Catalyst component for olefin polymerization, preparation method of catalyst component, catalyst and application of catalyst component

Abstract

The invention relates to a catalyst component for olefin polymerization, a preparation method of the catalyst component, a catalyst and application of the catalyst component. The catalyst component comprises a reaction product of a magnesium compound, an organic anhydride compound, an acetate compound, a first alcohol compound, a titanium-containing compound and an organosilicon compound, the general formula of the organic silicon compound is R1aR2b (OR3) cSi-M-Si (OR3 ') dR1'eR2'f. According to the invention, the performance of the existing Ziegler-Natta type olefin polymerization catalyst particles is improved, and the prepared catalyst component is spherical / sphere-like, has better polymerization activity, hydrogen regulation sensitivity, stacking density, particle size distribution and fluidity, and has extremely high popularization and application values.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of olefin polymerization, further relates to a catalyst component for olefin polymerization and a preparation method thereof, in addition, the present application also relates to a catalyst comprising the aforementioned catalyst component, and application of the catalyst component and the catalyst. BACKGROUND

[0002] At present, the slurry polymerization industrial production device has a higher requirement on the bulk density of polyethylene powder. This is because in the slurry polymerization process, the polymer / hexane slurry is separated by centrifugation, and the hexane carrying amount of the high bulk density powder is lower, which is beneficial to reduce the energy consumption of powder drying and improve the load of the drying unit. In addition, the high bulk density powder is beneficial to the efficient operation of the powder conveying unit of the industrial production device, and can make the production device achieve a higher production load.

[0003] In order to obtain a higher bulk density, it is usually necessary to first prepare polyethylene catalyst particles with good particle morphology. For example, when an organic acid anhydride / acetate / cyclic ketone compound is introduced into the N series polyolefin catalyst preparation system as a complex electron donor, spherical / spherical-like polyethylene catalyst and polymerized powder particles are first prepared. However, the polymerization activity and hydrogen regulation sensitivity of the above-mentioned spherical / spherical-like polyethylene catalyst are relatively low, and the application range is relatively limited, which cannot meet the requirements of CX, Hostalen, ACP, Innovene S and other industrial slurry polyethylene production devices for high activity and high hydrogen regulation sensitivity catalysts.

[0004] Therefore, it is necessary to develop a spherical / spherical-like polyethylene catalyst with simple preparation steps, which can polymerize to obtain spherical / spherical-like powder particles with high bulk density, and has high polymerization activity, bulk density and hydrogen regulation sensitivity. SUMMARY

[0005] In order to solve the problems existing in the prior art, the present application provides a catalyst component for olefin polymerization and a preparation method thereof, a catalyst and application thereof. When an organic acid anhydride compound, an acetate compound, an alcohol compound and an organic silicon compound are introduced into the N series polyolefin catalyst preparation system as a complex electron donor, spherical or spherical-like solid particles (i.e. a catalyst component for olefin polymerization) can be prepared. After the catalyst component contacts with an organic aluminum compound, a catalyst is obtained. The olefin polymerization activity and hydrogen regulation sensitivity of the catalyst are relatively high, which can polymerize to obtain spherical or spherical-like polymerized powder particles, and the catalyst can also polymerize to obtain powder with high bulk density.

[0006] An object of the present invention is to provide a catalyst component for olefin polymerization, the catalyst component for olefin polymerization comprising a reaction product of a magnesium complex, an organic acid anhydride compound, an acetic acid ester compound, a first alcohol compound, a titanium-containing compound, and an organosilicon compound;

[0007] wherein the magnesium complex is obtained by dissolving a magnesium halide in a solvent system comprising an organic epoxy compound and an organic phosphorus compound; the organosilicon compound has a general formula as shown in formula (1),

[0008] R 1a R 2b (OR3) c Si—M—Si(OR 3’ ) d R 1’e R 2’f formula (1)

[0009] In formula (1), R1, R2, R 1’ , R 2’ are each independently selected from C1-C 10 alkyl or halogen, R3, R 3’ are C1-C 10 alkyl; 0≤a≤2, 0≤b≤2, 0≤c≤3, 0≤d≤3, 0≤e≤2, 0≤f≤2, a+b+c=3, d+e+f=3, a, b, c, d, e, f, n are integers, c and d are not simultaneously 0; M is O or -(CH2) n -, n≥0. Preferably, R1, R2, R 1’ , R 2’ are each independently selected from C1-C6 alkyl or halogen, R3, R 3’ are C1-C 10 alkyl, n is 1-10; more preferably, R1, R2, R 1’ , R 2’ are each independently selected from -CH3, -C2H5, -Cl, -Br, R3, R 3’ are selected from -CH3, -C2H5, -C3H7, n is 1-5. Most preferably, R1, R2, R 1’ , R 2’ are each independently selected from -CH3, -Cl, R3, R 3’ are each independently selected from -CH3, -C2H5, M is -(CH2) n -.

[0010] For example, the organosilicon compound represented by the general formula (1) may be selected from one or more of the following compounds: hexamethoxyethylsilane, hexaethoxyethylsilane, hexapropoxyethylsilane, hexabutoxyethylsilane, Me(EtO)2Si-Si(OEt)2Me, Cl(EtO)2Si-Si(OEt)2Me; hexamethyl pyrosilicon, hexaethyl pyrosilicon, hexapropyl pyrosilicon, hexabutyl pyrosilicon, Et(EtO)2Si-O-Si(OEt)2Cl, Cl3Si-O-Si(OEt)3; (MeO)3Si-CH2-Si(OMe)3, (EtO)3Si-CH2-Si(OEt)3, (EtO)3Si-CH2-CH2-Si(OEt)3, etc.

[0011] In a preferred embodiment of the present invention, the magnesium halide is selected from magnesium dihalide or a complex formed by magnesium dihalide with at least one of water, a second alcohol compound, and an electron carrier; preferably, the magnesium dihalide is selected from at least one of magnesium dichloride, magnesium dibromide, magnesium difluoride, and magnesium diiodide; the second alcohol compound is selected from at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, and isooctanol; and the electron carrier is selected from at least one of ammonia, hydroxylamine, ether, and ester. It should be noted that the magnesium halide can be used alone or in combination with at least one of water, a second alcohol compound, and an electron carrier.

[0012] The organic epoxy compound is selected from C2 to C3. 18 The organic epoxy compound is selected from at least one of aliphatic olefins, aliphatic dienes, halogenated aliphatic olefins or oxides of halogenated aliphatic dienes, glycidyl ethers and internal ethers; preferably, the organic epoxy compound is selected from at least one of ethylene oxide, propylene oxide, butane oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether, butyl glycidyl ether.

[0013] The organophosphorus compound is a hydrocarbon ester or haloalkyl ester of phosphoric acid or phosphorous acid; preferably, the organophosphorus compound is selected from at least one of trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, triisopropyl phosphate, tri-n-butyl phosphate, triisobutyl phosphate, tri-tert-butyl phosphate, tri-n-pentyl phosphate, triisopentyl phosphate, tri-n-hexyl phosphate, triisohexyl phosphate, tri-n-heptyl phosphate, triisoheptyl phosphate, tri-n-octyl phosphate, triisooctyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, tri-tert-butyl phosphite, tri-n-pentyl phosphite, triisopentyl phosphite, tri-n-hexyl phosphite, triisohexyl phosphite, tri-n-heptyl phosphite, triisoheptyl phosphite, tri-n-octyl phosphite, triisooctyl phosphite, triphenyl phosphite, and di-n-butyl phosphite.

[0014] The structure of the organic acid anhydride compound is shown in formula (2):

[0015]

[0016] In formula (2), R5and R6are the same or different, and each is independently hydrogen, C1-C 10 alkyl, C2-C 10 alkenyl, C2-C 10 alkynyl, C3-C 10 cycloalkyl, or C6-C 10 aromatic hydrocarbon group, and R5and R6may be arbitrarily annulated. Exemplarily, C1-C 10 alkyl is selected from C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 straight chain or branched alkyl, preferably methyl, ethyl, n-propyl, n-butyl, iso-butyl, n-pentyl, n-hexyl, etc. Exemplarily, C2-C 10 alkenyl includes C2, C3, C4, C5, C6, C7, C8, C9, C 10 straight chain or branched alkenyl, preferably vinyl, propenyl, butenyl, etc. C3-C8cycloalkyl includes but is not limited to cyclopropyl, methylcyclopropyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl, etc. Exemplarily, C6-C 20 aromatic hydrocarbon group includes but is not limited to phenyl, benzyl, dimethylphenyl, etc. Preferably, the organic acid anhydride compound is selected from at least one of acetic anhydride, propionic anhydride, butyric anhydride, acrylic anhydride, phthalic anhydride, butenyl anhydride, and maleic anhydride.

[0017] The general formula of the titanium-containing compound is Ti(OR4) a X b ; wherein R4is a C1-C 10 aliphatic hydrocarbon group or an aromatic hydrocarbon group; X is halogen, preferably fluorine, chlorine, bromine; a is an integer of 0-2, b is an integer of 1-4, a+b=3 or 4. Preferably, R4is selected from C1-C6alkyl, C2-C6alkenyl, C3-C8cycloalkyl, or C6-C 10 aromatic hydrocarbon group. More preferably, R4is selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclopropyl, methylcyclopropyl, n-pentyl, methylcyclopentyl, cyclohexyl, phenyl, benzyl, dimethylphenyl. Exemplarily, the titanium-containing compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, chlorotriethoxy titanium, titanium trichloride, dichlorodiethoxy titanium, and trichloro monoethoxy titanium.

[0018] The general formula of the acetic ester compound is CH3COOR7, wherein R7is C1-C 10 alkyl, C2-C 10alkenyl, C3-C 10 cycloalkyl, C2-C 10 alkynyl or C6-C 10 aromatic hydrocarbon group; preferably, R7 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, cyclopropyl, methylcyclopropyl, n-pentyl, methylcyclopentyl, cyclohexyl, phenyl, benzyl or xylyl. Illustratively, the acetic ester compound is selected from at least one of methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-pentyl acetate, n-hexyl acetate and n-octyl acetate.

[0019] The first alcohol compound is selected from at least one of a fatty alcohol or an aromatic alcohol having 1-20 carbon atoms, preferably, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, hexanol, cyclohexanol, octanol, isooctanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol and isohexylene glycol; more preferably, at least one of butanol, isobutanol, t-butanol, hexanol, cyclohexanol, octanol, isooctanol, benzyl alcohol, phenethyl alcohol, butylene glycol, hexylene glycol and isohexylene glycol. 18

[0020] The skilled person can select the specific substances of the magnesium halide, the organic epoxy compound, the organic phosphorus compound, the organic acid anhydride compound, the acetic ester compound, the first alcohol compound, the titanium-containing compound and the organosilicon compound according to the actual needs.

[0021] In a preferred embodiment of the present application, the amount of the organic epoxy compound is 0.2-10 moles per mole of magnesium in the magnesium halide; the amount of the organic phosphorus compound is 0.1-10 moles; the amount of the organic acid anhydride compound is 0.03-1.0 moles; the amount of the titanium-containing compound is 0.5-120 moles; the amount of the acetic ester compound is 0.01-1 moles; the amount of the first alcohol compound is 0.1-4 moles; and the amount of the organosilicon compound is 0.01-1 moles.

[0022] Preferably, the amount of the organic epoxy compound is 0.5-2.0 moles per mole of magnesium in the magnesium halide; the amount of the organic phosphorus compound is 0.5-2.0 moles; the amount of the organic acid anhydride compound is 0.1-0.3 moles; the amount of the titanium-containing compound is 5-20 moles; the amount of the acetic ester compound is 0.05-0.4 moles; the amount of the first alcohol compound is 0.1-2.0 moles; and the amount of the organosilicon compound is 0.1-0.5 moles.

[0023] ​More preferably, the amount of the organic epoxy compound is 0.5-1.5 moles per mole of magnesium in the magnesium halide; the amount of the organic phosphorus compound is 0.5-1.5 moles; the amount of the organic acid anhydride compound is 0.15-0.3 moles; the amount of the titanium-containing compound is 5-15 moles; the amount of the acetic acid ester compound is 0.05-0.2 moles; the amount of the first alcohol compound is 0.1-1 moles; and the amount of the organic silicon compound is 0.1-0.3 moles.

[0024] The skilled person can select appropriate molar ratios of the magnesium halide, the organic epoxy compound, the organic phosphorus compound, the organic acid anhydride compound, the acetic acid ester compound, the first alcohol compound, the titanium-containing compound and the organic silicon compound according to actual needs.

[0025] In a preferred embodiment of the present application, the solvent system further comprises an inert diluent selected from aromatic compounds and / or alkanes; preferably, the aromatic compounds comprise at least one of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene and / or derivatives; and / or, the alkanes comprise at least one of linear, branched or cyclic alkanes having 3-20 carbon atoms. More preferably, the amount of the inert diluent is 2-60 moles, preferably 15-30 moles, per mole of magnesium in the magnesium halide. The skilled person can select appropriate specific substances and amounts of the inert diluent according to actual needs.

[0026] A second object of the present application is to provide a preparation method of the catalyst component for olefin polymerization according to the first object of the present application, the preparation method comprising:

[0027] S1: dissolving the magnesium halide in the solvent system and reacting at elevated temperature to obtain a magnesium complex;

[0028] S2: mixing the magnesium complex with the organic acid anhydride compound and reacting at elevated temperature to obtain a first mixture and then cooling;

[0029] S3: reacting the first mixture with the titanium-containing compound to obtain a second mixture;

[0030] S4: reacting the second mixture with the first alcohol compound and reacting at elevated temperature to obtain a reaction mother liquor and a precipitate;

[0031] S5: aging the reaction mother liquor and the precipitate to obtain the catalyst component for olefin polymerization;

[0032] The acetic ester compound is added in at least one of the steps S1, S2, S3, S4, and S5. The organic silicon compound is added in at least one of the steps S3, S4, and S5.

[0033] The acetic ester compound is added in at least one of the steps S1, S2, S3, S4, and S5. The organic silicon compound is added in at least one of the steps S3, S4, and S5.

[0034] In a preferred embodiment of the present application, the acetic ester compound is added in the step S4. When the acetic ester compound is added in the step S4, the preparation method of the catalyst component for olefin polymerization includes three kinds in total. Preferably, the organic silicon compound is added in the step S4; or the organic silicon compound is added in the step S5.

[0035] For example, the preparation method (the organic silicon compound is added in the step S5) can specifically include:

[0036] S1: dissolving the magnesium halide in the solvent system containing the organic epoxy compound and the organic phosphorus compound to form a uniform solution, to obtain a magnesium complex;

[0037] S2: reacting the magnesium complex with the organic acid anhydride compound, mixing, warming, to obtain a first mixture, and cooling;

[0038] S3: contacting the first mixture with the titanium-containing compound under the temperature condition after cooling, to obtain a second mixture;

[0039] S4: reacting the second mixture with the acetic ester compound and the alcohol compound again under the temperature condition after cooling, warming to a preset temperature, reacting, so that the spherical or spherical-like solid particles are precipitated from the second mixture, to obtain a reaction mother liquor and a precipitate;

[0040] S5: continuing to keep the temperature constant, aging the reaction mother liquor and the precipitate; and adding the organic silicon compound to react during the aging treatment of the reaction mother liquor and the solid particles.

[0041] S6: removing unreacted substances and solvents from the catalyst component obtained in step S5 to obtain a catalyst component for olefin polymerization.

[0042] The prepared catalyst component is spherical or spheroidal, the polymerization activity is ≥ 24000 g of polyethylene / g of catalyst, and the bulk density is ≥ 0.36 g / ml (when the specific reaction conditions are as follows: hydrogen 0.28 MPa, ethylene 0.45 MPa, polymerization temperature 80°C, and polymerization time 2 h).

[0043] For example, the preparation method (adding the organosilicon compound in step S4) can specifically include:

[0044] S1: dissolving a magnesium halide in a solvent system containing an organic epoxy compound and an organic phosphorus compound to form a uniform solution to obtain a magnesium complex;

[0045] S2: mixing the magnesium complex with an organic acid anhydride compound, reacting at a high temperature to obtain a first mixture, and cooling;

[0046] S3: contacting the first mixture with a titanium-containing compound at the temperature after cooling to obtain a second mixture;

[0047] S4: reacting the second mixture with an acetic ester compound, an alcohol compound, and an organosilicon compound at the temperature after cooling, and then heating and keeping the temperature to make spherical or spheroidal solid particles precipitate from the second mixture to obtain a reaction mother liquor and a precipitate;

[0048] S5: continuing to keep the temperature and aging the reaction mother liquor and the precipitate.

[0049] S6: removing unreacted substances and solvents from the catalyst component obtained in step S5 to obtain a catalyst component for olefin polymerization.

[0050] In a preferred embodiment of the present application, in step S1, the temperature is raised to 50-70°C, preferably 55-60°C; the reaction time is 1-4 hours, preferably 1-3 hours; and / or in step S2, the reaction temperature is 50-70°C, preferably 55-60°C; the reaction time is 0.5-2 hours, preferably 1-2 hours; and / or in step S2, the temperature is lowered to -60 to 0°C, preferably -50 to -30°C; and / or in step S3, the reaction temperature is -60 to 0°C, preferably -50 to -30°C; and / or in step S4, the temperature is raised to 70-120°C, preferably 80-90°C; the reaction time is 0.2-10 hours, preferably 1-6 hours; and / or in step S5, the temperature for the aging treatment is 70-120°C, preferably 80-90°C; the time for the aging treatment is 0.2-4 hours, preferably 0.8-2 hours. The person skilled in the art can select appropriate reaction temperatures and reaction times according to actual needs.

[0051] A third object of the present application is to provide a catalyst for olefin polymerization comprising the catalyst component according to the first object of the present application or the catalyst component prepared by the method according to the second object of the present application, specifically comprising the following components:

[0052] A) the catalyst component for olefin polymerization prepared by the method according to the first object of the present application or the catalyst component for olefin polymerization according to the second object of the present application;

[0053] B) an organoaluminum compound with the general formula of AlR' d X' 3-d , wherein R' is hydrogen or a hydrocarbon group with 1-20 carbon atoms, preferably an alkyl group with 1-10 carbon atoms, more preferably a methyl group, X' is a halogen atom, preferably fluorine, chlorine or bromine, 0 < d ≤ 3, and d is an integer. l 20 l 20

[0054] Preferably, the molar ratio of aluminum in component B) to titanium in component A) is (20-200): 1, more preferably (50-100): 1. The person skilled in the art can select appropriate component B) and appropriate molar ratio of component B) to component A) according to actual needs.

[0055] In a preferred embodiment of the present application, R' can be hydrogen or a hydrocarbon group with 1-20 carbon atoms, in particular an alkyl group with 1-10 carbon atoms, more preferably a methyl group. l 20 l 20 l 20 l 20 l 20 ​R' is an alkyl group, an aryl group or a combination thereof. The R' is particularly an alkyl group. The alkyl group is exemplified by Al(CH3)3, Al(CH2CH3)3, Al(i-Bu)3, AlH(CH2CH3)2, AlH(i-Bu)2, AlCl(CH2CH3)2, Al2Cl3(CH2CH3)3, AlCl(CH2CH3)2, AlCl2(CH2CH3), and the like. Al(CH2CH3)3 and Al(i-Bu)3 are preferred.

[0056] The fourth object of the present application is to provide the use of the catalyst component for olefin polymerization according to the first object of the present application or the catalyst component for olefin polymerization prepared by the method according to the second object of the present application or the catalyst for olefin polymerization according to the third object of the present application in ethylene polymerization. The polymerization can be slurry polymerization or gas phase polymerization. If the slurry polymerization is used, the slurry polymerization medium can be selected from any one of isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, xylene, and the like.

[0057] The catalyst prepared by adding the organosilicon compound in step S5 is polymerized under the conditions of hydrogen 0.28 MPa / ethylene 0.45 MPa / temperature 80℃ for 2 hours, and the polymerization activity of the catalyst is ≥24000 g·polyethylene / g·catalyst, and the bulk density is ≥0.36 g / ml.

[0058] Compared with the prior art, the present application has the following advantages:

[0059] (1) The catalyst for olefin polymerization of the present application has excellent comprehensive performance. In the first aspect, the present application can obtain spherical / subspherical polyethylene catalyst particles with very uniform particle morphology, and can polymerize to obtain spherical / subspherical powder particles; in the second aspect, the catalyst obtained by the present application has excellent polymerization activity and hydrogen sensitivity; in the third aspect, the spherical / subspherical powder particles obtained by the present application have high bulk density and fluidity.

[0060] (2) The preparation method of the catalyst component for olefin polymerization of the present application is simpler and more controllable, and can obtain spherical / subspherical catalyst components, polymer powders and catalysts.

[0061] (3) The catalyst for olefin polymerization of the present application belongs to a dissolution and precipitation type catalyst, and different particle sizes of the catalyst can be obtained by using different conditions. Therefore, the catalyst with a relatively wide particle size range can be obtained by the method of the present application, which is an important embodiment of one of the superiorities of the present application. The catalyst product with a specific particle size can be produced according to the needs of different markets.

[0062] In summary, the present application realizes the improvement of the performance of the existing Ziegler-Natta type olefin polymerization catalyst particles, and the prepared catalyst component is spherical / spherical-like and has better polymerization activity, hydrogen sensitivity, bulk density, particle size distribution, and has extremely high popularization and application value. BRIEF DESCRIPTION OF DRAWINGS

[0063] Figure 1 Electron micrograph of the prior art non-spherical N series polyolefin catalyst (scale is 20 μm).

[0064] Figure 2 Electron micrograph of the catalyst component of Example 1 (scale is 1 μm).

[0065] Figure 3 Electron micrograph of the catalyst component of Example 2 (scale is 10 μm).

[0066] Figure 4 Electron micrograph of the polymer powder of Example 2 (scale is 50 μm).

[0067] Figure 5 Electron micrograph of the catalyst component of Comparative Example 4 (scale is 4 μm).

[0068] Note: Some catalyst particles have cracking phenomenon, which is caused by vacuum extraction during electron micrograph testing, and is not due to the original particle cracking. DETAILED DESCRIPTION

[0069] The following specific embodiments of the present application will be described in detail with reference to the specific drawings, and it is necessary to point out here that the following embodiments are only used to further illustrate the present application, and cannot be understood as limiting the protection scope of the present application. Some non-essential improvements and adjustments of the present application made by those skilled in the art according to the content of the present application still belong to the protection scope of the present application.

[0070] In the present application, the inert diluent used after aging is completed and the mother liquor is filtered off includes any one of isobutane, hexane, heptane, cyclohexane, naphtha, raffinate oil, hydrogenated gasoline, kerosene, benzene, toluene, xylene and other saturated aliphatic hydrocarbons or aromatic hydrocarbons and other inert solvents.

[0071] In the present application, the term "aliphatic hydrocarbon group" refers to a straight-chain or branched-chain alkyl group, which is composed of only carbon atoms and hydrogen atoms, and specific examples include but are not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, ethenyl, 1-propenyl, allyl, ethynyl, 1-propynyl, 2-propynyl, butynyl, etc.

[0072] In the present application, "aromatic hydrocarbon group" refers to a hydrocarbon group having a benzene ring, including aryl group, aryl-substituted hydrocarbon group or hydrocarbon-substituted aryl group, such as phenyl, benzyl, anthracenyl and naphthyl, etc.

[0073] In the present application, the triethyl aluminum solution is a solution of triethyl aluminum dissolved in hexane.

[0074] In the present application, Figure 1 An electron microscope photograph of a prior art non-spherical N-series polyolefin catalyst prepared by the following method: 4.8 g of magnesium chloride, 90 ml of toluene, 5.0 ml of epichlorohydrin, and 15.0 ml of tri-n-butyl phosphate were added into a reaction kettle, and stirred at a stirring speed of 450 rpm and a temperature of 60°C for 2 hours. Then, 1.1 g of phthalic anhydride was added, and the temperature was kept constant for 1 hour. The temperature was then lowered to -40°C, and 70 ml of titanium tetrachloride was added dropwise. Then, the temperature was gradually increased to 90°C, and kept constant for 1 hour. The mother liquor was filtered off, and washed with inert diluent toluene and organic solvent hexane for several times, and dried to obtain a solid catalyst component with good fluidity.

[0075] In the present application, the test methods used in the examples and comparative examples are as follows:

[0076] (1) Measurement of catalyst component / polymer powder morphology: Hitachi S-4800 scanning electron microscope was used.

[0077] (2) Measurement of polymer bulk density: ASTM D1895 Plastic Apparent Density, Volume Factor and Pourability Test Method was used.

[0078] (3) Particle size distribution of catalyst component: Malvern laser particle size analyzer was used.

[0079] (4) Relative weight percentage of titanium element in catalyst component: spectrophotometry was used.

[0080] (5) Melt index (MI / 2.16 Kg) of polymer powder: ASTM D1238-99 was used.

[0081] (6) Polymer powder repose angle: BOS-1007 repose angle tester of Xiamen Boshi Testing Equipment Co., Ltd. was used according to GB / T 16913-2008.

[0082] The raw materials used in the examples and comparative examples are all conventional commercially available raw materials.

[0083] The instruments used in the examples and comparative examples are all conventional commercially available instruments.

[0084] Example 1

[0085] (1) Preparation of catalyst component A1

[0086] Into a reaction vessel were introduced 4.8 g of magnesium chloride, 90 ml of toluene, 5.0 ml of epichlorohydrin, 15.0 ml of tri-n-butyl phosphate, and the mixture was stirred at 450 rpm and 60°C for 2 hours. Then, 1.2 g of phthalic anhydride was added and the mixture was stirred at the same temperature for another hour. The temperature was then lowered to -40°C, and 70 ml of titanium tetrachloride and 2 ml of ethyl acetate and 4 ml of ethanol were added dropwise. The temperature was then raised to 90°C and the mixture was stirred at this temperature for 1 hour to obtain a reaction mother liquor and a precipitate. To the reaction mother liquor and the precipitate was added 2 ml of hexaethoxydisilane, and the mixture was stirred at the same temperature for another hour. The mother liquor was filtered off and washed with toluene and hexane to obtain catalyst component A1 in the form of a solid having good flowability. The titanium content and particle size of catalyst component A1 are shown in Table 1, and the electron micrograph of catalyst component A1 is shown in Fig. 1. Figure 2 .

[0087] (2) Polymerization

[0088] Polymerization with low hydrogen / ethylene ratio: Into a 2 L stainless steel reaction vessel which had been sufficiently purged with high-purity nitrogen was introduced 1 L of hexane and 1.0 ml of a 1 M triethylaluminum solution, followed by catalyst component A1 (containing 0.6 mg of titanium) prepared by the above method. The temperature was raised to 70°C, and hydrogen was introduced to make the pressure in the vessel 0.28 MPa (gauge pressure). Then, ethylene was introduced to make the total pressure in the vessel 0.73 MPa, and the mixture was polymerized at 80°C for 2 hours. The polymerization results are shown in Table 2, and the rest angle of the polymer was measured after the polymerization, and the results are shown in Table 3.

[0089] Polymerization with high hydrogen / ethylene ratio: Into a 2 L stainless steel reaction vessel which had been sufficiently purged with high-purity nitrogen was introduced 1 L of hexane and 1.0 ml of a 1 M triethylaluminum solution, followed by catalyst component A1 (containing 1.8 mg of titanium) prepared by the above method. The temperature was raised to 75°C, and hydrogen was introduced to make the pressure in the vessel 0.58 MPa (gauge pressure). Then, ethylene was introduced to make the total pressure in the vessel 0.73 MPa, and the mixture was polymerized at 85°C for 2 hours. The polymerization results are shown in Table 2.

[0090] Example 2

[0091] (1) Preparation of catalyst component A2

[0092] Into a reaction vessel were introduced 4.8 g of magnesium chloride, 90 ml of toluene, 3.6 ml of epichlorohydrin, and 16.0 ml of tri-n-butyl phosphate, and the mixture was reacted at 70°C for 2 hours under stirring at 300 rpm. Then, 1.5 g of phthalic anhydride was added, and the mixture was further reacted at the same temperature for 1 hour. After the temperature was lowered to -40°C, 50 ml of titanium tetrachloride was added dropwise, followed by dropwise addition of 1 ml of ethyl acetate, 2 ml of ethanol, and 2 ml of butanol. Subsequently, the temperature was gradually increased to 90°C, and the mixture was reacted for 1 hour to obtain a reaction mother liquor and a precipitate. To the reaction mother liquor and the precipitate was added 3 ml of hexaethyl disilazane, and the mixture was further reacted at the same temperature for 1 hour. The mother liquor was filtered off, and the precipitate was washed with toluene and hexane, and then dried to obtain a solid catalyst component A2 having good fluidity. The titanium content and particle size of the catalyst component A2 are shown in Table 1, and an electron microscope photograph of the catalyst component A2 is shown in Fig. 1. Figure 3 .

[0093] (2) Polymerization reaction

[0094] Polymerization at a low hydrogen / ethylene ratio: The polymerization was carried out in the same manner as in Example 1, except that the catalyst component A2 was used instead of the catalyst component Al. The polymerization results are shown in Table 2. Figure 4 .

[0095] Polymerization at a high hydrogen / ethylene ratio: The polymerization was carried out in the same manner as in Example 1, except that the catalyst component A2 was used instead of the catalyst component Al. The polymerization results are shown in Table 2.

[0096] Example 3

[0097] (1) Preparation of catalyst component A3

[0098] Into a reaction vessel were introduced 4.8 g of magnesium chloride, 90 ml of toluene, 3.6 ml of epichlorohydrin, and 16.0 ml of tri-n-butyl phosphate, and the mixture was reacted at 70°C for 2 hours under stirring at 300 rpm. Then, 1.5 g of phthalic anhydride was added, and the mixture was further reacted at the same temperature for 1 hour. After the temperature was lowered to -40°C, 50 ml of titanium tetrachloride was added dropwise, followed by dropwise addition of 1 ml of ethyl acetate, 2 ml of ethanol, and 2 ml of butanol. Subsequently, the temperature was gradually increased to 90°C, and the mixture was reacted for 1 hour to obtain a reaction mother liquor and a precipitate. To the reaction mother liquor and the precipitate was added 3 ml of hexaethyl disilazane, and the mixture was further reacted at the same temperature for 1 hour. The mother liquor was filtered off, and the precipitate was washed with toluene and hexane, and then dried to obtain a solid catalyst component A2 having good fluidity. The titanium content and particle size of the catalyst component A2 are shown in Table 1, and an electron microscope photograph of the catalyst component A2 is shown in Fig. 1.

[0099] (2) Polymerization reaction

[0100] Polymerization at a low hydrogen / ethylene ratio: The polymerization was carried out in the same manner as in Example 1, except that the catalyst component A2 was used instead of the catalyst component Al. The polymerization results are shown in Table 2.

[0101] Polymerization with a high hydrogen-to-ethyl ratio: This is basically the same as in Example 1, except that catalyst component A3 is used instead of catalyst component A1. The polymerization results are shown in Table 2.

[0102] Example 4

[0103] (1) Preparation of catalyst component A4

[0104] 4.8 g magnesium chloride, 120 ml toluene, 8.0 ml epichlorohydrin, and 14.0 ml triisobutyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 55°C with a stirring speed of 400 rpm. Then, 1.2 g 3-methylphthalic anhydride was added, and the mixture was kept at a constant temperature for another hour. The temperature was then lowered to -40°C, and 80 ml titanium tetrachloride was added dropwise, followed by 1.0 ml methyl acetate and 3.0 ml isopropanol. The temperature was then gradually increased to 85°C, and the reaction was continued for 1 hour, yielding a mother liquor and a precipitate. 2 ml of 1,2-bis(triethoxysilyl)ethane ((EtO)3Si-CH2-CH2-Si(OEt)3) was added dropwise to the mother liquor and precipitate, and the mixture was kept at a constant temperature for another hour. The mother liquor was filtered off, and the mixture was washed repeatedly with toluene (an inert diluent) and hexane (an organic solvent), and then dried to obtain a solid with good flowability—catalyst component A4. The titanium content and particle size of catalyst component A4 are shown in Table 1.

[0105] (2) Polymerization reaction

[0106] Polymerization with low hydrogen-to-ethyl ratio: It is basically the same as in Example 1, except that catalyst component A4 is used instead of catalyst component A1. The polymerization results are shown in Table 2.

[0107] Polymerization with a high hydrogen-to-ethyl ratio: This is basically the same as in Example 1, except that catalyst component A4 is used instead of catalyst component A1. The polymerization results are shown in Table 2.

[0108] Example 5

[0109] (1) Preparation of catalyst component A5

[0110] 4.8 g magnesium chloride, 90 ml toluene, 5.0 ml epichlorohydrin, and 15.0 ml triisobutyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 55°C with a stirring speed of 400 rpm. Then, 1.2 g phthalic anhydride was added, and the reaction was maintained at this temperature for another hour. The temperature was then lowered to -40°C, and 70 ml titanium tetrachloride was added dropwise, followed by 1.0 ml ethyl acetate, 1.5 ml n-butanol, and 3 ml hexaethyl pyrosilicon. The temperature was then gradually increased to 85°C and maintained at this temperature for 1 hour. During this isothermal process, a mother liquor and a precipitate were obtained. The mother liquor and precipitate were then aged at this isothermal temperature. The mother liquor was filtered off, and the mixture was washed multiple times with inert diluent toluene and organic solvent hexane, and then dried to obtain a solid with good flowability—catalyst component A5. The titanium content and particle size of catalyst component A5 are shown in Table 1.

[0111] (2) Polymerization reaction

[0112] Polymerization with low hydrogen-to-ethyl ratio: It is basically the same as in Example 1, except that catalyst component A5 is used instead of catalyst component A1. The polymerization results are shown in Table 2.

[0113] Polymerization with a high hydrogen-to-ethyl ratio: This is basically the same as in Example 1, except that catalyst component A5 is used instead of catalyst component A1. The polymerization results are shown in Table 2.

[0114] Comparative Example 1

[0115] (1) Preparation of catalyst component D1

[0116] 4.8 g magnesium chloride, 90 ml toluene, 5.0 ml epichlorohydrin, and 15.0 ml tri-n-butyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 450 rpm and 60°C. Then, 1.2 g phthalic anhydride was added, and the reaction was continued at a constant temperature for 1 hour. The temperature was then lowered to -40°C, and 70 ml titanium tetrachloride was added dropwise, followed by 2 ml ethyl acetate and 4 ml ethanol. The temperature was then gradually increased to 90°C, and the reaction was continued for 1 hour, yielding a mother liquor and a precipitate. The mother liquor was filtered off, and the mixture was washed repeatedly with inert diluent toluene and organic solvent hexane, then dried to obtain a solid with good flowability—catalyst component D1. The titanium content and particle size of catalyst component D1 are shown in Table 1.

[0117] (2) Polymerization reaction

[0118] Polymerization with low hydrogen-to-ethyl ratio: It is basically the same as in Example 1, except that catalyst component D1 is used instead of catalyst component A1. The polymerization results are shown in Table 2.

[0119] Polymerization with a high hydrogen-to-ethyl ratio: This is basically the same as in Example 1, except that catalyst component D1 is used instead of catalyst component A1. The polymerization results are shown in Table 2.

[0120] A 2L stainless steel reactor was fully purged with high-purity nitrogen, then 1L of hexane and 1.0ml of 1M triethylaluminum solution were added, followed by solid catalyst component D1 (containing 0.6 mg of titanium) prepared by the above method. The temperature was raised to 80℃, and ethylene was introduced to bring the total pressure inside the reactor to 1.0 MPa (gauge pressure). Polymerization was carried out at 80℃ for 2 hours. The polymerization results are shown in Table 3.

[0121] Comparative Example 2

[0122] (1) Preparation of catalyst component D2

[0123] 4.8 g magnesium chloride, 90 ml toluene, 3.6 ml epichlorohydrin, and 16.0 ml tri-n-butyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 70°C and 300 rpm. Then, 1.5 g phthalic anhydride was added, and the reaction was continued at this temperature for another hour. The temperature was then lowered to -40°C, and 50 ml titanium tetrachloride was added dropwise, followed by 1 ml ethyl acetate, 2 ml ethanol, and 2 ml butanol. The temperature was then gradually increased to 90°C, and the reaction was continued for 1 hour, yielding a mother liquor and a precipitate. 3 ml ethyl benzoate was added dropwise to the mother liquor and precipitate, and the reaction was continued at this temperature for another hour. The mother liquor was filtered off, and the mixture was washed repeatedly with toluene (an inert diluent) and hexane (an organic solvent), and then dried to obtain a solid with good flowability—catalyst component D2. The titanium content and particle size of catalyst component D2 are shown in Table 1.

[0124] (2) Polymerization reaction

[0125] Polymerization with low hydrogen-to-ethyl ratio: It is basically the same as in Example 1, except that catalyst component D2 is used instead of catalyst component A1. The polymerization results are shown in Table 2.

[0126] Polymerization with a high hydrogen-to-ethyl ratio: This is basically the same as in Example 1, except that catalyst component D2 is used instead of catalyst component A1. The polymerization results are shown in Table 2.

[0127] Comparative Example 3

[0128] (1) Preparation of catalyst component D3

[0129] 4.8 g magnesium chloride, 105 ml toluene, 6.0 ml epichlorohydrin, and 20.0 ml tri-n-butyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 50°C and 350 rpm. Then, 1.0 g phthalic anhydride was added, and the reaction was continued at this temperature for another hour. The temperature was then lowered to -40°C, and 60 ml titanium tetrachloride was added dropwise, followed by 1.5 ml ethyl acetate and 4 ml ethanol. The temperature was then gradually increased to 85°C, and the reaction was continued for 1 hour, yielding a mother liquor and a precipitate. 3 ml tetraethyl orthocarbonate was added dropwise to the mother liquor and precipitate, and the reaction was continued at this temperature for another hour. The mother liquor was filtered off, and the mixture was washed repeatedly with toluene (an inert diluent) and hexane (an organic solvent), and then dried to obtain a solid with good flowability—catalyst component D3. The titanium content and particle size of catalyst component D3 are shown in Table 1.

[0130] (2) Polymerization reaction

[0131] Polymerization with low hydrogen-to-ethyl ratio: It is basically the same as in Example 1, except that catalyst component D3 is used instead of catalyst component A1. The polymerization results are shown in Table 2.

[0132] Polymerization with a high hydrogen-to-ethyl ratio: This is basically the same as in Example 1, except that catalyst component D3 is used instead of catalyst component A1. The polymerization results are shown in Table 2.

[0133] Comparative Example 4

[0134] (1) Preparation of catalyst component D4

[0135] Catalyst component D4 was prepared according to the method described in Example 1 of patent CN1958620A. The titanium content and particle size of catalyst component D4 are shown in Table 1. Electron micrographs of catalyst component D4 are shown in... Figure 5 .

[0136] (2) Polymerization reaction

[0137] Polymerization with low hydrogen-to-ethyl ratio: It is basically the same as in Example 1, except that catalyst component D4 is used instead of catalyst component A1. The polymerization results are shown in Table 2. The angle of repose was measured after polymerization, and the results are shown in Table 3.

[0138] Polymerization with a high hydrogen-to-ethyl ratio: This is basically the same as in Example 1, except that catalyst component D4 is used instead of catalyst component A1. The polymerization results are shown in Table 2.

[0139] Comparative Example 5

[0140] (1) Preparation of catalyst component D5

[0141] 4.8 g magnesium chloride, 90 ml toluene, 5.0 ml epichlorohydrin, and 15.0 ml triisobutyl phosphate were added to a reactor. The mixture was reacted for 2 hours at 55°C with a stirring speed of 400 rpm. Then, 1.2 g phthalic anhydride was added, and the reaction was continued at a constant temperature for 1 hour. The temperature was then lowered to -40°C, and 70 ml titanium tetrachloride was added dropwise, followed by 1.0 ml ethyl acetate, 1.5 ml n-butanol, and 3 ml tetraethyl orthocarbonate. The temperature was then gradually increased to 85°C and the reaction was continued for 1 hour. During this constant temperature process, a mother liquor and a precipitate were obtained. The mother liquor and precipitate were then aged at a constant temperature. The mother liquor was filtered off, and the mixture was washed multiple times with inert diluent toluene and organic solvent hexane, and then dried to obtain a solid with good flowability—catalyst component D5. The titanium content and particle size of catalyst component D5 are shown in Table 1.

[0142] (2) Polymerization reaction

[0143] Polymerization with low hydrogen-to-ethyl ratio: It is basically the same as in Example 1, except that catalyst component D5 is used instead of catalyst component A1. The polymerization results are shown in Table 2.

[0144] Polymerization with a high hydrogen-to-ethyl ratio: This is basically the same as in Example 1, except that catalyst component D5 is used instead of catalyst component A1. The polymerization results are shown in Table 2.

[0145] Will Figures 2 to 5 and Figure 1 As can be seen from the comparison, the embodiments of the present invention can obtain spherical / quasi-spherical polyethylene catalyst particles with very uniform particle morphology, and can polymerize to obtain spherical / quasi-spherical powder particles, which is something that existing N-series polyolefin catalysts and Comparative Example 4 cannot achieve.

[0146] Table 1. Particle size and titanium content of the catalyst components prepared in Examples 1-5 and Comparative Examples 1-5

[0147]

[0148]

[0149] As shown in Table 1, adding organosilicon compounds during the aging stage only affects the titanium content of the catalyst, but not the particle size of the catalyst components. This is because the catalyst has already completed its growth at this stage, and the organosilicon compounds only optimize the active sites. However, adding organosilicon compounds before the aging stage of the catalyst will affect both the titanium content and the particle size of the catalyst.

[0150] Meanwhile, as can be seen from Examples 1 to 5 of this application, the present invention belongs to the dissolution-eluent type catalyst, which can obtain a relatively wide particle size range. This is another important manifestation of the superiority of the present invention, thereby enabling the production of catalyst products with specific particle sizes to meet different needs.

[0151] Table 2 shows the polymerization results of the catalyst components prepared in Examples 1-5 and Comparative Examples 1-5.

[0152]

[0153]

[0154] As shown in Table 2, a comparison of Examples 1-5 of the present invention with existing commercial catalysts (Comparative Example 4) reveals that the catalyst of the present invention has a significantly higher powder bulk density and superior hydrogen sensitivity (melt index). For polyethylene catalysts, in the production of bimodal resins, it is necessary to produce low molecular weight components in the first reactor with a high hydrogen-to-ethyl ratio and produce high molecular weight components in the second reactor with a low hydrogen-to-ethyl ratio. Relatively speaking, the hydrogen sensitivity of the catalyst in the first reactor directly affects its polymerization activity; therefore, higher polymerization activity under high hydrogen-to-ethyl ratio conditions is more important for the catalyst.

[0155] Although the polymerization activity of the catalyst of the present invention is slightly lower than that of Comparative Example 4 under low hydrogen-to-ethyl ratio conditions, its polymerization activity is higher than that of Comparative Example 4 under high hydrogen-to-ethyl ratio conditions. Furthermore, the melt index of the catalyst of the present invention is comparable to that of Comparative Example 4 under low hydrogen-to-ethyl ratio conditions, but higher under high hydrogen-to-ethyl ratio conditions. This indicates that the catalyst of the present invention exhibits superior polymerization activity and hydrogen sensitivity compared to Comparative Example 4 when producing bimodal resins (such as pipe materials and membrane materials) in industrial applications. In other words, the catalyst of the present invention can meet the requirements of industrial production equipment for high polymerization activity and high hydrogen sensitivity.

[0156] As shown in Table 2, comparing Examples 1-5 with Comparative Examples 1-5, the catalyst of the present invention exhibits significantly higher polymerization activity and relatively higher powder bulk density. This is because the organosilicon compound can modify the active sites of the catalyst. Furthermore, Examples 1-5 of the present invention show lower melt flow indexes under low ethylene hydrogen-to-hydrogen ratio (HHH-E) conditions and higher melt flow indexes under high HHH-E ratio conditions, making them highly suitable for producing bimodal resin products. This is because when producing low molecular weight components in the first reactor with a high HHH-E ratio, Examples 1-5 can achieve the required melt flow index even with a relatively low HHH-E ratio, resulting in higher catalyst polymerization activity. However, when producing high molecular weight components in the second reactor with a low HHH-E ratio, Examples 1-5 require an increased HHH-E ratio to achieve the required melt flow index, leading to more stable production control and reducing the likelihood of product quality fluctuations.

[0157] Table 3 shows the comparison of the angle of repose of the low-hydrogen ethyl ratio powders from Example 1 and Comparative Example 4.

[0158] Repose angle (°) Example 1 45.7 Comparative Example 4 54.2

[0159] As shown in Table 3, a comparison of the angle of repose of the low hydrogen-to-ethyl ratio powders of Example 1 and Comparative Example 4 shows that the powder of Example 1 has a smaller angle of repose, indicating that it has better flowability, which is consistent with its spherical / quasi-spherical powder morphology.

Claims

1. A catalyst component for olefin polymerization, characterized in that: The catalyst component for olefin polymerization includes the reaction products of the following components: magnesium complex, organic acid anhydride compounds, acetate compounds, primary alcohol compounds, titanium-containing compounds, and organosilicon compounds; The magnesium complex is obtained by dissolving magnesium halide in a solvent system, wherein the solvent system includes an organic epoxy compound and an organophosphorus compound; the general formula of the organosilicon compound is shown in formula (1). R 1a R 2b (OR3) c Si—M—Si(OR 3’ ) d R 1’e R 2’f Formula (1) In equation (1), R1, R2, R 1’ R 2’ Each is independently selected from C1 to C2. 10 Hydrocarbon groups or halogens, R3, R 3’ For C1~C 10 Hydrocarbon group; M is O or -(CH2) n -, n≥0; 0≤a≤2, 0≤b≤2, 0≤c≤3, 0≤d≤3, 0≤e≤2, 0≤f≤2, a+b+c=3, d+e+f=3, a, b, c, d, e, f, n are integers, and c and d are not both 0.

2. The catalyst component as described in claim 1, characterized in that: R1, R2, R 1’ R 2’ Each is independently selected from C1–C6 hydrocarbon groups or halogens; and / or R3, R 3’ Each is independently selected from C1 to C2. 10 Alkyl groups; and / or n is 0-10; Preferred, R1, R2, R 1’ R 2’ Each is independently selected from -CH3, -C2H5, -Cl, -Br; and / or R3, R 3’ Each is independently selected from -CH3, -C2H5, -C3H7; and / or n is 0-5; More preferably, R1, R2, R 1’ R 2’ Each is independently selected from -CH3, -Cl; and / or R3, R 3’ Each is independently selected from -CH3, -C2H5; and / or M is -(CH2) n - 3. The catalyst component as described in claim 1, characterized in that: The magnesium halide is selected from magnesium dihalide or a complex formed by magnesium dihalide with water, a second alcohol compound, and an electron carrier; preferably, the magnesium dihalide is selected from at least one of magnesium dichloride, magnesium dibromide, magnesium difluoride, and magnesium diiodide; the second alcohol compound is selected from at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, and isooctyl alcohol; the electron carrier is selected from at least one of ammonia, hydroxylamine, ether, and ester; and / or The organic epoxy compound is selected from C2 to C3. 18 The organic epoxy compound is selected from at least one of aliphatic olefins, aliphatic dienes, halogenated aliphatic olefins or oxides of halogenated aliphatic dienes, glycidyl ethers, and internal ethers; preferably, the organic epoxy compound is selected from at least one of ethylene oxide, propylene oxide, epibutane oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether, and butyl glycidyl ether; and / or The organophosphorus compound is a hydrocarbon ester or haloalkyl ester of phosphoric acid or phosphorous acid; preferably, the organophosphorus compound is selected from at least one of trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, triisopropyl phosphate, tri-n-butyl phosphate, triisobutyl phosphate, tri-tert-butyl phosphate, tri-n-pentyl phosphate, triisopentyl phosphate, tri-n-hexyl phosphate, triisohexyl phosphate, tri-n-heptyl phosphate, triisoheptyl phosphate, tri-n-octyl phosphate, triisooctyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, tri-tert-butyl phosphite, tri-n-pentyl phosphite, triisopentyl phosphite, tri-n-hexyl phosphite, triisoheptyl phosphite, tri-n-octyl phosphite, triisooctyl phosphite, triphenyl phosphite, and di-n-butyl phosphite; and / or, The structure of the organic acid anhydride compound is shown in formula (2): In equation (2), R5 and R6 may be the same or different, and each is independently hydrogen, C1 to C6. 10 Alkyl, C2-C 10 alkenyl, C2-C 10 alkynyl group, C3~C 10 cycloalkyl or C6-C 10 Aromatic hydrocarbon groups, and R5 and R6 can form rings in any way; and / or, The general formula of the titanium-containing compound is Ti(OR4). a X b ; Where R4 is C1~C 10 The aliphatic or aromatic hydrocarbon group; X is a halogen, preferably fluorine, chlorine, or bromine; a is an integer from 0 to 2, b is an integer from 1 to 4, a+b=3 or 4; and / or, The general formula of the acetate compounds is CH3COOR7, where R7 is C1 to C2. 10 Alkyl, C2-C 10 alkenyl, C3~C 10 cycloalkyl, C2-C 10 Alkyne group or C6~C 10 The aromatic hydrocarbon group; preferably, R7 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, cyclopropyl, methylcyclopropyl, n-pentyl, methylcyclopentyl, cyclohexyl, phenyl, benzyl, or xylyl; and / or, The first alcohol compound is selected from C1 to C2. 18 The fatty alcohol or aromatic alcohol is preferably at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, hexanol, cyclohexanol, octanol, isooctanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, propylene glycol, butanediol, hexanediol, and isohexanediol; more preferably at least one of butanol, isobutanol, tert-butanol, hexanol, cyclohexanol, octanol, isooctanol, benzyl alcohol, phenethyl alcohol, butanediol, hexanediol, and isohexanediol.

4. The catalyst component as described in claim 1, characterized in that: Based on each mole of magnesium in the magnesium halide, the amount of the organic epoxy compound is 0.2 to 10 moles; the amount of the organic phosphorus compound is 0.1 to 10 moles; the amount of the organic acid anhydride compound is 0.03 to 1.0 moles; the amount of the titanium-containing compound is 0.5 to 120 moles; the amount of the acetate compound is 0.01 to 1 mole; the amount of the first alcohol compound is 0.1 to 4 moles; and the amount of the organosilicon compound is 0.01 to 1 mole. Preferably, based on each mole of magnesium in the magnesium halide, the amount of the organic epoxy compound is 0.5–2.0 moles; the amount of the organic phosphorus compound is 0.5–2.0 moles; the amount of the organic acid anhydride compound is 0.1–0.3 moles; the amount of the titanium-containing compound is 5–20 moles; the amount of the acetate compound is 0.05–0.4 moles; the amount of the first alcohol compound is 0.1–2.0 moles; and the amount of the organosilicon compound is 0.1–0.5 moles. More preferably, based on each mole of magnesium in the magnesium halide, the amount of the organic epoxy compound is 0.5 to 1.5 moles; the amount of the organic phosphorus compound is 0.5 to 1.5 moles; the amount of the organic acid anhydride compound is 0.15 to 0.3 moles; the amount of the titanium-containing compound is 5 to 15 moles; the amount of the acetate compound is 0.05 to 0.2 moles; the amount of the first alcohol compound is 0.1 to 1 mole; and the amount of the organosilicon compound is 0.1 to 0.3 moles.

5. The catalyst component as described in claim 1, characterized in that: The solvent system further includes an inert diluent, which is selected from aromatic compounds and / or alkane compounds; Preferably, The aromatic compounds include at least one of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene, and / or derivatives; and / or, The alkane compounds include at least one of straight-chain alkanes, branched alkanes, or cycloalkanes having 3 to 20 carbon atoms; More preferably, the amount of the inert diluent is 2 to 60 moles per mole of magnesium in the magnesium halide, preferably 15 to 30 moles.

6. A method for preparing a catalyst component for olefin polymerization as described in any one of claims 1 to 5, characterized in that... The preparation method includes: S1: Dissolve magnesium halide in the solvent system and react with the temperature to obtain a magnesium complex; S2: The magnesium complex is mixed with the organic acid anhydride compound, heated to react, and then cooled; S3: The first mixture reacts with the titanium-containing compound to obtain a second mixture; S4: The second mixture reacts with the first alcohol compound, and the reaction is heated to obtain a mother liquor and a precipitate; S5: The reaction mother liquor and the precipitate are subjected to aging treatment to obtain a catalyst component for olefin polymerization; The organosilicon compound is added in at least one of steps S3, S4, and S5; and / or The acetate compound is added in at least one of steps S1, S2, S3, S4, and S5; Preferably, the acetate compound is added in step S4.

7. The preparation method according to claim 6, characterized in that: The organosilicon compound is added in step S4; or The organosilicon compound is added in step S5.

8. The preparation method according to claim 6, characterized in that: In step S1, the temperature is raised to 40–100°C, preferably 55–60°C; the reaction time is 1–4 hours, preferably 1–3 hours; and / or In step S2, the reaction temperature is 40–100°C, preferably 55–60°C; the reaction time is 0.5–2 hours, preferably 1–2 hours; and / or In step S2, the temperature is lowered to -60 to 0°C, preferably -50 to -20°C; and / or In step S3, the reaction temperature is -60 to 0°C, preferably -50 to -20°C; and / or In step S4, the temperature is raised to 70–120°C, preferably 80–90°C; the reaction time is 0.2–10 hours, preferably 1–6 hours; and / or In step S5, the aging treatment temperature is 70-120℃, preferably 80-90℃; the aging treatment time is 0.2-4 hours, preferably 0.8-2 hours.

9. A catalyst for olefin polymerization, characterized in that: Includes the following components: A): The catalyst component for olefin polymerization as described in any one of claims 1 to 5, or the catalyst component for olefin polymerization prepared by the preparation method as described in any one of claims 6 to 8; B): An organoaluminum compound with the general formula AlR’ d X’ 3-d where R’ is hydrogen or a C l -C 20 hydrocarbyl group; X’ is a halogen atom, preferably fluorine, chlorine or bromine, 0 < d ≤ 3, and d is an integer; Preferably, the molar ratio of aluminum in component B) to titanium in component A) is (20-200):1, more preferably (50-100):

1.

10. The use of a catalyst component as described in any one of claims 1 to 5, or a catalyst component prepared by any one of claims 6 to 8, or a catalyst as described in claim 9, in ethylene polymerization.

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