A catalyst solid component, a method for preparing the same, and a catalyst

Abstract

This invention provides a solid catalyst component, its preparation method, and the catalyst itself. The invention uses alkoxymagnesium as the starting material, prepares an alkoxymagnesium solution using a non-toxic material system, then adds a titanium halide in the presence of a precipitation aid, and uses an electron donor compound to prepare the solid catalyst component through dissolution and precipitation. This invention can prepare polyolefin catalysts with good particle morphology and high polymerization activity.

Description

Technical Field

[0001] This invention relates to the field of catalysts, and more specifically, to solid catalyst components for CH2=CHR polymerization, methods for their preparation, and catalysts. Background Technology

[0002] Currently, countries worldwide widely utilize polymers and copolymers of lower α-olefins to meet various needs in daily life. These polymers are characterized by low manufacturing costs and wide industrial applications. The most common form of these polymers is a highly crystalline solid. During polymerization, whether through liquid-phase, gas-phase, slurry polymerization, or any other commonly used method, the morphology of both catalyst particles and polymer particles must meet specific requirements, with the morphology of the catalyst support particles playing a decisive role. Therefore, the preparation process of the main catalyst is crucial for producing polymer particles of the required shape and size.

[0003] As is well known, there are currently two main methods for preparing Ziegler-Natta catalysts using alkoxymagnesium as the starting material. Chinese patents CN 101906017A and CN 102399326A disclose methods for preparing Ziegler-Natta catalysts using alkoxymagnesium as the starting material. These methods involve first reacting metallic magnesium, alcohols, and a halogenating agent under specific conditions to prepare alkoxymagnesium support particles. Then, these alkoxymagnesium particles are brought into contact with titanium halide at a controlled temperature, and then reacted with a compound acting as an internal electron donor. After further treatment with titanium halide, a solid catalyst component is obtained. The catalyst prepared by this method has high packing density and good particle morphology, and exhibits high activity during polymerization. The resulting polymer has good stereoregularity, good particle morphology, and low fine powder content. However, during the preparation of the alkoxymagnesium support particles, some of the support particles are unsuitable for subsequent catalyst preparation due to their morphology or size and are treated as hazardous waste, increasing treatment costs and causing resource waste.

[0004] US patents US5082907, US5151399, US5229342, US5106806, US5146028, US5066737, US5124298, and US5077357 disclose various magnesium and titanium-containing catalyst precursors, some of which are prepared using the aforementioned alkoxymagnesium as a starting material. These precursors lack polymerization catalytic activity; they do not contain any effective electron donors, but they are precisely the starting materials used in the subsequent conversion into active pre-catalysts. The magnesium and titanium-containing pre-catalysts are formed either by the direct chlorination of the magnesium and titanium-containing precursors or by reacting the magnesium and titanium-containing precursors with tetravalent titanium halide, optionally a hydrocarbon, and optionally an electron donor. The resulting pre-catalyst solids are then separated from the reaction slurry (through processes such as filtration, precipitation, and crystallization), and these main catalysts are then reacted with a co-catalyst and a selectivity control agent to convert them into polymerization catalysts. US Patent 5034361 discloses a method for dissolving magnesium alkoxy compounds in an alkanol solvent by interacting the magnesium alkoxy compound with a certain acidic substance. This magnesium-containing catalyst precursor is then reacted with various titanium compounds to prepare a magnesium- and titanium-containing catalyst precursor.

[0005] When alkoxymagnesium, such as ethoxymagnesium, is used as a starting material to form a precatalyst precursor, a cutoff agent is often needed to break up the aggregated ethoxymagnesium and allow it to react with other components. As disclosed in US patents US5124298 and US5077357, the precursor is prepared using chlorobenzene as a solvent and o-cresol, which chemically breaks up aggregated ethoxymagnesium, as a cutoff agent. A small amount of o-cresol (1-3%) remains in the precursor product, which, besides being physiologically irritating, can still become a catalyst poison if not effectively filtered out during catalyst preparation. In addition to the physiologically irritating phenolic compounds such as p-cresol, 3-methoxyphenol, and 4-dimethylaminophenol described in the aforementioned patents, many methods employ borate ester solubilizers to dissolve the alkoxymagnesium, allowing the magnesium compound reaction to occur in the liquid phase. This method is complex because it requires a precipitant to precipitate the solid product, and it is costly and inefficient due to the loss of some raw materials during the dissolution process.

[0006] Therefore, it is of great significance to find a substance or system that will not irritate the catalyst preparation personnel or cause toxicity to the polymerization catalyst to promote the dissolution of alkoxymagnesium. Based on this, finding a method to utilize the solution after dissolving alkoxymagnesium to complete the final catalyst preparation can overcome the limitations imposed by the particle morphology of the alkoxymagnesium support on catalyst preparation. Summary of the Invention

[0007] The purpose of this invention is to use alkoxymagnesium, which is not limited by particle morphology, as the initial raw material, and to prepare alkoxymagnesium solution by using a non-toxic substance system. Under the condition of the presence of a precipitation aid, a transition metal titanium halide or its derivative is added, and the solution is treated with a polyol ester compound electron donor with a special structure to precipitate the solid component. Then, an internal electron donor is loaded, and finally a polyolefin catalyst with good particle morphology and high polymerization activity is prepared.

[0008] One objective of this invention is to provide a method for preparing a solid catalyst component, which uses alkoxymagnesium as the starting material and includes the following steps:

[0009] (1) Alkoxy magnesium, alcohol compounds and titanium halides are subjected to a first contact reaction in the presence of a dispersant to form a uniformly dispersed slurry;

[0010] (2) Add the solvent system of organic epoxy compound and organic phosphorus compound to the homogeneous slurry obtained in step (1) to carry out the second contact reaction and form a homogeneous solution;

[0011] (3) In the presence of a precipitation aid, titanium halide is added to the homogeneous solution obtained in step (2) and treated with an electron donor compound to carry out a third contact reaction, precipitating a solid precipitate mixture containing magnesium / titanium.

[0012] (4) The mixture obtained in step (3) is reacted with an internal electron donor compound in a fourth contact reaction to obtain a suspension;

[0013] (5) Separate the solid and liquid components of the suspension obtained in step (4), and conduct a fifth contact reaction with the titanium halide to obtain the catalyst solid component.

[0014] According to the present invention, the alkoxymagnesium described in step (1) has the structural formula Mg(OR9)2, where R9 is C1 to C2. 10 The hydrocarbon group (such as a hydrocarbon group or an aromatic group), preferably a C1 to C5 hydrocarbon group, can be any alkoxy magnesium, preferably dialkoxy magnesium, wherein each alkoxy group can be the same or different, and each alkoxy group can contain 1 to 10 carbon atoms, preferably 1 to 5, such as at least one of ethoxy magnesium, propoxy magnesium, butoxy magnesium, phenoxy magnesium, etc.

[0015] The alcohols mentioned in step (1) are C1 to C2. 10 One or more of straight-chain or branched alcohols, preferably C2-C3. 10 Straight-chain alcohols, more preferably C2 to C4 straight-chain alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, isopentanol, hexanol, heptanol, octanol, isooctanol, nonanol, decanol, etc.

[0016] The titanium halide mentioned in step (1) can be any of the various titanium compounds conventionally used in the art, preferably of the general formula Ti(OR) 10 ) m X 4－m The titanium compound shown, in the general formula, R 10 It can be an alkyl group, preferably C1 to C2. 10 The alkyl group, where X is a halogen such as Cl, Br, or I, 0 ≤ m ≤ 3, and m is an integer. Preferably, the tetravalent titanium halide is one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, alkoxy titanium trihalide, dialkoxy titanium dihalide, and trialkoxy titanium halide, preferably titanium tetrachloride.

[0017] The dispersant in step (1) can be at least one of various alkane compounds, aromatic compounds or mineral oils that do not chemically interact with alkoxy magnesium or alcohol compounds commonly used in the art. Specific examples can be one or more of alkanes, cycloalkanes, aromatics, kerosene, petrolatum oil, and white oil, preferably one or more of decane, benzene, toluene, and xylene, and more preferably toluene.

[0018] According to the present invention, in step (1), the molar ratio of the alcohol compound to magnesium alkoxy is controlled at (0.01-2):1, more preferably (0.02-0.8):1, specifically 0.01:1, 0.02:1, 0.05:1, 0.08:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 1:1, 1.5:1, 2:1, etc.; the molar ratio of the titanium halide to magnesium alkoxy is (0.45-1):1, preferably The ratio of dispersant to magnesium alkoxylate should be (0.5-0.8):1, specifically 0.45:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, etc.; the molar ratio of dispersant to magnesium alkoxylate should be controlled at (5-50):1, preferably (5-20):1, specifically 5:1, 8:1, 10:1, 13:1, 15:1, 18:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, etc.

[0019] According to the present invention, in step (1), the purpose of the first contact reaction is to allow the alkoxymagnesium, alcohol compounds, and titanium halides to react in the presence of a dispersant to form a homogeneous slurry. The present invention does not specifically limit the conditions for carrying out the first contact reaction to form a homogeneous slurry, and these conditions can be determined according to the specific alkoxymagnesium used. Preferably, the reaction conditions typically include a temperature of 10–150°C, preferably 60–120°C; and a time of 1–10 hours, preferably 2–6 hours.

[0020] According to the present invention, in step (1), the order of addition of alkoxymagnesium, alcohol compounds, titanium halides, and dispersants is not specifically limited. Preferably, the addition order may be: first, add alkoxymagnesium, then add dispersants and stir to achieve uniform dispersion, and then add titanium halides and alcohol compounds to react in contact.

[0021] According to the present invention, the organic epoxy compound mentioned in step (2) is selected from at least one of C2-C8 aliphatic monoolefins, dienes, or oxides of halogenated aliphatic olefins or dienes, glycidyl ethers, and internal ethers. Specifically, it includes at least one of ethylene oxide, propylene oxide, butane oxide, butadiene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether, and diglycidyl ether.

[0022] According to the present invention, the organophosphorus compound in step (2) is a hydrocarbon ester of phosphoric acid or phosphorous acid, or a halohydrocarbon ester of phosphoric acid or phosphorous acid, for example: at least one of trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, phenyl phosphite, etc.

[0023] According to the present invention, in step (2), relative to 1 mole of alkoxymagnesium (calculated as magnesium element), the organic epoxy compound is 0.2 to 10 moles, preferably 0.5 to 4 moles, for example 0.2 moles, 0.5 moles, 1 mole, 2 moles, 3 moles, 4 moles, 5 moles, 6 moles, 7 moles, 8 moles, 9 moles, 10 moles, etc.; the organic phosphorus compound is 0.1 to 3 moles, preferably 0.3 to 1 mole, for example 0.1 moles, 0.2 moles, 0.3 moles, 0.4 moles, 0.5 moles, 0.6 moles, 0.7 moles, 0.8 moles, 0.9 moles, 1 mole, 1.5 moles, 2 moles, 3 moles, etc.

[0024] According to the present invention, in step (2), in a preferred case, the second contact reaction conditions typically include a temperature of 10 to 150°C, preferably 50 to 140°C, and a time of 0.1 to 10 hours, preferably 0.5 to 6 hours.

[0025] According to the present invention, in step (3), the precipitation aid is selected from one of organic acids, organic acid anhydrides, ethers, ketones, or mixtures thereof. Specifically, it includes at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, dimethyl ether, diethyl ether, propyl ether, butyl ether, pentyl ether, etc., preferably phthalic anhydride.

[0026] The electron donor compound mentioned in step (3) is a diol ester compound represented by formula (I):

[0027]

[0028] In formula (I), R1 to R2 may be the same or different, and each is an independent linear chain of C1 to C2, either substituted or unsubstituted. 20 Alkyl, substituted or unsubstituted branched C3-C 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl, substituted or unsubstituted C6-C 20 Aryl, substituted or unsubstituted C7-C 20 Alkyl, substituted or unsubstituted C7-C 20 Aryl, substituted or unsubstituted C2-C 10 olefinic, substituted or unsubstituted C 10 ~C 20 Fused ring aryl group; R3 to R8 may be the same or different, each being an independent straight-chain C1 to C2 group consisting of hydrogen, halogen, substituted or unsubstituted hydrogen atoms. 20 Alkyl, substituted or unsubstituted branched C3-C 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl, substituted or unsubstituted C6-C 20 Aryl, substituted or unsubstituted C7-C 20 Alkyl, substituted or unsubstituted C7-C 20 Aryl, substituted or unsubstituted C2-C 10 olefinic, substituted or unsubstituted C 10 ~C 20 A fused-ring aryl group; or at least one of R3 to R6 forming a ring with at least one of R7 to R8.

[0029] Preferably, the electron-donating compound may be 2-ethyl-1,3-propanediol dibenzoate, 2-propyl-1,3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol dibenzoate, 1,3-butanediol dimethylbenzoate, 2-methyl-1,3-butanediol di-m-chlorobenzoate, 2,3-dimethyl-1,3-butanediol dibenzoate, 1,3-pentanediol dinepentate, 2,4-pentanediol dibenzoate, 2- At least one of methyl-1,3-pentanediol benzoate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2,4-heptanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, and 2-methyl-3,5-heptanediol dibenzoate, preferably at least one of 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, and 2,4-pentanediol dibenzoate.

[0030] According to the present invention, the titanium halide described in step (3) may be the same as or different from the titanium halide described in step (1), and may be various titanium compounds conventionally used in the art, such as those of the general formula Ti(OR). 10 ) m X 4－m The titanium compound shown, in the general formula, R 10 It can be an alkyl group, preferably C1 to C2. 10 The alkyl group, X can be a halogen, such as Cl, Br or I, 0≤m≤3, where m is an integer. Preferably, the titanium halide is one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, alkoxy titanium trihalide, dialkoxy titanium dihalide, and trialkoxy titanium halide, preferably titanium tetrachloride.

[0031] According to the present invention, in step (3), the amount of the precipitant added relative to 1 mole of alkoxymagnesium (calculated as magnesium element) can be 0.03 to 1 mole, preferably 0.05 to 0.4 moles, for example, 0.03 moles, 0.05 moles, 0.1 moles, 0.2 moles, 0.3 moles, 0.4 moles, 0.5 moles, 0.6 moles, 0.7 moles, 0.8 moles, 0.9 moles, 1 mole, etc. The amount of the electron donor compound added can be 0.005 to 1 mole, preferably 0.02 to 0.4 moles, for example, 0.005 moles, 0.01 moles, 0.05 moles, 0.1 moles, 0.2 moles, 0.3 moles, 0.4 moles, 0.5 moles, 0.6 moles, 0.7 moles, 0.8 moles, 0.9 moles, 1 mole, etc. The amount of titanium halide added can be 0.5 to 20 moles, preferably 1 to 15 moles, for example 0.5 moles, 1 mole, 2 moles, 3 moles, 4 moles, 5 moles, 6 moles, 7 moles, 8 moles, 9 moles, 10 moles, 12 moles, 15 moles, 18 moles, 20 moles, etc.

[0032] According to the present invention, the conditions for the third contact reaction in step (3) include: treating the homogeneous solution obtained in step (2) with an electron donor compound in the presence of a precipitation aid and contacting it with a titanium halide for 1 to 8 hours at a temperature of -40°C to 0°C, and then raising the temperature to 40 to 150°C; preferably, contacting the homogeneous solution obtained in step (2) with the titanium compound at a temperature of -30°C to -20°C for 1 to 5 hours, and then raising the temperature to 50 to 110°C to obtain a mixture containing a solid precipitate.

[0033] The dispersant in step (3) may be the same as or different from that in step (1). It may be at least one of various alkane compounds, aromatic compounds or mineral oils that do not chemically interact with alkoxymagnesium or alcohol compounds commonly used in the art. Specific examples may be one or more of alkanes, cycloalkanes, aromatics, kerosene, petrolatum oil, and white oil. Preferably, it may be one or more of decane, benzene, toluene, and xylene, and more preferably toluene.

[0034] Generally, depending on the needs of practical applications, especially for catalyst solid components used in propylene polymerization, at least one internal electron donor compound needs to be added during the preparation of the catalyst solid component in order to obtain a highly isotactic propylene polymer. The internal electron donor compound mentioned in step (4) of this invention can be any internal electron donor compound selected in the art, including but not limited to one or more of phthalate compounds, glycol ester compounds, diether compounds, succinate compounds, and cyanosuccinate compounds.

[0035] According to the present invention, the internal electron donor compound in step (4) may be the same as or different from the electron donor compound (I) mentioned above. The mass ratio of the total content of the internal electron donor compound to the content of the electron donor compound in the prepared catalyst solid component should be controlled at (1 to 8):1, preferably (3 to 5):1, and specifically can be 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, etc.

[0036] According to the present invention, in step (4), the conditions for the fourth contact reaction include a reaction temperature of 20 to 120°C, preferably 70 to 110°C; and a reaction time of 0.5 to 6 hours, preferably 1 to 4 hours.

[0037] According to the present invention, the titanium halide described in step (5) may be the same as or different from the titanium halide described in step (1), and each may be a variety of titanium compounds conventionally used in the art, such as those of the general formula Ti(OR). 10 ) m X 4－m The titanium compound shown, in the general formula, R 10 It can be an alkyl group, preferably C1 to C2. 10 The alkyl group, X can be a halogen, such as Cl, Br or I, 0≤m≤3, where m is an integer. Preferably, the titanium compound is one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, alkoxy titanium trihalide, dialkoxy titanium dihalide, and trialkoxy titanium halide, preferably titanium tetrachloride.

[0038] According to the present invention, there are no particular limitations on the form in which the titanium compound is used in step (5). For example, the titanium halide in step (5) can be mixed with a dispersant and reacted with the solid product after solid-liquid separation of the suspension obtained in step (4). The types of dispersants have been described in detail above and will not be repeated here.

[0039] The fifth contact reaction conditions in step (5) include a reaction temperature of 50–150°C, preferably 80–120°C; and a reaction time of 0.5–6 hours, preferably 1–4.5 hours. After the reaction is completed, the liquid in the reactants is filtered off to obtain a solid reaction product. The contact reaction is then repeated 1–3 times. After washing and drying, a titanium-containing catalyst solid component is obtained.

[0040] In step (5), the molar ratio of the alkoxymagnesium to the titanium halide can be 1:(3-40), preferably 1:(5-35), and specifically can be 1:3, 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, etc.

[0041] The solid catalyst component of this invention is suitable for use in preparing olefin polymerization catalyst systems.

[0042] The second objective of this invention is to provide the catalyst solid component obtained by the preparation method described above.

[0043] The third objective of this invention is to provide the application of the catalyst solid component obtained by the above preparation method in olefin polymerization catalyst systems.

[0044] A fourth objective of this invention is to provide a catalyst comprising a catalyst solid component obtained by the preparation method, an alkylaluminum compound, and optionally an external electron donor compound.

[0045] According to the olefin polymerization catalyst system of the present invention, the catalyst system is used for the polymerization reaction of olefins represented by the general formula CH2=CHR, wherein R is hydrogen or C6~ 20 alkyl groups,

[0046] According to a preferred embodiment of the present invention, the catalyst comprises the reaction products of the following substances:

[0047] (1) Solid component A of the catalyst;

[0048] (2) Alkyl aluminum compound B;

[0049] (3)Optionally, external electron donor compound C.

[0050] In the above-mentioned olefin polymerization catalysts, the alkylaluminum compound can be any alkylaluminum compound commonly used in the field of olefin polymerization that can be used as a co-catalyst for Ziegler-Natta type catalysts. Preferably, the alkylaluminum compound can be the compound shown in formula (II).

[0051] AlR' n' X' 3-n' (II),

[0052] In formula (II), R' represents hydrogen, C1~ 20 Alkyl or C6~ 20 The aryl group, X' is a halogen, and n' is an integer from 1 to 3. Specific examples of the alkylaluminum compound may be at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydrogen, diisobutylaluminum hydrogen, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, or diethylaluminum chloride.

[0053] In this invention, the amount of the alkylaluminum compound used can be a conventional amount in the art. Generally, the molar ratio of aluminum in the alkylaluminum compound to titanium in the solid catalyst component is (5-5000):1. Preferably, the molar ratio of aluminum in the alkylaluminum compound to titanium in the solid catalyst component is (20-1000):1. More preferably, the molar ratio of aluminum in the alkylaluminum compound to titanium in the solid catalyst component is (50-500):1.

[0054] Since only the precipitant used in the preparation process of the olefin polymerization catalyst components has been improved in the olefin polymerization catalyst of the present invention, the type and content of the external electron donor compound in the olefin polymerization catalyst of the present invention are not particularly limited. In a preferred embodiment, the molar ratio of aluminum in the alkylaluminum compound to the external electron donor compound is (0.1 to 500:1), preferably (1 to 300):1, and more preferably (3 to 100):1.

[0055] In the above-mentioned olefin polymerization catalyst, the external electron donor component can be an organosilicon compound represented by formula (III).

[0056] R1” m” R2” n” Si(OR3”) 4-m”-n” (III),

[0057] In formula (III), R1” and R2” may be the same or different, and each is independently a halogen, hydrogen, or Cl-. 20 Alkyl, C3~ 20 cycloalkyl, C6~ 20 aryl, C1~ 20One of the haloalkyl groups; R3” is C1~ 20 Alkyl, C3~ 20 cycloalkyl, C6~ 20 aryl, C1~ 20One of the haloalkyl groups; m” and n” are integers from 0 to 3, and m”+n”<4. Specific examples of the organosilicon compounds include trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxytriethylmethoxysilane, triethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butylpropyldimethoxysilane, tert-butylisopropyldimethoxysilane, tert-butyl, tert-Butylbutyldimethoxysilane, tert-Butylisobutyldimethoxysilane, tert-Butyl(sec-Butyl)dimethoxysilane, tert-Butylpentyldimethoxysilane, tert-Butylnonyldimethoxysilane, tert-Butylhexyldimethoxysilane, tert-Butylheptyldimethoxysilane, tert-Butyloctyldimethoxysilane, tert-Butyldecyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexyl-tert-Butyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane Silane oxyalkylene, cyclopentylpropyl dimethoxysilane, cyclopentyl tert-butyl dimethoxysilane, dicyclopentyl dimethoxysilane, cyclopentylcyclohexyl dimethoxysilane, bis(2-methylcyclopentyl)dimethoxysilane, diphenyl dimethoxysilane, diphenyl diethoxysilane, phenyl triethoxysilane, methyl trimethoxysilane, methyl triethoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane, propyl trimethoxysilane, isopropyl trimethoxysilane, butyl trimethoxysilane, butyl triethoxysilane, isobutyl trimethoxysilane, tert-butyl trimethoxysilane, sec-butyl trimethoxysilane, penta-butyl trimethoxysilane, cyclopentyl propyltri ... Organosilicon compounds include methyltrimethoxysilane, isopentyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, and (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane, etc. These organosilicon compounds can be used individually or in combination of two or more. More preferably, compound C, as an external electron donor, is at least one of dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, cyclohexylmethyldimethoxysilane, methyl tert-butyldimethoxysilane, and tetramethoxysilane.

[0058] The catalyst system according to the present invention is suitable for olefin polymerization reactions.

[0059] According to the olefin polymerization method of the present invention, the method includes contacting one or more olefins with the above-described catalyst system under olefin polymerization conditions, wherein at least one of the olefins is an olefin represented by the general formula CH2=CHR, wherein R is hydrogen or a C1-6 alkyl group.

[0060] The olefin polymerization method of the present invention can be used for homopolymerization of olefins, and also for copolymerization of multiple olefins. At least one of the olefins is an olefin represented by the general formula CH2=CHR, wherein R is hydrogen or a C1-6 alkyl group. Specific examples of the olefin represented by the general formula CH2=CHR include: ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 4-methyl-1-pentene. Preferably, the α-olefin CH2=CHR is one or more of ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 1-hexene. More preferably, the olefin represented by the general formula CH2=CHR is propylene.

[0061] According to the catalyst of the present invention, the components of the olefin polymerization catalyst, namely the solid catalyst component A, the organoaluminum compound B as a co-catalyst, and the compound C as an external electron donor, can be contacted before contacting the olefin monomer, a process referred to in the industry as "pre-contact" or "pre-complexation"; alternatively, components A, B, and C can be added separately to the olefin monomer before the polymerization reaction, i.e., without "pre-contact". Preferably, the reaction of the components of the olefin polymerization catalyst is carried out using the "pre-contact" method. The "pre-contact" time is 0.1 to 30 minutes, preferably 1 to 10 minutes; the "pre-contact" temperature is -20 to 80°C, preferably 10 to 50°C.

[0062] Olefin polymerization catalysts are first polymerized to a certain extent in the presence of a small amount of olefin monomers to obtain prepolymerization catalysts. These prepolymerization catalysts are then further reacted with olefin monomers to obtain olefin polymers. This technique is known in the industry as the "prepolymerization" process, which helps to improve catalyst polymerization activity and polymer bulk density. According to the olefin polymerization method of the present invention, the olefin polymerization catalyst may or may not employ a "prepolymerization" process, but a "prepolymerization" process is preferred. The "prepolymerization" ratio is 5–1000 gPP / gCat, preferably 10–500 gPP / gCat; the "prepolymerization" temperature is -20 to 80°C, preferably 10–50°C.

[0063] According to the olefin polymerization method of the present invention, the olefin polymerization conditions can be conventional conditions in the art. The amount of catalyst used can be the amount of various catalysts in the prior art.

[0064] This invention utilizes alkoxymagnesium, which is not limited by particle morphology, as the initial raw material. An alkoxymagnesium solution is prepared using a non-toxic substance system. Then, in the presence of a precipitation aid, a transition metal titanium halide or its derivative is added, and the solution is treated with a polyol ester compound electron donor with a special structure to precipitate a solid component. On this solid component, an optional internal electron donor and at least one titanium halide or its derivative are loaded to prepare a polyolefin catalyst with good particle morphology and high polymerization activity. Detailed Implementation

[0065] The embodiments given below are for illustrative purposes only and are not intended to limit the invention; that is, the invention is not limited to the embodiments described below.

[0066] Unless otherwise specified in the examples, the conditions were performed under standard conditions or as recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified were either readily available for purchase or prepared using methods disclosed in the prior art.

[0067] (I) Testing Method:

[0068] 1. Catalyst yield: Catalyst yield % = Mass of catalyst obtained / Mass of magnesium chloride corresponding to the number of moles of alkoxy magnesium used × 100%.

[0069] 2. Titanium content in the catalyst: measured using a 721 spectrophotometer.

[0070] 3. The content of internal electron donors in the olefin polymerization catalyst components was determined using a Waters 600E liquid chromatograph or an Agilent 7890 gas chromatograph.

[0071] 4. Determination of polymer melt index: determined according to GB / T3682-2000.

[0072] 5. Polymer isotacticity is determined by heptane extraction method: 2 grams of dry polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours. After drying the residue to constant weight, the ratio of the polymer weight (g) to 2 (g) is the isotacticity.

[0073] 6. Activity calculation: Catalyst activity = (mass of prepared polyolefin) / (mass of solid catalyst component) g / g.

[0074] 7. Bulk density determination: The prepared polymer powder is dropped freely from a height of 10 cm into a 100 ml container through a funnel. The weight of the polymer powder in the container is M g. The bulk density of the polymer is then M / 100 g / cm³. 3 .

[0075] (II) Catalyst component preparation and polymerization:

[0076] Example 1

[0077] Preparation of catalyst component A1:

[0078] In a reactor that has undergone repeated high-purity nitrogen replacement, 5.7 g of magnesium diethoxy, 100 ml of toluene, 1 ml of ethanol, and 2.75 ml of titanium tetrachloride were added sequentially. The mixture was stirred at 200 rpm and reacted at 80°C for 4.0 hours to obtain a stable and homogeneous magnesium-containing compound slurry. After cooling to 55°C, 4 ml of epichlorohydrin and 12.5 ml of tributyl phosphate were added, and the mixture was reacted for 1.0 hour to obtain a magnesium compound solution. Then, 0.7 g of phthalic anhydride (a precipitation aid) and 0.5 ml of 3,5-heptanediol dibenzoate (an electron donor) were added, and the mixture was stirred for 60 minutes and then cooled to room temperature.

[0079] The homogeneous solution prepared above was added to a reactor that had been fully purged with nitrogen and cooled to -25°C. 60 ml of titanium tetrachloride was added to ensure sufficient contact at low temperature. After 5 hours, the temperature was raised to 110°C, during which a solid precipitate formed. 2.7 g of diisobutyl phthalate was added, and the reaction was continued for 1 hour. After the reaction was complete, the liquid was filtered out. Then, 72 ml of toluene and 48 ml of titanium tetrachloride were added, and the mixture was contacted at 110°C for 0.5 hours. This process was repeated once more. The mixture was washed five times with 120 ml of hexane and dried to obtain titanium-containing solid catalyst component A1.

[0080] The analysis results of titanium content and internal electron donor content of catalyst solid component A1 are shown in Table 1.

[0081] Catalyst polymerization:

[0082] Polymerization evaluation: In a 5L high-pressure reactor, after complete purging with gaseous propylene, 5 mL of triethylaluminum in hexane (0.5 mmol / mL), 1 mL of cyclohexylmethyldimethoxysilane (CHMMS) in hexane (0.1 mmol / mL), 10 mL of anhydrous hexane, and 10 mg of solid catalyst were added at room temperature. The reactor was closed, and 0.18 mol of hydrogen and 1.15 kg of liquid propylene were introduced. The temperature was raised to 70°C with stirring. The polymerization reaction was carried out at 70°C for a certain time. After the reaction was completed, stirring was stopped, unpolymerized propylene monomers were removed, the polymer was collected, vacuum dried, weighed, and the catalyst activity was calculated.

[0083] The polymerization activity of the catalyst system containing solid catalyst component A1 in propylene polymerization and the performance parameters of the polymer are shown in Table 1.

[0084] Example 2

[0085] Preparation of catalyst component A2:

[0086] The preparation method of catalyst solid component A2 is the same as that of A1 in Example 1, except that 2.7g of diisobutyl phthalate is replaced with 2.7g of di-n-butyl phthalate.

[0087] The results of titanium content and internal electron donor content of catalyst solid component A2 are shown in Table 1.

[0088] Catalyst polymerization:

[0089] Polymerization was carried out using A2 according to the polymerization method of Example 1. The polymerization activity of the catalyst system containing catalyst solid component A2 in propylene polymerization and the performance parameters of the polymer are shown in Table 1.

[0090] Example 3

[0091] Preparation of catalyst component A3:

[0092] The preparation method of catalyst solid component A3 is the same as that of A1 in Example 1, except that 0.5 ml of 3,5-heptanediol dibenzoate is replaced with 0.5 ml of 2,4-pentanediol dibenzoate.

[0093] The results of titanium content and internal electron donor content of catalyst solid component A3 are shown in Table 1.

[0094] Olefin polymerization reaction:

[0095] Polymerization was carried out using A3 according to the polymerization method of Example 1. The polymerization activity of the catalyst system containing catalyst solid component A3 in propylene polymerization and the performance parameters of the polymer are shown in Table 1.

[0096] Example 4

[0097] Preparation of solid component A4 of catalyst

[0098] The preparation method of catalyst solid component A4 is the same as that of A1 in Example 1, except that 0.5 ml of 3,5-heptanediol dibenzoate is replaced with 0.7 ml of 3,5-heptanediol dibenzoate.

[0099] The results of titanium content and internal electron donor content of catalyst solid component A4 are shown in Table 1.

[0100] Olefin polymerization reaction:

[0101] Polymerization was carried out using A4 according to the polymerization method of Example 1. The polymerization activity of the catalyst system containing solid catalyst component A4 in propylene polymerization and the performance parameters of the polymer are shown in Table 1.

[0102] Example 5

[0103] Preparation of catalyst component A5:

[0104] The preparation method of catalyst solid component A5 is the same as that of A1 in Example 1, except that 0.5 ml of 3,5-heptanediol dibenzoate is replaced with 0.7 ml of 2,4-pentanediol dibenzoate.

[0105] The results of titanium content and internal electron donor content of solid component A5 are shown in Table 1.

[0106] Catalyst polymerization:

[0107] Propylene polymerization was carried out using A5 according to the polymerization method of Example 1. The polymerization activity of the catalyst system containing catalyst solid component A5 in propylene polymerization and the performance parameters of the polymer are shown in Table 2.

[0108] Example 6

[0109] Preparation of catalyst component A6:

[0110] The preparation method of catalyst solid component A6 is the same as that of A1 in Example 1, except that the internal electron donor is replaced by 2.3g of 9,9-di(methoxymethyl)fluorene.

[0111] The results of titanium content and internal electron donor content of catalyst solid component A6 are shown in Table 1.

[0112] Olefin polymerization reaction:

[0113] Propylene polymerization was carried out using A6 according to the polymerization method of Example 1. The polymerization activity of the catalyst system containing solid catalyst component A6 in propylene polymerization and the performance parameters of the polymer are shown in Table 1.

[0114] Example 7

[0115] Preparation of catalyst component A7:

[0116] The preparation method of catalyst solid component A7 is the same as that of A1 in Example 1, except that the internal electron donor is replaced by 2.3g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane.

[0117] The results of titanium content and internal electron donor content of catalyst solid component A7 are shown in Table 1.

[0118] Olefin polymerization reaction:

[0119] Propylene polymerization was carried out using A7 according to the polymerization method of Example 1. The polymerization activity of the catalyst system containing solid catalyst component A7 in propylene polymerization and the performance parameters of the polymer are shown in Table 1.

[0120] Example 8

[0121] Preparation of solid component A8 of catalyst

[0122] The preparation method of catalyst solid component A8 is the same as that of A1 in Example 1, except that the internal electron donor is replaced by 3.1g of 3,5-heptanediol dibenzoate.

[0123] The results of titanium content and internal electron donor content of solid component A8 are shown in Table 1.

[0124] Catalyst polymerization:

[0125] Propylene polymerization was carried out using A8 according to the polymerization method of Example 1. The polymerization activity of the catalyst system containing catalyst solid component A8 in propylene polymerization and the performance parameters of the polymer are shown in Table 1.

[0126] Example 9

[0127] Preparation of solid component A9 of the catalyst

[0128] The preparation method of catalyst solid component A9 is the same as that of A1 in Example 1, except that the internal electron donor is replaced by 3.1g of 2,4-pentanediol dibenzoate.

[0129] The results of titanium content and internal electron donor content of solid component A9 are shown in Table 1.

[0130] Catalyst polymerization:

[0131] Propylene polymerization was carried out using A9 according to the polymerization method of Example 1. The polymerization activity of the catalyst system containing catalyst solid component A9 in propylene polymerization and the performance parameters of the polymer are shown in Table 1.

[0132] Example 10

[0133] Preparation of solid component A10 of catalyst

[0134] The preparation method of catalyst solid component A10 is the same as that of A1 in Example 1, except that the internal electron donor is replaced with 5 mmol of diethyl 2,3-diisopropylsuccinate.

[0135] The results of titanium content and internal electron donor content of solid component A10 are shown in Table 1.

[0136] Catalyst polymerization:

[0137] Propylene polymerization was carried out using A10 according to the polymerization method of Example 1. The polymerization activity of the catalyst system containing the catalyst solid component A10 in propylene polymerization and the performance parameters of the polymer are shown in Table 1.

[0138] Example 11

[0139] Preparation of solid component A11 of catalyst

[0140] The preparation method of catalyst solid component A11 is the same as that of A1 in Example 1, except that the internal electron donor is replaced by 2g of diethyl 2-cyano-2,3-diisopropylsuccinate.

[0141] The results of titanium content and internal electron donor content of solid component A10 are shown in Table 1.

[0142] Catalyst polymerization:

[0143] Propylene polymerization was carried out using A11 according to the polymerization method of Example 1. The polymerization activity of the catalyst system containing the catalyst solid component A11 in propylene polymerization and the performance parameters of the polymer are shown in Table 1.

[0144] Example 12

[0145] Preparation of solid component A12 of catalyst

[0146] The preparation method of catalyst solid component A12 is the same as that of A1 in Example 1, except that 4 ml epichlorohydrin and 12.5 ml tributyl phosphate are replaced with 8 ml epichlorohydrin and 10 ml tributyl phosphate.

[0147] The results of titanium content and internal electron donor content of catalyst solid component Al2 are shown in Table 1.

[0148] Olefin polymerization reaction:

[0149] Polymerization was carried out using A12 according to the polymerization method of Example 1. The polymerization activity of the catalyst system containing the catalyst solid component A12 in propylene polymerization and the performance parameters of the polymer are shown in Table 1.

[0150] Example 13

[0151] Preparation of solid component A13 of catalyst

[0152] The preparation method of catalyst solid component A13 is the same as that of A1 in Example 1, except that 1 ml of ethanol is replaced with 2 ml of ethanol.

[0153] The results of titanium content and internal electron donor content of catalyst solid component A13 are shown in Table 1.

[0154] Olefin polymerization reaction:

[0155] Polymerization was carried out using A13 according to the polymerization method of Example 1. The polymerization activity of the catalyst system containing the catalyst solid component A13 in propylene polymerization and the performance parameters of the polymer are shown in Table 1.

[0156] Example 14

[0157] Preparation of solid component A14 of catalyst

[0158] The preparation method of catalyst solid component A14 is the same as that of A1 in Example 1, except that 2.75 ml of titanium tetrachloride is replaced with 3 ml of titanium tetrachloride.

[0159] The results of titanium content and internal electron donor content of catalyst solid component A14 are shown in Table 1.

[0160] Olefin polymerization reaction:

[0161] Polymerization was carried out using A14 according to the polymerization method of Example 1. The polymerization activity of the catalyst system containing the catalyst solid component A14 in propylene polymerization and the performance parameters of the polymer are shown in Table 1.

[0162] Comparative Example 1

[0163] Preparation of catalyst solid component D1

[0164] The catalyst solid component D1 was prepared according to Example 1, except that 1 ml of ethanol was not added.

[0165] The results of titanium content and internal electron donor content of catalyst solid component D1 are shown in Table 1.

[0166] Using D1, propylene polymerization was carried out according to the method of Example 1. The polymerization activity of the catalyst system prepared by the catalyst components in propylene polymerization and the performance parameters of the prepared propylene polymer are shown in Table 1.

[0167] Comparative Example 2

[0168] Preparation of solid catalyst component D2

[0169] Catalyst solid component D2 was prepared according to Example 1, except that 2.75 ml of titanium tetrachloride was replaced with 2 ml of titanium tetrachloride.

[0170] The results of titanium content and internal electron donor content of catalyst solid component D2 are shown in Table 1.

[0171] Propylene polymer was polymerized using D2 according to the method of Example 1. The polymerization activity of the catalyst system prepared by the catalyst components in propylene polymerization and the performance parameters of the prepared propylene polymer are shown in Table 1.

[0172] Comparative Example 3

[0173] Preparation of catalyst solid component D3

[0174] Catalyst solid component D3 was prepared according to Example 1, except that the reaction time in step 1 was adjusted from 4 hours to 0.5 hours.

[0175] The titanium content and internal electron donor content of the catalyst solid component D3 are shown in Table 1.

[0176] Propylene polymer was polymerized using D3 according to the method of Example 1. The polymerization activity of the catalyst system prepared by the catalyst components in propylene polymerization and the performance parameters of the prepared propylene polymer are shown in Table 1.

[0177] (III) Test Results:

[0178] Table 1

[0179]

[0180]

[0181] As can be seen from the data in Table 1, the catalyst prepared by this invention has good performance in terms of composition, activity, and polymerization properties.

[0182] Compared with Comparative Example 1 (no ethanol added in step 1), Comparative Example 2 (insufficient titanium tetrachloride in step 1), and Comparative Example 3 (insufficient reaction time in step 1), the catalyst solid components prepared in the examples have the characteristics of high yield and high activity. In the comparative examples, the absence of ethanol, insufficient titanium tetrachloride, and insufficient reaction time in step 1 all lead to insufficient dissolution in step (2), resulting in a significant reduction in the yield of the precipitated solid components and affecting the overall performance of the catalyst.

Claims

1. A method for preparing a solid component of a catalyst, comprising the following steps: (1) An alkoxymagnesium, an alcohol compound and a titanium halide are subjected to a first contact reaction in the presence of a dispersant to form a uniformly dispersed slurry, wherein the molar ratio of the titanium halide to the alkoxymagnesium is (0.45~1):

1. (2) Add the solvent system of organic epoxy compound and organic phosphorus compound to the homogeneous slurry obtained in step (1) to carry out the second contact reaction and form a homogeneous solution; (3) In the presence of a precipitation aid, titanium halide is added to the homogeneous solution obtained in step (2) and treated with an electron donor compound to carry out a third contact reaction, precipitating a magnesium / titanium solid precipitate mixture; (4) The mixture obtained in step (3) is reacted with an internal electron donor compound in a fourth contact reaction to obtain a suspension; (5) Separate the solid and liquid components of the suspension obtained in step (4), and conduct a fifth contact reaction with the titanium halide to obtain the catalyst solid component.

2. The method of claim 1, wherein In step (1): The alkoxymagnesium has the structural formula Mg(OR9)2, where R9 is C1~C9. 10 hydrocarbon groups; and / or, said alcohol compound is a linear or branched alcohol of C1-C 10 ; and / or, The titanium halide has the general formula Ti(OR 10 ) m X 4－m wherein R 10 is an alkyl group, X is a halogen, 0 < m < 3, m is an integer; and / or, The dispersant is at least one of alkane compounds, aromatic hydrocarbon compounds, or mineral oils that do not chemically interact with alkoxymagnesium or alcohol compounds.

3. The preparation method according to claim 2, characterized in that: The alkoxymagnesium is at least one selected from ethoxymagnesium, propoxymagnesium, butoxymagnesium, and phenoxymagnesium; and / or, The titanium halide is at least one selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium alkoxytrihalide, titanium dialkoxydihalide, and titanium trialkoxyhalide; and / or, The dispersant is at least one of alkanes, cycloalkanes, aromatic hydrocarbons, kerosene, petrolatum oil, and white oil.

4. The preparation method according to claim 3, characterized in that: The dispersant is at least one of decane, benzene, toluene, and xylene.

5. The method of claim 1, wherein In step (1): The molar ratio of the alcohol compound to magnesium alkoxy is (0.01~2):1; and / or, The molar ratio of the titanium halide to magnesium alkoxy is (0.5~0.8):1; and / or, The molar ratio of the dispersant to alkoxymagnesium is (5~50):1; and / or, The first contact reaction conditions include a temperature of 10~150℃ and a time of 1~10 hours.

6. The preparation method according to claim 5, characterized in that: The molar ratio of the alcohol compound to magnesium alkoxy is (0.02~0.8):1; and / or, The molar ratio of the dispersant to alkoxymagnesium is (5~20):1; and / or, The first contact reaction conditions include a temperature of 60~120℃ and a time of 2~6 hours.

7. The method of claim 1, wherein In step (2): The organic epoxy compound is selected from at least one of C2-C8 aliphatic monoolefins, dienes, or oxides of halogenated aliphatic olefins or dienes, glycidyl ethers, and internal ethers; and / or, The organophosphorus compound is a hydrocarbon ester of orthophosphoric acid or phosphorous acid, or a halohydrophosphoric acid or phosphorous acid.

8. The preparation method according to claim 7, characterized in that: The organic epoxy compound is at least one of ethylene oxide, propylene oxide, butane oxide, butadiene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether, and diglycidyl ether; and / or, The organophosphorus compound is at least one of trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and benzoyl phosphite.

9. The method of claim 1, wherein In step (2): Relative to 1 mole of alkoxymagnesium (based on elemental magnesium), the organic epoxy compound is 0.2–10 moles; the organophosphorus compound is 0.1–3 moles; and / or, The second contact reaction conditions include a temperature of 10~150℃ and a time of 0.1~10 hours.

10. The preparation method according to claim 9, characterized in that: Relative to 1 mole of alkoxymagnesium (based on elemental magnesium), the organic epoxy compound is 0.5–4 moles; the organophosphorus compound is 0.3–1 mole; and / or, The second contact reaction conditions include a temperature of 50~140℃ and a time of 0.5~6 hours.

11. The method of claim 1, wherein In step (3): The precipitation aid is selected from at least one of organic acids, organic acid anhydrides, ethers, and ketones; and / or, The electron-donating compound is a diol ester compound of formula (I): （I）， In formula (I), R1~R2 may be the same or different, and each is an independent linear chain of C1~C1 with or without substitution. 20 Alkyl, substituted or unsubstituted branched C3~C 20 Alkyl, substituted or unsubstituted C3~C 20 Cycloalkyl, substituted or unsubstituted C6~C 20 aryl, substituted or unsubstituted C7~C 20 Alkyl, substituted or unsubstituted C7~C 20 Aryl, substituted or unsubstituted C2~C 10 olefinic, substituted or unsubstituted C 10 ~C 20 Fused ring aryl; R3~R8 may be the same or different, each being an independent straight-chain C1~C1 with hydrogen, halogen, substituted or unsubstituted hydrogen. 20 Alkyl, substituted or unsubstituted branched C3~C 20 Alkyl, substituted or unsubstituted C3~C 20 Cycloalkyl, substituted or unsubstituted C6~C 20 aryl, substituted or unsubstituted C7~C 20 Alkyl, substituted or unsubstituted C7~C 20 Aryl, substituted or unsubstituted C2~C 10 olefinic, substituted or unsubstituted C 10 ~C 20 A fused-ring aryl group; or at least one of R3 to R6 forming a ring with at least one of R7 to R8.

12. The preparation method according to claim 11, characterized in that: The precipitation aid is at least one selected from acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, dimethyl ether, diethyl ether, propyl ether, butyl ether, and pentyl ether; and / or, The electron-donating compound is at least one selected from 2-ethyl-1,3-propanediol dibenzoate, 2-propyl-1,3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol dibenzoate, 1,3-butanediol dimethylbenzoate, 2-methyl-1,3-butanediol di-m-chlorobenzoate, 2,3-dimethyl-1,3-butanediol dibenzoate, 1,3-pentanediol dinepentyl ester, 2,4-pentanediol dibenzoate, 2-methyl-1,3-pentanediol cinnamic acid ester, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2,4-heptanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, and 2-methyl-3,5-heptanediol dibenzoate.

13. The method of claim 1, wherein In step (3): The co-precipitant is 0.03 to 1 mol relative to 1 mole of alkoxymagnesium (based on elemental magnesium); the electron donor compound is 0.005 to 1 mol; the titanium halide is 0.5 to 20 mol; and / or, The third contact reaction conditions include contacting at a temperature of -40°C to 0°C for 1 to 8 hours, followed by heating to 40 to 150°C.

14. The preparation method according to claim 13, characterized in that: The amount of the precipitation aid relative to 1 mole of alkoxymagnesium (based on elemental magnesium) is 0.05 to 0.4 moles; the amount of the electron donor compound is 0.02 to 0.4 moles; the amount of the titanium halide is 1 to 15 moles; and / or, The third contact reaction conditions include contacting at -30°C to -20°C for 1 to 5 hours, followed by heating to 50 to 110°C.

15. The method of claim 1, wherein In step (4): The internal electron-donating compound is selected from at least one of phthalate compounds, glycol ester compounds, diether compounds, succinate compounds, and cyanosuccinate compounds; and / or, The mass ratio of the internal electron donor compound to the electron donor compound is (1~8):1; and / or, The fourth contact reaction conditions include a reaction temperature of 20~120℃ and a reaction time of 0.5~6 hours.

16. The preparation method according to claim 15, characterized in that: The mass ratio of the internal electron donor compound to the electron donor compound is (3~5):1; and / or, The fourth contact reaction conditions include a reaction temperature of 70~110℃ and a reaction time of 1~4 hours.

17. The method of claim 1, wherein In step (5): The molar ratio of the alkoxymagnesium to the titanium halide is 1:(3~40); and / or, The fifth contact reaction conditions include a reaction temperature of 50~150℃ and a reaction time of 0.5~6 hours.

18. The preparation method according to claim 17, characterized in that: The molar ratio of the alkoxymagnesium to the titanium halide is 1:(5~35); and / or, The fifth contact reaction conditions include a reaction temperature of 80~120℃ and a reaction time of 1~4.5 hours.

19. The catalyst solid component obtained by the preparation method according to any one of claims 1 to 18.

20. The application of the catalyst solid component obtained by the preparation method according to any one of claims 1 to 18 in an olefin polymerization catalyst system.

21. A catalyst comprising a catalyst solid component obtained by any one of the preparation methods of claims 1 to 18, an alkylaluminum compound, and optionally an external electron donor compound.

22. The catalyst according to claim 21, characterized in that: The alkylaluminum compound is the compound represented by formula (II). AlR' n' X' 3-n' (II), In formula (II), R' represents hydrogen, C1~ 20 Alkyl or C6~ 20 aryl, X' is a halogen, n' is an integer from 1 to 3; and / or, The external electron donor compound is an organosilicon compound represented by formula (III). R1' m'' R2' n'' Si(OR3' 4-m''- n'' (III), In equation (III), R1'' and R2'' may be the same or different, and each is independently a halogen, hydrogen, or Cl-. 20 Alkyl, C3~ 20 cycloalkyl, C6~ 20 Aryl, C1~ 20 One of the haloalkyl groups; R3'' is C1~ 20 Alkyl, C3~ 20 cycloalkyl, C6~ 20 Aryl, C1~ 20 One of the haloalkyl groups; m'' and n'' are integers from 0 to 3, and m'' + n'' < 4.

23. The catalyst according to claim 21, characterized in that: The molar ratio of aluminum to titanium in the alkylaluminum compound and the solid catalyst component is (5~5000):1; and / or, The molar ratio of aluminum to the external electron donor compound in the alkylaluminum compound is (0.1~500:1).

24. The catalyst according to claim 23, characterized in that: The molar ratio of aluminum to titanium in the alkylaluminum compound and the solid catalyst component is (20~1000):1; and / or, The molar ratio of aluminum to the external electron donor compound in the alkylaluminum compound is (1~300):1.

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