Catalyst component for olefin polymerization as well as preparation method, catalyst and application thereof

Abstract

The invention provides 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 magnesium compound, an organic anhydride compound, an acetate compound, an alcohol compound, a titanium-containing compound and a reaction product of an internal electron donor. The magnesium compound is a compound formed by dissolving magnesium halide in a solvent system containing an organic epoxy compound and an organic phosphorus compound. The catalyst particles are high in polymerization activity and narrow in particle size distribution, polyethylene powder which is high in stacking density, good in particle morphology, high in molecular weight and narrow in molecular weight distribution can be obtained through polymerization, and the requirement of an industrial production device for the catalyst is met.

Description

Technical Field

[0001] This invention belongs to the field of olefin polymerization, specifically relating to a catalyst component for olefin polymerization, its preparation method, the catalyst, and its application. Background Technology

[0002] Ultra-high molecular weight polyethylene (UHMWPE) is a special type of polyethylene with a molecular weight greater than 1.5 million. Most commercially available UHMWPE is currently prepared using Ziegler-Natta catalysts (ZN catalysts), possessing 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. Currently, products such as lithium-ion battery separators, with molecular weights between 500,000 and 1.5 million, are also generally referred to as UHMWPE due to their similar properties.

[0003] For specialized resins used in the production of high-end UHMWPE products, different application scenarios require suitable molecular weight, narrow particle size distribution, good particle morphology, and low ash content. Generally, molecular weight distribution is also an important performance indicator; a narrow molecular weight distribution typically imparts higher mechanical strength to the separator, while a wide molecular weight distribution provides better processability. In the wet-process production of lithium-ion battery separators, UHMWPE is commonly used as the raw material. During processing, it is first swollen using a high-boiling-point, low-molecular-weight solvent. Therefore, a narrow particle size distribution, low content of large and fine particles, and a narrow molecular weight distribution are particularly important for lithium-ion battery separator-specific materials. This results in separators with good mechanical properties, good processing uniformity, and high yield. Currently, most high-end lithium-ion battery separator-specific resins are imported, and domestic UHMWPE powder manufacturers still have room for improvement.

[0004] Through research, the inventors discovered that introducing the internal electron donor into the ZN catalyst can reduce the active centers that generate low molecular weight PE components. The resulting catalyst exhibits high catalytic activity, narrow particle size distribution, good polymer particle morphology, high packing density, high molecular weight, and narrow molecular weight distribution. Summary of the Invention

[0005] The inventors discovered that, according to this invention, when organic acid anhydrides, acetate compounds, alcohol electron donors, and haloether internal electron donors are introduced as composite electron donors into the N-series polyolefin catalyst preparation system, the reaction of magnesium complexes, organic acid anhydrides, acetate compounds, alcohol compounds, titanium-containing compounds, and internal electron donors can produce spherical or near-spherical solid particles (solid catalyst components) containing magnesium and titanium. These catalyst particles exhibit high polymerization activity and can polymerize to obtain polyethylene powder with high bulk density, narrow particle size distribution, and narrow molecular weight distribution.

[0006] The first aspect of the present invention is to provide a catalyst component for olefin polymerization, comprising a magnesium complex, an organic acid anhydride compound, an acetate compound, an alcohol compound, a titanium-containing compound, and a reaction product of an internal electron donor;

[0007] The magnesium complex is a complex formed by dissolving magnesium halide in a solvent system containing organic epoxy compounds and organophosphorus compounds.

[0008] The internal electron donor is selected from at least one of the compounds represented by general formula (I):

[0009]

[0010] In formula (Ⅰ), R1 and R2 are independently C1-C10 hydrocarbon groups substituted or unsubstituted with halogen atoms, and R3 and R4 are independently C1-C10 hydrocarbon groups substituted or unsubstituted with hydrogen, halogen, or halogen atoms. At least one of R1 and R2 is substituted with a halogen atom.

[0011] Preferably, in formula (Ⅰ), R1 and R2 are independently methyl, ethyl, halomethyl or haloethyl, and at least one of R1 and R2 is substituted with a halogen atom; and / or, R3 and R4 are independently hydrogen, halogen or methyl.

[0012] According to the present invention, the halogen is one or more of the elements fluorine, chlorine, bromine, and iodine; preferably chlorine and / or bromine.

[0013] More preferably, the internal electron donor is selected from at least one of the following compounds:

[0014] Compound A: R1 = CH3; R2 = ClCH2; R3 = CH3; R4 = CH3;

[0015] Compound B: R1=CH3; R2=ClCHCH3; R3=CH3; R4=CH3;

[0016] Compound C: R1 = CH2CH3; R2 = ClCH2; R3 = CH3; R4 = CH3;

[0017] Compound D: R1=CH2CH3; R2=ClCHCH3; R3=CH3; R4=CH3;

[0018] Compound E: R1 = ClCH2; R2 = ClCH2; R3 = CH3; R4 = CH3;

[0019] Compound F: R1=ClCHCH3; R2=ClCHCH3; R3=CH3; R4=CH3;

[0020] Compound G: R1 = ClCH2; R2 = ClCHCH3; R3 = CH3; R4 = CH3;

[0021] Compound H: R1 = CH3; R2 = BrCH2; R3 = CH3; R4 = CH3;

[0022] Compound I: R1=CH3; R2=BrCHCH3; R3=CH3; R4=CH3;

[0023] Compound J: R1 = CH2CH3; R2 = BrCH2; R3 = CH3; R4 = CH3;

[0024] Compound K: R1=CH2CH3; R2=BrCHCH3; R3=CH3; R4=CH3;

[0025] Compound L: R1 = BrCH2; R2 = BrCH2; R3 = CH3; R4 = CH3;

[0026] Compound M: R1=BrCHCH3; R2=BrCHCH3; R3=CH3; R4=CH3;

[0027] Compound N: R1 = BrCH2; R2 = BrCHCH3; R3 = CH3; R4 = CH3.

[0028] In some preferred embodiments of the catalyst component of the present invention, the catalyst component includes the reaction product prepared according to the following steps:

[0029] (a) Dissolve magnesium halide in a solvent system containing organic epoxy compounds and organic phosphorus compounds to obtain a magnesium complex;

[0030] (b) The magnesium complex was reacted with an organic acid anhydride to obtain a reaction mixture;

[0031] (c) The reaction mixture obtained in step (b) is contacted with a titanium-containing compound to obtain a reaction mixture;

[0032] (d) React the reaction mixture from step (c) with an alcohol compound to obtain a reaction mixture;

[0033] In one or more of steps (a), (b), (c), and (d), one or both of an acetate compound and an internal electron donor are added.

[0034] (e) After step (d), the temperature is raised to a high temperature, preferably in the range of 60°C to 100°C, and an internal electron donor is added and subjected to high-temperature treatment to obtain a mixture containing the catalyst components;

[0035] Preferably, the process further includes (f) removing unreacted substances and solvent from the mixture obtained in step (e), washing it, and obtaining the catalyst component.

[0036] According to an embodiment of the catalyst component of the present invention, the magnesium complex is a complex formed by dissolving magnesium halide in a solvent system containing an organic epoxy compound and an organophosphorus compound.

[0037] In a preferred embodiment of the catalyst component of the present invention, the magnesium halide is selected from magnesium dihalide or a complex formed by magnesium dihalide with water, alcohol, or an electron carrier; preferably, the magnesium dihalide is selected from at least one of magnesium dichloride, magnesium dibromide, magnesium difluoride, and magnesium diiodide, more preferably magnesium dichloride; and / or, the alcohol is selected from at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, and isooctanol; and / or, the electron carrier is selected from at least one of ammonia, hydroxylamine, ether, and ester.

[0038] As an example, the magnesium halide is selected from at least one of magnesium dichloride, magnesium dibromide, magnesium difluoride, and magnesium diiodide, and / or a complex formed by at least one of magnesium dichloride, magnesium dibromide, magnesium difluoride, and magnesium diiodide with at least one of water, methanol, ethanol, propanol, butanol, pentanol, hexanol, isooctanol, ammonia, hydroxylamine, ether, and ester. The magnesium halide can be used alone or in combination.

[0039] According to a preferred embodiment of the catalyst component of the present invention, the organic epoxide compound is selected from C2-C4. 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.

[0040] According to a preferred embodiment of the catalyst component of the present invention, the organophosphorus compound is selected from at least one of a hydrocarbon ester or a halohydrocarbon ester of phosphoric acid or phosphorous acid; preferably, the organophosphorus compound is selected from 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, and phosphorus. The following is a list of at least one of trioctyl phosphate, triisooctyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triisopropyl phosphite, tributyl phosphite, triisobutyl phosphite, tritert-butyl phosphite, tripentyl phosphite, triisopentyl phosphite, trihexyl phosphite, triheptanyl phosphite, triisoheptyl phosphite, trioctyl phosphite, triisooctyl phosphite, triphenyl phosphite, and dibutyl phosphite.

[0041] To ensure more complete dissolution, an inert diluent may optionally be added to the solvent system. Typically, this inert diluent is selected from aromatic compounds and / or alkane compounds. More preferably, the aromatic compounds include at least one of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, and monochlorotoluene, and / or their derivatives. The alkane compounds include at least one of straight-chain alkanes, branched alkanes, or cycloalkanes having 3 to 20 carbon atoms, such as butane, pentane, hexane, cyclohexane, heptane, etc., as long as they contribute to the dissolution of magnesium halides. The aforementioned inert diluents can be used alone or in combination.

[0042] According to a preferred embodiment of the catalyst component of the present invention, the structure of the organic acid anhydride compound is shown in formula (II):

[0043] In formula (II), R5 and R6 may be the same or different, and each is independently hydrogen or C1-C. 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;

[0044] According to a preferred embodiment of the catalyst component of the present invention, C1-C 10 Examples of alkyl groups include C1, C2, C3, C4, C5, C6, C7, C8, C9 ... 10 Straight-chain or branched alkyl groups, preferably methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, n-hexyl, etc. C2-C 10 Alkenyl groups include C2, C3, C4, C5, C6, C7, C8, C9 ...10 Straight-chain or branched alkenyl groups, such as vinyl, propenyl, butenyl, etc. Examples of C3-C8 cycloalkyl groups include, but are not limited to, cyclopropyl, methylcyclopropyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl, etc. C6-C 20 Examples of aromatic hydrocarbon groups include, but are not limited to, phenyl, benzyl, dimethylphenyl, etc.

[0045] According to a preferred embodiment of the catalyst component of the present invention, the organic acid anhydride compound is selected from at least one of acetic anhydride, propionic anhydride, butyric anhydride, acrylic anhydride, phthalic anhydride, butylene anhydride and maleic anhydride.

[0046] According to a preferred embodiment of the catalyst component of the present invention, the titanium-containing compound has the general formula Ti(OR8). a X b R8 is C1-C 10 The aliphatic or aromatic hydrocarbon group, X is a halogen, preferably fluorine, chlorine, or bromine, a is 0, 1, or 2, b is an integer from 1 to 4, and a+b=3 or 4.

[0047] According to a preferred embodiment of the catalyst component of the present invention, R8 is selected from C1-C6 alkyl, C2-C6 alkenyl, C3-C8 cycloalkyl, or C6-C 10 The aromatic hydrocarbon group. Preferably, R8 is selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclopropyl, methylcyclopropyl, n-pentyl, methylcyclopentyl, cyclohexyl, phenyl, benzyl, and xylylyl.

[0048] According to a preferred embodiment of the catalyst component of the present invention, the titanium-containing compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium monochlorotriethoxy, titanium trichloride, titanium dichlorodiethoxy, and titanium trichloromonoethoxy.

[0049] According to a preferred embodiment of the catalyst component of the present invention, the general formula of the acetate compound is CH3COOR7, wherein R7 is C1-C. 10 Alkyl, C2-C 10 alkenyl, C3-C 10 cycloalkyl, C2-C 10 alkynyl 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 xylylyl.

[0050] According to a preferred embodiment of the preferred catalyst component of the present invention, the acetate 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.

[0051] According to a preferred embodiment of the catalyst component of the present invention, the alcohol compound is selected from C1-C6. 18 It contains at least one of fatty alcohols or aromatic alcohols, 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.

[0052] According to the present invention, the proportions of each raw material can be selected within a wide range. In a preferred embodiment of the present invention, relative to magnesium halide per mole of magnesium, the amount of organic epoxy compound is 0.2-10 mol; the amount of organic phosphorus compound is 0.1-10 mol; the amount of organic acid anhydride compound is 0.03-1 mol; the amount of acetate compound is 0.01-1 mol; the amount of alcohol compound is 0.1-4 mol; the amount of titanium-containing compound is 0.5-120 mol; and the amount of internal electron donor is 0.01-1 mol. In this preferred embodiment, the resulting catalyst composition corresponds to a higher catalyst polymerization activity, and can polymerize polyethylene powder with higher bulk density, narrower particle size distribution, and narrower molecular weight distribution.

[0053] More preferably, relative to magnesium halide per mole of magnesium, the amount of organic epoxy compound is 0.5-2 moles; the amount of organic phosphorus compound is 0.5-2 moles; the amount of organic acid anhydride compound is 0.1-0.3 moles; the amount of acetate compound is 0.05-0.2 moles; the amount of alcohol compound is 0.1-2 moles; the amount of titanium-containing compound is 5-20 moles; and the amount of internal electron donor is 0.05-0.2 moles.

[0054] A second aspect of the present invention is to provide a method for preparing a catalyst component as described in the first aspect of the present invention, comprising reacting the magnesium complex, organic acid anhydride compound, acetate compound, alcohol compound, titanium-containing compound, and internal electron donor;

[0055] Preferably, it includes the following steps:

[0056] (a) Dissolve magnesium halide in a solvent system containing organic epoxy compounds and organic phosphorus compounds to obtain a magnesium complex;

[0057] (b) The magnesium complex was reacted with an organic acid anhydride to obtain a reaction mixture;

[0058] (c) The reaction mixture obtained in step (b) is contacted with a titanium-containing compound to obtain a reaction mixture;

[0059] (d) React the reaction mixture from step (c) with an alcohol compound to obtain a reaction mixture;

[0060] In one or more of steps (a), (b), (c), and (d), one or both of an acetate compound and an internal electron donor are added.

[0061] (e) After step (d), the temperature is raised to a high temperature, preferably in the range of 60°C to 100°C, and an internal electron donor is added and subjected to high-temperature treatment to obtain a mixture containing the catalyst components;

[0062] Preferably, the process further includes (f) removing unreacted substances and solvent from the mixture obtained in step (e), washing it, and obtaining the catalyst component.

[0063] In this preferred embodiment, an acetate compound and / or an internal electron donor are added in one or more of steps (a), (b), (c), and (d). The catalyst component and the corresponding catalyst prepared according to the specific method steps described above exhibit higher polymerization activity and a narrower particle size distribution, enabling the polymerization of polyethylene powder with higher bulk density and a narrower molecular weight distribution.

[0064] In the above technical solution, "adding one or more of the acetate compound and internal electron donor in one or more of steps (a), (b), (c), and (d)" means that the acetate compound and / or internal electron donor can be added in one of the steps (a), (b), (c), and (d), or the acetate compound and / or internal electron donor can be added independently in two, three, or four of the above four steps, all of which can achieve the present invention.

[0065] The inventors of this invention have discovered through research that, in a more preferred embodiment of this invention, the reaction product is prepared by the following method:

[0066] S1. Dissolve magnesium halide in a solvent system containing organic epoxy compounds and organic phosphorus compounds to obtain a magnesium complex;

[0067] S2. The magnesium complex is reacted with an organic acid anhydride compound, and the reaction mixture is then contacted with a titanium-containing compound to obtain a reaction mixture.

[0068] S3. The reaction mixture obtained in S2 is reacted with an acetate compound, an alcohol compound, and an internal electron donor. After washing, the solid catalyst component is obtained. When organic acid anhydrides, acetate compounds, alcohol electron donors, and halodiether internal electron donors are introduced as compound electron donors into the N-series polyolefin catalyst preparation system according to the more preferred specific method steps of the present invention, especially when alcohol compounds, acetate compounds, and halodiether internal electron donor compounds are added at the specific timing of the present invention, the polymerization activity of the obtained catalyst component and the corresponding catalyst is unexpectedly further improved. It is also possible to polymerize polyethylene powder with further improved bulk density, particle size distribution, molecular weight, and narrower molecular weight distribution.

[0069] In this application, high temperature can refer to a temperature above 70°C, preferably a temperature range of 75°C to 100°C.

[0070] In a preferred embodiment of the present invention, in step S1, magnesium halide and a solvent system containing organic epoxy compounds and organic phosphorus compounds are reacted at 50-70°C for 1-3 hours to form a homogeneous solution.

[0071] In some embodiments, the reaction temperature is 60°C. In some embodiments, the reaction time is 2 hours.

[0072] In a preferred embodiment of the present invention, in step S2, the reaction temperature of the solution with the organic acid anhydride compound is the same as or different from the temperature in step S1, preferably 50-70°C, and the reaction time is 0.5-2 hours. Afterwards, the temperature of the system after the reaction is lowered to -60°C to -20°C, and then it is contacted with titanium-containing compounds, acetate compounds and alcohol compounds. Then the temperature is gradually increased, preferably at a rate of 0.2-2°C / min, to 75°C-100°C, and then the reaction is carried out for 1-4 hours. In step S3, it is then contacted with an internal electron donor, and the reaction temperature is preferably in the range of 70°C to 90°C, and the reaction time is 0.5-2 hours.

[0073] The selection and proportioning of raw materials used in the preparation method are the same as those described in the first aspect of this invention, and will not be repeated here.

[0074] A third aspect of the present invention is to provide a catalyst for olefin polymerization, comprising the following components:

[0075] A): The catalyst component described in the first aspect or the catalyst component obtained according to the preparation method described in the second aspect;

[0076] B): The general formula is AlR' d X' 3-d Organoaluminum compounds, wherein R' is hydrogen or C l -C20 Hydrocarbon group, X' is a halogen atom, preferably fluorine, chlorine or bromine, 0 <d≤3;

[0077] Preferably, the molar ratio of aluminum in component B) to titanium in component A) is (20-200):1, more preferably (50-100):1.

[0078] According to some embodiments of the present invention, R' can be a hydrogen group or a hydrocarbon group having 1-20 carbon atoms, particularly C. l -C 20 alkyl, C l -C 20 Aryl or C l -C 20 The aryl group. Specific compounds include alkylaluminum compounds such as 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, and AlCl2(CH2CH3). Al(CH2CH3)3 and Al(i-Bu)3 are preferred.

[0079] According to some embodiments of the present invention, the molar ratio of aluminum in component B) to titanium in component A) is 5:1-500:1, more preferably 20:1-200:1, and most preferably 50:1-100:1.

[0080] In this specification, inert solvents include: isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, xylene, and other saturated aliphatic or aromatic hydrocarbons.

[0081] In this specification, the term "aliphatic hydrocarbon group" refers to a straight-chain or branched chain hydrocarbon group consisting only of carbon and hydrogen atoms. Specific examples include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, vinyl, 1-propenyl, allyl, ethynyl, 1-propynyl, 2-propynyl, butynyl, etc.

[0082] In this specification, "aromatic hydrocarbon group" refers to a hydrocarbon group having a benzene ring, including aryl, aryl-substituted hydrocarbon groups, or hydrocarbon-substituted aryl groups, such as phenyl, benzyl, anthracene, and naphthyl.

[0083] A fourth aspect of the present invention is to provide a method for preparing ultra-high molecular weight polyolefins, comprising reacting one or more olefins in the presence of a catalyst component described in the first aspect, a catalyst component obtained by the preparation method described in the second aspect, or a catalyst described in the third aspect, wherein the olefin has the general formula CH2=CHR, wherein R is hydrogen or a C1-C6 alkyl group.

[0084] Preferably, the olefin is one or more selected from ethylene, propylene, and butene.

[0085] Preferably, the reaction conditions include:

[0086] The reaction pressure is 0.5-3 MPa, and / or the reaction temperature is 50℃-100℃, and / or the reaction time is 1.5-10 h.

[0087] Polymerization can be carried out using either slurry polymerization or gas-phase polymerization.

[0088] Slurry polymerization media include: isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, xylene and other saturated aliphatic hydrocarbons or aromatic hydrocarbons and other inert solvents.

[0089] According to an embodiment of the present invention, when ethylene is polymerized for 2 hours at 0.35 MPa and 70°C, the bulk density of the polyethylene powder of the present invention can be ≥0.38 g / ml and the molecular weight distribution ≤6.

[0090] The fifth aspect of the present invention is to provide the application of the catalyst component described in the first aspect, the catalyst component prepared by the preparation method described in the second aspect, the catalyst described in the third aspect, or the method for preparing polyolefins as described in the fourth aspect, in the preparation of ultra-high molecular weight polyolefins, particularly ultra-high molecular weight polyethylene.

[0091] By introducing organic acid anhydrides, acetate compounds, alcohols, and haloethers as internal electron donors into the N-series polyolefin catalyst preparation system according to the method of the present invention, and reacting the magnesium complex, organic acid anhydrides, acetate compounds, alcohols, titanium-containing compounds, and internal electron donors, spherical or near-spherical solid particles (solid catalyst components) containing magnesium and titanium can be prepared. These catalyst particles exhibit high polymerization activity and narrow particle size distribution, enabling polymerization to obtain polyethylene powder with high bulk density. Under further preferred conditions, the polymerized powder exhibits high sphericity, high molecular weight, and narrow molecular weight distribution.

[0092] Compared with the prior art, the present invention has the following advantages:

[0093] (1) As described above, the catalyst particles of the present invention have high polymerization activity and narrow particle size distribution, and can be polymerized to obtain polyethylene powder with high bulk density and narrow molecular weight distribution.

[0094] (2) The present invention uses simple raw materials, the raw materials are simple to source, the preparation method is simple and controllable, and the cost is low.

[0095] (3) This invention belongs to the category of dissolution-emission catalysts. As can be verified, different catalysts can be obtained by using different conditions and different electron donors. After the catalyst is polymerized, products with specific particle size and specific molecular weight can be obtained. This is an important manifestation of the superiority of this invention. It can produce special catalyst products with specific particle size and different molecular weights to meet the needs of different markets.

[0096] In summary, this invention improves the performance of existing Ziegler-Natta type olefin polymerization catalyst particles using simple raw materials, at a lower cost, and has extremely high value for widespread application. Attached Figure Description

[0097] Figure 1 This is an electron microscope image of the catalyst particles from Example 1.

[0098] Figure 2 This is an electron microscope image of the catalyst particles in Comparative Example 1.

[0099] pass Figure 1 and Figure 2 As can be seen from the comparison, Figure 1 The particles have a superior morphology, a concentrated particle size distribution, and a higher degree of sphericity. Detailed Implementation

[0100] 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.

[0101] Test method:

[0102] 1. Determination of polymer bulk density: The apparent density, volume factor and pourability of plastics are determined using the test method (ASTM D1895).

[0103] 2. Determination of polymer molecular weight and molecular weight distribution: The molecular weight and molecular weight distribution of the polymer were determined using a Polymer Laboratories PL-GPC220. Eluent: Trichlorobenzene (containing 0.1% antioxidant by mass). Calibration sample: Polystyrene. Flow rate: 1.0 ml / min. Test temperature: 135℃.

[0104] 3. Determination of polymer sphericity: The sphericity was determined using a Camsizer particle size analyzer from Retsch GmbH, Germany.

[0105] 4. Particle size distribution of catalyst components: determined using a Malvern laser particle size and shape analyzer.

[0106] 5. Determination of polymerization activity: The activity is calculated by dividing the mass of the powder obtained from polymerization by the amount of catalyst added.

[0107] 6. The relative weight percentage of titanium in the catalyst component was determined by spectrophotometry.

[0108] The following embodiments are examples of the present invention in more detail, but the present invention is not limited to these embodiments.

[0109] In the following embodiments, electron donor A is

[0110] Electron donor B is

[0111] Example 1

[0112] (1) Preparation of catalyst components

[0113] 4.8 g magnesium chloride, 100 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 this temperature for another hour. The temperature was then lowered to -30°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 (controlled within the range of 0.2-2°C / min) to 80°C and held at this temperature for 1 hour. 2 ml of electron donor A was added, and the reaction was continued at this temperature for another hour. 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 catalyst component with good flowability.

[0114] (2) Polymerization reaction

[0115] 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 0.6 mg of titanium) prepared by the above method. The temperature was raised to 60℃, and ethylene was introduced to bring the total pressure inside the reactor to 0.35 MPa (gauge pressure). Polymerization was carried out at 70℃ for 2 hours. The polymerization results are shown in Table 1.

[0116] Example 2

[0117] (1) Preparation of catalyst components

[0118] 4.8 g magnesium chloride, 100 ml toluene, 8.0 ml epichlorohydrin, and 18.0 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 this temperature for another hour. The temperature was then lowered to -30°C, and 70 ml titanium tetrachloride was added dropwise, followed by 2 ml ethyl acetate and 6 ml ethanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 80°C and held for 1 hour. 2 ml of electron donor A was added, and the reaction was continued at this temperature for another hour. 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 catalyst component with good flowability.

[0119] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0120] Example 3

[0121] (1) Preparation of catalyst components

[0122] 4.8 g magnesium chloride, 110 ml toluene, 6.0 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 this temperature for another hour. The temperature was then lowered to -30°C, and 60 ml titanium tetrachloride was added dropwise, followed by 2 ml ethyl acetate and 4 ml butanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 80°C and held for 1 hour. 2 ml of electron donor A was added, and the reaction was continued at this temperature for another hour. 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 catalyst component with good flowability.

[0123] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0124] Example 4

[0125] (1) Preparation of catalyst components

[0126] 4.8 g magnesium chloride, 120 ml toluene, 6.0 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 this temperature for another hour. The temperature was then lowered to -30°C, and 60 ml titanium tetrachloride was added dropwise, followed by 2 ml ethyl acetate and 4 ml butanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 80°C and held for 1 hour. 2 ml of electron donor B was added, and the reaction was continued at this temperature for another hour. 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 catalyst component with good flowability.

[0127] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0128] Example 5

[0129] (1) Preparation of catalyst component A5

[0130] 4.8 g magnesium chloride, 120 ml toluene, 6.0 ml epichlorohydrin, 15.0 ml triisobutyl phosphate, and 2 ml electron donor A were added to a reactor. The mixture was reacted for 2 hours at 400 rpm and 62°C. Then, 1.2 g phthalic anhydride was added, and the mixture was kept at this temperature for another hour. The temperature was then lowered to -30°C. 60 ml titanium tetrachloride was added dropwise, followed by 2 ml ethyl acetate and 4 ml butanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 85°C and kept at this temperature for 1 hour. 2 ml electron donor B was added, and the mixture was kept at this temperature for another hour. The mother liquor was filtered off, and the mixture was washed multiple times with inert diluent toluene and organic solvent hexane, then dried to obtain a solid catalyst component with good flowability.

[0131] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0132] Example 6

[0133] (1) Preparation of catalyst components

[0134] 4.8 g magnesium chloride, 120 ml toluene, 8.0 ml epichlorohydrin, and 20.0 ml triisobutyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 400 rpm and 62°C. Then, 1.2 g phthalic anhydride was added, and the reaction was continued at this temperature for another hour. The temperature was then lowered to -30°C. 60 ml titanium tetrachloride was added dropwise, followed by 2 ml ethyl acetate and 4 ml n-hexanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 85°C and held at this temperature for 1 hour. 2 ml of electron donor B was added, and the reaction was continued at this temperature for another hour. The mother liquor was filtered off, and the mixture was washed multiple times with inert diluent toluene and organic solvent hexane, then dried to obtain a solid catalyst component with good flowability.

[0135] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0136] Example 7

[0137] (1) Preparation of catalyst components

[0138] 4.8 g magnesium chloride, 150 ml toluene, 8.0 ml epichlorohydrin, and 20.0 ml triisopropyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 400 rpm and 62°C. Then, 1.2 g phthalic anhydride was added, and the reaction was continued at this temperature for another hour. The temperature was then lowered to -35°C. 70 ml titanium tetrachloride was added dropwise, followed by 2 ml n-butyl acetate and 6 ml isooctyl alcohol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 85°C and held at this temperature for 1 hour. 2 ml electron donor B was added, and the reaction was continued at this temperature for another hour. The mother liquor was filtered off, and the mixture was washed multiple times with inert diluent toluene and organic solvent hexane, then dried to obtain a solid catalyst component with good flowability.

[0139] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0140] Example 8

[0141] (1) Preparation of catalyst components

[0142] 4.8 g magnesium chloride, 120 ml toluene, 10.0 ml epichlorohydrin, and 20.0 ml triisobutyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 400 rpm and 62°C. Then, 2 g acetic anhydride was added, and the reaction was continued at this temperature for 1 hour. The temperature was then lowered to -30°C. First, 80 ml of titanium trichlorotriethoxy was added dropwise, followed by 2 ml of n-propyl acetate and 8 ml of butanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 85°C and held at this temperature for 1 hour. Then, 1 ml of electron donor A and 1 ml of electron donor B were added, and the reaction was continued at this temperature for 1 hour. 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 catalyst component with good flowability.

[0143] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0144] Example 9

[0145] (1) Preparation of catalyst components

[0146] 4.8 g magnesium chloride, 50 ml toluene, 1.5 ml epichlorohydrin, and 4.0 ml tri-tert-butyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 400 rpm and 60°C. Then, 0.5 g phthalic anhydride was added, and the reaction was continued at this temperature for 1 hour. The temperature was then lowered to -30°C, and 20 ml titanium tetrachloride was added dropwise, followed by 0.2 ml ethyl acetate and 0.4 ml ethanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 85°C and held at this temperature for 1 hour. Then, 0.3 ml electron donor A was added, and the reaction was continued at this temperature for 1 hour. 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 catalyst component with good flowability.

[0147] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0148] Example 10

[0149] (1) Preparation of catalyst components

[0150] 4.8 g magnesium chloride, 200 ml toluene, 15 ml epichlorohydrin, and 40.0 ml tri-tert-butyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 400 rpm and 62°C. Then, 4 g phthalic anhydride was added, and the reaction was continued at this temperature for 1 hour. The temperature was then lowered to -30°C, and 250 ml titanium tetrachloride was added dropwise, followed by 7.5 ml ethyl acetate and 15 ml ethanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 85°C and held at this temperature for 1 hour. 5 ml of electron donor A was added, and the reaction was continued at this temperature for another 1 hour. 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 catalyst component with good flowability.

[0151] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0152] Example 11

[0153] (1) Preparation of catalyst components

[0154] 4.8 g magnesium chloride, 100 ml toluene, 8.0 ml epichlorohydrin, 18.0 ml tri-n-butyl phosphate, and 2.0 ml ethyl acetate were added to a reaction vessel. The mixture was reacted for 2 hours at a stirring speed of 450 rpm and a temperature of 60°C. Then, 1.2 g phthalic anhydride was added, and the reaction was continued at this temperature for another hour. The temperature was then lowered to -30°C, and 70 ml titanium tetrachloride was added dropwise, followed by 6 ml ethanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 80°C and held at this temperature for 1 hour. 2 ml of electron donor A was added, and the reaction was continued at this temperature for another hour. 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 catalyst component with good flowability.

[0155] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0156] Comparative Example 1

[0157] (1) Preparation of catalyst components

[0158] 4.8 g magnesium chloride, 100 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 mixture was kept at this temperature for another hour. The temperature was then lowered to -30°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 (controlled within the range of 0.2-2°C / min) to 80°C and kept at this temperature for 2 hours. 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 catalyst component with good flowability.

[0159] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0160] Comparative Example 2

[0161] (1) Preparation of catalyst components

[0162] 4.8 g magnesium chloride, 100 ml toluene, 8.0 ml epichlorohydrin, and 18.0 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 mixture was kept at this temperature for another hour. The temperature was then lowered to -30°C, and 70 ml titanium tetrachloride was added dropwise, followed by 2 ml ethyl acetate and 6 ml ethanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 80°C and kept at this temperature for 2 hours. The mother liquor was filtered off, and the mixture was washed multiple times with toluene (an inert diluent) and hexane (an organic solvent) and dried to obtain a solid catalyst component with good flowability.

[0163] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0164] Comparative Example 3

[0165] 4.8 g magnesium chloride, 110 ml toluene, 6.0 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 mixture was kept at this temperature for another hour. The temperature was then lowered to -30°C, and 60 ml titanium tetrachloride was added dropwise, followed by 2 ml ethyl acetate and 4 ml butanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 80°C and kept at this temperature for 2 hours, followed by another hour. The mother liquor was filtered off, and the mixture was washed multiple times with toluene (an inert diluent) and hexane (an organic solvent) and dried to obtain a solid catalyst component with good flowability.

[0166] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0167] Comparative Example 4

[0168] (1) Preparation of catalyst components

[0169] 4.8 g magnesium chloride, 120 ml toluene, 8.0 ml epichlorohydrin, and 20.0 ml triisobutyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 400 rpm and 62°C. Then, 1.2 g phthalic anhydride was added, and the mixture was kept at this temperature for another hour. The temperature was then lowered to -30°C, and 60 ml titanium tetrachloride was added dropwise, followed by 2 ml ethyl acetate and 4 ml n-hexanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 85°C and kept at this temperature for 2 hours. 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 catalyst component with good flowability.

[0170] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0171] Comparative Example 5:

[0172] (1) Preparation of catalyst components

[0173] 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 with a stirring speed of 450 rpm. Then, 1.1 g phthalic anhydride and 0.7 ml ethyl acetate were added, and the mixture was kept at this temperature for another hour. The temperature was then lowered to -40°C, and 70 ml titanium tetrachloride was added dropwise. The temperature was gradually increased to 90°C and kept at this temperature for another hour. Finally, 1 ml of 2,2-dimethyl-1,3-diethoxy-propane was added, and the mixture was kept 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 catalyst component with good flowability.

[0174] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0175] Comparative Example 6:

[0176] (1) Preparation of catalyst components

[0177] 4.8 g magnesium chloride, 100 ml toluene, 5.5 ml epichlorohydrin, and 14 ml triisobutyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 450 rpm and 60°C. Then, 1.5 g phthalic anhydride and 1 ml methyl acetate were added, and the mixture was kept at this temperature for another hour. The temperature was then lowered to -40°C, and 65 ml titanium tetrachloride was added dropwise. The temperature was gradually increased to 80°C and kept at this temperature for 3 hours. Finally, 1 ml 1-ethoxy-3-methoxy-propane was added, and the mixture was kept 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 catalyst component with good flowability.

[0178] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0179] Comparative Example 7:

[0180] (1) Preparation of catalyst components

[0181] Example 1 in patent CN 114478861 A.

[0182] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0183] Table 1

[0184]

[0185] As shown in Table 1, when a halodiether-type internal electron donor is introduced into the catalyst, the activity of the resulting catalyst increases significantly, the particle size distribution of the catalyst narrows, and the packing density and sphericity of the polymer increase significantly under the synergistic effect of the raw materials. The polymer has a higher molecular weight and a more concentrated molecular weight distribution, resulting in better overall performance.

[0186] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

[0187] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0188] When this specification uses the prefixes “known to those skilled in the art,” “prior art,” or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those commonly used in the art at the time of this application’s filing, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0189] The endpoints and any values ​​of the ranges disclosed in this application are not limited to the precise ranges or values; such ranges or values ​​should be understood to include values ​​close to them. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. In principle, various technical solutions can be combined with each other to obtain new technical solutions, which should also be considered as specifically disclosed herein.

[0190] In the context of this specification, except where expressly stated otherwise, any matters or issues not mentioned shall apply directly to those known in the art without any modification.

[0191] Furthermore, any implementation described herein can be freely combined with one or more other implementations described herein, and the resulting technical solutions or technical ideas shall be regarded as part of the original disclosure or original record of the present invention, and should not be regarded as new content not disclosed or anticipated herein, unless those skilled in the art consider the combination to be obviously unreasonable.

Claims

1. A catalyst component for olefin polymerization, comprising a magnesium complex, an organic acid anhydride compound, an acetate compound, an alcohol compound, a titanium-containing compound, and a reaction product of an internal electron donor; The magnesium complex is a complex formed by dissolving magnesium halide in a solvent system containing organic epoxy compounds and organophosphorus compounds. The internal electron donor is selected from at least one of the compounds represented by general formula (I): In formula (Ⅰ), R1 and R2 are independently C1-C10 hydrocarbon groups substituted or unsubstituted with halogen atoms, and R3 and R4 are independently C1-C10 hydrocarbon groups substituted or unsubstituted with hydrogen, halogen, or halogen atoms. At least one of R1 and R2 is substituted with a halogen atom.

2. The catalyst component according to claim 1, characterized in that: In formula (Ⅰ), R1 and R2 are independently methyl, ethyl, halomethyl or haloethyl, and at least one of R1 and R2 is substituted with a halogen atom; and / or, R3 and R4 are independently hydrogen, halogen or methyl; Preferably, the internal electron donor is selected from at least one of the following compounds: Compound A: R1 = CH3; R2 = ClCH2; R3 = CH3; R4 = CH3; Compound B: R1=CH3; R2=ClCHCH3; R3=CH3; R4=CH3; Compound C: R1 = CH2CH3; R2 = ClCH2; R3 = CH3; R4 = CH3; Compound D: R1=CH2CH3; R2=ClCHCH3; R3=CH3; R4=CH3; Compound E: R1 = ClCH2; R2 = ClCH2; R3 = CH3; R4 = CH3; Compound F: R1=ClCHCH3; R2=ClCHCH3; R3=CH3; R4=CH3; Compound G: R1 = ClCH2; R2 = ClCHCH3; R3 = CH3; R4 = CH3; Compound H: R1 = CH3; R2 = BrCH2; R3 = CH3; R4 = CH3; Compound I: R1=CH3; R2=BrCHCH3; R3=CH3; R4=CH3; Compound J: R1 = CH2CH3; R2 = BrCH2; R3 = CH3; R4 = CH3; Compound K: R1=CH2CH3; R2=BrCHCH3; R3=CH3; R4=CH3; Compound L: R1 = BrCH2; R2 = BrCH2; R3 = CH3; R4 = CH3; Compound M: R1=BrCHCH3; R2=BrCHCH3; R3=CH3; R4=CH3; Compound N: R1 = BrCH2; R2 = BrCHCH3; R3 = CH3; R4 = CH3.

3. The catalyst component according to claim 1, characterized in that... Including the reaction products prepared according to the following steps: (a) Dissolve magnesium halide in a solvent system containing organic epoxy compounds and organic phosphorus compounds to obtain a magnesium complex; (b) The magnesium complex was reacted with an organic acid anhydride to obtain a reaction mixture; (c) The reaction mixture obtained in step (b) is contacted with a titanium-containing compound to obtain a reaction mixture; (d) React the reaction mixture from step (c) with an alcohol compound to obtain a reaction mixture; In one or more of steps (a), (b), (c), and (d), one or both of an acetate compound and an internal electron donor are added. (e) After step (d), the temperature is raised to a high temperature, preferably in the range of 60°C to 100°C, and an internal electron donor is added and subjected to high-temperature treatment to obtain a mixture containing the catalyst components; Preferably, the process further includes (f) removing unreacted substances and solvent from the mixture obtained in step (e), washing it, and obtaining the catalyst component.

4. The catalyst component according to any one of claims 1-3, characterized in that: The magnesium halide is selected from magnesium dihalides or complexes formed by magnesium dihalides with at least one of water, alcohol, and an electron carrier; preferably, the magnesium dihalide is selected from at least one of magnesium dichloride, magnesium dibromide, magnesium difluoride, and magnesium diiodide; and / or, the alcohol is selected from at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, and isooctanol; and / or, 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-C4. 18 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, and butyl glycidyl ether; and / or, The organophosphorus compound is selected from at least one of the hydrocarbon esters or halohydrocarbon esters 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.

5. The catalyst component according to any one of claims 1-3, characterized in that: An inert diluent may be optionally added to the solvent system; preferably, the inert diluent is selected from aromatic compounds and / or alkane compounds; more preferably, the aromatic compounds include at least one of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene, and / or their derivatives; the alkane compounds include at least one of straight-chain alkanes, branched alkanes, or cycloalkanes having 3 to 20 carbon atoms; and / or, The structure of the organic acid anhydride compound is shown in formula (II): In formula (II), R5 and R6 may be the same or different, and each is independently hydrogen or C1-C. 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(OR8). a X b R8 is C1-C 10 The aliphatic or aromatic hydrocarbon group, X is a halogen, preferably fluorine, chlorine or bromine, a is 0, 1 or 2, b is an integer from 1 to 4, and a+b=3 or 4.

6. The catalyst component according to any one of claims 1-3, characterized in that: The general formula of the acetate compounds is CH3COOR7, where R7 is C1-C. 10 Alkyl, C2-C 10 alkenyl, C3-C 10 cycloalkyl, C2-C 10 alkynyl 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 alcohols are selected from C1-C1. 18 It contains at least one of fatty alcohols or aromatic alcohols, 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.

7. The catalyst component according to any one of claims 1-3, characterized in that: The amount of organic epoxy compound used is 0.2-10 moles per mole of magnesium halide; the amount of organic phosphorus compound used is 0.1-10 moles per mole of magnesium. The amount of organic acid anhydrides is 0.03-1 mol; the amount of acetate compounds is 0.01-1 mol; the amount of alcohol compounds is 0.1-4 mol; the amount of titanium-containing compounds is 0.5-120 mol; the amount of internal electron donors is 0.01-1 mol; preferably, The amount of organic epoxy compounds used relative to magnesium halides per mole of magnesium is 0.5-2 mol; the amount of organic phosphorus compounds is 0.5-2 mol; the amount of organic acid anhydrides is 0.1-0.3 mol; the amount of acetate compounds is 0.05-0.2 mol; the amount of alcohol compounds is 0.1-2 mol; the amount of titanium-containing compounds is 5-20 mol; and the amount of internal electron donors is 0.05-0.2 mol.

8. A method for preparing a catalyst component according to any one of claims 1-7, comprising reacting the magnesium complex, organic acid anhydride compound, acetate compound, alcohol compound, titanium-containing compound, and internal electron donor; preferably, Includes the following steps: (a) Dissolve magnesium halide in a solvent system containing organic epoxy compounds and organic phosphorus compounds to obtain a magnesium complex; (b) The magnesium complex was reacted with an organic acid anhydride to obtain a reaction mixture; (c) The reaction mixture obtained in step (b) is contacted with a titanium-containing compound to obtain a reaction mixture; (d) React the reaction mixture from step (c) with an alcohol compound to obtain a reaction mixture; In one or more of steps (a), (b), (c), and (d), one or both of an acetate compound and an internal electron donor are added. (e) After step (d), the temperature is raised to a high temperature, preferably in the range of 60°C to 100°C, and an internal electron donor is added and subjected to high-temperature treatment to obtain a mixture containing the catalyst components; Preferably, the process further includes (f) removing unreacted substances and solvent from the mixture obtained in step (e), washing it, and obtaining the catalyst component.

9. The preparation method according to claim 8, characterized in that, The reaction product is prepared by the following method: S1. Dissolve magnesium halide in a solvent system containing organic epoxy compounds and organic phosphorus compounds to obtain a magnesium complex; S2. The magnesium complex is reacted with an organic acid anhydride compound, and the reaction mixture is then contacted with a titanium-containing compound to obtain a reaction mixture. S3. The reaction mixture obtained in S2 is reacted with an acetate compound, an alcohol compound, and an internal electron donor, and the mixture is washed to obtain the catalyst component; preferably, In step S1, magnesium halide and a solvent system containing organic epoxy compounds and organophosphorus compounds are reacted at 50-70°C for 1-3 hours to form a homogeneous solution; and / or, In step S2, the reaction temperature of the solution with the organic acid anhydride compound is the same as or different from that in step S1, preferably 50-70°C, and the reaction time is 0.5-2 hours. After that, the temperature of the system after the reaction is lowered to -60°C to -20°C, and then it is contacted with titanium-containing compounds, acetate compounds and alcohol compounds. Then the temperature is gradually increased, preferably at a rate of 0.2-2°C / min, to 75°C-100°C, and then the reaction is carried out for 1-4 hours. In step S3, the mixture is brought into contact with an internal electron donor. The preferred reaction temperature is between 70°C and 90°C, and the reaction time is 0.5-2 hours.

10. A catalyst for olefin polymerization, comprising the following components: A): The catalyst component according to any one of claims 1-7 or the catalyst component obtained by the preparation method according to claim 8 or 9; B): The general formula is AlR' d X' 3-d Organoaluminum compounds, wherein R' is hydrogen or C l -C 20 Hydrocarbon group, X' is a halogen atom, preferably fluorine, chlorine or bromine, 0 <d≤3; Preferably, the molar ratio of aluminum in component B) to titanium in component A) is (20-200):1, more preferably (50-100):

1.

11. A method for preparing a polyolefin, comprising reacting one or more olefins in the presence of a catalyst component according to any one of claims 1-7, a catalyst component obtained by the preparation method according to claim 8 or 9, or a catalyst according to claim 10, wherein the olefin has the general formula CH2=CHR, wherein R is hydrogen or a C1-C6 alkyl group; preferably, The olefin is preferably one or more selected from ethylene, propylene, and butene; and / or, The conditions for the reaction include: The reaction is carried out at a pressure of 0.5-3 MPa and / or at a temperature of 50-100°C and / or for a time of 1.5-10 h.

12. The use of a catalyst component according to any one of claims 1-7, or a catalyst component prepared by the preparation method according to claim 8 or 9, or a catalyst according to claim 10, or a method for preparing polyolefins according to claim 11, in the preparation of polyolefins, particularly ultra-high molecular weight polyethylene.

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