A catalyst component for the polymerization of olefins, a process for its preparation, a catalyst and the use thereof

Abstract

This invention provides a catalyst component for olefin polymerization, its preparation method, the catalyst itself, and its applications. The catalyst component is prepared by reacting raw materials including a magnesium complex, a precipitation aid, a titanium-containing compound, an acetate compound, an organic alcohol compound, an organoaluminum compound (N), and an electron donor compound. The catalyst provided by this invention is used in olefin polymerization to prepare high / ultra-high molecular weight polyolefins. The prepared polymers exhibit controllable molecular weight, narrow molecular weight distribution, low hexane extract content, low content of large particles and fine powders, low branching degree, high sphericity, and good low entanglement properties.

Description

Technical Field

[0001] This invention relates to the field of olefin polymerization technology, and more specifically, to a catalyst component for olefin polymerization and its preparation method, as well as the catalyst obtained from the catalyst component and its application. Background Technology

[0002] Ultra-high molecular weight polyethylene (UHMWPE) is a special polyethylene product with a molecular weight greater than 1.5 million. It possesses comprehensive properties unmatched by ordinary polyethylene and other engineering plastics, including wear resistance, impact resistance, self-lubrication, corrosion resistance, low-temperature resistance, hygiene and non-toxicity, non-adhesion, low water absorption, and low density. However, the difficulty in processing UHMWPE has hindered its large-scale application.

[0003] Very high molecular weight polyethylene (VHMWPE) is a polyethylene product with a molecular weight between 300,000 and 1,500,000. It has excellent mechanical properties, ultra-high impact strength and excellent wear resistance.

[0004] Compared to ultra-high molecular weight polyethylene (UHMWPE), UHMWPE offers superior molding and processing properties, making it suitable for applications where performance is better than conventional polyethylene at a lower cost. Its downstream applications typically include pressed sheets, extruded profiles, pipes, battery separators, sintered filter media, and modified extruded UHMWPE granules. A novel application for UHMWPE is in wet-process lithium-ion battery separators, particularly separators produced using the wet biaxial stretching method, which exhibits higher longitudinal and transverse strength.

[0005] Currently, most widely used high-end special / ultra-high molecular weight polyethylene products are imported. Key factors required for high-end polyethylene products include:

[0006] 1. It has a sufficiently high molecular weight and a narrow molecular weight distribution;

[0007] 2. It has a low content of hexane extract and low ash content;

[0008] 3. Low content of large particles and fine powder.

[0009] For example, when polyethylene products are used in fields such as lithium battery separators or artificial joints, lower ash content can improve the product's resistance to puncture and reduce its impact on the human body; a low content of large particles and fine powder can ensure the stability and continuity of the production process and improve product performance.

[0010] Meanwhile, researchers found that when polymer particles are uniform, have a narrow molecular weight distribution, low hexane extractable content, high sphericity, low content of large particles and fine powder, and low branching and entanglement, it is easier to process and produces higher quality ultra-high molecular weight polyethylene (UHMWPE) using plunger extrusion, compression molding, and dry / wet biaxial stretching methods. Currently, most commercially available UHMWPE or UHMWPE is prepared using Ziegler-Natta catalysts (ZN catalysts), but polyethylene products prepared with this catalyst rarely meet the above requirements. Summary of the Invention

[0011] To address the aforementioned problems, this invention provides a catalyst component for olefin polymerization, its preparation method, and the catalyst itself. The catalyst provided by this invention not only possesses high activity and packing density, but also produces polymers with tunable molecular weight, narrow molecular weight distribution, low hexane extract content, low content of large particles and fine powders, low branching degree, high sphericity, and good low entanglement properties.

[0012] Firstly, the purpose of this method is to provide a catalyst component for olefin polymerization.

[0013] Specifically, the catalyst component includes the reaction products of the raw materials, including the following components: magnesium complex, precipitation aid, titanium-containing compound, acetate compound, organic alcohol compound, organoaluminum compound N, and electron donor compound; wherein the electron donor compound includes electron donor compound a and / or electron donor compound b.

[0014] Furthermore, in the catalyst composition, each component is defined as follows per mole of magnesium in the magnesium complex:

[0015]

[0016]

[0017] Furthermore, the molar amounts of electron donor a and electron donor b are not both 0.

[0018] Furthermore, the general formula (I) of the electron-donating compound a is as follows:

[0019]

[0020] R1 and R2 are independently methyl or ethyl, and R3 and R4 are independently hydrogen or methyl. Specifically, the electron donor compound a is one or a combination of 2,2-dimethyl-1,3-diethoxy-propane, 2,2-dimethyl-1,3-dimethoxy-propane, 1-ethoxy-3-methoxy-propane, and 2,2-dimethyl-1-ethoxy-3-methoxy-propane.

[0021] Furthermore, the general formula (II) for the electron-donating compound b is as follows:

[0022]

[0023] R5 and R6 are independently methyl or ethyl; R7, R8, R9, R 10 Whether the groups are the same or different, they can be independently hydrogen-based, halogenated, or C1–C2. 10 Straight-chain alkyl groups, C1-C 10 Branched alkyl groups, C1-C 10 One of the alkoxy groups; preferably, R7, R8, R9, R 10 They are, respectively, one of fluorine, chlorine, bromine, iodine, a C1-C6 straight-chain alkyl group, a C1-C6 branched-chain alkyl group, or a C1-C6 alkoxy group. Specifically, the electron donor compound b is one or a combination of o-phenylenedimethyl ether, o-phenylenediethyl ether, and 1-ethoxy-2-methoxybenzene.

[0024] Furthermore, when the electron donor compound is a mixture of electron donor compound a and electron donor compound b, the molar ratio of electron donor compound a to electron donor compound b is 0.01 to 100; preferably 0.05 to 20; more preferably 0.1 to 20.

[0025] Furthermore, in this invention, the magnesium complex is prepared by dissolving a magnesium halide compound in a solvent system comprising an organic epoxy compound and an organophosphorus compound to obtain the magnesium complex.

[0026] Preferably, the organic epoxide is 0.01 to 1 mole per mole of magnesium; more preferably, it is 0.03 to 0.5 moles; and the added organophosphorus compound is 0.01 to 1 mole; more preferably, it is 0.01 to 0.3 moles.

[0027] Preferably, the magnesium halide compound can be one or a combination of magnesium halide, magnesium halide complex with water, alcohol or electron donor Y, magnesium phenoxychloride, magnesium isopropoxychloride, and magnesium butoxychloride.

[0028] More preferably, the magnesium halide is one or a combination of magnesium dichloride, magnesium dibromide, magnesium difluoride, and magnesium diiodide.

[0029] More preferably, the complex of magnesium halide with an alcohol or electron donor Y is a complex of magnesium dihalide with methanol, ethanol, propanol, butanol, pentanol, hexanol, isooctanol, ammonia compounds, hydroxyamine compounds, ether compounds, or ester compounds.

[0030] Preferably, the organic epoxy compound contains C2 to C3. 18The organic epoxy compound is one or a combination of aliphatic olefins, dienes, halogenated aliphatic olefins, oxides of halogenated dienes, glycidyl ethers, and internal ethers. Specifically, the organic epoxy compound is one or a combination of ethylene oxide, propylene oxide, butane oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether, and butyl glycidyl ether.

[0031] Preferably, the organophosphorus compound is one or a combination of a hydrocarbon ester of orthophosphoric acid or phosphorous acid, or a halohydrocarbon ester of orthophosphoric acid or phosphorous acid.

[0032] Specifically, the organophosphorus compound is one or a combination 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.

[0033] Furthermore, in this invention, the precipitation aid is one or a combination of organic acids, organic acid anhydrides, organic ethers, and organic ketones.

[0034] Preferably, the precipitation aid contains C2-C2. 20 One or a combination of organic acids, organic anhydrides, organic ethers, and organic ketones.

[0035] Specifically, the precipitation aid is one or a combination of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, dimethyl ether, diethyl ether, propyl ether, butyl ether, and pentyl ether. Particularly preferred is phthalic anhydride.

[0036] Furthermore, in this invention, the general formula of the titanium-containing compound is Ti(OR) 4 ) e X 1 f Among them, R 4 For those containing C1 to C 10 aliphatic hydrocarbon groups or C6-C 14 The aromatic hydrocarbon group is preferably an alkyl group containing C1 to C6, an alkenyl group containing C2 to C6, or a C3 to C6 group containing C4 to C5. 10 cycloalkyl, C6-C 10 Aromatic hydrocarbon groups, for example, R4 It can be one of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclopropyl, methylcyclopropyl, methylcyclopentyl, cyclohexyl, phenyl, benzyl, and xylylyl; X 1 It is a halogen, preferably one of fluorine, chlorine, bromine, or iodine; e is an integer from 0 to 2, f is an integer from 1 to 4, and e + f = 3 or 4.

[0037] Specifically, the titanium-containing compound is one or a combination of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium trichloride, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloromonoethoxy.

[0038] Furthermore, in this invention, the general formula of the acetate compounds is CH3COOR. 3 , where R 3 For those containing C1 to C 10 Alkyl groups, C2-C 10 alkenyl, C3~C 10 cycloalkyl, C2-C 10 alkynyl group, C6~C 10 One of the aromatic hydrocarbon groups, for example, R 3 It can be one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-octyl ester, cyclopropyl, methylcyclopropyl, methylcyclopentyl, cyclohexyl, phenyl, benzyl, and xylylyl.

[0039] Specifically, the acetate compounds are one or a combination of methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-pentyl acetate, n-hexyl acetate, and n-octyl acetate.

[0040] Furthermore, in this invention, the general formula of the organic alcohol compound is R. 5 OH, where R 5 For those containing C1 to C 10 Alkyl groups, for example, R 5 It can be one of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, or isooctyl.

[0041] Specifically, the alcohol compounds are one or a combination of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, n-hexanol, n-octanol, and isooctanol.

[0042] Furthermore, in this invention, the general formula of organoaluminum compound N is AlR. 6 n X 2 3-n Among them, R 6 It is hydrogen and contains C1 to C2. 20 One or a combination of hydrocarbon groups; X2 The halogen is 0; n is an integer 0 ≤ n ≤ 3.

[0043] Specifically, the organoaluminum compound N is one or a combination of triethylaluminum, diethylaluminum chloride, diethylaluminum chloride, sesquiethylaluminum, diisobutylaluminum chloride, triisobutylaluminum chloride, diisopropylaluminum chloride, methylpropylaluminum chloride, and diphenylaluminum chloride.

[0044] Secondly, another objective of the present invention is to provide a method for preparing a catalyst component for olefin polymerization, which is one of the objectives of the present invention.

[0045] The method includes the following steps:

[0046] Step 1: Dissolve magnesium halide compounds in organic epoxy compounds, organic phosphorus compounds and inert diluent A to form a magnesium-containing complex solution system;

[0047] Step 2: Add a precipitation aid to the solution system obtained in Step 1 and continue the reaction;

[0048] Step 3: Then lower the temperature of the reaction system from Step 2 and add a titanium-containing compound to continue the reaction;

[0049] Step 4: Then, add a mixed solution of inert diluent B containing acetate compounds and organic alcohol compounds to the reaction system of Step 3, either all at once or in stages, and continue the reaction.

[0050] Step 5: Then, add an electron donor compound to the reaction system from Step 4 and continue the reaction.

[0051] Step 6: Wash the mixture obtained in Step 5 with inert diluent A, and then add organoaluminum compound N to continue the reaction treatment to obtain the catalyst component.

[0052] Further, in step one, the reaction conditions for preparing the magnesium-containing complex are: temperature of 40-80℃, preferably 50-70℃; time of 1-5h, preferably 1-3h; and the amount of inert diluent A added per mole of magnesium is 0.01-5 moles, preferably 0.4-2 moles.

[0053] Furthermore, the inert diluent A used in this invention is one or a combination of aromatic compounds and alkane compounds; wherein, the aromatic compound is one or a combination of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene and their derivatives; the alkane compound contains C3 to C4. 20 One or a combination of straight-chain alkanes, branched alkanes, or cycloalkanes with 1 carbon atom.

[0054] Furthermore, in step two, the reaction conditions for adding the precipitation aid are: a temperature of 40–80°C, preferably 50–70°C; and a time of 0.5–3 h.

[0055] Furthermore, in step three, the reaction conditions for adding the titanium-containing compound are: temperature -60 to -30°C; time 0.5 to 3 hours. It is worth mentioning that in this step three, the titanium-containing compound is added dropwise into the reaction vessel over a period of 0.5 to 3 hours. After the titanium-containing compound is added dropwise while the temperature is decreasing, the subsequent components can be added.

[0056] Further, in step four, the amount of inert diluent B added per mole of magnesium is 0.001–2 moles, preferably 0.05–0.5 moles; wherein the conditions under which the inert diluents for acetate compounds and organic alcohol compounds are added in whole or in batches to the reaction system of step three are as follows:

[0057] When a single addition is used, the reaction conditions are: temperature -60 to 30°C, preferably -20 to 20°C; time 0.5 to 3 hours, preferably 1 to 2 hours.

[0058] When using batch addition, the reaction conditions are as follows: the mixed solution of acetate esters and organic alcohols inert diluent B is added in at least two batches; preferably: after the first batch is added, the reaction is kept at a constant temperature for 0.5 to 1 hour, then the temperature is gradually increased to 0 to 30°C, then the remaining mixed solution is added, and the reaction is kept at a constant temperature for another 0.5 to 1 hour, then the temperature is gradually increased to 60 to 100°C, and the reaction is kept at a constant temperature for another 1 to 3 hours; the preferred heating rate of the system is 0.2 to 2°C / min.

[0059] Furthermore, the inert diluent B used in this invention is one or a combination of haloaromatic compounds and haloalkane compounds; wherein, the haloaromatic compounds are aromatic hydrocarbons containing C6 to C8 and their derivatives, for example, they can be monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene and their derivatives, monobromobenzene, dibromobenzene, tribromobenzene, monobromotoluene and their derivatives; the haloalkane compounds are aromatic hydrocarbons containing C3 to C8 and their derivatives. 20 It can be one or a combination of straight-chain haloalkanes, branched haloalkanes, and halocycloalkanes, for example, it can be one or a combination of dichloromethane, trichloromethane, tetrachloromethane, bromoethane, and chloroethane.

[0060] Furthermore, in step five, the reaction conditions for adding the electron donor are: a temperature of 70–95°C; preferably 80–90°C; and a time of 0.5–3 h; preferably 1–2 h.

[0061] Furthermore, in step six, the reaction conditions for adding organoaluminum compound N are: temperature -10 to 100°C; preferably 0 to 20°C; time 0.5 to 3 hours; preferably 1 to 2 hours.

[0062] Among them, in step six, after the reaction of organoaluminum compound N is completed, the reaction system is allowed to stand, the unreacted substances and the solvent are removed, and a solid catalyst component is obtained.

[0063] Thirdly, the third object of the present invention is to provide a catalyst for olefin polymerization, and the catalyst comprises the following components:

[0064] Component 1, the catalyst component for olefin polymerization of the first object of the present invention or the catalyst component prepared by the method of the second object of the present invention;

[0065] Component 2, organoaluminum compound D.

[0066] Among them, the molar ratio of titanium atoms in Component 1 to aluminum atoms in Component 2 is 0.1:1 to 20:1; preferably 0.5:1 to 10:1; more preferably 0.5:1 to 5:1.

[0067] Furthermore, the general formula of organoaluminum compound D is AlR 7 d X 3 3-d ; where R 7 is one or a combination of hydrogen and a hydrocarbon group containing C1-C 20 ; X 3 is a halogen; preferably one of fluorine, chlorine, and bromine; d is an integer of 0 < d ≤ 3.

[0068] Specifically, organoaluminum compound D is one or a combination of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum, diisobutylaluminum, monochlorodiethylaluminum, sesquiethylaluminum, and dichloroethylaluminum.

[0069] Finally, the fourth object of the present invention is to provide the application of the catalyst for olefin polymerization of the third object of the present invention. The catalyst of the third object of the present invention can be used in olefin polymerization reactions. Specifically, it is used in olefin polymerization reactions to prepare special / ultra-high molecular weight polyolefins. The obtained special / ultra-high molecular weight polyolefins have a molecular weight greater than 500,000, a particle size distribution between 75 and 500 μm with a mass fraction ≥ 99%, a span of powder particles ≤ 0.8, a branching degree ≤ 0.5 SCB / 1000C, and have good low entanglement properties.

[0070] Preferably, in the olefin polymerization reaction, the general formula of at least one olefin in the raw material olefins is CH2=CHR, where R is one of hydrogen and an alkyl group of C1-C6.

[0071] It is worth mentioning that in the olefin polymerization reaction, the raw material olefin can be a homopolymer system of ethylene; or a copolymer system of ethylene and / or α-olefin with other comonomers; wherein, the comonomer is preferably one or a combination of propylene, butene, pentene, hexene, octene, and 4-methyl-1-pentene.

[0072] Preferably, the olefin polymerization reaction can be carried out by slurry polymerization or by gas-phase polymerization; wherein the medium for slurry polymerization is one or a combination of isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, and xylene.

[0073] Preferably, the conditions for the olefin polymerization reaction are:

[0074] Reaction pressure: 0.2–1.5 MPa; preferably 0.5–1 MPa;

[0075] Reaction temperature: 70–100℃; preferably 75–85℃;

[0076] Reaction time: 1.5 to 8 hours, preferably 1.5 to 3 hours.

[0077] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0078] 1. By introducing electron-donating compounds into the ZN catalyst system, this invention can reduce the active centers that generate low molecular weight PE components, thereby increasing the molecular weight of the polymer product. The molecular weight of the polymer can be controlled by adjusting the amount added.

[0079] 2. In this invention, when acetate compounds and organic alcohol compounds are added to the reaction, an inert diluent B is used for dilution. Because inert diluent B has a different polarity than inert diluent A, and under the synergistic effect of the acetate and organic alcohol compounds, it affects the dissolution and release state of the catalyst particles, resulting in a catalyst with better sphericity and particle morphology. Furthermore, the dilution effect of the inert solvent slows down the reaction rate, allowing for more uniform modification of the catalyst's active sites, increasing the effective titanium content, and improving the catalyst's activity.

[0080] 3. In this invention, when introducing acetate compounds, organic alcohol compounds, and electron donor compounds into the catalyst components, the method of their addition was optimized. The inventors unexpectedly discovered that after first mixing the acetate compounds and organic alcohol compounds in an inert solvent for dilution and then adding them in batches or all at once, and then adding the electron donor compounds, the performance of the resulting catalyst was improved. The obtained polymer had a lower degree of branching and better deentanglement properties, resulting in better processing performance.

[0081] 4. This invention introduces organoaluminum compound N into the catalyst component, and after treatment, obtains a solid particle catalyst containing magnesium and titanium, which has higher catalyst performance. In olefin polymerization reaction, the obtained polymer has a narrow molecular weight distribution, less content of large particles and fine powder, and high sphericity. Detailed Implementation

[0082] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0083] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art. For example, they can be directly purchased or obtained according to the preparation methods disclosed in the prior art.

[0084] In this invention, the testing method is as follows:

[0085] 1. Determination of polymer bulk density: The apparent density, volume factor and pourability of plastics are determined using the test method (ASTM D1895).

[0086] 2. Polymer molecular weight test: determined according to ASTM D4020-18.

[0087] 3. Determination of polymer sphericity: The sphericity was determined using a Camsizer particle size analyzer from Retsch GmbH, Germany.

[0088] 4. Determination of polymerization activity: The activity is calculated by dividing the mass of the powder obtained from polymerization by the amount of catalyst added.

[0089] 5. Determination of polymer particle size distribution: Sieve using standard sieves.

[0090] 6. Determination of polymer Span value: The Span value was determined using a Microtrac laser particle size and shape analyzer.

[0091] 7. Determination of polymer sequence distribution and branching degree: Measured using a Bruker 400MHz NMR spectrometer. The test solvent was C6D4Cl2, the test temperature was 125℃, the number of scans was 5000–6000, the sampling time was 5 seconds, and the sample tube was Φ = 10 mm. Qualitative and quantitative analysis of branching was obtained using relevant software.

[0092] Example 1

[0093] (1) Preparation of catalyst components

[0094] 4.0 g magnesium chloride, 60 ml toluene, 3.0 ml epichlorohydrin, and 9 ml tri-n-butyl phosphate were added to a reactor and reacted at 70°C for 2 hours. Then, 2 g phthalic anhydride was added, and the reaction continued for 1 hour. The system was cooled to -20°C, and 70 ml titanium tetrachloride was slowly added dropwise. Then, 50% of a mixture of 3 ml ethyl acetate, 3 ml ethanol, and 20 ml monochlorobenzene was added, and the mixture was kept at a constant temperature for 1 hour. The temperature was then gradually increased to 10°C, and the remaining mixture was added, kept at a constant temperature for 1 hour, and then gradually increased to 85°C, kept at a constant temperature for 1 hour. 1 ml of 2,2-dimethyl-1,3-diethoxy-propane was added, and the mixture was kept at a constant temperature for 1 hour. Stirring was stopped, and the mixture was allowed to stand, then washed twice with inert diluent toluene. 60 ml hexane was added to the reactor, and the temperature was lowered to 0°C. 10 ml of a 0.9 M diethylaluminum heptane solution was slowly added, and the reaction was carried out for 0.5 hours. The temperature was then increased to 50°C, and the reaction continued for 1 hour. Stop stirring and let stand. The suspension will quickly separate into layers. Remove the supernatant and wash the solution multiple times with inert diluent toluene and organic solvent hexane, then dry to obtain a solid catalyst component with good flowability.

[0095] (2) Polymer preparation

[0096] A 2L stainless steel reactor was fully purged with high-purity nitrogen, then 1L of hexane and 1.0ml of 1M triethylaluminum were added, followed by the solid catalyst component (containing 0.6mg titanium) prepared by the above method. The temperature was raised to 70℃, hydrogen was introduced to bring the pressure inside the reactor to 0.28MPa, and ethylene was introduced to bring the total pressure inside the reactor to 0.73MPa (gauge pressure). Polymerization was carried out at 80℃ for 2 hours. The polymerization results are shown in Table 1.

[0097] Example 2

[0098] (1) Preparation of catalyst components

[0099] 4.0 g magnesium chloride, 90 ml toluene, 3.0 ml ethylene oxide, and 9 ml triisobutyl phosphate were added to a reaction vessel and reacted at 60°C for 4 hours. Then, 2 g phthalic anhydride was added, and the reaction continued for 2 hours. The system was cooled to -35°C, and 70 ml titanium tetrachloride was slowly added dropwise. Then, 40% of a mixture of 3 ml isopropyl acetate, 3 ml ethanol, and 20 ml dichlorobenzene was added. The mixture was kept at this temperature for 0.5 hours, then gradually heated to 20°C. The remaining mixture was then added, and the mixture was kept at this temperature for 1 hour, then gradually heated to 85°C and kept at this temperature for 1 hour. 1 ml of 2,2-dimethyl-1,3-diethoxy-propane was added, and the mixture was kept at this temperature for another 1 hour. Stirring was stopped, the mixture was allowed to stand, and then washed twice with toluene, an inert diluent. 60 ml of hexane was added to the reactor, and the temperature was lowered to -10 °C. 10 ml of a 0.9 M triethylaluminum heptane solution was slowly added, and the reaction was allowed to proceed for 0.5 hours. The temperature was then raised to 50 °C and the reaction was allowed to continue for 1 hour. Stirring was stopped, and the mixture was allowed to stand. The suspension quickly separated into layers. The supernatant was removed, and the mixture was washed multiple times with toluene (an inert diluent) and hexane (an organic solvent), and then dried to obtain a solid catalyst component with good flowability.

[0100] (2) Polymer preparation

[0101] Same as Example 1, the polymerization results are shown in Table 1.

[0102] Example 3

[0103] (1) Preparation of catalyst components

[0104] 4.5 g magnesium chloride, 90 ml toluene, 3.0 ml epichlorohydrin, and 9 ml trimethyl phosphate were added to a reaction vessel and reacted at 60 °C for 4 hours. Then, 4 g phthalic anhydride was added, and the reaction continued for 1 hour. The system was cooled to -30 °C, and 80 ml titanium tetrachloride was slowly added dropwise. Then, 30% of a mixture of 4 ml ethyl acetate, 3 ml n-butanol, and 30 ml chloroform was added, and the mixture was kept at a constant temperature for 1 hour. The temperature was then gradually increased to 10 °C, and the remaining mixture was added, gradually increasing the temperature to 85 °C and keeping it at a constant temperature for 1 hour. 1 ml of 2,2-dimethyl-1,3-diethoxy-propane and 1 ml phthalic acid ether were added, and the mixture was kept at a constant temperature for 1 hour. Stirring was stopped, and the mixture was allowed to stand, then washed twice with inert diluent toluene. 60 ml hexane was added to the reactor, and the temperature was lowered to 0 °C. 10 ml of a 0.9 M diethylaluminum heptane solution was slowly added, and the reaction was carried out for 1 hour. The temperature was then increased to 50 °C and the reaction was carried out for another 1 hour. Stop stirring and let stand. The suspension will quickly separate into layers. Remove the supernatant and wash the solution multiple times with inert diluent toluene and organic solvent hexane, then dry to obtain a solid catalyst component with good flowability.

[0105] (2) Polymer preparation

[0106] Same as Example 1, the polymerization results are shown in Table 1.

[0107] Example 4

[0108] (1) Preparation of catalyst components

[0109] 4.8 g magnesium chloride, 100 ml toluene, 3.0 ml epichlorohydrin, and 9 ml triethyl phosphate were added to a reaction vessel and reacted at 80°C for 2 hours. Then, 5 g phthalic anhydride was added, and the reaction continued for 1 hour. The system was cooled to -10°C, and 90 ml titanium tetrachloride was slowly added dropwise. The temperature was then gradually raised to 0°C, followed by the addition of a mixed solution of 3 ml ethyl acetate, 3 ml ethanol, and 30 ml monochlorobenzene. The mixture was kept at this temperature for 1 hour, then gradually raised to 85°C and kept at this temperature for 1 hour. 1 ml of 2,2-dimethyl-1,3-diethoxy-propane and 1 ml diethyl phthalate were added, and the mixture was kept at this temperature for 1 hour. Stirring was stopped, and the mixture was allowed to stand, then washed twice with toluene (an inert diluent). 60 ml hexane was added to the reactor, and the temperature was lowered to 0°C. 10 ml of a 0.9 M diethylaluminum heptane solution was slowly added, and the reaction was carried out for 0.5 hours. The temperature was then raised to 50°C and the reaction continued for 1 hour. Stop stirring and let stand. The suspension will quickly separate into layers. Remove the supernatant and wash the solution multiple times with inert diluent toluene and organic solvent hexane, then dry to obtain a solid catalyst component with good flowability.

[0110] (2) Polymer preparation

[0111] Same as Example 1, the polymerization results are shown in Table 1.

[0112] Example 5

[0113] (1) Preparation of catalyst components

[0114] 4.0 g magnesium chloride, 120 ml toluene, 5.0 ml epichlorohydrin, and 15 ml tri-n-butyl phosphate were added to a reaction vessel and reacted at 50°C for 3 hours. Then, 2 g phthalic anhydride was added, and the reaction continued for 1 hour. The system was cooled to -20°C, and 50 ml titanium tetrachloride was slowly added dropwise, followed by a mixture of 4 ml ethyl acetate, 4 ml isooctyl alcohol, and 30 ml chloroform. The mixture was kept at this temperature for 1 hour, then gradually heated to 85°C and kept at this temperature for 1 hour. 1 ml of 2,2-dimethyl-1,3-diethoxy-propane and 1 ml phthalic acid ether were added, and the mixture was kept at this temperature for 1 hour. Stirring was stopped, and the mixture was allowed to stand, then washed twice with inert diluent toluene. 60 ml hexane was added to the reactor, and the temperature was lowered to 0°C. 10 ml of a 0.9 M diethylaluminum heptane solution was slowly added, and the reaction was carried out for 0.5 hours. The temperature was then raised to 50°C and the reaction continued for 1 hour. Stop stirring and let stand. The suspension will quickly separate into layers. Remove the supernatant and wash the solution multiple times with inert diluent toluene and organic solvent hexane, then dry to obtain a solid catalyst component with good flowability.

[0115] (2) Polymer preparation

[0116] Same as Example 1, the polymerization results are shown in Table 1.

[0117] Example 6

[0118] (1) Preparation of catalyst components

[0119] 4.0 g magnesium chloride, 90 ml toluene, 3.0 ml ethylene oxide, and 9 ml tripropyl phosphate were added to a reaction vessel and reacted at 60°C for 3 hours. Then, 4 g phthalic anhydride was added, and the reaction continued for another 3 hours. The system was cooled to -30°C, and 70 ml titanium tetrachloride was slowly added dropwise. The temperature was then gradually increased to 10°C, followed by the addition of a mixed solution of 3 ml methyl acetate, 6 ml butanol, and 30 ml monochlorobenzene. The mixture was kept at this temperature for 2 hours, then gradually increased to 90°C and kept at this temperature for 2 hours. 1 ml of 2,2-dimethyl-1,3-diethoxy-propane and 1 ml phthalic acid ether were added, and the mixture was kept at this temperature for another 3 hours. Stirring was stopped, and the mixture was allowed to stand, then washed twice with toluene (an inert diluent). 80 ml hexane was added to the reactor, and the temperature was lowered to 0°C. 10 ml of a 0.9 M diethylaluminum heptane solution was slowly added, and the reaction was carried out for 1 hour. The temperature was then increased to 50°C and the reaction continued for another hour. Stop stirring and let stand. The suspension will quickly separate into layers. Remove the supernatant and wash the solution multiple times with inert diluent toluene and organic solvent hexane, then dry to obtain a solid catalyst component with good flowability.

[0120] (2) Polymer preparation

[0121] Same as Example 1, the polymerization results are shown in Table 1.

[0122] Example 7

[0123] (1) Preparation of catalyst components

[0124] 4.0 g magnesium chloride, 60 ml toluene, 3.0 ml epichlorohydrin, and 9 ml tri-n-butyl phosphate were added to a reaction vessel and reacted at 70°C for 2 hours. Then, 1 g phthalic anhydride was added, and the reaction continued for 1 hour. The system was cooled to -20°C, and 70 ml titanium tetrachloride was slowly added dropwise. Then, 50% of a mixture of 3 ml ethyl acetate, 3 ml ethanol, and 20 ml monochlorobenzene was added, and the mixture was kept at a constant temperature for 1 hour. The temperature was then gradually increased to 10°C, and the remaining mixture was added, kept at a constant temperature for 1 hour, and then gradually increased to 85°C, kept at a constant temperature for 1 hour. 1 ml phthalic acid ether was added, and the mixture was kept at a constant temperature for 1 hour. Stirring was stopped, and the mixture was allowed to stand, then washed twice with inert diluent toluene. 60 ml hexane was added to the reactor, and the temperature was lowered to -10°C. 10 ml of a 0.9 M diethylaluminum heptane solution was slowly added, and the reaction was carried out for 1 hour. The temperature was then increased to 50°C, and the reaction was carried out for another 1 hour. Stop stirring and let stand. The suspension will quickly separate into layers. Remove the supernatant and wash the solution multiple times with inert diluent toluene and organic solvent hexane, then dry to obtain a solid catalyst component with good flowability.

[0125] (2) Polymer preparation

[0126] Same as Example 1, except that organoaluminum compound D is triisobutylaluminum, and the polymerization results are shown in Table 1.

[0127] Example 8

[0128] (1) Preparation of catalyst components

[0129] Add 4.0 g magnesium chloride, 100 ml xylene, 5.0 ml epichlorohydrin, and 15 ml tri-n-butyl phosphate to a reactor and react at 80°C for 3 hours. Then add 5 g phthalic anhydride and continue the reaction for 1 hour. Cool the system to -20°C and slowly add 90 ml tetraethoxytitanium, followed by 50% of a mixture of 3 ml ethyl acetate, 3 ml butanol, 1 ml ethanol, and 20 ml dichloromethane. Maintain the temperature for 1 hour, then gradually increase the temperature to 10°C. Add the remaining mixture and maintain the temperature for 1 hour, then gradually increase the temperature to 85°C and maintain the temperature for 1 hour. Add 1 ml phthalic acid ether and maintain the temperature for 1 hour. Stop stirring, let stand, and wash twice with xylene (an inert diluent). Add 60 ml hexane to the reactor, cool to -10°C, and slowly add 15 ml of a 0.9 M triisobutylaluminum heptane solution. React for 1 hour, then increase the temperature to 50°C and react for 1 hour. Stop stirring and let stand. The suspension quickly separates into layers. Remove the supernatant, wash repeatedly with xylene (an inert diluent) and hexane (an organic solvent), and then dry to obtain a solid catalyst component with good flowability.

[0130] (2) Polymer preparation

[0131] Same as Example 1, except that organoaluminum compound D is triisobutylaluminum, and the polymerization results are shown in Table 1.

[0132] Example 9

[0133] (1) Preparation of catalyst components

[0134] 4.8 g magnesium chloride, 120 ml toluene, 5.0 ml epichlorohydrin, and 18 ml tri-n-butyl phosphate were added to a reaction vessel and reacted at 50°C for 4 hours. Then, 3 g phthalic anhydride was added, and the reaction continued for 1 hour. The system was cooled to -30°C, and 70 ml titanium tetrachloride was slowly added dropwise. Then, 50% of a mixture of 3 ml ethyl acetate, 2 ml butanol, 1 ml isooctyl alcohol, and 20 ml dichlorobenzene was added. The mixture was kept at this temperature for 1 hour, then gradually heated to 10°C. The remaining mixture was then added, and the mixture was kept at this temperature for 1 hour, then gradually heated to 85°C and kept at this temperature for 1 hour. 2 ml 1-ethoxy-3-methoxy-propane and 1 ml phthalic acid were added, and the mixture was kept at this temperature for 2 hours. Stirring was stopped, the mixture was allowed to stand, and then washed twice with inert diluent toluene. 80 ml of hexane was added to the reactor, and the temperature was lowered to -10 °C. 20 ml of a 0.9 M diethylaluminum heptane solution was slowly added, and the reaction was carried out for 1 hour. The temperature was then raised to 50 °C and the reaction was carried out for 2 hours. Stirring was stopped, and the mixture was allowed to stand. The suspension quickly separated into layers. The supernatant was removed, and the mixture was washed multiple times with toluene (an inert diluent) and hexane (an organic solvent) and then dried to obtain a solid catalyst component with good flowability.

[0135] (2) Polymer preparation

[0136] Same as Example 1, the polymerization results are shown in Table 1.

[0137] Example 10

[0138] (1) Preparation of catalyst components

[0139] 4.8 g magnesium chloride, 150 ml toluene, 6.0 ml epichlorohydrin, and 18 ml tri-n-butyl phosphate were added to a reaction vessel and reacted at 60°C for 3 hours. Then, 4 g phthalic anhydride was added, and the reaction continued for 2 hours. The system was cooled to -30°C, and 70 ml titanium tetrachloride was slowly added dropwise. Then, 50% of a mixture of 3 ml ethyl acetate, 2 ml butanol, 1 ml isooctyl alcohol, and 20 ml dichlorobenzene was added. The mixture was kept at this temperature for 1 hour, then gradually heated to 10°C. The remaining mixture was then added, and the mixture was kept at this temperature for 1 hour, then gradually heated to 85°C and kept at this temperature for 1 hour. 2 ml 1-ethoxy-3-methoxy-propane and 1 ml phthalic acid were added, and the mixture was kept at this temperature for 2 hours. Stirring was stopped, the mixture was allowed to stand, and then washed twice with inert diluent toluene. 80 ml of hexane was added to the reactor, and the temperature was lowered to -10 °C. 20 ml of a 0.9 M sesquiethylaluminum heptane solution was slowly added, and the reaction was carried out for 1 hour. The temperature was then raised to 50 °C and the reaction was carried out for 2 hours. Stirring was stopped, and the mixture was allowed to stand. The suspension quickly separated into layers. The supernatant was removed, and the mixture was washed multiple times with toluene (an inert diluent) and hexane (an organic solvent) and then dried to obtain a solid catalyst component with good flowability.

[0140] (2) Polymer preparation

[0141] Same as Example 1, the polymerization results are shown in Table 1.

[0142] Example 11

[0143] (1) Preparation of catalyst components

[0144] 4.8 g magnesium chloride, 120 ml toluene, 6.0 ml epichlorohydrin, and 18 ml tri-n-butyl phosphate were added to a reaction vessel and reacted at 60°C for 3 hours. Then, 3 g phthalic anhydride was added, and the reaction continued for 2 hours. The system was cooled to -20°C, and 70 ml titanium tetrachloride was slowly added dropwise. Then, 40% of a mixture of 5 ml ethyl acetate, 2 ml ethanol, 1 ml isooctyl alcohol, and 30 ml dichlorobenzene was added. The mixture was kept at this temperature for 1 hour, then gradually heated to 10°C. The remaining mixture was then added, and the mixture was kept at this temperature for 1 hour, then gradually heated to 85°C and kept at this temperature for 1 hour. 2 ml of 2,2-dimethyl-1,3-dimethoxy-propane and 1 ml phthalic acid were added, and the mixture was kept at this temperature for 2 hours. Stirring was stopped, the mixture was allowed to stand, and then washed twice with inert diluent toluene. 80 ml of hexane was added to the reactor, and the temperature was lowered to -10 °C. 20 ml of a 0.9 M diethylaluminum heptane solution was slowly added, and the reaction was carried out for 2 hours. The temperature was then raised to 50 °C and the reaction was carried out for another 2 hours. Stirring was stopped, and the mixture was allowed to stand. The suspension quickly separated into layers. The supernatant was removed, and the mixture was washed multiple times with toluene (an inert diluent) and hexane (an organic solvent) and then dried to obtain a solid catalyst component with good flowability.

[0145] (2) Polymer preparation

[0146] Same as Example 1, the polymerization results are shown in Table 1.

[0147] Example 12

[0148] (1) Preparation of catalyst components

[0149] 4.8 g magnesium chloride, 150 ml toluene, 4.0 ml epichlorohydrin, and 15 ml tri-n-butyl phosphate were added to a reaction vessel and reacted at 60°C for 2 hours. Then, 5 g phthalic anhydride was added, and the reaction continued for another 2 hours. The system was cooled to -20°C, and 90 ml titanium tetrachloride was slowly added dropwise. Then, 40% of a mixture of 5 ml ethyl acetate, 2 ml ethanol, 1 ml propanol, and 20 ml dichlorobenzene was added, and the mixture was kept at a constant temperature for 1 hour. The temperature was then gradually increased to 10°C, and the remaining mixture was added, kept at a constant temperature for 1 hour, and then gradually increased to 85°C, kept at a constant temperature for 1 hour. 2 ml 1-ethoxy-3-methoxy-propane and 1 ml diethyl phthalate were added, and the mixture was kept at a constant temperature for another 2 hours. Stirring was stopped, the mixture was allowed to stand, and then washed twice with inert diluent toluene. 80 ml of hexane was added to the reactor, and the temperature was lowered to -10 °C. 20 ml of a 0.9 M diethylaluminum heptane solution was slowly added, and the reaction was carried out for 2 hours. The temperature was then raised to 50 °C and the reaction was carried out for another 2 hours. Stirring was stopped, and the mixture was allowed to stand. The suspension quickly separated into layers. The supernatant was removed, and the mixture was washed multiple times with toluene (an inert diluent) and hexane (an organic solvent) and then dried to obtain a solid catalyst component with good flowability.

[0150] (2) Polymer preparation

[0151] Same as Example 1, the polymerization results are shown in Table 1.

[0152] Comparative Example 1

[0153] (1) Preparation of catalyst components

[0154] 4.0 g magnesium chloride, 60 ml toluene, 3.0 ml epichlorohydrin, and 9 ml tri-n-butyl phosphate were added to a reaction vessel and reacted at 70°C for 2 hours. Then, 2 g phthalic anhydride was added, and the reaction continued for 1 hour. The system was cooled to -20°C, and 70 ml titanium tetrachloride was slowly added dropwise, followed by 3 ml ethyl acetate and 3 ml ethanol, maintaining the temperature for 1 hour. The temperature was then gradually increased to 85°C and maintained for 1 hour. 1 ml 2,2-dimethyl-1,3-diethoxy-propane was added, and the temperature was maintained for 1 hour. Stirring was stopped, and the mixture was allowed to stand, then washed twice with toluene (an inert diluent). 60 ml hexane was added to the reactor, and the temperature was lowered to 0°C. 10 ml of a 0.9 M diethylaluminum heptane solution was slowly added, and the reaction was carried out for 0.5 hours. The temperature was then increased to 50°C and the reaction continued for 1 hour. Stop stirring and let stand. The suspension will quickly separate into layers. Remove the supernatant and wash the solution multiple times with inert diluent toluene and organic solvent hexane, then dry to obtain a solid catalyst component with good flowability.

[0155] (2) Polymer preparation

[0156] Same as Example 1, the polymerization results are shown in Table 1.

[0157] Comparative Example 2

[0158] (1) Preparation of catalyst components

[0159] 4.0 g magnesium chloride, 60 ml toluene, 3.0 ml epichlorohydrin, and 9 ml tri-n-butyl phosphate were added to a reaction vessel and reacted at 70°C for 2 hours. Then, 2 g phthalic anhydride was added, and the reaction continued for 1 hour. The system was cooled to -20°C, and 70 ml titanium tetrachloride was slowly added dropwise, followed by 3 ml ethyl acetate, 3 ml ethanol, and 20 ml monochlorobenzene. The mixture was kept at a constant temperature for 1 hour, then gradually heated to 85°C and kept at a constant temperature for 1 hour. 1 ml 2,2-dimethyl-1,3-diethoxy-propane was added, and the mixture was kept at a constant temperature for 1 hour. Stirring was stopped, and the mixture was allowed to stand, then washed twice with toluene (an inert diluent). 60 ml hexane was added to the reactor, and the mixture was cooled to 0°C. 10 ml of a 0.9 M diethylaluminum heptane solution was slowly added, and the reaction was carried out for 0.5 hours. The temperature was then increased to 50°C and the reaction continued for 1 hour. Stop stirring and let stand. The suspension will quickly separate into layers. Remove the supernatant and wash the solution multiple times with inert diluent toluene and organic solvent hexane, then dry to obtain a solid catalyst component with good flowability.

[0160] (2) Polymer preparation

[0161] Same as Example 1, the polymerization results are shown in Table 1.

[0162] Comparative Example 3

[0163] (1) Preparation of catalyst components

[0164] 4.0 g magnesium chloride, 60 ml toluene, 3.0 ml epichlorohydrin, and 9 ml tri-n-butyl phosphate were added to a reaction vessel and reacted at 70°C for 2 hours. Then, 2 g phthalic anhydride was added, and the reaction continued for 1 hour. The system was cooled to -20°C, and 70 ml titanium tetrachloride was slowly added dropwise, followed by 1 ml ethyl acetate and 1 ml ethanol, maintaining the temperature for 1 hour. The temperature was then gradually increased to 10°C, followed by the addition of 2 ml ethyl acetate and 2 ml ethanol, maintaining the temperature for 1 hour. The temperature was then gradually increased to 85°C and maintained for 1 hour. 1 ml 2,2-dimethyl-1,3-diethoxy-propane was added, and the temperature was maintained for 1 hour. Stirring was stopped, and the mixture was allowed to stand, then washed twice with inert diluent toluene. 60 ml hexane was added to the reactor, and the temperature was lowered to 0°C. 10 ml of a 0.9 M diethylaluminum heptane solution was slowly added, and the reaction was carried out for 0.5 hours. The temperature was then increased to 50°C and the reaction continued for 1 hour. Stop stirring and let stand. The suspension will quickly separate into layers. Remove the supernatant and wash the solution multiple times with inert diluent toluene and organic solvent hexane, then dry to obtain a solid catalyst component with good flowability.

[0165] (2) Polymer preparation

[0166] Same as Example 1, the polymerization results are shown in Table 1.

[0167] Comparative Example 4

[0168] (1) Preparation of catalyst

[0169] 4.0 g of magnesium chloride, 60 ml of toluene, 3.0 ml of epichlorohydrin, and 9 ml of tri-n-butyl phosphate were added to a reaction vessel and reacted at 70 °C for 2 hours. Then, 2 g of phthalic anhydride was added, and the reaction continued for 1 hour. The system was cooled to -20 °C, and 70 ml of titanium tetrachloride was slowly added dropwise, followed by 3 ml of ethyl acetate, 3 ml of ethanol, and 20 ml of monochlorobenzene. The mixture was kept at a constant temperature for 1 hour, then gradually heated to 85 °C and kept at a constant temperature for 1 hour. 1 ml of 2,2-dimethyl-1,3-diethoxy-propane was added, and the mixture was kept at a constant temperature for 1 hour. Stirring was stopped, and the mixture was allowed to stand. The suspension quickly separated into layers. The supernatant was removed, and the mixture was washed repeatedly with toluene (an inert diluent) and hexane (an organic solvent), and then dried to obtain a solid catalyst component with good flowability.

[0170] (2) Polymer preparation

[0171] Same as Example 1, the polymerization results are shown in Table 1.

[0172] The polymerization results of Examples 1-12 and Comparative Examples 1-4 were analyzed, and the specific analysis data are shown in Table 1.

[0173] Table 1

[0174]

[0175] As shown in Table 1, compared with the catalysts prepared in Comparative Examples 1-4, the polymers obtained by using the catalysts prepared in Examples 1-12 have a more concentrated particle size distribution. The particle size distribution of the extra-high molecular weight polyethylene is between 75-500 μm with a mass fraction ≥99%, the particle span is ≤0.8, the degree of branching of the polymer is ≤0.5SCB / 1000C, the sphericity of the polymer is significantly increased, and it has better low entanglement properties.

Claims

1. A catalyst component for olefin polymerization, comprising the reaction product of the feedstock including: a magnesium complex, a precipitation aid, a titanium-containing compound, an acetate compound, an organic alcohol compound, an organoaluminum compound N, and an electron donor compound; wherein the electron donor compound includes electron donor compound a and / or electron donor compound b; The general formula of the electron donor compound a is as follows: （I） R1 and R2 are independently methyl or ethyl, and R3 and R4 are independently hydrogen-based or methyl; and / or, The general formula of the electron donor compound b is as follows: (II) R5 and R6 are independently methyl or ethyl; R7, R8, R9, R 10 Same or different, independently selected from hydrogen group, halogen, C1~C 10 Straight-chain alkyl, C1~C 10 Branched alkyl groups, C1~C 10 One of the alkoxy groups; The preparation method of the catalyst component includes the following steps: Step 1: Dissolve magnesium halide compounds in organic epoxy compounds, organic phosphorus compounds and inert diluent A to form a magnesium-containing complex solution system; Step 2: Add a precipitation aid to the solution system obtained in Step 1 and continue the reaction; Step 3: Then lower the temperature of the reaction system from Step 2 and add a titanium-containing compound to continue the reaction; Step four: Then, add a mixed solution of inert diluent B containing the acetate compound and organic alcohol compound to the reaction system of step three, either all at once or in stages, and continue the reaction; Step 5: Then, add the electron donor compound to the reaction system from Step 4 and continue the reaction; Step 6: Wash the mixture obtained in Step 5 with inert diluent A, and then add the organoaluminum compound N to continue the reaction treatment to obtain the catalyst component; The inert diluent A is one or a combination of aromatic compounds and alkane compounds; The inert diluent B is one or a combination of halogenated aromatic compounds and halogenated alkane compounds.

2. The catalyst component for olefin polymerization according to claim 1, characterized in that, Each component, expressed as a mole of magnesium in the magnesium complex, is: 0.001~1 mol of precipitation aid; Titanium-containing compounds, 0.01–5 moles; Acetate compounds, 0.01~1 mole; 0.001~2 moles of organic alcohol compounds; Organoaluminum compounds N 0.01~5 moles; Donor electrons a = 0 to 1.0 moles; Donor electrons b0~1.0 moles; Furthermore, the molar amounts of electron donor a and electron donor b are not both 0.

3. The catalyst component for olefin polymerization according to claim 2, characterized in that, Each component, expressed as a mole of magnesium in the magnesium complex, is: 0.003~0.5 mol of precipitation aid; 0.02~2 moles of titanium-containing compounds; Acetate compounds, 0.03~0.2 moles; 0.01~0.2 moles of organic alcohol compounds; Organoaluminum compounds N 0.05~2 moles; Donor electrons a: 0~0.2 moles; Donate 0.2 moles of electron-bending electrons.

4. The catalyst component for olefin polymerization according to claim 1, characterized in that, The magnesium complex is a product obtained by dissolving magnesium halide compounds in a solvent system including organic epoxy compounds and organophosphorus compounds; Based on per mole of magnesium, The amount of the added organic epoxy compound is 0.01 to 1 mole; The amount of the added organophosphorus compound is 0.01 to 1 mole.

5. The catalyst component for olefin polymerization according to claim 4, characterized in that, The amount of the added organic epoxy compound is 0.03 to 0.5 mol; the amount of the added organic phosphorus compound is 0.01 to 0.3 mol.

6. The catalyst component for olefin polymerization according to claim 4, characterized in that, The magnesium halide compound is one or a combination of magnesium halide, magnesium halide complexes with water, alcohol or electron donor Y, magnesium phenoxychloride, magnesium isopropoxychloride, and magnesium butoxychloride.

7. The catalyst component for olefin polymerization according to claim 6, characterized in that, The magnesium halide is one or a combination of magnesium dichloride, magnesium dibromide, magnesium difluoride, and magnesium diiodide.

8. The catalyst component for olefin polymerization according to claim 6, characterized in that, The complex of magnesium halide with an alcohol or electron donor Y is a complex of magnesium halide with methanol, ethanol, propanol, butanol, pentanol, hexanol, isooctyl alcohol, ammonia compounds, hydroxyamine compounds, ether compounds, or ester compounds.

9. The catalyst component for olefin polymerization according to claim 4, characterized in that, The organic epoxy compound contains C2~C3. 18 One or a combination of oxides of aliphatic olefins, oxides of halogenated aliphatic olefins, and glycidyl ethers.

10. The catalyst component for olefin polymerization according to claim 9, characterized in that, The organic epoxy compound is one or a combination of ethylene oxide, propylene oxide, butane oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether, and butyl glycidyl ether.

11. The catalyst component for olefin polymerization according to claim 4, characterized in that, The organic epoxy compound is one or a combination of oxides of halodienes and oxides of dienes.

12. The catalyst component for olefin polymerization according to claim 11, characterized in that, The organic epoxy compound is butadiene oxide.

13. The catalyst component for olefin polymerization according to claim 4, characterized in that, The organophosphorus compound is one or a combination of a hydrocarbon ester of orthophosphoric acid or phosphorous acid, or a halohydrocarbon ester of orthophosphoric acid or phosphorous acid.

14. The catalyst component for olefin polymerization according to claim 13, characterized in that, The organophosphorus compound is one or a combination 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, and di-n-butyl phosphite.

15. The catalyst component for olefin polymerization according to claim 1, characterized in that, The precipitation aid is one or a combination of organic acids, organic acid anhydrides, organic ethers, and organic ketones.

16. The catalyst component for olefin polymerization according to claim 15, characterized in that, The precipitation aid contains C2~C 20 One or a combination of organic acids, organic anhydrides, organic ethers, and organic ketones.

17. The catalyst component for olefin polymerization according to claim 16, characterized in that, The precipitation aid is one or a combination of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, diethyl ether, propyl ether, butyl ether, and pentyl ether.

18. The catalyst component for olefin polymerization according to claim 1, characterized in that, The general formula of the titanium-containing compound is Ti(OR). 4 ) e X 1 f ; The R 4 For those containing C1~C 10 aliphatic hydrocarbon groups or C6~C 14 Aromatic hydrocarbon groups; The X 1 It is a halogen; The value of e is an integer from 0 to 2, the value of f is an integer from 1 to 4, and e + f = 3 or 4.

19. The catalyst component for olefin polymerization according to claim 18, characterized in that, The X 1 It is one of the following: fluorine, chlorine, bromine, and iodine.

20. The catalyst component for olefin polymerization according to claim 18, characterized in that, The titanium-containing compound is one or a combination of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium trichloride, titanium dichloroethoxy, and titanium trichloromonoethoxy.

21. The catalyst component for olefin polymerization according to claim 1, characterized in that, The general formula of the acetate compounds is CH3COOR 3 The R 3 For those containing C1~C 10 Alkyl groups, C2~C 10 alkenyl, C3~C 10 cycloalkyl, C2~C 10 alkynyl group, C6~C 10 It is one of the aromatic hydrocarbon groups.

22. The catalyst component for olefin polymerization according to claim 21, characterized in that, The R 3 It is one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-octyl ester, cyclopropyl, methylcyclopropyl, methylcyclopentyl, cyclohexyl, phenyl, benzyl, and xylylyl.

23. The catalyst component for olefin polymerization according to claim 1, characterized in that, The general formula of the organic alcohol compound is R 5 OH, the R 5 For those containing C1~C 10 Alkyl groups.

24. The catalyst component for olefin polymerization according to claim 23, characterized in that, The R 5 It is one of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, and isooctyl.

25. The catalyst component for olefin polymerization according to claim 1, characterized in that, The electron donor compound b, comprising R7, R8, R9, and R... 10 They are, respectively, one of fluorine, chlorine, bromine, iodine, a straight-chain alkyl group of C1 to C6, a branched alkyl group of C1 to C6, or an alkoxy group of C1 to C6.

26. The catalyst component for olefin polymerization according to claim 25, characterized in that, The electron donor compound b is one of o-phenylenedimethyl ether, o-phenylenediethyl ether, and 1-ethoxy-2-methoxybenzene.

27. The catalyst component for olefin polymerization according to claim 1, characterized in that, When the electron donor compound is a mixture of electron donor compound a and electron donor compound b, the molar ratio of electron donor compound a to electron donor compound b is 0.01 to 100.

28. The catalyst component for olefin polymerization according to claim 27, characterized in that, The molar ratio of electron donor compound a to electron donor compound b is 0.05 to 20.

29. The catalyst component for olefin polymerization according to claim 28, characterized in that, The molar ratio of electron donor compound a to electron donor compound b is 0.1 to 20.

30. The catalyst component for olefin polymerization according to claim 1, characterized in that, The general formula of the organoaluminum compound N is AlR. 6 n X 2 3-n ; wherein each of the R 6 Independently hydrogen, containing C1~C 20 One of the hydrocarbon groups; the X 2 The halogen is used; n is an integer that is 0 ≤ n ≤ 3.

31. The catalyst component for olefin polymerization according to claim 30, characterized in that, The organoaluminum compound N is one or a combination of triethylaluminum, diethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, triisobutylaluminum chloride, diisopropylaluminum chloride, methylpropylaluminum chloride, and diphenylaluminum chloride.

32. The catalyst component for olefin polymerization according to claim 1, characterized in that, The aromatic compounds are one or a combination of benzene, toluene, xylene and their derivatives; and / or, The alkane compounds include those containing C3 to C4. 20 It is at least one of a straight-chain alkane, a branched-chain alkane, or a cycloalkane with 1 carbon atom.

33. The catalyst component for olefin polymerization according to claim 1, characterized in that, The haloaromatic compounds are haloaromatic compounds containing C6-C8 aromatics and their derivatives; and / or, The haloalkane compound contains C3~C4. 20 One or a combination of straight-chain haloalkanes, branched haloalkanes, and halocycloalkanes.

34. The catalyst component for olefin polymerization according to claim 33, characterized in that, The halogenated aromatic compounds are monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene and their derivatives, monobromobenzene, dibromobenzene, tribromobenzene, monobromotoluene and their derivatives; and / or, The haloalkane compound is one or a combination of dichloromethane, trichloromethane, tetrachloromethane, bromoethane, and chloroethane.

35. The method for preparing the catalyst component for olefin polymerization according to any one of claims 1 to 34, characterized in that, The method includes the following steps: Step 1: Dissolve magnesium halide compounds in organic epoxy compounds, organic phosphorus compounds and inert diluent A to form a magnesium-containing complex solution system; Step 2: Add a precipitation aid to the solution system obtained in Step 1 and continue the reaction; Step 3: Then lower the temperature of the reaction system from Step 2 and add a titanium-containing compound to continue the reaction; Step four: Then, add a mixed solution of inert diluent B containing the acetate compound and organic alcohol compound to the reaction system of step three, either all at once or in stages, and continue the reaction; Step 5: Then, add the electron donor compound to the reaction system from Step 4 and continue the reaction; Step 6: Wash the mixture obtained in Step 5 with inert diluent A, and then add the organoaluminum compound N to continue the reaction treatment to obtain the catalyst component.

36. The method for preparing the catalyst component for olefin polymerization according to claim 35, characterized in that, In step one, the reaction conditions for preparing the magnesium-containing complex are: temperature 40-80℃, time 1-5h; and / or, In step two, the reaction conditions for adding the precipitation aid are: temperature 40~80℃, time 0.5~3h; and / or, In step three, the reaction conditions for adding the titanium-containing compound are: temperature -60~-30℃; time 0.5~3h; and / or, In step five, the reaction conditions for adding the electron donor are: temperature 70~95℃, time 0.5~3h; and / or, In step six, the reaction conditions for adding organoaluminum compound N are: temperature -10~100℃, time 0.5~3h; and / or, In step six, after the reaction of organoaluminum compound N is completed, the reaction system is allowed to stand, unreacted substances and solvents are removed, and a solid catalyst component is obtained.

37. The method for preparing the catalyst component for olefin polymerization according to claim 36, characterized in that, In step one, the reaction conditions for preparing the magnesium-containing complex are: temperature 50-70℃, time 1-3 h; and / or, In step two, the reaction conditions for adding the precipitation aid are: a temperature of 50-70°C; and / or, In step five, the reaction conditions for adding the electron donor are: temperature 80-90℃, time 1-2 hours; and / or, In step six, the reaction conditions for adding organoaluminum compound N are: temperature 0~20℃, time 1~2h.

38. The method for preparing the catalyst component for olefin polymerization according to claim 35, characterized in that, In step four, the mixed solution of the acetate compound and the organic alcohol compound inert diluent B is added in whole or in batches to the reaction system of step three; The reaction conditions for the complete addition are: temperature -60~30℃, time 0.5~3hh; The reaction conditions for the batch addition are as follows: the mixed solution of the acetate compound and the organic alcohol compound inert diluent B is added in at least two batches.

39. The method for preparing the catalyst component for olefin polymerization according to claim 38, characterized in that, The reaction conditions for all additions are: temperature -20~20℃, time 1~2h; The reaction conditions for the batch addition are as follows: after the first batch is added, the reaction is kept at a constant temperature for 0.5 to 1 hour, then the temperature is gradually increased to 0 to 30°C, then the remaining mixed solution is added, and the reaction is kept at a constant temperature for 0.5 to 1 hour, then the temperature is gradually increased to 60 to 100°C, and the reaction is kept at a constant temperature for 1 to 3 hours; the heating rate of the system is 0.2 to 2°C / min.

40. The method for preparing the catalyst component for olefin polymerization according to claim 35, characterized in that, Based on per mole of magnesium, In step one, the amount of inert diluent A is 0.01~5 mol; In step four, the amount of inert diluent B is 0.001 to 2 mol.

41. The method for preparing the catalyst component for olefin polymerization according to claim 40, characterized in that, In the first step, the amount of the inert diluent A is 0.4 to 2 moles; In the fourth step, the amount of the inert diluent B is 0.05 to 0.5 moles.

42. A catalyst for olefin polymerization, characterized in that, The catalyst comprises: Component 1, the catalyst component for olefin polymerization according to any one of claims 1 to 34 or the catalyst component prepared by the method according to any one of claims 35 to 41; Component 2, an organoaluminum compound D; The general formula of the organoaluminum compound D is AlR. 7 d X 3 3-d ; Each of the R 7 Independently hydrogen, containing C1~C 20 One of the hydrocarbon groups; The X 3 It is a halogen; d is an integer where 0 < d ≤ 3.

43. The catalyst for olefin polymerization according to claim 42, characterized in that, The X 3 It is one of fluorine, chlorine, and bromine.

44. The catalyst for olefin polymerization according to claim 42, characterized in that, The molar ratio of titanium atoms in Component 1 to aluminum atoms in Component 2 is 0.1:1 to 20:

1.

45. The catalyst for olefin polymerization according to claim 44, characterized in that, The molar ratio of titanium atoms in Component 1 to aluminum atoms in Component 2 is 0.5:1 to 10:

1.

46. ​​The catalyst for olefin polymerization according to claim 45, characterized in that, The molar ratio of titanium atoms in Component 1 to aluminum atoms in Component 2 is 0.5:1 to 5:

1.

47. The catalyst for olefin polymerization according to claim 42, wherein The organoaluminum compound D is one or a combination of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum, diisobutylaluminum, dichloroethylaluminum.

48. The catalyst for olefin polymerization according to claim 47, wherein The organoaluminum compound D is dichloroethylaluminum.

49. The application of the catalyst for olefin polymerization according to any one of claims 42 to 48, characterized in that, The catalyst is used for olefin polymerization reaction.

50. The application of the catalyst for olefin polymerization according to claim 49, characterized in that, The catalyst is used for olefin polymerization reaction to prepare special / ultra-high molecular weight polyolefin; the viscosity-average molecular weight of the special / ultra-high molecular weight polyolefin is greater than 500,000.

51. The application of the catalyst for olefin polymerization according to claim 49, characterized in that, In the olefin polymerization reaction, the general formula of at least one olefin in the raw material olefin is CH2=CHR, and R is hydrogen or a C1-C6 alkyl group.

52. The application of the catalyst for olefin polymerization according to claim 51, characterized in that, The raw material olefin is ethylene; or, the raw material olefin is ethylene and / or an α-olefin and other comonomers.

53. The application of the catalyst for olefin polymerization according to claim 52, characterized in that, The comonomer is one or a combination of propylene, butene, pentene, hexene, octene, 4-methyl-1-pentene.

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