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

Abstract

The invention provides a catalyst component for olefin polymerization, which comprises a reaction product of a magnesium compound, an organic anhydride compound, a titanium-containing compound, an acetate compound, an alcohol compound, a long carbon chain monoester compound and an optional aromatic ester compound, 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 method can be used for preparing spherical or sphere-like solid particles (solid catalyst components) containing magnesium and titanium. The polymerization activity and hydrogen regulation sensitivity of the catalyst particles are high, polyethylene powder with high stacking density can be obtained through polymerization, and the requirement of an industrial production device for the catalyst is met.

Description

TECHNICAL FIELD

[0001] The present application relates to a catalyst component for the polymerization of olefins, a catalyst and a process for its preparation and use. BACKGROUND

[0002] In actual production, industrial polymerization devices have high requirements for the particle morphology of Ziegler-Natta type olefin polymerization catalyst particles, because the spherical / quasi-spherical catalyst particles with good particle morphology can generally polymerize to generate powder particles with better comprehensive performance. The preparation process of the dissolution precipitation type catalyst is short, and the controllability of the particle shape of the catalyst is strong, so it is a good choice. The N series polyolefin catalyst of Beijing Chemical Research Institute is a typical representative of the dissolution precipitation type catalyst. The particles of such catalysts are non-spherical, and the particle size is usually less than 50 μm. The powder particles obtained by ethylene polymerization are also non-spherical. If you want to prepare N type polyolefin catalyst particles with narrow distribution, spherical / quasi-spherical, you need to achieve accurate control of the precipitation and shaping of the catalyst particles.

[0003] As disclosed in patent document CN105482002A, when introducing organic acid anhydride / acetic acid ester / cyclic ketone compounds as a complex electron donor into the preparation system of N series polyolefin catalyst, spherical / quasi-spherical polyethylene catalyst particles are first prepared. However, the polymerization activity and hydrogen sensitivity of the above-mentioned spherical / quasi-spherical polyethylene catalyst are relatively low, which cannot meet the requirements of CX, Hostalen, ACP, Innovene S and other industrial slurry polyethylene production devices for high activity and high hydrogen sensitivity catalysts.

[0004] In addition to the polymerization activity and hydrogen sensitivity, the bulk density of the polymerized powder is also an important factor affecting the industrial application of the catalyst. This is because in the slurry polymerization process, the polymer / hexane slurry is separated by centrifugation, and the hexane carrying amount of the high bulk density powder is lower, which is beneficial to reduce the energy consumption of the powder drying and improve the load of the drying unit. In addition, high bulk density powder is beneficial to the efficient operation of the powder conveying unit of the industrial production device, which can make the production device achieve higher production load.

[0005] Therefore, it is necessary to develop a spherical / quasi-spherical polyethylene catalyst with high activity and high hydrogen sensitivity, and the preparation steps of the catalyst are simple. The catalyst can polymerize to obtain powder particles with high bulk density. SUMMARY

[0006] The inventors discovered that by introducing organic acid anhydrides, acetates, alcohols as electron donors, long-chain monoesters, and optionally aromatic esters as composite electron donors into the N-series polyolefin catalyst preparation system, and reacting the magnesium complex, organic acid anhydrides, titanium-containing compounds, acetates, alcohols, long-chain monoesters, and optionally aromatic esters, spherical or near-spherical solid particles (solid catalyst components) containing magnesium and titanium can be prepared. These catalyst particles exhibit high polymerization activity and hydrogen sensitivity, enabling the polymerization of polyethylene powder with high bulk density.

[0007] A first aspect of the present invention is to provide a catalyst component for olefin polymerization, comprising a reaction product of a magnesium complex, an organic acid anhydride compound, a titanium-containing compound, an acetate compound, an alcohol compound, a long-chain monoester compound, and optionally an aromatic ester compound.

[0008] The magnesium complex is a complex formed by dissolving magnesium halide in a solvent system containing organic epoxy compounds and organophosphorus compounds.

[0009] According to some preferred embodiments of the catalyst component of the present invention, the preparation method of the catalyst component includes the following steps:

[0010] S1, dissolve magnesium halide in a solvent system containing organic epoxy compounds and organic phosphorus compounds to form a homogeneous solution, and obtain a magnesium complex;

[0011] S2, reacting the solution obtained in step S1 (i.e., the magnesium complex) with an organic acid anhydride compound, then contacting it first with a titanium compound, then with an acetate compound and an alcohol compound, followed by heating to precipitate spherical or near-spherical solid particles containing magnesium / titanium, and then contacting it with a long-chain monoester compound and optionally an aromatic ester compound during a high-temperature aging stage, preferably above 70°C, more preferably 75°C-100°C, to obtain a mixture containing a catalyst component; preferably, it further includes:

[0012] S3. Remove unreacted substances and solvent from the mixture obtained in step S2, wash, and obtain spherical or near-spherical solid catalyst components. The solid catalyst components obtained by this method have higher polymerization activity and hydrogen sensitivity, and can be polymerized to obtain polyethylene powder with higher bulk density.

[0013] 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.

[0014] According to some preferred embodiments of the catalyst component of the present invention, the magnesium halide is selected from magnesium dihalides or complexes of magnesium dihalides with water, alcohols, or electron donors. Specific compounds include at least one of magnesium dichloride, magnesium dibromide, magnesium difluoride, and magnesium diiodide, with magnesium dichloride being preferred. The complexes of magnesium dihalides with water, alcohols, or electron donors include complexes of magnesium dihalides with at least one of water, methanol, ethanol, propanol, butanol, pentanol, hexanol, isooctanol, ammonia, hydroxylamine, ethers, and esters. The magnesium halide can be used alone or in combination. 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 donor is selected from at least one of ammonia, hydroxylamine, ethers, and esters.

[0015] According to some preferred embodiments of the catalyst component of the present invention, the organic epoxide is C2-C. 18 The organic epoxy compound is selected from at least one of aliphatic olefins, dienes, or oxides of halogenated aliphatic olefins or 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, etc.

[0016] According to some preferred embodiments of the catalyst component of the present invention, the organophosphorus compound is at least one of a hydrocarbon ester or halohydrocarbon ester of phosphoric acid or phosphorous acid; preferably 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.

[0017] To ensure more complete dissolution, an inert diluent may optionally be added to the solvent system. Typically, such inert diluents include aromatic or alkane compounds. Aromatic compounds include benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene, and their derivatives. Alkane compounds include one or a mixture of straight-chain alkanes, branched alkanes, or cycloalkanes with 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. 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.

[0018] According to some preferred embodiments of the catalyst component of the present invention, the structure of the organic acid anhydride compound is shown in formula (II):

[0019]

[0020] In formula (II), R5 and R6 are independently hydrogen or C1-C 10 Alkyl, C2-C 10 alkenyl, C2-C 10 alkynyl, C3-C8 cycloalkyl or C6-C 10 Aromatic hydrocarbon groups, R5 and R6 can form rings in any order.

[0021] According to some preferred embodiments of the catalyst components 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.

[0022] According to some preferred embodiments of the catalyst components 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, butenoic anhydride and maleic anhydride.

[0023] According to some preferred embodiments of the catalyst component of the present invention, the general formula of the acetate compound is CH3COOR7, where R7 is C1-C. 10 Alkyl, C2-C 10 alkenyl, C3-C8 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. More preferably, R7 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, or n-hexyl.

[0024] According to some preferred embodiments of the catalyst components 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.

[0025] According to some preferred embodiments of the catalyst composition of the present invention, the titanium-containing compound has the general formula Ti(OR8). a X b In the formula, R8 is C1-C 10 Aliphatic or aromatic hydrocarbon groups (e.g., C6-C) 14 (aromatic hydrocarbon group), where 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.

[0026] In some preferred embodiments of the catalyst component according to 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.

[0027] In some more preferred embodiments of the catalyst component according to 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.

[0028] According to some preferred embodiments of the catalyst components of the present invention, the alcohol compounds are selected from C1-C64. 18It 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, isoooctanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, propylene glycol, butanediol, hexanediol, and isohexanediol.

[0029] According to some preferred embodiments of the catalyst components of the present invention, the general formula of the aromatic ester compound is C5H5[(CH2)]. n [COOR9], where R9 is selected from C1-C 10 Aliphatic hydrocarbon group or aromatic hydrocarbon group, where n is an integer between 0 and 9.

[0030] In some preferred embodiments of the catalyst component according to the present invention, R9 is selected from C1-C9 alkyl, C3-C8 cycloalkyl, or C6-C 10 The aromatic hydrocarbon group. Preferably, R9 is selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclopropyl, methylcyclopropyl, n-pentyl, methylcyclopentyl, cyclohexyl, phenyl, benzyl, and xylylyl.

[0031] In some further preferred embodiments of the catalyst component according to the present invention, the aromatic ester compound is selected from at least one of methyl benzoate, ethyl benzoate, propyl benzoate, isopropyl benzoate, butyl benzoate, tert-butyl benzoate, hexyl benzoate, octyl benzoate, cyclohexyl benzoate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate, hexyl phenylacetate, and octyl phenylacetate.

[0032] According to some preferred embodiments of the catalyst components of the present invention, the long-chain monoester compound has the general formula R. 10 COOR 11 , where R 10 For C1~C 10 Straight-chain, branched-chain hydrocarbon groups or cyclic hydrocarbon groups, R 11 C6~C 18 Long-chain straight-chain or branched hydrocarbon groups, R 10 Selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclopropyl, methylcyclopropyl, n-pentyl, methylcyclopentyl, cyclohexyl, R 11 Selected from n-hexyl, n-octyl, isooctyl, n-heptyl, n-nonyl, n-decyl, methylcyclopentyl, and cyclohexyl.

[0033] According to some preferred embodiments of the catalyst components of the present invention, the long-chain monoester compound is selected from at least one of n-hexyl formate, n-octyl formate, isooctyl formate, n-hexyl acetate, n-octyl acetate, isooctyl acetate, n-hexyl propionate, n-octyl propionate, and isooctyl propionate.

[0034] According to some preferred embodiments of the catalyst components of the present invention, the proportions between the reactants, based on one mole of magnesium in the magnesium complex, are as follows: organic epoxy compound 0.2-10 moles; organophosphorus compound 0.1-10 moles; organic acid anhydride compound 0.03-1.0 moles; acetate compound 0.01-1 moles; aromatic ester compound 0-1 moles; long-chain monoester compound 0.01-1 moles; alcohol compound 0.1-4 moles; and titanium-containing compound 0. 5-120 mol; more preferably, the proportions of the reactants, based on each mole of magnesium in the magnesium complex, are as follows: 0.3-2 mol of organic epoxy compounds; 0.3-2 mol of organic phosphorus compounds; 0.1-0.4 mol of organic acid anhydrides; 0.05-0.4 mol of acetate compounds; 0-0.3 mol of aromatic ester compounds; 0.03-0.3 mol of long-chain monoester compounds; 0.5-4 mol of alcohol compounds; and 5-25 mol of titanium-containing compounds.

[0035] A second aspect of the present invention is to provide a method for preparing the above-mentioned catalyst component, comprising reacting a magnesium complex, an organic acid anhydride compound, a titanium-containing compound, an acetate compound, an alcohol compound, a long-chain monoester compound, and optionally an aromatic ester compound.

[0036] Preferably, the method for preparing the catalyst component includes the following steps:

[0037] S1, dissolve magnesium halide in a solvent system containing organic epoxy compounds and organic phosphorus compounds to form a homogeneous solution, and obtain a magnesium complex;

[0038] S2, react the solution obtained in step S1 (i.e., the magnesium complex) with organic acid anhydride compounds, then first contact it with titanium compounds, then with acetate compounds and alcohol compounds, and then raise the temperature to precipitate spherical or near-spherical solid particles containing magnesium / titanium, and then contact it with long carbon chain monoester compounds and optional aromatic ester compounds during the high-temperature curing stage.

[0039] S3. Remove unreacted substances and solvent from the mixture obtained in step S2, wash, and obtain the solid catalyst component.

[0040] In this invention, high temperature can refer to a temperature above 70°C, preferably a temperature range of 75°C-100°C.

[0041] According to some preferred embodiments of the method for preparing the catalyst component of the present invention, in step S1, magnesium halide and a solvent system containing an organic epoxy compound and an organophosphorus compound are reacted at 50-70°C for 1-3 hours to form a homogeneous solution. In some embodiments, the reaction temperature is 60°C. In some embodiments, the reaction time is 2 hours.

[0042] In some preferred embodiments of the preparation method of the catalyst component according to 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 dissolution temperature, the reaction time is 0.5-2 hours, the temperature of the system after reaction is lowered to -60°C to -20°C, and then it is contacted with titanium compound, acetate compound and alcohol compound; the heating is gradual, the heating rate can be 0.2-2°C / min, and the temperature is raised to 75°C-100°C, and then it is contacted with long-chain monoester compound and optional aromatic ester compound during the ripening stage. The contact time with long-chain monoester compound and optional aromatic ester compound is preferably 0.5-2 hours. For example, in some embodiments, the contact time is 1 hour.

[0043] A third aspect of the present invention is to provide a catalyst for olefin polymerization, comprising the following components:

[0044] A): The catalyst component described in the first aspect of the present invention or the catalyst component prepared by the preparation method described in the second aspect of the present invention;

[0045] B): The general formula is AlR' d X' 3-d Organoaluminum compounds, where R' is hydrogen or C l -C 20 Hydrocarbon group, X' is a halogen atom, preferably fluorine, chlorine or bromine, 0 <d≤3。

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] The fourth aspect of the present invention provides the application of the above-described catalyst component, the catalyst component prepared by the above-described preparation method, or the above-described catalyst in ethylene polymerization.

[0052] Polymerization can be carried out using either slurry polymerization or gas-phase polymerization.

[0053] 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.

[0054] According to some preferred embodiments of the present invention, when polymerized for 2 hours under the conditions of hydrogen 0.28MPa / ethylene 0.45MPa / temperature 80°C, the bulk density of the polyethylene powder of the present invention can be ≥0.37g / ml.

[0055] Compared with the prior art, the advantages of the present invention are:

[0056] Compared with existing commercial catalysts, the solid catalyst composition of this invention shows that the catalyst of this invention has a significantly higher powder packing density and superior hydrogen regulation sensitivity. This catalyst significantly improves hydrogen regulation performance while maintaining activity and packing density. Attached Figure Description

[0057] Figure 1 Electron micrographs of non-spherical N-series polyolefin catalysts in the prior art.

[0058] Figure 2 This is an electron microscope image of the catalyst particles from Example 1.

[0059] Figure 3 This is an electron microscope image of the catalyst particles from Example 2.

[0060] Figure 4This is an electron microscope image of the catalyst particles in Comparative Example 7.

[0061] Depend on Figures 1-4 As can be seen from the comparison, the embodiments of the present invention can obtain spherical catalyst particles with better particle morphology, while the N catalyst and the comparative catalyst can only obtain grape-shaped catalysts with rough surfaces. This indicates that under the conditions of the present invention, the catalyst has better particle morphology and can be polymerized to obtain spherical powder particles. Detailed Implementation

[0062] 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.

[0063] Test method:

[0064] 1. Determination of catalyst / polymer powder morphology: Hitachi S-4800 scanning electron microscope was used.

[0065] 2. Determination of polymer bulk density: The apparent density, volume factor and pourability of plastics are determined using the test method (ASTM D1895).

[0066] 3. Particle size distribution of catalyst components: determined using a Malvern laser particle size and shape analyzer.

[0067] 4. The relative weight percentage of titanium in the catalyst component was determined by spectrophotometry.

[0068] 5. Melt index of polymer (MI / 2.16Kg): determined according to ASTM D1238-99.

[0069] 6. Determination of polymerization activity: The activity is calculated by dividing the mass of the powder obtained from polymerization by the amount of catalyst added.

[0070] The following embodiments are examples of the present invention in more detail, but the present invention is not limited to these embodiments.

[0071] Example 1

[0072] (1) Preparation of catalyst component A1

[0073] 4.8 g magnesium chloride, 90 ml toluene, 4 ml epichlorohydrin, and 15 ml tri-n-butyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 60°C and 450 rpm. 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 -40°C. 75 ml titanium tetrachloride was added dropwise, followed by 2 ml ethyl acetate, 2 ml ethanol, and 2 ml butanol. The temperature was then gradually increased (at a rate controlled at 0.2-2°C / min) to 90°C and held for 1 hour. 0.5 ml ethyl benzoate and 1 ml n-octyl acetate were added, and the reaction was continued at this temperature for another hour. The mother liquor was filtered off, and the mixture was washed repeatedly with toluene (an inert diluent) and hexane (an organic solvent) and dried to obtain a solid catalyst component with good flowability.

[0074] (2) Polymerization reaction

[0075] Polymerization with low hydrogen-to-ethylene ratio: 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 catalyst component 1 (containing 0.6mg titanium) prepared by the above method. The temperature was raised to 70℃, and hydrogen was introduced to bring the pressure inside the reactor to 0.28MPa (gauge pressure). Ethylene was then introduced to bring the total pressure inside the reactor to 0.73MPa. Polymerization was carried out at 80℃ for 2 hours. The polymerization results are shown in Table 2.

[0076] Polymerization with a high hydrogen-to-ethylene ratio: 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 catalyst component 1 (containing 1.8 mg of titanium) prepared by the above method. The temperature was raised to 75°C, and hydrogen was introduced to bring the pressure inside the reactor to 0.58MPa (gauge pressure). Ethylene was then introduced to bring the total pressure inside the reactor to 0.73MPa. Polymerization was carried out at 85°C for 2 hours. The polymerization results are shown in Table 2.

[0077] (3) Electron micrographs: Electron micrographs of the catalyst particles can be found in [reference needed]. Figure 2 .

[0078] Example 2

[0079] (1) Preparation of catalyst component A2

[0080] 4.8 g magnesium chloride, 90 ml toluene, 4 ml epichlorohydrin, and 15 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, 1.6 g phthalic anhydride was added, and the reaction was continued at this temperature for another hour. The temperature was then lowered to -40°C, and 75 ml titanium tetrachloride was added dropwise, followed by 1 ml ethyl acetate and 2 ml ethanol. The temperature was then gradually increased (at a rate controlled at 0.2-2°C / min) to 90°C and held at this temperature for 1 hour. Then, 1 ml isooctyl acetate 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 toluene (an inert diluent) and hexane (an organic solvent), and then dried to obtain a solid catalyst component with good flowability.

[0081] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0082] (3) Electron micrographs: Electron micrographs of the catalyst particles can be found in [reference needed]. Figure 3 .

[0083] Example 3

[0084] (1) Preparation of catalyst component A3

[0085] 4.8 g magnesium chloride, 100 ml toluene, 4 ml epichlorohydrin, and 20 ml tri-n-butyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 70°C and 300 rpm. Then, 0.9 g phthalic anhydride was added, and the reaction was continued at this temperature for 1 hour. The temperature was then lowered to -40°C, and 65 ml titanium tetrachloride was added dropwise, followed by 1.5 ml ethyl acetate and 4 ml ethanol. The temperature was then gradually increased (at a rate controlled at 0.2-2°C / min) to 85°C and held at this temperature for 1 hour. Then, 1 ml butyl phenylacetate and 1 ml n-hexyl acetate were 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 toluene (an inert diluent) and hexane (an organic solvent) and dried to obtain a solid catalyst component with good flowability.

[0086] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0087] Example 4

[0088] (1) Preparation of catalyst component A4

[0089] 4.8 g magnesium chloride, 100 ml toluene, 3 ml epichlorohydrin, and 20 ml triisobutyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 300 rpm and 60°C. Then, 1.2 g 3-methylphthalic anhydride was added, and the reaction was continued at this temperature for 1 hour. The temperature was then lowered to -40°C, and 80 ml titanium tetrachloride was added dropwise, followed by 1.5 ml methyl acetate and 3 ml butanol. The temperature was then gradually increased (at a rate controlled at 0.2-2°C / min) to 85°C and held at this temperature for 1 hour. Then, 2 ml methyl benzoate and 1 ml n-octyl propionate were 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 toluene (an inert diluent) and hexane (an organic solvent), and then dried to obtain a solid catalyst component with good flowability.

[0090] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0091] Example 5

[0092] (1) Preparation of catalyst component A5

[0093] 4.8 g magnesium chloride, 110 ml toluene, 3 ml epichlorohydrin, and 12.5 ml triisobutyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 400 rpm and 60°C. Then, 1.8 g phthalic anhydride was added, and the reaction was continued at this temperature for 1 hour. The temperature was then lowered to -40°C, and 50 ml titanium tetrachloride was added dropwise, followed by 1 ml n-propyl acetate and 6 ml ethanol. The temperature was then gradually increased (at a rate controlled at 0.2-2°C / min) to 80°C and held at this temperature for 1 hour. Then, 2 ml ethyl benzoate and 2 ml n-octyl acetate were 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 toluene (an inert diluent) and hexane (an organic solvent), and then dried to obtain a solid catalyst component with good flowability.

[0094] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0095] Example 6

[0096] (1) Preparation of catalyst component A6

[0097] 4.8 g magnesium chloride, 110 ml toluene, 6 ml epichlorohydrin, and 16 ml triisobutyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 70°C and 350 rpm. Then, 1.6 g phthalic anhydride was added, and the reaction was continued at this temperature for 1 hour. The temperature was then lowered to -35°C. 55 ml titanium tetrachloride was added dropwise, followed by 1 ml ethyl acetate, 2 ml ethanol, and 2 ml isooctyl alcohol. The temperature was then gradually increased (at a rate controlled at 0.2-2°C / min) to 80°C and held at this temperature for 1 hour. 2 ml n-hexyl acetate 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 toluene (an inert diluent) and hexane (an organic solvent), and then dried to obtain a solid catalyst component with good flowability.

[0098] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0099] Example 7

[0100] (1) Preparation of catalyst component A7

[0101] 4.8 g magnesium chloride, 100 ml toluene, 6 ml epichlorohydrin, and 13 ml tributyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 50°C and 350 rpm. Then, 0.9 g phthalic anhydride was added, and the reaction was continued at this temperature for 1 hour. The temperature was then lowered to -40°C, and 65 ml titanium tetrachloride was added dropwise, followed by 1 ml ethyl acetate and 8 ml ethanol. The temperature was then gradually increased (at a rate controlled at 0.2-2°C / min) to 85°C and held at this temperature for 1 hour. Then, 2 ml butyl benzoate and 2.5 ml n-hexyl acetate 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 toluene (an inert diluent) and hexane (an organic solvent), and then dried to obtain a solid catalyst component with good flowability.

[0102] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0103] Example 8

[0104] (1) Preparation of catalyst component A8

[0105] 4.8 g magnesium chloride, 100 ml toluene, 8 ml epichlorohydrin, and 15 ml tri-n-pentyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 55°C and stirred at 400 rpm. Then, 1.3 g 3-methylphthalic anhydride was added, and the reaction was continued at this temperature for 1 hour. The temperature was then lowered to -40°C, and 80 ml titanium tetrachloride was added dropwise, followed by 1 ml methyl acetate and 5 ml ethanol. The temperature was then gradually increased (at a rate controlled at 0.2-2°C / min) to 85°C and held at this temperature for 1 hour. Then, 1 ml ethyl phenylacetate and 0.5 ml n-octyl propionate were 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 toluene (an inert diluent) and hexane (an organic solvent) and dried to obtain a solid catalyst component with good flowability.

[0106] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0107] Example 9

[0108] (1) Preparation of catalyst component A9

[0109] 4.8 g magnesium chloride, 90 ml toluene, 8 ml epichlorohydrin, and 16 ml tri-n-butyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 70°C and 300 rpm. Then, 1.6 g phthalic anhydride was added, and the reaction was continued at this temperature for 1 hour. The temperature was then lowered to -40°C, and 55 ml titanium tetrachloride was added dropwise, followed by 1 ml methyl acetate and 4 ml butanol. The temperature was then gradually increased (at a rate controlled at 0.2-2°C / min) to 75°C and held at this temperature for 1 hour. Then, 1.5 ml isooctyl acetate 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 toluene (an inert diluent) and hexane (an organic solvent), and then dried to obtain a solid catalyst component with good flowability.

[0110] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0111] Example 10

[0112] (1) Preparation of catalyst component A10

[0113] 4.8 g magnesium chloride, 90 ml toluene, 6 ml epichlorohydrin, and 12 ml tri-n-butyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 50°C and 350 rpm. Then, 0.9 g phthalic anhydride was added, and the reaction was continued at this temperature for another hour. The temperature was then lowered to -40°C. 65 ml titanium tetrachloride was added dropwise, followed by 1 ml isopropyl acetate, 4 ml ethanol, and 2 ml isooctyl alcohol. The temperature was then gradually increased (at a rate controlled at 0.2-2°C / min) to 85°C and held at this temperature for 2 hours. Then, 1 ml octyl benzoate and 1 ml isooctyl acetate were 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 toluene (an inert diluent) and hexane (an organic solvent), and then dried to obtain a solid catalyst component with good flowability.

[0114] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0115] Example 11

[0116] (1) Preparation of catalyst component A11

[0117] 4.8 g magnesium chloride, 110 ml toluene, 6 ml epichlorohydrin, and 15 ml tri-n-butyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 55°C with a stirring speed of 400 rpm. Then, 1.2 g phthalic anhydride was added, and the reaction was continued at this temperature for another hour. The temperature was then lowered to -40°C, and 75 ml titanium tetrachloride was added dropwise, followed by 1 ml ethyl acetate, 3 ml ethanol, and 1 ml butanol. The temperature was then gradually increased (at a rate controlled at 0.2-2°C / min) to 85°C and held at this temperature for 1 hour. Then, 1.5 ml n-octyl propionate and 1.5 ml propyl benzoate were 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 toluene (an inert diluent) and hexane (an organic solvent), and then dried to obtain a solid catalyst component with good flowability.

[0118] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0119] Comparative Example 1

[0120] (1) Preparation of catalyst component D1

[0121] 4.8 g magnesium chloride, 90 ml toluene, 5.0 ml epichlorohydrin, and 15.0 ml tri-n-butyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 450 rpm and 60°C. Then, 1.2 g phthalic anhydride was added, and the 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, followed by 2 ml ethyl acetate. The temperature was then gradually increased (at a rate controlled at 0.2-2°C / min) to 90°C and held at this temperature for 1 hour. The mother liquor was filtered off, and the mixture was washed repeatedly with toluene (an inert diluent) and hexane (an organic solvent) and dried to obtain a solid catalyst component with good flowability.

[0122] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0123] Comparative Example 2

[0124] (1) Preparation of catalyst component D2

[0125] 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 60°C and 450 rpm. 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 -40°C. 70 ml titanium tetrachloride was added dropwise, followed by 2 ml ethyl acetate, 2 ml ethanol, and 2 ml butanol. The temperature was then gradually increased (at a rate controlled at 0.2-2°C / min) to 90°C and held at this temperature for 1 hour. The mother liquor was filtered off, and the mixture was washed repeatedly with toluene (an inert diluent) and hexane (an organic solvent) and dried to obtain a solid catalyst component with good flowability.

[0126] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0127] Comparative Example 3

[0128] (1) Preparation of catalyst component D3

[0129] 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 60°C and 450 rpm. 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 -40°C. 70 ml titanium tetrachloride was added dropwise, followed by 2 ml ethyl acetate and 2 ml ethanol. The temperature was then gradually increased (at a rate controlled at 0.2-2°C / min) to 75°C and held for 1 hour. Finally, the temperature was gradually increased to 90°C and held for 1 hour. The mother liquor was filtered off, and the mixture was washed repeatedly with toluene (an inert diluent) and hexane (an organic solvent) and dried to obtain a solid catalyst component with good flowability.

[0130] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0131] Comparative Example 4

[0132] (1) Preparation of catalyst component D4

[0133] 4.8 g magnesium chloride, 90 ml toluene, 5.0 ml epichlorohydrin, and 15.0 ml tri-n-butyl phosphate were added to a reaction vessel. The mixture was reacted for 2 hours at 450 rpm and 60°C. Then, 1.2 g phthalic anhydride was added, and the reaction was continued at this temperature for another hour. The temperature was then lowered to -40°C. 70 ml titanium tetrachloride was added dropwise, followed by 2 ml ethyl acetate and 1 ml butanol. The temperature was then gradually increased (at a rate controlled at 0.2-2°C / min) to 90°C and held at this temperature for 1 hour. The mother liquor was filtered off, and the mixture was washed repeatedly with toluene (an inert diluent) and hexane (an organic solvent) and dried to obtain a solid catalyst component with good flowability.

[0134] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0135] Comparative Example 5

[0136] (1) Preparation of catalyst component D5

[0137] Prepared according to the method described in Example 1 of patent CN1958620A.

[0138] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0139] Comparative Example 6

[0140] (1) Preparation of catalyst component D6

[0141] 4.8 g of magnesium chloride, 90 ml of toluene, 5 ml of epichlorohydrin, and 15 ml of 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 of phthalic anhydride was added, and the reaction was continued at this temperature for 1 hour. The temperature was then lowered to -40°C, and 65 ml of titanium tetrachloride was added dropwise, followed by 2 ml of ethyl acetate. The temperature was then gradually increased (at a rate controlled at 0.2-2°C / min) to 90°C and held at this temperature for 1 hour. 1 ml of n-octyl acetate 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 toluene (an inert diluent) and hexane (an organic solvent), and then dried to obtain a solid catalyst component with good flowability.

[0142] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0143] Comparative Example 7

[0144] (1) Preparation of catalyst component D7

[0145] 4.8 g of magnesium chloride, 90 ml of toluene, 5 ml of epichlorohydrin, and 15 ml of 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 of phthalic anhydride was added, and the reaction was continued at this temperature for another hour. The temperature was then lowered to -40°C, and 65 ml of titanium tetrachloride was added dropwise, followed by 4 ml of ethanol. The temperature was then gradually increased (at a rate controlled at 0.2-2°C / min) to 90°C and held at this temperature for 1 hour. 1 ml of n-octyl acetate 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 toluene (an inert diluent) and hexane (an organic solvent), and then dried to obtain a solid catalyst component with good flowability.

[0146] (2) Polymerization reaction: Same as in Example 1, the polymerization results are shown in Table 1.

[0147] (3) Electron micrographs: Electron micrographs of the catalyst particles can be found in [reference needed]. Figure 4 .

[0148] Table 1

[0149]

[0150] Table 2

[0151]

[0152]

[0153]

[0154] As shown in Table 2, a comparison of Examples 1-11 of the present invention with existing commercial catalysts (Comparative Example 5) reveals that the catalyst of the present invention has a significantly higher powder packing density and superior hydrogen sensitivity. Although the polymerization activity of the catalyst of the present invention under low hydrogen-to-ethyl ratio conditions is lower than that of Comparative Example 5, its polymerization activity under high hydrogen-to-ethyl ratio conditions is slightly higher. This indicates that the polymerization activity of the catalyst of the present invention is slightly higher than that of Comparative Example 5 when producing bimodal resins (such as pipe materials and membrane materials) in industrial plants. In other words, the catalyst of the present invention meets the requirements of industrial production plants for high polymerization activity of catalysts.

[0155] As shown in Table 2, a comparison of Examples 1-11 and Comparative Example 1 shows that the catalyst of the present invention exhibits significantly higher polymerization activity and hydrogen sensitivity, but the bulk density of the polymer powder is relatively low. However, the catalyst of Comparative Example 1 does not meet the requirements of industrial production equipment for high polymerization activity of the catalyst, and therefore cannot be used in industrial production.

[0156] As shown in Table 2, a comparison of Examples 1-11 and Comparative Examples 2-4 according to the present invention shows that the catalyst of the present invention significantly improves hydrogen regulation performance while ensuring activity and packing density.

[0157] As shown in Table 2, a comparison of Examples 1-11 and Comparative Example 6 according to the present invention shows that the catalyst of the present invention significantly improves activity and hydrogen regulation performance while ensuring packing density.

[0158] As shown in Table 2, a comparison of Examples 1-11 and Comparative Example 7 according to the present invention shows that the catalyst of the present invention significantly improves the packing density and hydrogen regulation performance while ensuring the activity.

[0159] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. It is impossible to exhaustively list all the implementation methods here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

[0160] 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.

[0161] 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.

[0162] 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, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0163] 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.

[0164] 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.

[0165] 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 reaction product of a magnesium complex, an organic acid anhydride, a titanium-containing compound, an acetate compound, an alcohol compound, a long-chain monoester compound, and optionally an aromatic ester compound; The magnesium complex is a complex formed by dissolving magnesium halide in a solvent system containing organic epoxy compounds and organophosphorus compounds.

2. The catalyst component according to claim 1, characterized in that... The method for preparing the catalyst component includes the following steps: S1, dissolve magnesium halide in a solvent system containing organic epoxy compounds and organic phosphorus compounds to obtain a magnesium complex; S2, reacting the magnesium complex obtained in step S1 with an organic acid anhydride compound, then contacting it first with a titanium compound, then with an acetate compound and an alcohol compound, followed by heating to precipitate spherical or near-spherical solid particles containing magnesium / titanium, and then contacting it with a long-chain monoester compound and optionally an aromatic ester compound during a high-temperature aging stage, preferably above 70°C, more preferably 75°C-100°C, to obtain a mixture containing a catalyst component; preferably, it further includes: S3. Remove unreacted substances and solvent from the mixture obtained in step S2, wash, and obtain spherical or near-spherical catalyst components.

3. The catalyst component according to claim 1 or 2, 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 at least one of C2-C18 aliphatic olefins, aliphatic dienes, halogenated aliphatic olefins or oxides of halogenated aliphatic dienes, glycidyl ethers, and internal ethers; preferably, the organic epoxy compound is selected from at least one of ethylene oxide, propylene oxide, epibutane oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether, and butyl glycidyl ether; and / or, The organophosphorus compound is at least one of a hydrocarbon ester or a halohydrocarbon ester of phosphoric acid or phosphorous acid; preferably, the organophosphorus compound is selected from at least one of trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, triisopropyl phosphate, tri-n-butyl phosphate, triisobutyl phosphate, tri-tert-butyl phosphate, tri-n-pentyl phosphate, triisopentyl phosphate, tri-n-hexyl phosphate, triisohexyl phosphate, tri-n-heptyl phosphate, triisoheptyl phosphate, tri-n-octyl phosphate, triisooctyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, tri-tert-butyl phosphite, tri-n-pentyl phosphite, triisopentyl phosphite, tri-n-hexyl phosphite, triisoheptyl phosphite, tri-n-octyl phosphite, triisooctyl phosphite, triphenyl phosphite, and di-n-butyl phosphite.

4. The catalyst component according to claim 1 or 2, 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 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 xylylyl.

5. The catalyst component according to claim 1 or 2, characterized in that: 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; 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, isoooctanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, propylene glycol, butanediol, hexanediol, and isohexanediol.

6. The catalyst component according to claim 1 or 2, characterized in that, The general formula of the aromatic ester compounds is C5H5[(CH2)] n [COOR9], where R9 is selected from C1-C 10 The hydrocarbon group is an aliphatic or aromatic hydrocarbon group, where n is an integer between 0 and 9, and preferably at least one of methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, hexyl benzoate, octyl benzoate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate, hexyl phenylacetate, and octyl phenylacetate; and / or, The long-chain monoester compound has the general formula R. 10 COOR 11 , where R 10 For C1~C 10 Straight-chain, branched-chain hydrocarbon groups or cyclic hydrocarbon groups, R 11 C6~C 18 The long-chain straight or branched hydrocarbon group is preferably at least one of n-hexyl formate, n-octyl formate, isooctyl formate, n-hexyl acetate, n-octyl acetate, isooctyl acetate, n-hexyl propionate, n-octyl propionate, and isooctyl propionate.

7. The catalyst component according to claim 1 or 2, characterized in that, The proportions of each reactant, based on one mole of magnesium in the magnesium complex, are as follows: organic epoxy compounds 0.2-10 mol; organophosphorus compounds 0.1-10 mol; organic acid anhydrides 0.03-1 mol; acetates 0.01-1 mol; aromatic esters 0-1 mol; long-chain monoesters 0.01-1 mol; alcohols 0.1-4 mol; and titanium-containing compounds 0.5-120 mol. Preferably, the proportions of the reactants, based on each mole of magnesium in the magnesium complex, are as follows: 0.3-2 moles of organic epoxy compounds; 0.3-2 moles of organic phosphorus compounds; 0.1-0.4 moles of organic acid anhydrides; 0.05-0.4 moles of acetate compounds; 0-0.3 moles of aromatic ester compounds; 0.03-0.3 moles of long-chain monoester compounds; 0.5-4 moles of alcohol compounds; and 5-25 moles of titanium-containing compounds.

8. A method for preparing a catalyst component according to any one of claims 1-7, comprising reacting a magnesium complex, an organic acid anhydride compound, a titanium-containing compound, an acetate compound, an alcohol compound, a long-chain monoester compound, and optionally an aromatic ester compound.

9. The preparation method according to claim 8, characterized in that, The method for preparing the catalyst component includes the following steps: S1, dissolve magnesium halide in a solvent system containing organic epoxy compounds and organic phosphorus compounds to obtain a magnesium complex; S2, reacting the magnesium complex obtained in step S1 with an organic acid anhydride compound, then contacting it first with a titanium compound, then with an acetate compound and an alcohol compound, followed by heating to precipitate spherical or near-spherical solid particles containing magnesium / titanium, and then contacting it with a long-chain monoester compound and optionally an aromatic ester compound during a high-temperature aging stage, preferably above 70°C, more preferably 75°C-100°C, to obtain a mixture containing a catalyst component; preferably, it further includes: S3, the mixture obtained in step S2 is subjected to a process of removing unreacted substances and solvent, followed by washing to obtain spherical or near-spherical catalyst components; 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 the dissolution temperature, and the reaction time is 0.5-2 hours. After the reaction, the temperature of the system is lowered to -60℃ to -20℃, and then it is contacted with titanium compound, acetate compound and alcohol compound. The heating is gradual, with a heating rate of 0.2-2℃ / min, and the temperature is raised to 75℃-100℃.

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): Organoaluminum compounds having the general formula AlR’ d X’ 3-d where R’ is hydrogen or a C l -C 20 hydrocarbyl group, X’ is a halogen atom, preferably fluorine, chlorine or bromine, and 0 < d ≤ 3; preferably, The molar ratio of aluminum in component B to titanium in component A) is 20:1-200:1, preferably 50:1-100:

1.

11. The use of a catalyst component according to any one of claims 1-7, a catalyst component prepared by the preparation method according to claim 8 or 9, or the catalyst according to claim 10 in ethylene polymerization.

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