Catalyst components for ethylene polymerization reactions, processes for their preparation and use

Abstract

This invention relates to the field of catalysts for the preparation of olefin polymers, specifically to a catalyst component for ethylene polymerization, a method for preparing the same, and the catalyst itself and its applications. The catalyst component comprises the reaction products of the following raw materials: at least one support, at least one magnesium compound, at least one oxygen-containing titanium compound, at least one alcohol ether compound, at least one ether compound, and at least one halogenating agent; the support has a cubic cage-like channel structure, a 1m³m crystal structure with a cubic core, an average pore size of 4-15 nm, and a specific surface area of ​​450-550 m². 2 The pore volume is 0.5-1.5 mL / g, and the average particle size is 0.5-10 μm. The magnesium-titanium compound solution of this invention has good solubility and transparency, high catalytic activity, and the resulting polymerized powder has high bulk density.

Description

Catalyst Component for Ethylene Polymerization, Its Preparation Method and Application Technical Field

[0001] The present invention relates to the field of catalysts for preparing olefin polymers. Specifically, it relates to a catalyst component for ethylene polymerization, its preparation method, a catalyst for ethylene polymerization and its application. Background Art

[0002] With the development of ethylene polymerization processes, the catalyst preparation technology supporting the polymerization processes has also been continuously advancing. Currently, the Ziegler-Natta catalyst system of Ti / Mg composites still occupies a dominant position in the industrial production of polyethylene. In industrial production, the polymerization activity of the catalyst, hydrogen response sensitivity, the particle morphology of the catalyst, and the bulk density of the polymer powder are all very important parameters. The improvement of catalyst activity can increase productivity and thus improve economic benefits. An increase in the bulk density of the polymer in industry allows for a longer catalyst residence time, which is beneficial for increasing reactor output and achieving better reactor operability. The catalyst affects parameters such as the bulk density, fluidity, and particle adhesion of the polymer powder. The polymer replicates the morphology of the catalyst. Poor catalyst morphology may lead to poor polymer morphology, which may in turn cause fouling or flaking in industrial plants. Therefore, industrially, a catalyst with well-controlled morphology, desired particle size and shape, narrow distribution, high bulk density, and low adhesion is required.

[0003] To obtain good particle morphology, technicians often use the loading method to prepare catalysts, impregnating the catalyst active components on particulate carrier materials, such as porous inorganic carrier materials like silica or organic particulate carrier materials. For example, US4293673, US4303771, US4302565, US4302566, and EP0835887A2 disclose preparing catalysts by loading magnesium compounds and titanium compounds on inorganic carriers. The morphology of the carrier determines the final morphology of the catalyst. This preparation method has high requirements for the morphology and surface properties of the carrier, resulting in an increase in catalyst preparation costs. In addition, the disadvantage of supported catalysts is that the impregnation step may lead to uneven loading of the active components on the carrier surface. At the same time, due to the limitations of the specific surface area of the carrier, the loading amount and distribution of active centers are restricted, thus limiting the improvement of catalyst activity.

[0004] CN1085915A discloses a method for preparing a Ziegler-Natta catalyst system. A TiCl3 tetrahydrofuran solution is prepared by reducing titanium tetrachloride with metallic magnesium in tetrahydrofuran. Magnesium chloride is then dissolved in tetrahydrofuran. The two solutions are thoroughly mixed, and unreacted magnesium and undissolved magnesium chloride are filtered out. The filtered solution is then thoroughly mixed with silica gel and spray-dried to obtain dispersed catalyst particles. This catalyst exhibits high activity and high titanium content. However, this preparation method requires a filtration step, generating a significant amount of waste residue and increasing post-processing steps and costs.

[0005] Therefore, there is a need for a catalyst suitable for ethylene polymerization, which not only needs to have high catalytic activity, but also good catalyst particle morphology and polymer particle morphology, and high polymer packing density. Summary of the Invention

[0006] To address the problems existing in the prior art, this invention proposes a catalyst component for ethylene polymerization, its preparation method, and the catalyst itself for ethylene polymerization and its application. The purpose of this invention is to overcome the limitations of existing polyolefin catalysts, such as the surface properties, pore structure, and solubility of the supported component, resulting in low effective loading of the active component on the support. This leads to poor catalytic activity in supported polyolefin catalysts prepared from existing supported polyolefin catalyst supports. This invention provides a method for preparing a polyolefin catalyst, the polyolefin catalyst prepared by the above method, the application of the polyolefin catalyst prepared by the above method in olefin monomer polymerization reactions, and the polyolefin obtained by the method. This invention exhibits high catalytic activity when used for homopolymerization or copolymerization of ethylene, and the resulting polymer powder has a high bulk density. The mother liquor of this invention does not require filtration before mixing with the support for reaction, making the process simple and environmentally friendly.

[0007] A first aspect of the present invention is to provide a catalyst component comprising a reaction product of the following raw materials: at least one support, at least one magnesium compound, at least one oxygen-containing titanium compound, at least one alcohol ether compound, at least one ether compound, and at least one halogenating agent;

[0008] The carrier is a hexagonal mesoporous material carrier, which has a cubic cage-like pore structure, a cubic core 1m3m crystal structure, an average pore size of 4-15nm, and a specific surface area of ​​450-550m². 2 / g, pore volume is 0.5-1.5mL / g, and average particle size is 0.5-10μm.

[0009] According to a preferred embodiment of the present invention, the carrier is prepared by the following method:

[0010] (a) The template agent, potassium sulfate, acid agent and tetraethyl orthosilicate are mixed and contacted, and the resulting mixture is crystallized and filtered to obtain hexagonal mesoporous material powder;

[0011] (b) The hexagonal mesoporous material powder is subjected to template release agent treatment, thermal activation treatment and ball milling treatment in sequence to obtain a hexagonal mesoporous material carrier.

[0012] According to the present invention, in step (a), the process of preparing the hexagonal mesoporous material powder with a cubic core 1m3m structure may include: mixing and contacting a template agent, potassium sulfate, an acid agent, and tetraethyl orthosilicate, and then crystallizing and filtering the resulting mixture. The order of mixing and contacting is not particularly limited; the template agent, potassium sulfate, acid agent, and tetraethyl orthosilicate may be mixed simultaneously, or any two or three of them may be mixed before adding other components and mixing thoroughly. According to a preferred embodiment, the template agent, potassium sulfate, and acid agent are first mixed thoroughly, and then tetraethyl orthosilicate is added and mixed thoroughly.

[0013] In this invention, the amounts of the template agent, potassium sulfate, and tetraethyl orthosilicate can vary within a wide range. For example, the molar ratio of the template agent, potassium sulfate, and tetraethyl orthosilicate can be 1:100-800:20-200, preferably 1:150-700:80-180, and more preferably 1:200-400:100-150.

[0014] In this invention, the template agent can be any type of template agent conventional in the art. For example, the template agent can be a triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene, which can be prepared by methods known to those skilled in the art or can be commercially available, for example, from Fuka Corporation, under the trade name Synperonic F108, with the molecular formula EO. 132 PO 60 EO 132 The average molecular weight Mn = 14600. The molar number of polyoxyethylene-polyoxypropylene-polyoxyethylene is calculated based on the average molecular weight of polyoxyethylene-polyoxypropylene-polyoxyethylene.

[0015] In this invention, the acid can be any of the acidic aqueous solutions commonly used in the art, for example, it can be an aqueous solution of at least one of hydrochloric acid, sulfuric acid, nitric acid and hydrobromic acid, preferably an aqueous solution of hydrochloric acid.

[0016] The amount of acid used is not particularly limited and can vary within a wide range, preferably so that the pH value of the mixture is 1-7.

[0017] The present invention does not particularly limit the conditions for the mixing contact. For example, the conditions for the mixing contact may include: a temperature of 25-60°C, a time of 10-240 min, and a pH value of 1-7. In order to facilitate the uniform mixing of the substances, according to a preferred embodiment of the present invention, the mixing contact is carried out under stirring conditions.

[0018] According to a preferred embodiment of the present invention, the process of mixing and contacting the template agent, potassium sulfate, acid agent, and tetraethyl orthosilicate includes: adding the template agent triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene F108 to an aqueous solution of hydrochloric acid at a molar ratio of triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene F108: potassium sulfate: water: hydrogen chloride = 1:200-400:10000-30000:100-900, stirring at 25-60°C until dissolved, and then adding tetraethyl orthosilicate to the above-obtained solution at a molar ratio of triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene F108: tetraethyl orthosilicate = 1:100-150, stirring at 25-60°C for 10-240 min.

[0019] In this invention, the crystallization conditions are not particularly limited. For example, the crystallization conditions may include: a temperature of 25-60°C, preferably 30-55°C; and a time of 10-72 hours, preferably 10-40 hours. According to a preferred embodiment, the crystallization is carried out by a hydrothermal crystallization method.

[0020] In this invention, the process of obtaining hexagonal mesoporous material powder with a cubic core Im3m structure by filtration may include: after filtration, repeatedly washing with deionized water (the number of washing times can be 2-10), and then performing vacuum filtration.

[0021] According to the present invention, in step (b), the method for removing the template agent is generally a calcination method. The conditions for removing the template agent can be conventionally selected in the art. For example, the process of removing the template agent may include calcining the hexagonal mesoporous material powder at 300-600°C for 8-20 hours.

[0022] According to the present invention, in step (b), in order to remove the hydroxyl groups and residual moisture from the hexagonal mesoporous material carrier, a thermal activation treatment is required before loading the hexagonal mesoporous material carrier with magnesium and / or titanium active components. The conditions for the thermal activation treatment may include calcining the hexagonal mesoporous material carrier at a temperature of 300-900°C for 7-10 hours in the presence of nitrogen.

[0023] According to the present invention, in step (b), the specific operation method and conditions of the ball milling treatment are based on not damaging or substantially not damaging the pore structure of the hexagonal mesoporous material with a cubic core 1m3m structure. Those skilled in the art can select various suitable conditions to implement the present invention based on the above principles. Specifically, the ball milling treatment can be carried out in a ball mill, wherein the diameter of the grinding balls in the ball mill can be 2-3 mm; the number of grinding balls can be reasonably selected according to the size of the grinding jar; for a grinding jar of 50-150 mL, 20-80 grinding balls can usually be used; the material of the grinding balls can be agate, polytetrafluoroethylene, etc., preferably agate. The conditions of the ball milling treatment include: a grinding ball rotation speed of 300-500 r / min, and / or, a temperature inside the grinding jar of 15-100℃, and / or, a ball milling time of 0.1-100 h. Preferably, the ball milling conditions include: a ball rotation speed of 300-500 r / min, a ball milling jar temperature of 15-100℃, and a ball milling time of 0.1-100 hours. Preferably, in step (b), the ball milling conditions result in an average particle diameter of 0.5-10 μm for the hexagonal mesoporous material carrier obtained through ball milling.

[0024] According to the present invention, the polyolefin catalyst comprises a support and a magnesium component and / or a titanium component supported on the support, wherein the support is a hexagonal mesoporous material support having a cubic cage-like pore structure, the crystal structure of the hexagonal mesoporous material having a cubic core 1m3m structure, the average pore size of the hexagonal mesoporous material being 4-15 nm, and the specific surface area being 450-550 m². 2 / g, pore volume is 0.5-1.5mL / g, and average particle size is 0.5-10μm.

[0025] According to the present invention, in the polyolefin catalyst, the hexagonal mesoporous material support prepared by the method of the present invention has a special cubic core crystal structure, which has a cubic core Im3m structure. The unique cubic cage-like pore structure of the hexagonal mesoporous material, combined with its narrow pore size distribution and uniform pore channel distribution, is conducive to the good dispersion of magnesium and / or titanium active components on the support surface. This results in a polyolefin catalyst with good dispersion and high loading of metal active components, ensuring that the supported catalyst made by using the hexagonal mesoporous material as a support has better catalytic activity in the polymerization reaction of olefin monomers and significantly improves the conversion rate of the reaction feedstock.

[0026] According to the present invention, the average particle size of the hexagonal mesoporous material is measured using a laser particle size analyzer, and the specific surface area, pore volume, and average pore size are measured using the nitrogen adsorption method. In the present invention, particle size refers to the particle size of the raw material particles. When the raw material particles are spheres, the particle size is expressed as the diameter of the sphere; when the raw material particles are cubes, the particle size is expressed as the side length of the cube; when the raw material particles are irregularly shaped, the particle size is expressed as the mesh size of the sieve that can just separate the raw material particles.

[0027] In a preferred embodiment, the hexagonal mesoporous material has an average pore size of 4-12 nm, such as 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 11 nm, and 12 nm, or any average pore size within a range formed by any two average pore sizes, and a specific surface area of ​​480-520 m². 2 The hexagonal mesoporous material has a pore volume of 0.5-1 mL / g and an average particle size of 0.8-8 μm. This ensures that the material has the advantages of large pore size, large pore volume, and large specific surface area, which is more conducive to the good dispersion of magnesium and / or titanium active components on the surface of the material. This, in turn, ensures that the polyolefin catalyst prepared from it has excellent catalytic performance, resulting in high olefin monomer conversion, high polymer bulk density, and excellent flowability.

[0028] According to a preferred embodiment of the present invention, the magnesium compound is of general formula (I)Mg(OR) 1 ) m Cl 2-m As shown, R 1 For C2-C 20 Saturated or unsaturated straight-chain or branched hydrocarbon groups, or C3-C 20 Saturated or unsaturated cyclic hydrocarbon groups, R 1 C2-C is preferred. 10 Alkyl group; 0 ≤ m ≤ 2; according to the catalyst component provided by the present invention, preferably, in general formula (I), R 1 For C2-C 10 The alkyl group; the magnesium compound is preferably selected from alkoxy magnesium compounds and / or magnesium chloride, more preferably from at least one of magnesium diethoxy, magnesium dipropoxy, magnesium dibutoxy, magnesium dioctyloxy, and magnesium dichloride.

[0029] According to a preferred embodiment of the present invention, the oxygen-containing titanium compound is of the general formula (II)Ti(OR). 2 ) n Cl 4-n As shown, R 2 For C2-C 20 Saturated or unsaturated straight-chain or branched hydrocarbon groups, or C3-C 20Saturated or unsaturated cyclic hydrocarbon groups, R 2 C2-C is preferred. 10 Alkyl groups, 0 < n ≤ 4.

[0030] According to the catalyst composition provided by the present invention, preferably, in general formula (II), R 2 For C2-C 10 The alkyl group; the oxygen-containing titanium compound is preferably a titanate, more preferably at least one selected from tetrabutyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, and tetratert-butyl titanate.

[0031] According to a preferred embodiment of the present invention, the alcohol ether compound is selected from low-carbon alcohol ethers of ethylene glycol and / or propylene glycol, and the alcohol ether compound is selected from at least one of propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, propylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, and propylene glycol monopropyl ether.

[0032] According to a preferred embodiment of the present invention, the ether compound is selected from at least one of anisole, phenethyl ether, propyl ether, butyl ether, isopropyl ether, isobutyl ether, 1,4-dioxane, tetrahydrofuran, ethylene oxide, 1,2-epoxypropane, 1,2-epoxybutane, cis-2,3-epoxybutane, trans-2,3-epoxybutane, 9,9-(dimethoxymethyl)fluorene, isopentyl ether, and pentyl ether, preferably a cyclic ether with 3-5 carbon atoms, such as tetrahydrofuran or methyltetrahydrofuran, preferably tetrahydrofuran. The molar ratio of cyclic ether to magnesium is 15-100, preferably 15-60.

[0033] According to a preferred embodiment of the present invention, the halogenating agent is of general formula (III)R. 3 a MX b As shown, M represents a Group 3, 4, or 5 element or a transition metal, X represents a halogen, and R represents a group 5. 3 For C2-C 20 Saturated or unsaturated straight-chain or branched hydrocarbon groups, C3-C 20 Saturated or unsaturated cyclic hydrocarbon groups or alkoxy groups, C6-C 20 Aromatic groups, a = 0, 1, 2, b = 1, 2, 3, 4.

[0034] According to the catalyst composition provided by the present invention, preferably, in general formula (Ⅲ), M is selected from aluminum, silicon, and R 3 For C2-C 10 Saturated or unsaturated straight-chain or branched hydrocarbon groups, or C3-C 10 Saturated or unsaturated cyclic hydrocarbon groups; the halogenating agent is preferably from R 4 P SiCl 4-P R 5q-1 AlCl 4-q , wherein R 4 , R 5 is a C2-C 20 saturated or unsaturated straight-chain or branched hydrocarbon group, C3-C 20 saturated or unsaturated cycloalkyl group or alkoxy group, C6-C 20 aromatic group, p and q are integers, 0 ≤ p < 4, 0 < q < 4; the halogenating reagent is more preferably selected from at least one of diethylaluminum chloride, diethylaluminum monochloride, isobutylaluminum dichloride, diisobutylaluminum monochloride, isopropylaluminum dichloride, diisopropylaluminum monochloride, silicon tetrachloride, methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, phenyltrichlorosilane. More preferably (C2H5)AlCl2, isobutylaluminum dichloride, silicon tetrachloride, (C2H5O)AlCl2, (C6H5)AlCl2, (C6H5O)AlCl2, (C6H 12 O)AlCl2.

[0035] According to a preferred technical solution of the present invention, based on the total weight of the catalyst component, the content of the hexagonal mesoporous material carrier is 20-90% by weight, preferably 20-70% by weight; the magnesium component is calculated as magnesium element, and the content of the magnesium component is 1-50% by weight, preferably 1-30% by weight; the titanium component is calculated as titanium element, and the content of the titanium component is 1-50% by weight, preferably 1-15% by weight.

[0036] According to a preferred technical solution of the present invention, the average pore diameter of the catalyst component is 4-15 nm, the specific surface area is 450-500 m 2 / g, the pore volume is 0.5-1 mL / g, and the average particle size is 5-40 μm.

[0037] The second aspect of the present invention is to provide a preparation method of the catalyst component described in the first aspect, including: in the presence of a protective atmosphere, subjecting the at least one hexagonal mesoporous material carrier to a first contact reaction with the following raw materials: at least one magnesium compound, at least one oxygen-containing titanium compound, at least one alcohol ether compound and at least one ether compound, and then subjecting it to a second contact reaction with a halogenating reagent to obtain a sprayable slurry, and then spray-drying the sprayable slurry to obtain the catalyst.

[0038] According to the present invention, the protective atmosphere can be nitrogen and / or an inert gas.

[0039] According to a preferred technical solution of the present invention, the conditions of the first contact reaction include:

[0040] The temperature is 0-100 °C, and the reaction time is 0.1-10 h.

[0041] According to a preferred embodiment of the present invention, the conditions for the second contact reaction include: a temperature of 0-80°C and a reaction time of 0.5-10 h.

[0042] According to a preferred embodiment of the present invention, the conditions for spray drying include: being carried out under a nitrogen protective atmosphere, with an inlet temperature of 100-200°C, an outlet temperature of 60-130°C, and a carrier gas flow rate of 200-600 L / h.

[0043] According to a preferred embodiment of the present invention, relative to each mole of magnesium compound calculated as magnesium element, the amount of the hexagonal mesoporous material carrier is 60-220 g, preferably 80-180 g, more preferably 90-160 g; the amount of the oxygen-containing titanium compound is 0.1-20 mol, preferably 0.1-5.0 mol, more preferably 0.1-3.0 mol; the amount of the alcohol ether compound is 0.1-10 mol, preferably 0.1-5.0 mol, more preferably 0.1-3.0 mol; the amount of the ether compound is 0.01-100 mol, preferably 5-80 mol, more preferably 15-60 mol; and the amount of the halogenating agent is 0.1-50 mol, preferably 0.1-10 mol, more preferably 0.1-5 mol.

[0044] According to a preferred embodiment of the present invention, the method for preparing the catalyst component includes:

[0045] (1) Magnesium compounds, oxygen-containing titanium compounds, alcohol ether compounds and ether compounds are reacted to form a magnesium-titanium compound component solution;

[0046] (2) The solution obtained in step (1) is reacted with the mesoporous material carrier to obtain a slurry;

[0047] (3) The slurry obtained in step (2) is reacted with a halogenating agent to obtain the slurry to be sprayed;

[0048] (4) The slurry to be sprayed obtained in step (3) is spray-dried to obtain the catalyst component used for ethylene polymerization reaction.

[0049] According to the preferred embodiment of the present invention described above, in step (1), the magnesium compound, oxygen-containing titanium compound, alcohol ether compound, and ether compound react with each other at 30-100°C, preferably at 40-80°C. Higher temperatures are advantageous for the reaction. The reaction is carried out under stirring conditions. The reaction time depends on the properties of the reactants and the operating conditions. The reaction time is required to obtain a transparent solution, and the required reaction time is 1-20 hours, preferably 2-10 hours, until a transparent solution is formed.

[0050] According to the preferred embodiment of the present invention described above, in step (2), the transparent solution obtained in step (1) is reacted with the mesoporous carrier at 0-100°C, preferably 0-80°C; the mixing time is generally selected from 30 minutes to 10 hours, preferably 0.5-4 hours.

[0051] According to the preferred embodiments of the present invention described above, steps (1) and (2) can be combined into a one-step reaction to simplify the preparation process.

[0052] According to the preferred embodiment of the present invention described above, step (3) involves reacting the suspension obtained in step (2) with a halogenating reagent at a reaction temperature of 0-80°C, preferably 20-70°C; and a reaction time of 0.5-10 h, preferably 0.5-5 h, to obtain the masterbatch to be sprayed. In this step, the chlorination reaction or chlorination reduction reaction of the magnesium-titanium complex is completed, that is, the chlorine element replaces the alkoxy group in the magnesium-titanium complex. At the same time, different halogenating reagents can also reduce the valence state of the oxygen-containing titanium compound to a lower valence state. The halogenation reaction is usually controlled at the kettle temperature to avoid local overheating of the reaction. Stirring is usually carried out during the feeding process to facilitate the stable progress of the reaction. The reaction time can be from 1 minute to 10 hours, preferably 0.5-5 hours.

[0053] According to the preferred embodiments of the present invention described above, in step (4), according to a preferred embodiment of the present invention, the spray drying adopts an airflow spray drying method. The spray drying can be carried out in an atomizer. The conditions for spray drying may include: being carried out under a nitrogen protective atmosphere, and the spray conditions include: an inlet temperature of 100-200°C, preferably 120-160°C; an outlet temperature of 60-130°C, preferably 90-115°C; and a carrier gas flow rate of 200-600 L / h.

[0054] In this invention, the polyolefin catalyst obtained by loading magnesium and / or titanium components onto the hexagonal mesoporous material support prepared by the above method has spherical morphology, higher magnesium and / or titanium component loading, and more reasonable pore structure. When used for olefin monomer polymerization, it has higher polymerization activity and the resulting polymer has higher packing density.

[0055] A third aspect of the present invention is to provide a catalyst comprising the reaction product of the following components:

[0056] Component (A): The catalyst component described in the first aspect or the catalyst component obtained by the preparation method described in the second aspect;

[0057] Component (B): General Formula (Ⅳ)AlR s X 3-sThe organoaluminum compounds shown in the formula are: R is a hydrocarbon group or hydrogen with 1-20 carbon atoms, X is a halogen atom, s is an integer, and 1 <s≤3。

[0058] Component (B) may be selected from one or more alkyl aluminum compounds used in combination, wherein the organoaluminum compound is preferably selected from AlEt3, Al(iso-Bu)3, Al(n-C6H)3, etc. 13 3. Al(n-C8H) 17 At least one of )3 and AlEt2Cl.

[0059] In the catalyst of the present invention, the molar ratio of aluminum in the organoaluminum compound to titanium in the catalyst component is the aluminum-titanium ratio commonly used in catalysts in the art, preferably 20-500, more preferably 30-300.

[0060] A fourth aspect of the present invention is to provide a method for preparing the catalyst described in the third aspect, comprising the step of mixing and reacting the catalyst component (A) and the organoaluminum compound.

[0061] The components (A) and (B) can be used directly in the polymerization reaction, or they can be mixed and reacted first before being applied to the polymerization reaction.

[0062] The fifth aspect of the present invention is to provide the application of the catalyst component described in the first aspect, the catalyst component obtained by the preparation method described in the second aspect, the catalyst described in the third aspect, or the catalyst prepared by the preparation method described in the fourth aspect in the ethylene polymerization reaction.

[0063] The catalyst described in this invention can be used in the homopolymerization of ethylene and the copolymerization of ethylene with other α-olefins.

[0064] The polymerization reaction conditions are not particularly limited and can be the olefin polymerization conditions commonly used in the field.

[0065] The α-olefin can be one of propylene, butene, pentene, hexene, octene, or 4-methyl-1-pentene.

[0066] In their research on the polymerization of olefin monomers to prepare polyolefins, the inventors of this invention discovered that the support in the polyolefin catalyst prepared by the method of this invention has a large pore size and a high specific surface area due to its special cubic core Im3m structure and hexagonal channel structure, which can effectively improve the loading of active components. Combined with the specific raw material composition of this invention, "the catalyst component includes the reaction products of the following raw materials: at least one support, at least one magnesium compound, at least one oxygen-containing titanium compound, at least one alcohol ether compound, at least one ether compound and at least one halogenating agent", the resulting catalyst component improves the catalytic activity of the obtained polyolefin catalyst, and the resulting polyolefin product has a high bulk density.

[0067] This invention exhibits high catalytic activity when used for homopolymerization or copolymerization of ethylene, and the resulting polymer powder has a high bulk density. Furthermore, the active center mother liquor requires no filtration before mixing with the carrier for the reaction, resulting in a simple and environmentally friendly process. Attached Figure Description

[0068] Figure 1 is a scanning electron microscope (SEM) image of the microstructure of the polyolefin catalyst prepared in Example 1.

[0069] Figure 2 is a scanning electron microscope (SEM) image of the microstructure of the polyolefin catalyst prepared in Comparative Example 1. Detailed Implementation

[0070] 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.

[0071] As previously described, a first aspect of the present invention provides a method for preparing a polyolefin catalyst, the method comprising the following steps:

[0072] (a) The template agent, potassium sulfate, acid agent and tetraethyl orthosilicate are mixed and contacted, and the resulting mixture is crystallized and filtered to obtain a hexagonal mesoporous material powder with a cubic core Im3m structure;

[0073] (b) The hexagonal mesoporous material powder is subjected to template release agent treatment, thermal activation treatment and ball milling treatment in sequence to obtain a hexagonal mesoporous material carrier;

[0074] (c) In the presence of an inert gas, the hexagonal mesoporous material carrier is mixed and reacted with a magnesium-titanium compound component solution. After the reaction is complete, it is reacted with a halogenating agent to obtain a slurry to be sprayed. Then, the slurry to be sprayed is spray-dried to obtain a catalyst.

[0075] The raw materials used in the specific embodiments of this invention are commercially available.

[0076] The present invention will be described in detail below through embodiments.

[0077] In the following examples and comparative examples, the polyoxyethylene-polyoxypropylene-polyoxyethylene was purchased from Fuka, under the trade name Synperonic F108, with the molecular formula EO. 132 PO 60 EO 132 Average molecular weight M n =14600.

[0078] Test method:

[0079] Catalyst morphology: determined using an SL-30 field emission environmental scanning electron microscope manufactured by FEI Corporation, USA; Catalyst particle size distribution: measured using a MASTERSIZE particle size analyzer with hexane as the dispersant, ranging from 0.02 to 2000 μm; X-ray diffraction analysis was performed using a D8 Advance X-ray diffractometer purchased from Bruker AXS, Germany; Pore structure parameter analysis was performed using an ASAP2020-M+C adsorption analyzer purchased from Micromeritics, USA, and the specific surface area and pore volume of the samples were calculated using the BET method; Titanium content in the catalyst was determined using a Spectrumlab 752s UV-Vis spectrophotometer; Magnesium content in the catalyst was determined using a chemical titration method; Melt index of polyolefins was determined using the method specified in ASTM D1238-99; Bulk density: determined according to the method specified in ASTM D1895-69.

[0080] Spray drying was carried out on a B-290 spray dryer manufactured by Buchi GmbH, Switzerland.

[0081] This example illustrates a polyolefin catalyst and its preparation method.

[0082] Example 1

[0083] 1) Preparation of the carrier

[0084] 2g (1.4×10 -4 5.24 g (0.03 mol) of template agent F108, 5.24 g (0.03 mol) of K2SO4 and 60 g of 2 mol / L hydrochloric acid solution were stirred at 38 °C until F108 was completely dissolved;

[0085] Add 4.2 g (0.02 mol) of tetraethyl orthosilicate to the above solution, stir at 38 °C for 15 min, and let it stand at 38 °C for 24 h to crystallize.

[0086] Then, 100g of deionized water was added to the above mixed solution for dilution, followed by filtration and washing with deionized water 4 times. Then, the raw powder of hexagonal mesoporous material with cubic core 1m3m structure was obtained by vacuum filtration.

[0087] The hexagonal mesoporous material powder with a cubic core 1m3m structure obtained above was calcined at 400℃ for 10h to remove the template agent, resulting in hexagonal mesoporous material A1; then, the product after removing the template agent was calcined at 400℃ for 10h under nitrogen protection to perform thermal activation treatment, removing the hydroxyl groups and residual moisture of the hexagonal mesoporous material, resulting in thermally activated hexagonal mesoporous material B1;

[0088] Take 10g of the above-mentioned thermally activated hexagonal mesoporous material B1 and put it into a 100ml ball mill jar. The ball mill jar is made of polytetrafluoroethylene, the grinding balls are made of agate, the diameter of the grinding balls is 3-15mm, the number of grinding balls is 30, the rotation speed is 400r / min, and the ball mill is carried out at 25℃ for 20h under nitrogen protection to obtain 10g of hexagonal mesoporous material carrier C1 with an average particle diameter of 0.8-8μm.

[0089] 2) Preparation of polyolefin catalysts

[0090] (1) Add 45 mmol of magnesium dichloride, 100 ml of tetrahydrofuran, 11 mmol of tetrabutyl titanate, and 9.8 mmol of ethylene glycol monobutyl ether to a glass reactor equipped with a stirrer that has been purged with N2 and kept under N2 atmosphere. Then heat the reactor to 70°C and stir until a transparent solution is formed.

[0091] (2) Cool the transparent solution obtained in step (1) to 25°C, add 6.0g of hexagonal mesoporous support C1 to it, stir at 50°C for 2 hours to obtain a suspension;

[0092] (3) Add 13.5 ml of 30 wt% dichloroethylaluminum solution to the suspension obtained in step (2) using a constant pressure dropper. After the addition is complete, stir the reaction for 1 hour to obtain the slurry to be sprayed.

[0093] (4) Under N2 protection, the inlet temperature of the spray dryer is controlled at 140℃, the outlet temperature is controlled at 105℃, and the carrier gas flow rate is controlled at 360L / h to obtain solid free-flowing powdered polyolefin catalyst Cat-1.

[0094] Catalyst evaluation:

[0095] 1 L of hexane, 1 mmol of triethylaluminum, and 20 mg of the above catalyst components were added to a 2 L stainless steel stirred tank. The temperature was then raised to 75 °C, and hydrogen gas was added at 0.18 MPa. After hydrogenation, ethylene gas was added at 0.75 MPa, and the temperature was raised to 85 °C for polymerization. After 2 hours of reaction, the addition of ethylene was stopped, the temperature was lowered, the pressure was released, the polyethylene powder was weighed, and the catalyst activity was calculated. The bulk density of the polyethylene powder was tested, and the polymerization results are shown in Table 3. The scanning electron microscopy results of the catalyst are shown in Figure 1.

[0096] The hexagonal mesoporous material support C1 and the polyolefin catalyst Cat-1 were characterized by XRD, TEM, and nitrogen adsorption.

[0097] In the catalyst Cat-1 obtained in this embodiment, the content of magnesium is 6.89% by weight and the content of titanium is 2.26% by weight.

[0098] The hexagonal mesoporous material carrier C1 was subjected to X-ray diffraction pattern detection, where the horizontal axis is 2θ and the vertical axis is intensity. From the XRD pattern, it can be clearly seen that the hexagonal mesoporous material carrier C1 has a diffraction peak (2θ = 0.6°) on the (110) plane that corresponds to the center of the cube Im3m and a diffraction shoulder peak (2θ = 1.2°) on the (200) plane in the small corner region. The high intensity and narrow shape of the diffraction peaks on the (110) plane indicate that the hexagonal mesoporous material carrier C1 has a good long-range ordered structure, which is consistent with the XRD pattern of the FDU-6 mesoporous material reported in the literature (Chengzhong Yu, Bozhi Tian, ​​Jie Fan, Galen D. Stucky, Dongyuan Zhao, J. Am. Chem. Soc. 2002, 124, 4556-4557). In addition, the position of the diffraction shoulder peak (2θ = 1.2°) on the (200) plane is completely different from that of the hexagonal or layered structure.

[0099] The nitrogen adsorption-desorption curves of the hexagonal mesoporous material support C1 (x-axis represents relative pressure, unit: p / p0) were analyzed. The pore size distribution of the hexagonal mesoporous material support C1 (x-axis represents pore size, unit: 0.1 nm) was also analyzed. The pore size distribution shows that the hexagonal mesoporous material support C1 has a narrow pore size distribution and very uniform pores. The nitrogen adsorption-desorption isotherm indicates that the hexagonal mesoporous material support C1 exhibits a typical Type IV adsorption-desorption isotherm as defined by IUPAC. The sample possesses an H2-type hysteresis loop, confirming that the hexagonal mesoporous material support C1 has the characteristic cubic cage-like mesoporous structure reported in the literature. The desorption branch between relative partial pressures of 0.4-0.5 also indicates that the material has a cage-like pore structure.

[0100] The shape of the pores on the (100) crystal plane of the hexagonal mesoporous material carrier C1 can be clearly seen by TEM transmission electron microscopy of the microstructure.

[0101] Figure 1 is a scanning electron microscope (SEM) image of the microstructure of the polyolefin catalyst Cat-1. As shown in the figure, the polyolefin catalyst Cat-1 has a spherical shape and a particle size in the micrometer range.

[0102] Table 1 shows the pore structure parameters of the hexagonal mesoporous material support C1 and the polyolefin catalyst Cat-1.

[0103] Table 1

[0104]

[0105] As can be seen from the data in Table 1, the specific surface area and pore volume of the hexagonal mesoporous material carrier C1 decreased after loading magnesium and titanium components, indicating that magnesium and titanium components entered the interior of the hexagonal mesoporous material carrier C1 during the loading reaction.

[0106] Example 2

[0107] This embodiment is used to illustrate the polyolefin catalyst and its preparation method of the present invention.

[0108] 1) Preparation of the carrier

[0109] 1.46g (1×10 -4 6.96 g (0.04 mol) of template agent F108, 6.96 g (0.04 mol) of K2SO4 and 60 g of 2 mol / L hydrochloric acid solution were stirred at 38 °C until F108 was completely dissolved.

[0110] Add 3.1 g (0.015 mol) of tetraethyl orthosilicate to the above solution, stir at 38 °C for 15 min, and let it stand at 40 °C for 20 h to crystallize.

[0111] Then, 100g of deionized water was added to the above mixed solution for dilution, followed by filtration and washing with deionized water 4 times. Then, the raw powder of hexagonal mesoporous material with cubic core 1m3m structure was obtained by vacuum filtration.

[0112] The hexagonal mesoporous material powder with a cubic core 1m3m structure obtained above was calcined at 600℃ for 20h to remove the template agent, resulting in hexagonal mesoporous material A2; then, the product after removing the template agent was calcined at 500℃ for 10h under nitrogen protection to perform thermal activation treatment, removing the hydroxyl groups and residual moisture of the hexagonal mesoporous material, resulting in thermally activated hexagonal mesoporous material B2;

[0113] Take 10g of the thermally activated hexagonal mesoporous material B2 and place it in a 100ml ball mill jar. The ball mill jar is made of polytetrafluoroethylene, and the grinding balls are made of agate with a diameter of 3-15mm. There are 30 grinding balls in total, and the rotation speed is 300r / min. Under nitrogen protection, the ball mill is milled at 30℃ for 20h to obtain approximately 10g of hexagonal mesoporous material carrier C2 with an average particle diameter of 0.9-7μm.

[0114] 2) Preparation of polyolefin catalysts

[0115] The catalyst components were prepared according to the method of Example 1, except that the amount of hexagonal mesoporous support C2 was changed from 6.0 g to 4.5 g, the catalyst was designated Cat-2, the catalyst evaluation was the same as in Example 1, and the polymerization reaction results are shown in Table 3.

[0116] The hexagonal mesoporous material support C2 and the polyolefin catalyst Cat-2 were characterized using a nitrogen adsorption analyzer.

[0117] In the catalyst Cat-2 obtained in this embodiment, the content of magnesium is 8.4 wt% and the content of titanium is 2.30 wt%.

[0118] Table 2 shows the pore structure parameters of the hexagonal mesoporous material support C2 and the polyolefin catalyst Cat-2.

[0119] Table 2

[0120]

[0121] As can be seen from the data in Table 2, the specific surface area and pore volume of the hexagonal mesoporous material carrier C2 decreased after loading magnesium and titanium components, indicating that magnesium and titanium components entered the interior of the hexagonal mesoporous material carrier C2 during the loading reaction.

[0122] Example 3

[0123] The catalyst component was prepared according to the method of Example 1, except that 9.8 mmol of ethylene glycol monobutyl ether in catalyst preparation step (1) was replaced with 9.8 mmol of propylene glycol monobutyl ether.

[0124] The catalyst was evaluated in the same manner as in Example 1, and the polymerization results are shown in Table 3.

[0125] Example 4

[0126] The catalyst component was prepared according to the method of Example 1, except that 11 mmol of tetrabutyl titanate in catalyst preparation step (1) was replaced with 11 mmol of tetraethyl titanate.

[0127] The catalyst was evaluated in the same manner as in Example 1, and the polymerization results are shown in Table 3.

[0128] Example 5

[0129] The catalyst components were prepared according to the method of Example 1, except that 100 ml of tetrahydrofuran in catalyst preparation step (1) was replaced with 130 ml of tetrahydrofuran. The catalyst was evaluated as in Example 1, and the polymerization results are shown in Table 3.

[0130] Example 6

[0131] The catalyst components were prepared according to the method of Example 1, except that the 13.5 ml 30 wt% dichloroethylaluminum solution in catalyst preparation step (3) was replaced with 2.8 ml silicon tetrachloride. The catalyst evaluation was the same as in Example 1, and the polymerization reaction results are shown in Table 3.

[0132] Example 7

[0133] The catalyst component was prepared according to the method of Example 1, except that 9.8 mmol of ethylene glycol monobutyl ether in catalyst preparation step (1) was replaced with 11 mmol of propylene glycol monomethyl ether. The catalyst was evaluated as in Example 1, and the polymerization results are shown in Table 3.

[0134] Comparative Example 1

[0135] (1) Add 45 mmol magnesium dichloride, 120 ml tetrahydrofuran, and 9.8 mmol titanium tetrachloride sequentially to a glass reactor equipped with a stirrer and maintained by N2 purging. Heat the reactor to 70°C and stir until a transparent solution is formed.

[0136] (2) Cool the transparent solution obtained in step (1) to 50°C, add 6.0g of fumed hydrophobic silica (Cabot Corporation TS-610, particle size 0.02-0.1 micrometers) to it, stir and react for 2 hours to obtain a suspension;

[0137] (3) Under N2 protection, the inlet temperature of the spray dryer is controlled at 140℃, the outlet temperature is controlled at 105℃, and the carrier gas flow rate is controlled at 360L / h to obtain a solid free-flowing powdered polyolefin catalyst.

[0138] The catalyst was evaluated in the same way as in Example 1. The polymerization results are shown in Table 3, and the scanning electron microscopy results of the catalyst are shown in Figure 2.

[0139] Comparative Example 2

[0140] (1) Add 45 mmol magnesium dichloride, 120 ml tetrahydrofuran, 9.8 mmol titanium tetrachloride, and 9.3 mmol epichlorohydrin sequentially to a glass reactor equipped with a stirrer and which has been purged with N2 and kept under N2 atmosphere. Heat the reactor to 70°C and stir until a transparent solution is formed.

[0141] (2) Cool the transparent solution obtained in step (1) to 50°C, add 5.6g of fumed hydrophobic silica (Cabot Corporation TS-610, particle size 0.02-0.1 micrometers) to it, stir and react for 2 hours to obtain a suspension;

[0142] (3) Under N2 protection, the inlet temperature of the spray dryer is controlled at 140℃, the outlet temperature is controlled at 105℃, and the carrier gas flow rate is controlled at 360L / h to obtain a solid free-flowing powdered polyolefin catalyst.

[0143] The catalyst was evaluated in the same manner as in Example 1, and the polymerization results are shown in Table 3.

[0144] Comparative Example 3

[0145] The polyolefin catalyst was prepared according to the method of Example 1, except that 9.8 mmol of ethylene glycol monobutyl ether was not added in step 2 of the catalyst preparation. The catalyst was evaluated as in Example 1, and the polymerization results are shown in Table 3.

[0146] Table 3

[0147]

[0148] (Where: BD—bulk density)

[0149] As can be seen from the experimental data of the examples and comparative examples in Table 3, the catalyst obtained in this invention maintains a high level of activity while also exhibiting a high polymer packing density. A comparison of Figures 1 and 2 shows that, compared to the comparative catalyst, the catalyst of this invention has a near-spherical particle shape, with uniform particle size, good sphericity, and good dispersibility.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] 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.

[0154] 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.

[0155] 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 comprising the reaction product of the following raw materials: at least one support, at least one magnesium compound, at least one oxygen-containing titanium compound, at least one alcohol ether compound, at least one ether compound, and at least one halogenating agent; wherein the support is a hexagonal mesoporous material support having a cubic cage-like pore structure, a 1m3m crystal structure with a cubic core, an average pore size of 4-15 nm, and a specific surface area of ​​450-550 m². 2 / g, pore volume of 0.5-1.5mL / g, average particle size of 0.5-10μm; the ether compound is selected from at least one of anisole, phenethyl ether, propyl ether, butyl ether, isopropyl ether, isobutyl ether, 1,4-dioxane, tetrahydrofuran, ethylene oxide, 1,2-epoxypropane, 1,2-epoxybutane, cis-2,3-epoxybutane, trans-2,3-epoxybutane, 9,9-(dimethoxymethyl)fluorene, isopentyl ether, pentyl ether; the amount of the hexagonal mesoporous material support is 60-220g relative to the amount of magnesium compound per mole of magnesium element; the amount of the oxygen-containing titanium compound is 0.1-20 mol; the amount of the alcohol ether compound is 0.1-10 mol; the amount of the ether compound is 15-60 mol; the amount of the halogenating agent is 0.1-50 mol; the preparation method of the catalyst component includes: In the presence of a protective atmosphere, the at least one hexagonal mesoporous material carrier is subjected to a first contact reaction with the following raw materials: at least one magnesium compound, at least one oxygen-containing titanium compound, at least one alcohol ether compound and at least one ether compound, followed by a second contact reaction with a halogenating agent to obtain a slurry to be sprayed. The slurry to be sprayed is then spray-dried to obtain a catalyst component.

2. The catalyst component according to claim 1, characterized in that: The carrier is prepared by the following method: (a) mixing and contacting a template agent, potassium sulfate, an acid agent and tetraethyl orthosilicate, and then crystallizing and filtering the resulting mixture to obtain hexagonal mesoporous material powder; (b) subjecting the hexagonal mesoporous material powder to template removal treatment, thermal activation treatment and ball milling treatment in sequence to obtain hexagonal mesoporous material carrier.

3. The catalyst component according to claim 2, characterized in that: In step (a), the molar ratio of the template agent, potassium sulfate, and tetraethyl orthosilicate is 1:100-800:20-200; and / or, the template agent is a triblock copolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide; and / or, the acid agent is at least one of hydrochloric acid, sulfuric acid, nitric acid, and hydrobromic acid.

4. The catalyst component according to claim 3, characterized in that: The conditions for the mixing contact include: a temperature of 25-60°C, a time of 10-240 min, and a pH value of 1-7; and / or, the conditions for crystallization include: a temperature of 25-60°C and a time of 10-72 h.

5. The catalyst component according to claim 2, characterized in that: In step (b), the template release agent treatment process includes: calcining the hexagonal mesoporous material powder at 300-600℃ for 8-20h; and / or, the conditions for the thermal activation treatment include: a thermal activation temperature of 300-900℃ and a thermal activation time of 7-10h; and / or, the conditions for the ball milling treatment include: a grinding ball rotation speed of 300-500r / min, and / or, a ball milling jar temperature of 15-100℃, and / or, a ball milling time of 0.1-100h.

6. The catalyst component according to claim 1, characterized in that: The magnesium compound is of general formula (I)Mg(OR) 1 ) m Cl 2-m As shown, R 1 For C2-C 20 Saturated or unsaturated straight-chain or branched hydrocarbon groups, or C3-C 20 Saturated or unsaturated cyclic hydrocarbon groups, 0 ≤ m ≤ 2.

7. The catalyst component according to claim 6, characterized in that: In general formula (Ⅰ), R 1 For C2-C 10 Alkyl groups.

8. The catalyst component according to claim 1, characterized in that: The oxygen-containing titanium compound is of general formula (II)Ti(OR) 2 ) n Cl 4-n As shown, R 2 For C2-C 20 Saturated or unsaturated straight-chain or branched hydrocarbon groups, or C3-C 20 Saturated or unsaturated cyclic hydrocarbon groups, 0 < n ≤ 4.

9. The catalyst component according to claim 8, characterized in that: In general formula (II), R 2 For C2-C 10 Alkyl groups.

10. The catalyst component according to claim 1, characterized in that: The alcohol ether compound is selected from low carbon alcohol ethers of ethylene glycol and / or propylene glycol.

11. The catalyst component according to claim 10, characterized in that: The alcohol ether compound is selected from at least one of propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, propylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol monopropyl ether.

12. The catalyst component according to claim 1, characterized in that: The halogenating agent is of general formula (III)R 3 a MX b As shown, M represents a Group 3, 4, or 5 element or a transition metal, X represents a halogen, and R represents a group 5. 3 For C2-C 20 Saturated or unsaturated straight-chain or branched hydrocarbon groups, C3-C 20 Saturated or unsaturated cyclic hydrocarbon groups or alkoxy groups, C6-C 20 Aromatic groups, a = 0, 1 or 2, b = 1, 2, 3 or 4.

13. The catalyst component according to any one of claims 1-12, characterized in that: Based on the total weight of the catalyst components, the content of the hexagonal mesoporous material support is 20-90% by weight; the content of the magnesium component (based on elemental magnesium) is 1-50% by weight; the content of the titanium component (based on elemental titanium) is 1-50% by weight; and / or, the average pore size of the catalyst components is 4-15 nm, and the specific surface area is 450-500 m². 2 / g, pore volume is 0.5-1mL / g, and average particle size is 5-40μm.

14. The catalyst component according to any one of claims 1-12, characterized in that: Based on the total weight of the catalyst components, the content of the hexagonal mesoporous material support is 20-70% by weight; the magnesium component, calculated as elemental magnesium, has a content of 1-30% by weight; and the titanium component, calculated as elemental titanium, has a content of 1-15% by weight.

15. A method for preparing a catalyst component according to any one of claims 1-14, comprising, in the presence of a protective atmosphere, subjecting the at least one hexagonal mesoporous material support to a first contact reaction with the following raw materials: at least one magnesium compound, at least one oxygen-containing titanium compound, at least one alcohol ether compound, and at least one ether compound, followed by a second contact reaction with a halogenating agent to obtain a slurry to be sprayed, and then spray-drying the slurry to obtain a catalyst; wherein the amount of the hexagonal mesoporous material support is 60-220 g relative to each mole of magnesium compound (calculated as magnesium element); the amount of the oxygen-containing titanium compound is 0.1-20 mol; the amount of the alcohol ether compound is 0.1-10 mol; the amount of the ether compound is 15-60 mol; and the amount of the halogenating agent is 0.1-50 mol.

16. The preparation method according to claim 15, characterized in that: The conditions for the first contact reaction include: a temperature of 0-100℃ and a reaction time of 0.1-10h; and / or, the conditions for the second contact reaction include: a temperature of 0-80℃ and a reaction time of 0.5-10h; and / or, the conditions for the spray drying include: being carried out under a nitrogen protective atmosphere, with an inlet temperature of 100-200℃, an outlet temperature of 60-130℃, and a carrier gas flow rate of 200-600L / h.

17. The preparation method according to claim 15 or 16, characterized in that: The amount of the hexagonal mesoporous material carrier is 80-180 g relative to each mole of magnesium compound (calculated as elemental magnesium); the amount of the oxygen-containing titanium compound is 0.1-5.0 moles; the amount of the alcohol ether compound is 0.1-5.0 moles; and the amount of the halogenating agent is 0.1-10 moles.

18. The preparation method according to claim 15 or 16, characterized in that: The amount of the hexagonal mesoporous material carrier is 90-160 g relative to each mole of magnesium compound (calculated as elemental magnesium); the amount of the oxygen-containing titanium compound is 0.1-3.0 moles; the amount of the alcohol ether compound is 0.1-3.0 moles; and the amount of the halogenating agent is 0.1-5 moles.

19. A catalyst comprising a reaction product of the following components: component (A): the catalyst component of any one of claims 1-14 or the catalyst component obtained by the preparation method of any one of claims 15-18; component (B): general formula (Ⅳ) AlR s X 3-s The organoaluminum compounds shown in the formula are: R is a hydrocarbon group or hydrogen with 1-20 carbon atoms, X is a halogen atom, s is an integer, and 1 <s≤3。 20. A method for preparing the catalyst according to claim 19, comprising the step of mixing and reacting the catalyst component (A) and the organoaluminum compound.

21. The use of a catalyst component according to any one of claims 1-14, a catalyst component obtained by any one of claims 15-18, a catalyst according to claim 19, or a catalyst prepared by any one of claims 20 in an ethylene polymerization reaction.

22. The application according to claim 21, characterized in that: The application is in the homopolymerization of ethylene or in the copolymerization of ethylene with α-olefins.

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