Component of olefin polymerization catalyst, olefin polymerization catalyst, and use thereof

Abstract

The application discloses a component of an olefin polymerization catalyst, an olefin polymerization catalyst and application of the component, and relates to the technical field of catalysts. The component of the olefin polymerization catalyst comprises Mg, Ti, halogen and an internal electron donor, and the internal electron donor is an ascorbate compound. The component of the olefin polymerization catalyst contains a biologically safe internal electron donor component, can reduce the toxicity of a catalyst residual component in a polyolefin, and is particularly suitable for production of medical polyolefin materials.

Description

Technical Field

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

[0002] Polyolefins are a class of polymer materials with the largest output and widest application due to their abundant raw materials, low price, ease of processing and molding, and excellent comprehensive properties. Polyethylene and polypropylene are the most important among them. Taking polypropylene as an example, polypropylene has excellent properties such as radiation resistance, high heat resistance, high pressure resistance, physiological degradability, good mechanical properties, and chemical stability, and is increasingly widely used in the medical field. In the medical field, polypropylene is mainly used as medical non-woven fabrics, disposable medical products, medical transparent tubes, blood filters, and artificial lungs. When polypropylene is used to manufacture disposable medical products, syringes, catheters, and other medical products, it is lightweight, not easily broken, high temperature resistant, non-toxic, easy to process, inexpensive, and can avoid iatrogenic cross-infection during use. However, the hygiene performance indicators of ordinary polypropylene cannot meet the standards for producing medical products, which limits its application.

[0003] One of the challenges in producing medical-grade clean polypropylene lies in the extremely high requirements for ash control. The total ash content of polypropylene resin and residual catalyst components are key indicators of concern in clean polypropylene production. If clean polypropylene is not obtained directly in the washing reactor using a process, highly active catalysts are often required. To fundamentally improve the properties of the active centers of Ziegler-Natta catalysts (ZN catalysts) and significantly enhance polymerization activity, internal electron donors are added during catalyst preparation, while external electron donors are added during polymerization. Both have a significant impact on olefin polymerization behavior and polymer properties. Among these, altering the internal electron donors in the catalyst can maximally change the properties of the active centers, thereby maximizing the modification of catalyst performance.

[0004] Therefore, the development of novel electron donors has always been a hot topic in the research and development of Zn polypropylene catalysts. Among the existing technologies, the more distinctive high-performance internal electron donor compounds mainly include: 1) fatty acid esters and aromatic esters, primarily phthalates; 2) diethers (e.g., EP0361493, EP0728724); 3) succinates (e.g., WO9856834, WO0063261, WO03022894); 4) glycol esters (e.g., WO9856834, WO0063261, WO03022894); and 5) compounds with other functional groups (CN1105671, CN1242780, US20060128558), etc. However, in practical applications, the above-mentioned compounds all have certain problems as internal electron donors for olefin polymerization catalysts. Although catalysts using 1,3-diether compounds as internal electron donors have high activity and good hydrogen-modulated sensitivity, the relative molecular mass distribution of the synthesized PP is narrow, which is not conducive to the development of different grades of PP. Succinate compounds as internal electron donors have the advantage of producing PP with a wider relative molecular mass distribution, but the stereoregularity of PP and the hydrogen-modulated sensitivity of the catalyst need to be improved. The activity of glycol ester catalytic systems is generally not as ideal as that of diether systems.

[0005] Currently, phthalate compounds are the most widely used internal electron donors in polyolefins in industry. Catalysts prepared from phthalates exhibit moderate activity, good stereoselectivity, and low cost. However, as commonly used plasticizers, phthalates pose significant risks to human reproductive health and the environment, creating a substantial demand for alternatives. Europe has already restricted the use of most phthalate substances.

[0006] To improve the performance of polyolefin catalysts, in existing technologies, internal electron donor compounds account for approximately 5-20% by weight of solid catalysts. As residual components in polymerization, these compounds negatively impact the cleanliness of polypropylene. This is especially true when catalysts containing high levels of phthalate-based internal electron donors are used, which can leave residual components with a certain degree of reproductive toxicity in the polyolefin, thus limiting its medical applications. Therefore, developing catalysts containing highly biosafe and highly active internal electron donor compounds will benefit the production of medical polyolefin products and promote the development of medical polyolefin materials. Summary of the Invention

[0007] To address the problems existing in the prior art, the present invention provides an olefin polymerization catalyst containing a biosafety internal electron donor component and its application. This olefin polymerization catalyst can reduce the toxicity of residual catalyst components in polyolefins and is particularly suitable for the production of medical polyolefin materials.

[0008] The purpose of this invention is to provide a component for an olefin polymerization catalyst.

[0009] Another object of the present invention is to provide a catalyst comprising this component.

[0010] Another object of the present invention is to provide the application of the catalyst in the polymerization of CH2=CHR olefins.

[0011] To achieve the objectives of this invention, the present invention provides a component for an olefin polymerization catalyst comprising Mg, Ti, a halogen, and an internal electron donor, wherein the internal electron donor is at least one ascorbate compound selected from general formulas (I), (II), and (III):

[0012]

[0013] Among them, R 1 R 2 R 3 and R 4 Whether the two are the same or different, they are each independently selected from C1-C. 20 The hydrocarbon group; preferably, R 1 R 2 R 3 and R 4 It may also contain at least one heteroatom selected from N, O, S, P, Si and halogens; preferably, R 1 R 2 R 3 and R 4 Two or more of them can bond together to form a ring.

[0014] Preferably, R 1 R 2 R 3 and R 4 They may be the same or different, each independently selected from straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indole, benzyl, halogenated or substituted with N, O, S, P, or Si heteroatoms; or each independently selected from heterocyclic aryl substituents.

[0015] Preferably, R 1 R 2 R 3 and R 4 Whether the groups are the same or different, each is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 ~C 20Straight-chain or branched alkyl or alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, substituted benzyl, substituted phenethyl, furanyl, pyrroleyl, thiophenyl, propenyl, butenyl, pentenyl, hexenyl, indene.

[0016] Preferably, the ascorbic acid monoester compound of general formula (I) is selected from methyl ascorbate, ethyl ascorbate, n-propyl ascorbate, isopropyl ascorbate, n-butyl ascorbate, isobutyl ascorbate, tert-butyl ascorbate, n-pentyl ascorbate, isopentyl ascorbate, cyclopentyl ascorbate, n-hexyl ascorbate, cyclohexyl ascorbate, heptayl ascorbate, octyl ascorbate, nonyl ascorbate, decyl ascorbate, lauryl ascorbate, myristyl ascorbate, palmitate ascorbate, and other ascorbic acid compounds. The following is a list of at least one of the following: ascorbic acid stearate, phenyl ascorbate, benzyl ascorbate, phenylacetic acid ascorbate, o-chlorophenyl ascorbate, m-chlorophenyl ascorbate, p-toluene ascorbate, p-methoxyphenyl ascorbate, p-methylphenyl ascorbate, m-trimethylphenyl kojic acid, p-nitrophenyl kojic acid, p-fluorophenyl kojic acid, p-trifluoromethylphenyl kojic acid, crotonyl ascorbate, naphthyl ascorbate, nicotinyl ascorbate, monoethyl ascorbate succinate, cinnamyl ascorbate, thiophene ascorbate, and furfuryl ascorbate.

[0017] Preferably, the ascorbic acid diester compound of general formula (II) is selected from dimethyl ascorbate, diethyl ascorbate, di-n-propyl ascorbate, diisopropyl ascorbate, di-n-butyl ascorbate, diisobutyl ascorbate, di-tert-butyl ascorbate, di-n-pentyl ascorbate, diisopentyl ascorbate, dicyclopentyl ascorbate, di-n-hexyl ascorbate, dicyclohexyl ascorbate, diheptyl ascorbate, dioctyl ascorbate, dinonyl ascorbate, didecyl ascorbate, dilauryl ascorbate, dimyristyl ascorbate, dipalmityl ascorbate, and di-ascorbate. Stearate, diphenyl ascorbate, dibenzyl ascorbate, diphenylacetic acid ascorbate, di-o-chlorophenyl ascorbate, di-m-chlorophenyl ascorbate, di-p-toluene ascorbate, di-p-methoxyphenyl ascorbate, di-p-methylphenyl ascorbate, m-trimethylphenyl ascorbate, p-nitrophenyl ascorbate, p-fluorophenyl ascorbate, p-trifluoromethylphenyl ascorbate, dicrotonyl ascorbate, dinaphthyl ascorbate, dinicotinyl ascorbate, monoethyl disuccinate ascorbate, dicinnamyl ascorbate, dithiophene ascorbate, and difurfuryl ascorbate.

[0018] Preferably, the ascorbic acid tetraester compound of general formula (III) is selected from tetramethyl ascorbate, tetraethyl ascorbate, tetra-n-propyl ascorbate, tetraisopropyl ascorbate, tetra-n-butyl ascorbate, tetraisobutyl ascorbate, tetra-tert-butyl ascorbate, tetra-n-pentyl ascorbate, tetraisopentyl ascorbate, tetracyclopentyl ascorbate, tetra-n-hexyl ascorbate, tetracyclohexyl ascorbate, tetraheptyl ascorbate, tetraoctyl ascorbate, tetranonyl ascorbate, tetradecyl ascorbate, tetralauryl ascorbate, tetramyristyl ascorbate, and tetrapalmityl ascorbate. The following is a list of at least one of the following: tetrastearate ascorbate, tetraphenyl ascorbate, tetrabenzyl ascorbate, tetraphenylacetic acid ascorbate, tetrao-chlorophenyl ascorbate, tetra-m-chlorophenyl ascorbate, tetra-p-toluene ascorbate, tetra-p-methoxyphenyl ascorbate, tetra-p-methylphenyl ascorbate, m-trimethylphenyl kojate, p-nitrophenyl kojate, p-fluorophenyl kojate, p-trifluoromethylphenyl kojate, tetracrotonyl ascorbate, tetranaphthyl ascorbate, tetranicotinamide ascorbate, monoethyl tetrasuccinate ascorbate, tetracinnamyl ascorbate, tetrathiophene ascorbate, and tetrafurfuryl ascorbate.

[0019] This invention does not limit the source or preparation method of ascorbic acid ester compounds, which can be commercially available products; or can be prepared from ascorbic acid as a raw material through main methods such as transesterification, direct esterification, acyl chloride esterification, and enzyme catalysis.

[0020] Preferably, the ascorbate compound is prepared by the acyl chloride esterification method, when R 1 R 2 R 3 and R 4 Similarly, ascorbic acid tetraester compounds of general formula (III) are obtained by a one-step reaction using four equivalents of acyl chloride, as shown in reaction formula I:

[0021]

[0022] Preferably, the composition of the olefin polymerization catalyst includes titanium compounds, magnesium compounds, and ascorbate compounds;

[0023] The precursor of the magnesium compound is selected from X. n Mg(OR a ) 2-n MgCl2·mR a OH, R a 2-n MgX n At least one of the following: a mixture of MgCl2 / SiO2, MgCl2 / Al2O3, magnesium halide, and titanium alkoxide, wherein m is 0.1-6, 0≤n≤2, X is a halogen, and R a For C1-C 20hydrocarbon group;

[0024] The general formula of the titanium compound is TiX. N (OR b ) 4-N In the formula, R b For C1-C 20 The hydrocarbon group, where X is a halogen and N is 1-4.

[0025] Preferably, the magnesium compound is an alkoxide of magnesium dihalide; or, the magnesium compound is a liquid magnesium compound; or, the magnesium compound is a derivative in which at least one halogen atom in a magnesium dihalide molecule is replaced by an alkyl group or a haloalkyl group; preferably, it is an alkyloxy magnesium compound; more preferably, it is an alkoxy magnesium and / or an aryloxy magnesium compound.

[0026] Preferably, the titanium compound includes at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, or alkyl titanium halide;

[0027] Preferably, the alkyl titanium halide includes at least one of methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, and tri-n-butoxy titanium chloride.

[0028] Preferably, the titanium compound is titanium tetrachloride.

[0029] Preferably, the halogen is at least one of chlorine, bromine, and iodine.

[0030] Preferably, in the components of the olefin polymerization catalyst, the molar ratio of the total number of internal electron donors to the magnesium compound is 0.01-5.0, more preferably 0.05-3.0, and the magnesium compound is calculated as magnesium element.

[0031] Preferably, when the internal electron donor is a mixture of two of general formulas (I), (II), and (III), the molar ratio of the two internal electron donors is 20:1 to 1:20. In other words, when the internal electron donor is a mixture of two of general formulas (I), (II), and (III), the internal electron donor can be added in the following ways: when the internal electron donor is an ascorbate compound of general formula (I) or (II), the molar ratio of the ascorbate compound of general formula (I) to (II) is 20:1 to 1:20;

[0032] When the internal electron donor is an ascorbate compound of general formula (I) or general formula (III), the molar ratio of the ascorbate compound of general formula (I) to general formula (III) is 20:1 to 1:20;

[0033] When the internal electron donor is an ascorbate compound of general formula (II) or general formula (III), the molar ratio of the ascorbate compound of general formula (II) to general formula (III) is 20:1 to 1:20.

[0034] Preferably, when the internal electron donor is a mixture of three of general formulas (I), (II), and (III), the molar ratio of any one of general formulas (I), (II), and (III) to the total amount of the feed is ≥1 / 20.

[0035] This invention does not specifically limit the preparation method of the components of the olefin polymerization catalyst, which can be carried out according to the following preparation methods:

[0036] Method 1: A magnesium alkoxide or chloroalkoxide and excess TiCl4, along with at least one ascorbate ester compound of general formulas (I), (II), and (III), are reacted at a temperature of 80-135°C. According to the preferred method, a compound of general formula TiX can be reacted. N (OR b ) 4-N Titanium compounds (where R) b For C1-C 20 The hydrocarbon group, where X is a halogen and N is 1-4; preferably TiCl4) and the general formula MgCl2·mR a OH (where m is a number from 0.1 to 6, preferably 2 to 4, and R) a For C1-C 20 The components of an olefin polymerization catalyst are prepared by reacting an adduct of a hydrocarbon group. The adduct can be suitably prepared into spherical form by mixing an alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, followed by rapid quenching of the emulsion, thereby solidifying the adduct into spherical particles. Spherical MgCl2·mR particles prepared according to this process... a Examples of OH adducts can be described in US4399054A and US4469648A. The adducts thus obtained can react directly with titanium compounds, or they can be pre-treated with a thermally controlled dealcoholization process (80-130°C) to yield an adduct in which the molar number of alcohol is generally less than 3, preferably between 0.1 and 2.5. The reaction with titanium compounds can be carried out by suspending the adduct (dealcoholized or otherwise) in cold TiCl4 (generally -25 to 0°C); the mixture is then heated to 80-130°C and held at this temperature for 0.5-2 hours. The treatment with TiCl4 can be performed once or multiple times. During the TiCl4 treatment, at least one ascorbate compound of general formulas (I), (II), and (III) can be added, and this treatment can be repeated once or multiple times.

[0037] Method 2: A magnesium compound is dissolved in a solvent system consisting of an organic epoxy compound, an organophosphorus compound, and an inert diluent to form a homogeneous solution. This solution is then mixed with a titanium compound, and a solid is precipitated in the presence of a precipitation aid. This solid is treated with at least one ascorbic acid ester compound of general formula (I), general formula (II), and general formula (III) to load it onto the solid. If necessary, further treatment with titanium tetrahalide and an inert diluent is performed. The precipitation aid is one of organic anhydrides, organic acids, ethers, and ketones. The components, per mole of magnesium halide, are: organic epoxy compound 0.2-10 mol, organophosphorus compound 0.1-3 mol, precipitation aid 0-1.0 mol, and Ti compound 0.5-150 mol.

[0038] Method 3: A solution of TiCl4 or hydroxyl-titanium aromatic hydrocarbons (e.g., toluene, xylene, etc.) can be reacted with dialkoxymagnesium compounds such as magnesium dialkoxy (preferably ethoxymagnesium) or diaryloxymagnesium at -25–0 °C, followed by halogenation at 80–130 °C. The treatment with the TiCl4 aromatic hydrocarbon solution can be repeated once or multiple times, with at least one ascorbate ester compound of general formulas (I), (II), and (III) added once or in batches during these multiple treatments. For example, the preparation method of the titanium-containing solid catalyst component disclosed in US5077357A can be used: ethoxymagnesium, tetraethoxytitanium, o-cresol, ethanol, and chlorobenzene are added sequentially, and the mixture is stirred; a TiCl4 / chlorobenzene solution is rapidly added to the above liquid, and the mixture is heated until completely dissolved, then heated to a specific temperature; the ethanol reactants are removed by bubbling with N2, and the mixture is stirred for a certain time, then washed once with hot chlorobenzene, twice with isooctane, and finally dried with N2 to obtain the support. Alternatively, follow another example: add TiCl4, tetraethoxytitanium, ethoxymagnesium, and o-cresol to chlorobenzene in sequence and stir; add ethanol, and continue stirring for 3 hours after the ethoxymagnesium dissolves at high temperature; filter while hot, then wash once with warm chlorobenzene, wash once with isooctane, and finally dry with N2.

[0039] Method 4: Magnesium dichloride is pre-activated using existing methods, and then treated with an excess of TiCl4 at a temperature of approximately 80-135°C, wherein the solution contains at least one ascorbate compound of general formula (I), general formula (II), and general formula (III). The solid is treated with TiCl4 multiple times and washed with hexane to remove any unreacted TiCl4.

[0040] Method 5: The preparation method of titanium-containing solid catalyst components disclosed in CN1208045A can be used as follows: First, liquid magnesium compound and liquid titanium compound are contacted at low temperature in the presence of a compound selected from alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and esters to precipitate solids. The contact temperature is generally -70 to 200°C, preferably -30 to 130°C. During the contact process, at least one ascorbate ester compound of general formula (I), general formula (II) and general formula (III) is used for treatment.

[0041] Method Six: Anhydrous magnesium chloride and at least one ascorbate compound of general formulas (I), (II), and (III) are co-milled under conditions where magnesium dichloride is activated. The resulting product can be treated once or multiple times with an excess of TiCl4 at a temperature of 80-130°C. After treatment, it is washed with a hydrocarbon solvent until chloride ions are removed. According to a further method, the product obtained by co-milling anhydrous magnesium dichloride, a titanium compound, and at least one ascorbate compound of general formulas (I), (II), and (III) is treated with a haloalkane such as 1,2-dichloroethane, chlorobenzene, or dichloromethane. This treatment is carried out at a temperature between 40°C and the boiling point of the haloalkane for 1-4 hours. The product is then washed with an inert hydrocarbon solvent, typically hexane, to obtain the final product.

[0042] Method 7: Magnesium compounds supported on inorganic oxides such as SiO2, alumina, or porous silica gel are used as carriers to prepare the product. The product is then activated by a well-known method and treated with an excess of TiCl4 at a temperature of about 80-135°C. During the treatment, at least one ascorbate ester compound of general formula (I), general formula (II), and general formula (III) is added.

[0043] The above reactions result in the formation of magnesium halides in an active form (typical crystalline magnesium halides have a regular structure and can support very little Ti, thus exhibiting low catalytic activity. To prepare highly active supported catalysts, magnesium halides must undergo activation treatment. Activation methods include using physical and / or chemical methods to prepare them into microcrystals so that active centers are supported on the surface, edges, and defects of the magnesium halide. These treated magnesium halide microcrystals suitable for supporting Ti are called "active magnesium halides"). In addition to these reactions, other methods are known in the literature for forming active magnesium halides from starting materials different from magnesium halides.

[0044] In any preparation method, the aforementioned internal electron donor compound can be added directly or optionally prepared in situ using a suitable precursor that can be converted in the desired internal electron donor compound via known chemical reactions such as esterification or transesterification. Typically, the aforementioned internal electron donor compound is used in a molar ratio of 0.01-5, preferably 0.05-3.0, relative to MgCl2.

[0045] In any preparation method, at least one ascorbate compound of general formula (I), general formula (II) and general formula (III) may be added simultaneously or separately in batches, in any order and in any combination during the preparation process.

[0046] The present invention also provides a catalyst for olefin polymerization, the raw material composition of which includes the components of the above-mentioned catalyst and an organoaluminum compound.

[0047] According to a specific embodiment of the present invention, preferably, the organoaluminum compound has the general formula AlR c p X (3-p) , where R c It is hydrogen or C1-C 20 The hydrocarbon group, X is a halogen, and p is an integer 0 ≤ p ≤ 3.

[0048] According to a specific embodiment of the present invention, preferably, the organoaluminum compound includes at least one selected from trialkylaluminum compound, alkylaluminum halide, alkylaluminum hydride, alkylaluminum sesquichloride, and alkylaluminoxane; more preferably, the trialkylaluminum compound includes at least one selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and trioctylaluminum; the alkylaluminum halide includes AlEt2Cl; the alkylaluminum sesquichloride includes Al2Et3Cl3; more preferably, the trialkylaluminum compound is a mixture of AlEt2Cl and Al2Et3Cl3.

[0049] According to a specific embodiment of the present invention, preferably, the molar ratio of titanium atoms in the organoaluminum compound to that in the catalyst is 1-1000:1, more preferably 50-800.

[0050] According to a specific embodiment of the present invention, preferably, the raw material composition of the catalyst further includes an external electron donor.

[0051] According to a specific embodiment of the present invention, preferably, the external electron donor is a siloxane compound.

[0052] According to a specific embodiment of the present invention, preferably, the general formula of the siloxane compound is R'. t Si(OR”)4-t In this context, R' and R” are each independently selected from C1-C 18 The hydrocarbon group, where t is an integer of 0 ≤ t ≤ 3; more preferably, R' and R” respectively contain heteroatoms; more preferably, the heteroatoms include at least one of N, O, S, P, and Si.

[0053] According to a specific embodiment of the present invention, preferably, the siloxane compound includes trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, triisobutylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diisobutyldimethoxysilane, di-tert- ... Silane, di-tert-butyldiethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, di(2-ethylhexyl)dimethoxysilane, di(2-ethylhexyl)diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldiethoxysilane, cyclopentylisopropyldiethoxysilane, cyclopentylisobutyldimethoxysilane, cyclohexyl-n-propyl Dimethoxysilane, cyclohexyl-n-propyldiethoxysilane, cyclohexyl-n-butyldiethoxysilane, pentylmethyldimethoxysilane, pentylmethyldiethoxysilane, pentylethyldimethoxysilane, pentylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane, cyclohexyldimethoxysilane, cyclohexyldiethoxysilane, 2-ethylhexyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyl 2-Ethylhexyltrimethoxysilane, isobutyltrimethoxysilane, tert-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,At least one of the following: 5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, di(3-methylcyclohexyl)dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, di(4-methylcyclohexyl)dimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, di(3,5-dimethylcyclohexyl)dimethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

[0054] According to a specific embodiment of the present invention, preferably, the siloxane compound includes at least one selected from di-n-propyl dimethoxysilane, diisopropyl dimethoxysilane, di-n-butyl dimethoxysilane, diisobutyl dimethoxysilane, di-tert-butyl dimethoxysilane, di-n-butyl diethoxysilane, tert-butyl trimethoxysilane, dicyclohexyl dimethoxysilane, dicyclohexyl diethoxysilane, cyclohexylmethyl dimethoxysilane, cyclohexylethyl diethoxysilane, cyclohexylethyl dimethoxysilane, cyclohexylethyl diethoxysilane, cyclopentylmethyl dimethoxysilane, cyclopentylmethyl diethoxysilane, cyclopentylethyl dimethoxysilane, cyclohexylcyclopentyl dimethoxysilane, cyclohexylcyclopentyl diethoxysilane, 3-methylcyclohexylcyclopentyl dimethoxysilane, 4-methylcyclohexylcyclopentyl dimethoxysilane, and 3,5-dimethylcyclopentyl dimethoxysilane.

[0055] According to a specific embodiment of the present invention, preferably, the siloxane compound includes at least one selected from cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, methyl tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane, cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane, and tert-hexyltrimethoxysilane.

[0056] According to a specific embodiment of the present invention, preferably, the molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100, more preferably 0.01-20, and even more preferably 0.01-5.

[0057] The present invention also provides the application of the above-mentioned catalyst in olefin polymerization.

[0058] According to a specific embodiment of the present invention, preferably, the olefin includes straight-chain or branched olefins, such as at least one of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, butadiene, vinylcyclopentene, and vinylcyclohexene.

[0059] According to a specific embodiment of the present invention, preferably, the polymerization includes ethylene and / or propylene polymerization.

[0060] According to a specific embodiment of the present invention, preferably, the polymerization includes homopolymerization or copolymerization.

[0061] According to a specific embodiment of the present invention, preferably, the order of adding the components in the catalyst during the catalytic process is arbitrary, with the organoaluminum compound being added to the polymerization system first, followed by the external electron donor, and finally the catalyst components.

[0062] According to a specific embodiment of the present invention, preferably, in the above applications, the polymerization process can be carried out with or without a solvent; the olefin monomer can be in the gas phase or liquid phase; more preferably, hydrogen can be further added as a molecular weight regulator (polymerization can also be carried out without a molecular weight regulator); continuous polymerization or batch polymerization processes can be applied, and the polymerization reaction can be carried out in one step, two steps or multiple steps.

[0063] According to a specific embodiment of the present invention, preferably, the polymerization temperature is ≤200℃, more preferably 20-100℃, and even more preferably 40-80℃; the polymerization pressure is ≤10MPa, more preferably 0.3-5MPa.

[0064] Ascorbate compounds are a class of non-toxic and harmless multifunctional nutritional antioxidant preservatives. Many of these compounds, such as ascorbyl palmitate, are nutritional antioxidants recognized by the Joint Commission on Food Additives of the World Health Organization. They are heat-resistant and suitable for use in pharmaceuticals, health products, cosmetics, and as antioxidants in baking and frying oils. They are commonly used in oily foods, edible oils, animal and vegetable oils, and high-end cosmetics. They can also be used in infant foods and milk powder.

[0065] The inventors unexpectedly discovered that using various ascorbate ester compounds as internal electron donors in the preparation of olefin polymerization catalysts yields olefin polymerization catalysts with superior activity and selectivity, and the catalytic performance can be tuned by the number of ester functional groups. Ascorbate ester compounds possess a five-membered epoxy heterostructure with multiple oxygen-containing functional groups. Based on the number of ester functional groups, they can be classified into ascorbate monoesters, ascorbate diesters, and ascorbate tetraesters. Different numbers of ester functional groups result in different electron-donating abilities in the compounds, allowing for controllable adjustment of catalytic performance, especially activity.

[0066] Some ascorbate compounds are commercially available food and pharmaceutical additives. Other substituent compounds can be prepared by reacting ascorbic acid with appropriate acyl chlorides, which is relatively inexpensive and offers a wide range of substituent choices. This allows for optimization of the internal electron donor structure through screening various substituents, thereby further improving catalyst performance, making it particularly suitable for industrial applications. Ascorbate compounds are highly stable and non-toxic to humans, making them particularly suitable catalysts with internal electron donors for the production of medical-grade polypropylene, which requires high cleanliness and biotoxicity. Detailed Implementation

[0067] The technical solution of the present invention will now be described in detail with reference to embodiments thereof. Obviously, the described embodiments are only a part of the implementation of the present invention, and not all of them.

[0068] In the following examples, the preparation of the catalyst was carried out under the protection of high-purity nitrogen.

[0069] Polymer isotacticity determination: The heptane extraction method was used (boiling heptane extraction for 6 hours). Two grams of dried polymer sample were placed in an extractor and extracted with boiling heptane for 6 hours. The residue was dried to constant weight. The ratio of the polymer weight (g) obtained to 2 is the isotacticity.

[0070] The bulk density of the polymer was determined using the method specified in JB / T 2412-2008.

[0071] The molecular weight distribution of the polymer was determined by PL-220 gel permeation chromatography at 150 °C with trichlorobenzene as solvent (standard: polystyrene, flow rate 1.0 mL / min, column: 3xPlgel 10um M1Xed-B 300x7.5nm).

[0072] The ascorbate compounds described in this invention, such as L-ascorbate palmitate, ascorbate dipalmitate, and ascorbate tetrapalmitate, are commercially available products. Non-commercial ascorbate compounds can also be prepared from ascorbic acid as a raw material through methods such as transesterification, direct esterification, acyl chloride esterification, and enzyme catalysis.

[0073] Synthesis of ascorbate compounds

[0074] Preparation Example 1. Synthesis of Ascorbate Palmitate

[0075] Palmitic acid (2.6 g, 10 mmol), 15 mL of dimethylethylenediamine, and 5 mL of dichloromethane were added sequentially to a single-necked flask and stirred at room temperature until dissolved. Thionyl chloride (950 μL, 13 mmol) was slowly added dropwise under ice-water bath cooling. The reaction was carried out at 10 °C for 30 minutes, followed by the direct addition of L-ascorbic acid (2.1 g, 12 mmol). The temperature was raised and maintained at 25 °C for 6 hours. After the reaction was complete, 50 mL of ethyl acetate and 40 mL of distilled water were added to the reaction mixture. The mixture was transferred to a separatory funnel, and the aqueous layer was extracted again with 50 mL of ethyl acetate. The organic layers were combined. The organic layers were washed with saturated saline solution until no L-ascorbic acid or dimethylethylenediamine was present (tissue chromatography monitoring). The mixture was dried over anhydrous sodium sulfate, and the organic solvent was rotary evaporated to obtain the crude product. The crude product was purified by column chromatography to obtain a white powder with a yield of 80% and a melting point of 112–115 °C. Its structure and NMR results are shown in Table 1.

[0076] Preparation Examples 2-12. Preparation of Other Ascorbate Compounds

[0077] Ascorbic acid monoesters were prepared using the aforementioned route or the route shown in Reaction Formula I, with the starting materials selected from one equivalent (slight excess) of the corresponding acid or acyl chloride and ascorbic acid; ascorbic acid diesters were prepared using the aforementioned route, with the starting materials selected from two equivalents (slight excess) of the corresponding acid or acyl chloride and ascorbic acid; ascorbic acid tetraesters were prepared using the aforementioned route, with the starting materials selected from four equivalents (slight excess) of the corresponding acid or acyl chloride and ascorbic acid. The structures and NMR results of the compounds obtained in Preparation Examples 2-12 are shown in Table 1.

[0078]

[0079] Table 1 Ascorbate compounds

[0080]

[0081]

[0082]

[0083]

[0084]

[0085] Catalyst preparation

[0086] Example 1

[0087] In a 500 mL stirred flask fully purged with nitrogen, 10 g of MgCl2·2.5C2H5OH microspheres and 150 mL of titanium tetrachloride were added to prepare a suspension. The suspension was then maintained at -15 °C for one hour, and the temperature was slowly increased to 80 °C. 2 g (5 mmol) of ascorbate palmitate was added, and the temperature was further increased to 110 °C and held for one hour. The liquid was then filtered clean, and the resulting solid was washed three times with 120 mL of titanium tetrachloride at 110 °C. The solid was then washed four times with 150 mL of hexane at 60 °C. The liquid was filtered off and the solid was dried to obtain the components of the olefin polymerization catalyst. The analytical evaluation data of the components of this olefin polymerization catalyst are shown in Table 2.

[0088] Example 2-12

[0089] The preparation process of the olefin polymerization catalyst components is as shown in Example 1, except that 5 mmol of ascorbate palmitate is replaced with 5 mmol of compounds numbered 2-12 in Table 1 in sequence.

[0090] Example 13

[0091] The component preparation process of the olefin polymerization catalyst is as shown in Example 1, except that 5 mmol ascorbate palmitate is replaced with 3 mmol ascorbate palmitate and 2 mmol ascorbate dipalmitate.

[0092] Example 14

[0093] The component preparation process of the olefin polymerization catalyst is as shown in Example 1, except that 5 mmol ascorbate palmitate is replaced with 3 mmol ascorbate dipalmitate and 2 mmol ascorbate tetraisopalmitate.

[0094] Example 15

[0095] The component preparation process of the olefin polymerization catalyst is as shown in Example 1, except that 5 mmol ascorbate palmitate is replaced with 3 mmol ascorbate palmitate and 2 mmol ascorbate tetraisopalmitate.

[0096] Example 16

[0097] The component preparation process of the olefin polymerization catalyst is as shown in Example 1, except that 5 mmol ascorbate palmitate is replaced with 2 mmol ascorbate palmitate, 2 mmol ascorbate dipalmitate and 1 mmol ascorbate tetraisopalmitate.

[0098] Example 17

[0099] In a 500 mL stirred flask fully purged with nitrogen, 10 g of anhydrous magnesium chloride, 150 mL of toluene, 17 mL of epichlorohydrin, and 16 mL of tributyl phosphate were added at room temperature. The mixture was heated to 50 °C with stirring and maintained for 2 hours until the solid was completely dissolved. Then, 2.40 g of phthalic anhydride was added, and the mixture was maintained for another hour. The solution was cooled to -25 °C, and 110 mL of titanium tetrachloride was added dropwise over 1 hour. The temperature was slowly raised to 80 °C, and the solid was gradually washed away during the heating process. 2 g of ascorbate palmitate was added, and the mixture was maintained at 80 °C for 1 hour. After filtration, the solution was washed twice with 200 mL of toluene, then 120 mL of toluene and 80 mL of titanium tetrachloride were added. The temperature was further raised to 110 °C and maintained for 2 hours. The liquid was then filtered clean, and the process was repeated once more. The liquid was filtered off, and the resulting solid was washed once with 100 mL of dichloroethane and four times with hexane. After drying, the component of the olefin polymerization catalyst was obtained. The titanium content, internal electron donor content, and polymerization data of the components of this olefin polymerization catalyst are shown in Table 2.

[0100] Example 18

[0101] In a 500 mL stirred flask fully purged with nitrogen, 8 g of magnesium diethoxy and 100 mL of toluene were added to prepare a suspension. 25 mL of titanium tetrachloride was added dropwise at -15 °C. After the addition was complete, the temperature was slowly raised to 0 °C, and 50 mL of titanium tetrachloride was added dropwise. The temperature was then slowly raised to 80 °C, and 2 g of ascorbate palmitate was added. The temperature was then raised to 110 °C and held constant for 2 hours. The liquid was then filtered off, and the resulting solid was washed three times with 100 mL of titanium tetrachloride at 125 °C. The resulting solid was washed four times with 120 mL of hexane at 60 °C. The liquid was then filtered off and dried to obtain the component of the olefin polymerization catalyst.

[0102] Comparative Example 1

[0103] The preparation process of the components of the olefin polymerization catalyst is the same as in Example 1, except that ascorbate palmitate is replaced with 5 mmol of di-n-butyl phthalate (DN).

[0104] Comparative Example 2

[0105] The preparation process of the components of the olefin polymerization catalyst is the same as in Example 1, except that ascorbate palmitate is replaced with 5 mmol of 9,9-dimethoxyfluorene (FLU).

[0106] Comparative Example 3

[0107] The preparation process of the components of the olefin polymerization catalyst is the same as in Example 1, except that ascorbate palmitate is replaced with 5 mmol of acetylated tributyl citrate.

[0108] polymerization

[0109] The polymerization evaluation was performed using the components of the olefin polymerization catalysts obtained in Examples 1-18 and Comparative Examples 1-3:

[0110] After purging the 5L stainless steel reactor with nitrogen, 5mL of a 0.5mol / L triethylaluminum hexane solution, 1mL of a 0.1mol / L cyclohexylmethyldimethoxysilane hexane solution, and 10mg of the components of the prepared olefin polymerization catalyst were added. Then, 10mL of hexane was added to flush the feed line, followed by 2L (under standard conditions) of hydrogen and 2.5L of purified propylene. The reaction was prepolymerized at 25℃ for 5 minutes, then the temperature was raised to 70℃, and polymerization was carried out at this temperature for 1 hour. After the reaction was completed, the reactor was cooled and stirring was stopped, and the reaction product was discharged and dried to obtain the polymer.

[0111] Table 2

[0112]

[0113]

[0114] As can be seen from the results in Table 2, the ascorbate compounds used as internal electron donor catalysts in Examples 1-12, under the same preparation conditions, exhibited significantly higher activity than catalysts using acetyl tributyl citrate (Comparative Example 3, a biosafe additive) as the internal electron donor. Furthermore, their activity was generally higher than that of the most commonly used phthalate internal electron donor catalysts in industry (Comparative Example 1). This demonstrates that ascorbate compounds can serve as a highly efficient alternative to reproductively toxic phthalate internal electron donors. Fluorene diether catalysts, due to their high activity, are currently commonly used in the development of low-ash polyolefin products. The catalytic activity of the ascorbate compound internal electron donors in Examples 1-12 of this invention is largely comparable to or higher than that of the fluorene diether catalyst (Comparative Example 2). Therefore, the ascorbate compound internal electron donors of this invention, as a biosafe and highly active catalyst, are particularly suitable for the production of medical polyolefin products. As can be seen from the examples in groups of three (e.g., Examples 1-3, Examples 4-6, Examples 7-9, Examples 10-12), the more ester groups a compound of the same type of ascorbate has, the higher its catalytic activity. As can be seen from Examples 13-16, the catalytic activity can also be adjusted by combining ascorbate compounds with different numbers of ester groups.

[0115] This invention is not limited to the specific embodiments described above. Any changes or modifications made by those skilled in the art within the scope of this invention are covered by the patent scope of this invention.

Claims

1. A component of an olefin polymerization catalyst, characterized in that, It comprises Mg, Ti, halogen, and an internal electron donor, wherein the internal electron donor is at least one ascorbate compound selected from general formula (I), general formula (II), and general formula (III): General Formula (I) General Formula (II) General Formula (III) Among them, R 1 R 2 R 3 and R 4 Whether the two are the same or different, they are each independently selected from C1-C. 20 Hydrocarbon group, or C1-C containing at least one heteroatom selected from N, O and halogen. 20 Group; Optional, R 1 R 2 R 3 and R 4 Two or more of them bond together to form a ring.

2. The components of the olefin polymerization catalyst according to claim 1, characterized in that, R 1 R 2 R 3 and R 4 They may be the same or different, each independently selected from straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indole groups with up to 20 carbon atoms; or each independently selected from halogenated or N, O heteroatoms-substituted alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indole groups with up to 20 carbon atoms; or each independently selected from heterocyclic aryl substituents.

3. The components of the olefin polymerization catalyst according to claim 2, characterized in that, The phenylalkyl group includes benzyl.

4. The components of the olefin polymerization catalyst according to claim 1, characterized in that, R 1 R 2 R 3 and R 4 Whether the groups are the same or different, each is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 ~C 20 Straight-chain or branched alkyl or alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, furanyl, pyrroleyl, indoleyl.

5. The components of the olefin polymerization catalyst according to claim 4, characterized in that, The alkenyl group includes at least one of propenyl, butenyl, pentenyl, and hexenyl.

6. The components of the olefin polymerization catalyst according to claim 1, characterized in that, The ascorbic acid monoester compound of general formula (I) is selected from methyl ascorbate, ethyl ascorbate, n-propyl ascorbate, isopropyl ascorbate, n-butyl ascorbate, isobutyl ascorbate, tert-butyl ascorbate, n-pentyl ascorbate, isopentyl ascorbate, cyclopentyl ascorbate, n-hexyl ascorbate, cyclohexyl ascorbate, heptayl ascorbate, octyl ascorbate, nonyl ascorbate, decyl ascorbate, lauryl ascorbate, and carboxylic acid. At least one of the following: myristyl ester, palmitate ascorbate, stearate ascorbate, phenyl ester ascorbate, benzyl ester ascorbate, phenylacetic acid ester ascorbate, o-chlorophenyl ester ascorbate, m-chlorophenyl ester ascorbate, p-toluene ester ascorbate, p-methoxyphenyl ester ascorbate, p-methylphenyl ester ascorbate, crotonyl ester ascorbate, naphthyl ester ascorbate, nicotinyl ester ascorbate, monoethyl succinate ascorbate, cinnamyl ester ascorbate, thiophene ester ascorbate, and furfuryl ascorbate.

7. The components of the olefin polymerization catalyst according to claim 1, characterized in that, The ascorbic acid diester compound of general formula (II) is selected from dimethyl ascorbate, diethyl ascorbate, di-n-propyl ascorbate, diisopropyl ascorbate, di-n-butyl ascorbate, diisobutyl ascorbate, di-tert-butyl ascorbate, di-n-pentyl ascorbate, diisopentyl ascorbate, dicyclopentyl ascorbate, di-n-hexyl ascorbate, dicyclohexyl ascorbate, diheptyl ascorbate, dioctyl ascorbate, dinonyl ascorbate, didecyl ascorbate, dilauryl ascorbate, dimyristyl ascorbate, dipalmityl ascorbate, and distearate ascorbate. The following is a list of at least one of the following: ascorbic acid ester, diphenyl ascorbate, dibenzyl ascorbate, diphenylacetic acid ascorbate, di-o-chlorophenyl ascorbate, di-m-chlorophenyl ascorbate, di-p-toluene ascorbate, di-p-methoxyphenyl ascorbate, di-p-methylphenyl ascorbate, m-trimethylphenyl ascorbate, p-nitrophenyl ascorbate, p-fluorophenyl ascorbate, p-trifluoromethylphenyl ascorbate, dicrotonyl ascorbate, dinaphthyl ascorbate, dinicotinyl ascorbate, monoethyl ascorbate disuccinate, dicinnamyl ascorbate, dithiophene ascorbate, and difurfuryl ascorbate.

8. The components of the olefin polymerization catalyst according to claim 1, characterized in that, The ascorbic acid tetraester compound of general formula (III) is selected from tetramethyl ascorbate, tetraethyl ascorbate, tetra-n-propyl ascorbate, tetraisopropyl ascorbate, tetra-n-butyl ascorbate, tetraisobutyl ascorbate, tetra-tert-butyl ascorbate, tetra-n-pentyl ascorbate, tetraisopentyl ascorbate, tetracyclopentyl ascorbate, tetra-n-hexyl ascorbate, tetracyclohexyl ascorbate, tetraheptyl ascorbate, tetraoctyl ascorbate, tetranonyl ascorbate, tetradecyl ascorbate, tetralauryl ascorbate, and tetra-ascorbate. Myristyl ester, tetrapalmitate ascorbate, tetrastearate ascorbate, tetraphenyl ascorbate, tetrabenzyl ascorbate, tetraphenylacetic acid ascorbate, tetrao-chlorophenyl ascorbate, tetra-m-chlorophenyl ascorbate, tetra-toluene ascorbate, tetra-methoxyphenyl ascorbate, tetra-methylphenyl ascorbate, tetracrotyl ascorbate, tetranaphthyl ascorbate, tetranicotinamide ascorbate, monoethyl tetrasuccinate ascorbate, tetracinnamyl ascorbate, tetrathiophene ascorbate, and tetrafurfuryl ascorbate.

9. The components of the olefin polymerization catalyst according to claim 1, characterized in that, The components of the olefin polymerization catalyst include titanium compounds, magnesium compounds, and ascorbate compounds; The precursor of the magnesium compound is selected from X. n Mg(OR a ) 2-n MgCl2·mR a OH, R a 2-n MgX n At least one of the following: a mixture of MgCl2 / SiO2, MgCl2 / Al2O3, magnesium halide, and titanium alkoxide, wherein m is 0.1-6, 0≤n≤2, X is a halogen, and R a For C1-C 20 hydrocarbon group; The general formula of the titanium compound is TiX. N (OR b ) 4-N In the formula, R b For C1-C 20 The hydrocarbon group, where X is a halogen and N is 1-4.

10. The components of the olefin polymerization catalyst according to claim 9, characterized in that, The magnesium compound is an alkoxide of magnesium dihalide; or, the magnesium compound is a liquid magnesium compound; or, the magnesium compound is a derivative in which at least one halogen atom in a magnesium dihalide molecule is replaced by an alkyl group or a haloalkyl group.

11. The components of the olefin polymerization catalyst according to claim 9, characterized in that, The titanium compound includes at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and titanium alkoxyhalide.

12. The components of the olefin polymerization catalyst according to claim 11, characterized in that, The alkoxy titanium halide includes at least one of methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, and tri-n-butoxy titanium chloride.

13. The components of the olefin polymerization catalyst according to claim 9, characterized in that, The halogen is at least one of chlorine, bromine, and iodine.

14. The components of the olefin polymerization catalyst according to claim 9, characterized in that, The total number of internal electron donors and the molar ratio of the magnesium compound fed are 0.01-5.0, and the magnesium compound is calculated in terms of magnesium element.

15. The components of the olefin polymerization catalyst according to claim 1, characterized in that, When the internal electron donor is a mixture of two of the general formulas (I), (II) and (III), the molar ratio of the two internal electron donors is 20:1 to 1:

20.

16. The components of the olefin polymerization catalyst according to claim 1, characterized in that, When the internal electron donor is a mixture of three of the general formulas (I), (II), and (III), the molar ratio of any one of the general formulas (I), (II), and (III) to the total amount of the feed is ≥1 / 20.

17. An olefin polymerization catalyst comprising the components of the catalyst according to any one of claims 1-16 and an organoaluminum compound.

18. The olefin polymerization catalyst according to claim 17, characterized in that, The general formula of the organoaluminum compound is AlR c p X (3-p) , where R c It is hydrogen or C1-C 20 The hydrocarbon group, X is a halogen, and p is an integer 0 ≤ p ≤ 3.

19. The olefin polymerization catalyst according to claim 17, characterized in that, The organoaluminum compounds include at least one of trialkylaluminum compounds, alkylaluminum halides, alkylaluminum hydrides, alkylaluminum sesquichlorides, and alkylaluminoxanes.

20. The olefin polymerization catalyst according to claim 17, characterized in that, The molar ratio of titanium atoms in the organoaluminum compound to that in the catalyst is 1-1000:

1.

21. The olefin polymerization catalyst according to claim 17, characterized in that, The catalyst's raw material composition also includes an external electron donor; The external electron donor is a siloxane compound.

22. The olefin polymerization catalyst according to claim 21, characterized in that, The general formula of the siloxane compound is R' t Si(OR'') 4-t Where R' and R'' are each independently selected from C1-C 18 The hydrocarbon group, where t is an integer 0 ≤ t ≤ 3.

23. The olefin polymerization catalyst according to claim 21, characterized in that, The molar ratio of silicon in the external electron donor to titanium in the catalyst composition is 0.002-100.

24. The use of an olefin polymerization catalyst according to any one of claims 17-23 in olefin polymerization.

25. The application according to claim 24, characterized in that, The olefins include at least one of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, butadiene, vinylcyclopentene, and vinylcyclohexene. The polymerization includes homopolymerization or copolymerization; The polymerization temperature is ≤200℃ and the polymerization pressure is ≤10MPa.

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