,4-p-phthalaldehyde in a weight ratio of 3:5 to a mixed solution formed by 20 ml of acetic acid and 10 ml of dioxane, react at 120 °C for 72 h, wash the obtained product three times with a 1:1 mixed solution of tetrahydrofuran and dioxane to obtain COF300; activate COF300 at 300 °C under nitrogen for 6 h; in a glove box filled with nitrogen, take 500 mg of activated COF300 and 40 mg of zirconocene dichloride, disperse them into 500 ml of n-hexane, stir and react at 80 °C for 24 h, filter, wash with toluene, and dry under vacuum at 50 °C to obtain COF300-supported zirconocene dichloride catalyst.

[0185] (2) Application of the catalyst in the slurry polymerization of ethylene:

[0186] A 2-L autoclave was evacuated at 140 °C for 3 h, 1.5 L of n-heptane was added to the autoclave, the ethylene pressure in the autoclave was adjusted to 35 bar, the temperature in the autoclave was adjusted to 80 °C, then 40 mg of the prepared COF300-supported zirconocene dichloride catalyst and 600 mg of methylaluminoxane were added, and the reaction was carried out for 0.5 h to obtain a polyethylene product, and the polymerization activity was 6.8×10 6 g polymer / gcat·bar·h.

[0187] Example 17

[0188] (1) Preparation of COF300-supported zirconocene dichloride catalyst:

[0189] COF300 [prepared according to the method in step (1) of Example 16] was activated at 150 °C under a nitrogen atmosphere for 3 h. In a glove box filled with nitrogen, 200 mg of the activated COF300 and 2 g of zirconocene dichloride were dispersed in 500 ml of n-hexane, and the reaction was stirred at 60 °C for 72 h, filtered, washed with toluene, and vacuum dried at 50 °C to obtain the COF300-supported zirconocene dichloride catalyst.

[0190] (2) Application of the catalyst in propylene slurry polymerization:

[0191] A 2-L autoclave was evacuated at 140 °C for 3 h, 1.5 L of n-hexane was added to the autoclave, the propylene pressure in the autoclave was adjusted to 15 bar, the temperature in the autoclave was adjusted to 70 °C, 5 mg of the COF300-supported zirconocene dichloride catalyst and 500 mg of triisobutylaluminum were added, and the reaction was carried out for 0.5 h to obtain a polypropylene product, and the polymerization activity was 9.7×10 5 g polymer / g cat·bar·h.

[0192] Example 18

[0193] (1) Preparation of COF300-supported zirconocene dichloride catalyst:

[0194] COF300 [prepared according to the method in step (1) of Example 16] was activated at 100 °C under a nitrogen atmosphere for 12 h. In a glove box filled with nitrogen, 100 mg of the activated COF300 and 200 mg of zirconocene dichloride were dispersed in 500 ml of n-hexane, and the reaction was stirred at 50 °C for 48 h, filtered, washed with toluene, and vacuum dried at 50 °C to obtain the COF300-supported zirconocene dichloride catalyst.

[0195] (2) Application of the catalyst in ethylene / 1-butene solution polymerization:

[0196] The 2 L autoclave was evacuated at 140 °C for 3 h. 1.5 L of n-hexane was added to the autoclave. The ethylene pressure in the autoclave was adjusted to 20 bar, and the temperature in the autoclave was adjusted to 160 °C. 5 mg of COF300 supported zirconocene dichloride catalyst and 400 mg of triethylaluminum were added. 1-butene was introduced into the autoclave until the reaction pressure reached 30 bar, and the reaction was carried out for 0.5 h to obtain an ethylene / 1-butene copolymer, and the polymerization activity was 2.25×10 7 g polymer / g cat·bar·h.

[0197] Example 19

[0198] (1) Preparation of COF300 supported phenoxyimine zirconium catalyst:

[0199] COF300 [prepared by the method in step (1) of Example 16] was activated at 300 °C under vacuum for 6 h; under the protection of a nitrogen atmosphere, 1 g of the activated COF300 and 100 mg of triethylaluminum were dispersed in 500 ml of n-hexane, and the reaction was stirred at 15 °C for 48 h, filtered, washed with toluene, and vacuum dried at 50 °C to obtain pretreated COF300. In a glove box filled with nitrogen, 100 mg of pretreated COF300 and 100 mg of phenoxyimine zirconium were dispersed in 300 ml of chlorobenzene, and the reaction was stirred at 5 °C for 72 h, filtered, washed with toluene, and vacuum dried at 50 °C to obtain COF300 supported phenoxyimine zirconium catalyst.

[0200] (2) Application of the catalyst in ethylene slurry polymerization:

[0201] The 2 L autoclave was evacuated at 140 °C for 3 h. 1.5 L of n-hexane was added to the autoclave. The ethylene pressure in the autoclave was adjusted to 25 bar, and the temperature in the autoclave was adjusted to 120 °C. 5 mg of COF300 supported phenoxyimine zirconium catalyst and 200 mg of methylaluminoxane were added, and the reaction was carried out for 0.5 h to obtain a polyethylene product, and the polymerization activity was 3.92×10 7 g polymer / g cat·bar·h.

[0202] Example 20

[0203] (1) Preparation of COF300 supported phenoxyimine zirconium catalyst:

[0204] Activate COF300 [prepared according to the method in step (1) of Example 16] at 400 °C under a nitrogen atmosphere for 12 h. In a glove box filled with nitrogen, take 500 mg of the activated COF300 and 50 mg of zirconium phenoxyimine and disperse them in 500 ml of n - hexane. Stir and react at 60 °C for 48 h, filter, wash with toluene, and dry under vacuum at 50 °C to obtain a COF300 - supported zirconium phenoxyimine catalyst.

[0205] (2) Application of the catalyst in the solution copolymerization of ethylene / butadiene:

[0206] Vacuum - treat a 2 - liter autoclave at 140 °C for 3 h. Add 1.5 L of n - hexane to the autoclave, adjust the ethylene pressure in the autoclave to 20 bar, adjust the temperature in the autoclave to 90 °C, add 5 mg of the COF300 - supported zirconium phenoxyimine catalyst and 500 mg of triethylaluminum, introduce butadiene, and the pressure in the reaction autoclave is 30 bar. React for 0.5 h to obtain an ethylene / butadiene copolymer, and the polymerization activity is 8.9×10 6 g polymer / g cat·bar·h.

[0207] Example 21

[0208] (1) Preparation of COF300 - supported diimine palladium catalyst:

[0209] Activate COF300 [prepared according to the method in step (1) of Example 16] at 200 °C under a nitrogen atmosphere for 4 h. In a glove box filled with nitrogen, take 200 mg of the activated COF300 and 20 mg of diimine palladium and disperse them in 500 ml of n - hexane. Stir and react at 60 °C for 48 h, filter, wash with toluene, and dry under vacuum at 50 °C to obtain a COF300 - supported diimine palladium catalyst.

[0210] (2) Application of the catalyst in the solution polymerization of ethylene:

[0211] Vacuum - treat a 2 - liter autoclave at 140 °C for 3 h. Add 1.5 L of n - hexane to the autoclave, adjust the ethylene pressure in the autoclave to 35 bar, adjust the temperature in the autoclave to 150 °C, add 35 mg of the COF300 - supported diimine palladium catalyst and 500 mg of modified methylaluminoxane, and react for 0.5 h to obtain a polyethylene product, and the polymerization activity is 9.1×10 4 g polymer / g cat·bar·h.

[0212] Example 22

[0213] (1) Preparation of COF300 - supported diimine palladium catalyst:

[0214] COF300 was activated for 8 h at 300 °C under vacuum conditions [prepared by the method in step (1) of Example 16]; under the protection of nitrogen atmosphere, 1 g of the activated COF300 and 2 g of trimethylaluminum were dispersed in 500 ml of n-hexane, and the mixture was stirred at 25 °C for 48 h, filtered, washed with toluene, and dried under vacuum at 50 °C to obtain pretreated COF300. In a glove box filled with nitrogen, 500 mg of the pretreated COF300 and 500 mg of diimine palladium were dispersed in 500 ml of chlorobenzene, and the mixture was stirred at 50 °C for 4 h, filtered, washed with toluene, and dried under vacuum at 50 °C to obtain a COF300-supported diimine palladium catalyst.

[0215] (2) Application of the catalyst in the solution polymerization of ethylene:

[0216] A 2-liter autoclave was evacuated at 140 °C for 3 h, 1.5 L of n-hexane was added to the autoclave, the ethylene pressure in the autoclave was adjusted to 40 bar, the temperature in the autoclave was adjusted to 180 °C, 10 mg of the COF300-supported diimine palladium catalyst and 500 mg of methylaluminoxane were added, and the reaction was carried out for 0.5 h to obtain a polyethylene product, and the polymerization activity was 4.4×10 5 g polymer / g cat·bar·h.

[0217] Example 23

[0218] (1) Preparation of a COF303-supported zirconocene dichloride catalyst:

[0219] Tetrakis(4-formylphenyl)methane and 1,4-phenylenediamine with a weight ratio of 2:3, totaling 1 g, were added to a mixed solution of 20 ml of mesitylene and 20 ml of dioxane, and the reaction was carried out at room temperature for 120 h. The obtained product was washed three times with n-hexane to obtain COF303; COF303 was activated at 300 °C under nitrogen conditions for 6 h; in a glove box filled with nitrogen, 500 mg of the activated COF303 and 40 mg of zirconocene dichloride were dispersed in 500 ml of n-hexane, and the mixture was stirred at 85 °C for 24 h, filtered, washed with toluene, and dried under vacuum at 50 °C to obtain a COF303-supported zirconocene dichloride catalyst.

[0220] (2) Application of the catalyst in the slurry polymerization of ethylene:

[0221] A 2-liter autoclave was evacuated at 140 °C for 3 h, 1.5 L of n-heptane was added to the autoclave, the ethylene pressure in the autoclave was adjusted to 35 bar, the temperature in the autoclave was adjusted to 80 °C, 40 mg of the COF303-supported zirconocene dichloride catalyst and 600 mg of methylaluminoxane were added, and the reaction was carried out for 0.5 h to obtain a polyethylene product, and the polymerization activity was 2.3×10 6g polymer / g cat·bar·h。

[0222] Example 24

[0223] (1) Preparation of COF303-supported zirconocene dichloride catalyst:

[0224] Activate COF303 [prepared according to the method in step (1) of Example 23] at 150 °C under nitrogen for 3 h; in a glove box filled with nitrogen, take 200 mg of the activated COF303 and 2 g of zirconocene dichloride and disperse them in 500 ml of n-hexane, stir and react at 60 °C for 72 h, filter, wash with toluene, and dry under vacuum at 50 °C to obtain the COF303-supported zirconocene dichloride catalyst.

[0225] (2) Application of the catalyst in propylene slurry polymerization:

[0226] Vacuum treat a 2-liter autoclave at 140 °C for 3 h, add 1.5 L of n-hexane to the autoclave, adjust the propylene pressure in the autoclave to 35 bar, adjust the temperature in the autoclave to 90 °C, add 5 mg of the COF303-supported zirconocene dichloride catalyst and 500 mg of triisobutylaluminum, react for 0.5 h to obtain a polypropylene product, and the polymerization activity is 5.92×10 6 g polymer / g cat·bar·h。

[0227] Example 25

[0228] (1) Preparation of COF303-supported zirconocene dichloride catalyst:

[0229] Activate COF303 [prepared according to the method in step (1) of Example 23] at 100 °C under nitrogen for 12 h; in a glove box filled with nitrogen, take 100 mg of the activated COF303 and 200 mg of zirconocene dichloride and disperse them in 500 ml of n-hexane, stir and react at 50 °C for 48 h, filter, wash with toluene, and dry under vacuum at 50 °C to obtain the COF303-supported zirconocene dichloride catalyst.

[0230] (2) Application of the catalyst in ethylene / 1-octene solution polymerization:

[0231] Vacuum treat a 2-liter autoclave at 140 °C for 3 h, add 1.5 L of n-hexane to the autoclave, adjust the ethylene pressure in the autoclave to 30 bar, adjust the temperature in the autoclave to 160 °C, add 5 mg of the COF303-supported zirconocene dichloride catalyst, 400 mg of triethylaluminum and 50 ml of octene, react for 0.5 h to obtain an ethylene-octene copolymer, and the polymerization activity is 6.83×10 6g polymer / g cat·bar·h。

[0232] Example 26

[0233] (1) Preparation of COF303-supported phenoxyimine zirconium catalyst:

[0234] Activate COF303 [prepared according to the method in step (1) of Example 23] at 300 °C under vacuum for 6 h; under nitrogen atmosphere protection, disperse 1 g of the activated COF303 and 100 mg of triethylaluminum into 500 ml of n-hexane, stir and react at 15 °C for 48 h, filter, wash with toluene, and dry under vacuum at 50 °C to obtain pretreated COF303; in a glove box filled with nitrogen, take 100 mg of the pretreated COF303 and 100 mg of phenoxyimine zirconium and disperse them into 300 ml of chlorobenzene, stir and react at 5 °C for 72 h, filter, wash with toluene, and dry under vacuum at 50 °C to obtain the COF303-supported phenoxyimine zirconium catalyst.

[0235] (2) Application of the catalyst in ethylene slurry polymerization:

[0236] Vacuum-treat a 2-liter autoclave at 140 °C for 3 h, add 1.5 L of n-hexane to the autoclave, adjust the ethylene pressure in the autoclave to 20 bar, adjust the temperature in the autoclave to 140 °C, add 5 mg of the COF303-supported phenoxyimine zirconium catalyst and 200 mg of methylaluminoxane, react for 0.5 h to obtain a polyethylene product, and the polymerization activity is 4.1×10 6 g g polymer / g cat·bar·h。

[0237] Example 27

[0238] (1) Preparation of COF303-supported phenoxyimine zirconium catalyst:

[0239] Activate COF303 [prepared according to the method in step (1) of Example 23] at 400 °C under nitrogen for 12 h; in a glove box filled with nitrogen, take 500 mg of the activated COF303 and 50 mg of phenoxyimine zirconium and disperse them into 500 ml of n-hexane, stir and react at 60 °C for 48 h, filter, wash with toluene, and dry under vacuum at 50 °C to obtain the COF303-supported phenoxyimine zirconium catalyst.

[0240] (2) Application of the catalyst in ethylene / 1-octene solution copolymerization:

[0241] A 2-L autoclave was evacuated at 140 °C for 3 h, 1.5 L of n-hexane was added to the autoclave, the ethylene pressure in the autoclave was adjusted to 25 bar, the temperature in the autoclave was adjusted to 100 °C, 5 mg of COF303-supported phenoxyimine zirconium catalyst, 500 mg of triethylaluminum and 50 ml of octene were added, and the reaction was carried out for 0.5 h to obtain an ethylene-octene copolymer, and the polymerization activity was 5.2×10 6 g polymer / g cat·bar·h.

[0242] Example 28

[0243] (1) Preparation of COF303-supported diimine palladium catalyst:

[0244] COF303 [prepared by the method in step (1) of Example 23] was activated at 200 °C under nitrogen for 4 h; in a glove box filled with nitrogen, 200 mg of the activated COF303 and 20 mg of diimine palladium were dispersed in 500 ml of n-hexane, and the mixture was stirred and reacted at 60 °C for 48 h, filtered, washed with toluene, and dried under vacuum at 50 °C to obtain the COF303-supported diimine palladium catalyst.

[0245] (2) Application of the catalyst in the solution polymerization of ethylene:

[0246] A 2-L autoclave was evacuated at 140 °C for 3 h, 1.5 L of n-hexane was added to the autoclave, the ethylene pressure in the autoclave was adjusted to 15 bar, the temperature in the autoclave was adjusted to 140 °C, 35 mg of COF303-supported diimine palladium catalyst and 500 mg of modified methylaluminoxane were added, and the reaction was carried out for 0.5 h to obtain a polyethylene product, and the polymerization activity was 5.2×10 6 g polymer / g cat·bar·h.

[0247] Example 29

[0248] (1) Preparation of COF303-supported diimine palladium catalyst:

[0249] COF303 [prepared by the method in step (1) of Example 23] was activated at 300 °C under vacuum for 8 h; under the protection of nitrogen atmosphere, 1 g of the activated COF303 and 2 g of trimethylaluminum were dispersed in 500 ml of n-hexane, and the mixture was stirred and reacted at 25 °C for 48 h, filtered, washed with toluene, and dried under vacuum at 50 °C to obtain the pretreated COF303. In a glove box filled with nitrogen, 500 mg of the pretreated COF303 and 500 mg of diimine palladium were dispersed in 500 ml of chlorobenzene, and the mixture was stirred and reacted at 50 °C for 4 h, filtered, washed with toluene, and dried under vacuum at 50 °C to obtain the COF303-supported diimine palladium catalyst.

[0250] (2) Application of the catalyst in the solution polymerization of ethylene:

[0251] A 2-L autoclave was evacuated at 140 °C for 3 h. 1.5 L of n-hexane was added to the autoclave. The ethylene pressure in the autoclave was adjusted to 35 bar, and the temperature in the autoclave was adjusted to 120 °C. 10 mg of the COF303-supported diimine palladium catalyst and 500 mg of methylaluminoxane were added, and the reaction was carried out for 0.5 h to obtain a polyethylene product. The polymerization activity was 6.6×10 6 g polymer / g cat·bar·h.

[0252] Example 30

[0253] (1) Preparation of the titanium tetrachloride-supported COF1 catalyst:

[0254] 5 ml of 1,4-benzenediboronic acid was added to a mixed solution formed by 40 ml of mesitylene and 40 ml of dioxane, and the reaction was carried out at 120 °C for 72 h to obtain COF1; COF1 was activated at 300 °C under vacuum conditions for 6 h; in a glove box filled with nitrogen, 500 mg of the activated COF1, 50 mg of titanium tetrachloride, and 500 ml of chlorobenzene were mixed, and the reaction was carried out with stirring at 0 °C for 72 h. After filtration, washing was carried out with toluene, and drying was carried out under vacuum at 50 °C to obtain the titanium tetrachloride-supported COF1 catalyst.

[0255] (2) Application of the catalyst in the slurry homopolymerization of ethylene:

[0256] A 2-L autoclave was evacuated at 140 °C for 3 h. 1.5 L of n-hexane was added to the autoclave. The ethylene pressure in the autoclave was adjusted to 40 bar, and the temperature in the autoclave was adjusted to 50 °C. Then, 20 mg of the prepared titanium tetrachloride-supported COF1 catalyst and 500 mg of triethylaluminum were added, and the reaction was carried out for 0.5 h to obtain a polyethylene product. The polymerization activity was 8.3×10 5 g polymer / gcat·bar·h.

[0257] It can be seen that the polymerization activity of the titanium tetrachloride-supported COF1 catalyst in Example 1 is two orders of magnitude higher than that of the titanium tetrachloride-supported COF1 catalyst in Example 30, indicating that the polymerization activity of the titanium tetrachloride-supported COF1 catalyst of the present invention is significantly higher.

[0258] Comparative Example 1

[0259] (1) Preparation of the zirconocene dichloride-supported silica catalyst:

[0260] Activate silica at 300 °C under a nitrogen atmosphere for 6 h; in a glove box filled with nitrogen, take 100 mg of activated silica, 100 mg of dry methylaluminoxane, and 50 mg of zirconocene dichloride and disperse them in 500 ml of n-hexane. Stir and react at 60 °C for 24 h, filter, wash with toluene, and dry at 50 °C to obtain a silica-supported zirconocene dichloride catalyst.

[0261] (2) Application of the catalyst in ethylene slurry polymerization:

[0262] Vacuum treat a 2-liter autoclave at 140 °C for 3 h, add 1.5 L of n-heptane to the autoclave, adjust the ethylene pressure in the autoclave to 45 bar, adjust the temperature in the autoclave to 50 °C, then add 10 mg of the prepared silica-supported zirconocene dichloride catalyst and 500 mg of methylaluminoxane, and react for 0.5 h to obtain a polyethylene product, and the polymerization activity is 2.3×10 5 g polymer / g cat·bar·h.

[0263] It can be seen that the polymerization activity of the catalyst in Example 9 is much higher than that of the catalyst in Comparative Example 1.

[0264] Comparative Example 2

[0265] Application of zirconocene dichloride catalyst in ethylene slurry polymerization:

[0266] Vacuum treat a 2-liter autoclave at 140 °C for 3 h, add 1.5 L of n-heptane to the autoclave, adjust the ethylene pressure in the autoclave to 45 bar, adjust the temperature in the autoclave to 50 °C, then add 10 mg of zirconocene dichloride catalyst and 500 mg of methylaluminoxane, and react for 0.5 h to obtain a polyethylene product, and the polymerization activity is 9.3×10 5 g polymer / g cat·bar·h.

[0267] It can be seen that the polymerization activity of the catalyst in Example 9 is much higher than that of the zirconocene dichloride catalyst.

[0268] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention and are not intended to limit them; although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that it is still possible to modify the specific implementation manners of the present invention or perform equivalent replacements for some technical features; without departing from the spirit of the technical solutions of the present invention, they should all be covered within the scope of the technical solutions claimed by the present invention.

Claims

1. A method for preparing a supported olefin polymerization catalyst, which is Method 1 or Method 2, wherein, Method 1 includes the following steps: (1) Under an inert atmosphere or vacuum protection, activate the COF at 0 °C to 800 °C for 0.1 to 48 hours; wherein, the COF is selected from imine-based COF, imide-based COF, borate-based COF, sp 2 -type COF, hydrazone-based COF, boroxine-based COF, borazine-based COF, triazine-based COF, and phenazine-based COF; (2) Under an inert atmosphere or vacuum protection, react the activated COF with an olefin polymerization catalyst in a reaction medium at -30°C to 150°C, perform solid-liquid separation, collect the solid phase, and optionally wash and dry the solid phase in sequence to obtain a supported olefin polymerization catalyst; wherein, the olefin polymerization catalyst is selected from Z-N catalysts, metallocene catalysts, and post-metallocene catalysts; Method 2 includes the following steps: 1) Under an inert atmosphere or vacuum protection, activate the COF at 0 °C to 800 °C for 0.1 to 48 hours; wherein, the COF is selected from imine-based COF, imide-based COF, borate ester-based COF, sp 2 -type COF, hydrazone-based COF, boroxine-based COF, borazine-based COF, triazine-based COF, and phenazine-based COF; 2) Under an inert atmosphere or vacuum protection, react the activated COF with an auxiliary agent in a reaction medium at 5°C to 120°C, perform solid-liquid separation, and collect the solid phase; wherein, the auxiliary agent is selected from metal alkyl compounds, borofluoroalkanes, alkylaluminum oxides, modified methylaluminoxanes, Lewis acids, and Grignard reagents; optionally, wash the solid phase and dry it to obtain a dried product; 3) Under an inert atmosphere or vacuum protection, react the solid phase or the optionally obtained dried product with an olefin polymerization catalyst in a reaction medium at -30°C to 150°C, perform solid-liquid separation, collect the solid phase, and optionally wash and dry the solid phase in sequence to obtain a supported olefin polymerization catalyst; wherein, the olefin polymerization catalyst is selected from Z-N catalysts, metallocene catalysts, and post-metallocene catalysts.

2. The method according to claim 1, wherein, in step 2), the auxiliary agent is selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, trimethylaluminum, triethylaluminum, tris(pentafluorophenyl)borane, and triisobutylaluminum.

3. The method according to claim 1, wherein, in step 2), the weight ratio of the activated COF to the auxiliary agent is (0.05 to 30):

1.

4. The method according to claim 1, wherein, in step 2), the ratio of the activated COF to the reaction medium is 1:(100 to 1000) g / mL.

5. The method according to claim 1, wherein, in step (2), the weight ratio of the activated COF to the olefin polymerization catalyst is (0.05 to 120):1, or in step 3), the weight ratio of the solid phase or the optionally obtained dried product to the olefin polymerization catalyst is (0.05 to 120):

1.

6. The method according to claim 1, wherein, in step (2) and / or step 3), the ratio of the olefin polymerization catalyst to the reaction medium is (0.001 to 1000):1 mg / mL.

7. The method according to claim 1, wherein, in step (1) and / or step 1), COF is selected from COF1, COF300, COF303, CTF1, COF5, and COF-LZU1.

8. The method according to claim 1, wherein, In step (2) and / or step (3), the olefin polymerization catalyst is selected from titanium tetrachloride, titanium trichloride, zirconium trichloride, vanadium trichloride, zirconocene dichloride, bis(cyclopentadienyl)dimethylhafnium, bis(indenyl)dimethylzirconium, rac-ethylenebis(indenyl)zirconium dichloride, diphenylcarbyne(cyclopentadienyl)(fluorenyl)zirconium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(tert-butylamido)dimethyltitanium, bis(indenyl)zirconium dichloride, bis[2-(3',5'-di-tert-butylphenyl)indenyl]zirconium dichloride, bis(2-methyl-4,5-phenylindenyl)zirconium dichloride, bis(cyclopentadienyl)bis(phenoxy)zirconium, dimethylsilylenebis(indenyl)zirconium dichloride, diphenylcarbyne(cyclopentadienyl)(2-dimethylamino-fluorenyl)zirconium dichloride, dimethylsilylene(3-pyrrolylindenyl)(tert-butylamido)dimethyltitanium, rac-dimethylsilyl-bis(2-methylindenyl)zirconium dichloride, dimethylsilylene(fluorenyl)(tert-butylamido)dimethyltitanium, imine-amine type catalysts, ketimine type catalysts, amidine type catalysts, diimine palladium nickel type catalysts, and phenoxyimine type catalysts.

9. According to the method of claim 1, wherein, in step (2) and / or step (3), the olefin polymerization catalyst is selected from titanium tetrachloride, titanium trichloride, zirconocene dichloride, silyl(N-tert-butylamido)(tetramethylcyclopentadienyl)titanium dichloride, phenoxyimine zirconium, rac-dimethylsilyl-bis(2-methylindenyl)zirconium dichloride, dimethylsilylene(fluorenyl)(tert-butylamido)dimethyltitanium, rac-ethylenebis(indenyl)zirconium dichloride, diimine palladium, phenoxyimine titanium, and diimine nickel.

10. According to the method of claim 1, wherein, the reaction medium in step (2) and in steps (2)-(3) is a non-polar organic solvent.

11. According to the method of claim 1, wherein, the reaction medium in step (2) and in steps (2)-(3) is independently selected from one or more mixtures of aliphatic compounds having 5-12 carbon atoms, cycloaliphatic compounds having 6-12 carbon atoms, aromatic compounds having 6-12 carbon atoms and their halogenated products, and ether compounds having 4-12 carbon atoms.

12. According to the method of claim 1, wherein, the reaction medium in step (2) and in steps (2)-(3) is independently selected from one or more mixtures of n-hexane, n-heptane, n-octane, n-dodecane, cyclohexane, toluene, xylene, mesitylene, chlorobenzene, 1,2,4-trichlorobenzene, and diethyl ether.

13. According to the method of claim 1, wherein, the inert atmosphere in step (1) and in steps (1) is independently selected from nitrogen, argon, helium, and supercritical carbon dioxide; the inert atmosphere in step (2) and in steps (2)-(3) is independently selected from nitrogen, argon, and helium.

14. According to the method according to any one of claims 1 to 13, characterized in that one or more of the following 1) to 8): 1) In step (2), the reaction time is 0.5 to 90 hours; 2) In step (2), toluene washing is used; 3) In step (2), the drying temperature is 40°C to 70°C; 4) In step (2) and / or step (3), the reaction time is 0.1 to 110 hours; 5) In step (2) and / or step (3), toluene is used for washing; 6) In step (2) and / or step (3), the drying is carried out under vacuum conditions; 7) In step (2) and / or step (3), the drying temperature is 40°C to 70°C; 8) In step (2) and step (2)-3), solid-liquid separation is carried out by filtration.

15. A supported olefin polymerization catalyst prepared by the method according to any one of claims 1 to 14.

16. The supported olefin polymerization catalyst according to claim 15, wherein, The polymerization activity of the supported olefin polymerization catalyst at 0 °C to 200 °C is 10 3 ~10 10 g polymer / g cat·bar·h.

17. The supported olefin polymerization catalyst according to claim 15, wherein, the olefin is selected from ethylene, propylene, linear or branched α-olefins having 4 to 20 carbon atoms, conjugated dienes having 4 to 20 carbon atoms, non-conjugated polyenes having 5 to 20 carbon atoms, cycloolefins having 5 to 20 carbon atoms, and aryl vinyls having 5 to 20 carbon atoms.

18. The supported olefin polymerization catalyst according to claim 15, wherein, the olefin is selected from ethylene, propylene, 1-butene, butadiene, 1-hexene, 1-octene, and styrene.

19. A catalyst product for olefin polymerization, comprising the supported olefin polymerization catalyst according to any one of claims 15 to 18.

20. The catalyst product according to claim 19, which further comprises a cocatalyst.

21. The catalyst product according to claim 20, wherein, the cocatalyst is selected from triethylaluminum, methylaluminoxane, triisobutylaluminum, and modified methylaluminoxane.

22. The catalyst product according to claim 20 or 21, wherein, the weight ratio of the supported olefin polymerization catalyst to the cocatalyst is 1:(1 to 125).

23. A method for olefin polymerization, comprising catalyzing olefin polymerization using the supported olefin polymerization catalyst according to any one of claims 15 to 18 or the catalyst product according to any one of claims 19 to 22.

24. The method according to claim 23, wherein, the olefin is selected from ethylene, propylene, linear or branched α-olefins having 4 to 20 carbon atoms, conjugated dienes having 4 to 20 carbon atoms, non-conjugated polyenes having 5 to 20 carbon atoms, cycloolefins having 5 to 20 carbon atoms, and aryl vinyls having 5 to 20 carbon atoms.

25. The method according to claim 23, wherein, the olefin is selected from ethylene, propylene, 1-butene, butadiene, 1-hexene, 1-octene, and styrene.

26. The method according to claim 23, wherein, the olefin polymerization is selected from gas-phase olefin polymerization, solution olefin polymerization, bulk olefin polymerization, and slurry olefin polymerization.

27. Use of the supported olefin polymerization catalyst according to any one of claims 15 to 18 or the catalyst product according to any one of claims 19 to 22 in catalyzing olefin polymerization.

28. The use according to claim 27, wherein, the olefin polymerization is selected from gas-phase olefin polymerization, solution olefin polymerization, bulk olefin polymerization, and slurry olefin polymerization.

29. The application according to claim 27, wherein, the olefin is selected from ethylene, propylene, linear or branched α-olefins having 4 to 20 carbon atoms, conjugated dienes having 4 to 20 carbon atoms, non-conjugated polyenes having 5 to 20 carbon atoms, cycloolefins having 5 to 20 carbon atoms, and aryl vinyls having 5 to 20 carbon atoms.

30. The application according to claim 27, wherein, the olefin is selected from ethylene, propylene, 1-butene, butadiene, 1-hexene, 1-octene, and styrene.

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