Catalyst components for olefin polymerization and their applications

Abstract

This invention provides alkoxymagnesium particles, a catalyst component for olefin polymerization, and their applications. The alkoxymagnesium particles comprise the reaction product of the following components: 1) magnesium powder, 2) a mixed alcohol, 3) a halogenating agent, and 4) a crosslinking agent, wherein the crosslinking agent comprises a titanate compound. Using the alkoxymagnesium particles of this invention as a support, and then using a carboxylic acid ester compound a, a diether compound b, and an organosilicon compound c containing Si-H functional groups as internal electron donors, the prepared catalyst component exhibits high polymerization activity, good hydrogen regulation sensitivity, and a high polymer isotactic index during the polymerization of α-olefins.

Description

Technical Field

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

[0002] As the demand for polyolefins increases, the requirements for olefin polymerization catalysts are also becoming more stringent. Currently, the most widely used catalyst is the Ziegler-Natta catalyst supported on magnesium chloride. Chinese patents CN85100997A and CN1453298A disclose catalyst preparation methods that generally consist of a solid catalyst component composed of magnesium, titanium, halogens, and electron-donating organic compounds. However, meeting various performance requirements, such as high stereoregularity, high catalyst activity, and low ash content, makes the preparation of such a catalyst component very difficult.

[0003] The stereotactic orientation of a catalyst determines the isotactic index of the polymer, which is an important performance indicator. A higher isotactic index for polypropylene indicates greater regularity and crystallinity, leading to increased mechanical properties such as hardness, stiffness, modulus, fracture strength, and yield strength. Melting point, thermal stability, aging resistance, and radiation resistance also improve accordingly. Therefore, researchers have been conducting extensive research to improve the stereotactic orientation of catalysts. Some studies use catalysts containing two (or more) internal electron donors in combination to compensate for the shortcomings of catalysts containing only a single internal electron donor, thereby improving catalyst performance. However, the effect of combination is not a simple superposition of the properties of several electron donors. For example, polypropylene obtained using a monocarboxylic acid ester as an internal electron donor generally has low isotacticity, requiring the removal of atactic compounds. While WO03002617 discloses a catalyst composition and catalyst for olefin polymerization obtained by using a combination of monocarboxylic acid esters and dicarboxylic acid esters, the stereotactic orientation and polymerization activity of this catalyst are still not very high. CN101643519A discloses a method for preparing a catalyst component for olefin polymerization. The titanium-containing catalyst component is formed by dissolving magnesium halide in an organic epoxide compound and an organophosphorus compound to form a homogeneous solution. This solution is mixed with titanium tetrahalide or its derivatives, and a solid precipitates in the presence of polyester compounds. At least one surface modifier, at least one titanium halide or its derivative, and an electron donor compound are then loaded onto the solid precipitate. The catalyst is washed with a diluent to obtain the final product. The preparation process of this catalyst is relatively complex, involves a wide variety of raw materials, and has a long reaction process. The activity and stereospecificity of propylene polymerization need to be improved, and the hydrogen sensitivity is not ideal.

[0004] Isotactic polybutene-1 possesses excellent mechanical properties, outstanding creep resistance, low-temperature fluidity, and resistance to environmental stress cracking, as well as abrasion resistance, flexibility, and high filler capacity. Compared to other polyolefins, polybutene-1 exhibits the best resistance to stress cracking and significantly higher creep resistance than polyethylene or polypropylene. Particularly under stress not exceeding the yield point, its outstanding creep resistance remains unchanged up to 110°C. Furthermore, isotactic polybutene-1 maintains excellent mechanical properties under heated conditions; its heat resistance allows for long-term use at 80-890°C, with an upper limit of 110°C for use in hot water. Its abrasion resistance is comparable to ultra-high molecular weight polyethylene, giving it a unique advantage in hot water pipe applications.

[0005] However, due to limitations in catalyst level and polymerization process, polybutene-1 has always had low polymerization activity and insufficient stereoregularity, often requiring deashing or removal of atactic substances. Furthermore, the complex polymerization process has resulted in excessively high prices for polybutene-1 polymer products, limiting its widespread application and development.

[0006] The preparation methods of isotactic polybutene-1 generally include gas-phase methods and liquid-phase methods using hydrocarbons as solvents or butene-1 monomers as solvents. In liquid-phase polymerization, the currently disclosed processes often use butene-1 monomer itself as the solvent or reaction medium to solve the problem of product separation after polymerization. Polymerization is carried out under the combined action of titanium trichloride as the main catalyst and diethylaluminum chloride (DEAC) as the co-catalyst. In some cases, a mixture of diethylaluminum iodide and DEAC is also used, such as the method disclosed in European Patent EP187034. However, the polymerization activity of this process system is low, and the stereoregularity of the obtained polybutene-1 is not high enough. It often requires deashing or removal of atactic compounds, and the post-polymerization processing is complex, and the performance of the obtained polymer is not ideal. The polybutene-1 prepared using patent US6306996 has improved isotacticity to 95% and activity to 14000 g / gcat.4h. However, due to the high ash content of the obtained polymer, the isotacticity and polymerization activity are not ideal, and the performance of the obtained polymer is not satisfactory.

[0007] In the preparation of α-olefin polymerization catalysts, the particle morphology of alkoxymagnesium powder faithfully reflects the particle morphology of the catalyst. Preparing alkoxymagnesium supports with good particle morphology and uniform particle size, and then using these supports to develop catalyst components with high activity, high stereotacticity, and hydrogen sensitivity, is a valuable endeavor. Summary of the Invention

[0008] To address the shortcomings of existing catalysts, this invention provides alkoxymagnesium particles, an olefin polymerization catalyst component, and an olefin polymerization catalyst. The catalyst component of this invention exhibits high polymerization activity, good hydrogen regulation sensitivity, and a high polymer isotactic index during the polymerization of α-olefins.

[0009] The alkoxy magnesium particles provided by the present invention comprise the reaction product of the following components: 1) magnesium powder, 2) mixed alcohol, 3) halogenating agent and 4) crosslinking agent, wherein the crosslinking agent comprises titanate compounds.

[0010] According to an embodiment of the present invention, the structure of the titanate compound is shown in Formula I:

[0011] (R 1 O) a Ti(OR 2 ) b (OR 3 ) c X d Formula I

[0012] In Equation I, R 1 R 2 and R 3 The groups can be the same or different, selected from H and alkyl groups, especially C1-C10 alkyl groups, where X is selected from alkoxy, carboxyl, chlorine, sulfonic acid, phosphoric acid, and sulfate groups, and a, b, c, and d are independent integers from 0 to 4, and a+b+c+d=4. Preferably, the titanate ester is selected from at least one of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, tetrapentyl titanate, tetrahexyl titanate, tetraheptyl titanate, tetraisooctyl titanate, tetranonyl titanate, tetradecyl titanate, and their isomers. Preferably, it is one or more of tetraethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate.

[0013] According to an embodiment of the present invention, the weight ratio of the titanate compound to magnesium powder is (0.01-5):1, preferably (0.05-2):1.

[0014] The magnesium powder used in this invention can be of any shape, such as granular, ribbon-like, or powdered, provided that its reactivity is good. To ensure good reactivity, the magnesium powder is preferably spherical with an average particle size of less than 360 μm. Furthermore, the surface of the magnesium powder is not particularly limited, but the formation of a hydroxide or other coating on the surface will slow down the reaction. Therefore, it is desirable for the oxide film on the magnesium powder surface to be as thin as possible. According to the invention, the thickness of the magnesium powder oxide film is less than 0.5 micrometers.

[0015] The mixed alcohols used in this invention are straight-chain or branched monohydric or polyhydric alcohols, preferably C1-C. 10A mixture of alcohols. C1-C 10 Specific examples of alcohols include: methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, 2-propanol, 2-butanol, 2-pentanol, 2-hexanol, 2-heptanol, 2-octanol, 2-nonanol, 2-decanol, 2-ethylbutanol, 2-ethylhexanol, 4-methyl-2-pentanol, 3,3,5-trimethylpentanol, 4-methyl-3-heptanol, benzyl alcohol, 2-phenylethanol, 1-phenyl-1-propanol, ethylene glycol, or glycerol, etc.

[0016] According to embodiments of the present invention, the mixed alcohol is a mixture of ethanol and isooctanol. According to some preferred embodiments, in the mixed alcohol, ethanol accounts for 80-99 wt% and isooctanol accounts for 1-20 wt%. The present invention does not particularly limit the water content of the alcohol; however, to obtain good alkoxymagnesium properties, a lower water content is preferred. The water content in the alcohol is generally controlled below 1000 ppm, preferably below 200 ppm.

[0017] According to an embodiment of the present invention, the molar ratio of the mixed alcohol to magnesium is (2-50):1, preferably (2.5-18):1.

[0018] According to embodiments of the present invention, the halogenating agent is an elemental halogen and / or an inorganic halide, preferably selected from at least one of elemental iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, mercuric chloride, mercuric bromide, mercuric iodide, and alkoxymagnesium halides; more preferably selected from at least one of elemental iodine, magnesium iodide, magnesium chloride, and alkoxymagnesium halides; particularly preferably a mixture of elemental iodine and magnesium chloride. Elemental iodine or magnesium chloride can be used in the reaction in pure form or in solution form. Elemental iodine and magnesium chloride can be added to the reaction system separately, or partially or completely mixed together and added to the reaction system.

[0019] According to an embodiment of the present invention, the molar ratio of the halogenating agent to magnesium powder, based on halogen atoms, is (0.0002-0.2):1, preferably (0.0025-0.05):1. The inventors have discovered that the amount of halogen atoms added affects the final particle morphology and particle size of the alkoxymagnesium. When the amount of halogen atoms used is too small, the resulting alkoxymagnesium particles have extremely poor morphology; if the amount of halogen atoms used is too large, not only will the cost of preparing alkoxymagnesium increase, but the particle size of the alkoxymagnesium will also be very uneven, and the reaction will be difficult to control.

[0020] The order in which the reactants are added can be determined as needed. Specifically, there are no particular restrictions on the method of adding titanate compounds and halogenating agents. They can be added dissolved in ethanol, or directly added to magnesium powder and alcohol in solid or liquid form. Alternatively, the halogenating agent in alcohol solution can be added dropwise while heating the magnesium powder and alcohol solution.

[0021] All reactions in this invention are carried out in an inert gas atmosphere, such as argon or nitrogen, with nitrogen being the preferred gas in this invention.

[0022] Furthermore, for the addition of magnesium powder, mixed alcohols, halogenated substances, and inert solvents, the reactants can be added all at once initially, or they can be added in stages. Adding the raw materials in stages prevents the instantaneous generation of large amounts of hydrogen gas and the resulting droplets of alcohols or halogens. From a safety perspective, this method of addition is preferred. The number of stages can be determined based on the reactor size and the amount of each material used.

[0023] The reaction temperature of this invention can be carried out at 0°C or the reflux temperature of the reaction system. Small changes in reaction pressure will cause changes in the reflux temperature; the higher the selected reaction temperature, the faster the reaction proceeds. The reaction temperature can also be varied during the reaction, and the particle size and morphology can be altered by selecting the appropriate reaction temperature. The preferred reaction temperature of this invention is the reflux temperature of the reaction system.

[0024] The extent of the reaction is determined by observing the amount of hydrogen emitted during the reaction; the reaction time is typically 2-30 hours. According to an embodiment of the invention, the product is either dried or suspended in a dispersant.

[0025] After the reaction, the product can be washed with the alcohol and / or mixture of alcohols used to prepare magnesium alkoxy; it can also be washed with the organic solvent used in the reaction; depending on the specific circumstances, washing may be optional, and there are no particular limitations on the method and number of washing treatments.

[0026] Another object of the present invention is to provide an olefin catalyst component, the olefin polymerization catalyst component comprising the reaction products of the following components:

[0027] A) The aforementioned alkoxy magnesium particles;

[0028] B) Internal electron donor compounds, including a) organosilicon compounds containing Si-H functional groups, b) diether compounds and c) other types of internal electron donor compounds;

[0029] C) Titanium-containing halides.

[0030] According to an embodiment of the present invention, in B), a) the organosilicon compound containing Si-H functional groups is selected from organosilicon compound a1 as shown in Formula II and organosilicon compound a2 as shown in Formula III.

[0031]

[0032] In Equation II, R 1 -R 7 The same or different, is one of the following: alkyl with 1-12 carbon atoms, cycloalkyl with 3-10 carbon atoms, alkylaryl with 6-20 carbon atoms, or substituted or unsubstituted aromatic group with 6-20 carbon atoms; the degree of polymerization n is an integer from 2 to 100;

[0033]

[0034] In Formula III, R 8 It is one of the following: alkyl with 1-12 carbon atoms, cycloalkyl with 3-10 carbon atoms, alkylaryl with 6-20 carbon atoms, or substituted or unsubstituted aromatic group with 6-20 carbon atoms; the degree of polymerization n is an integer from 3 to 20;

[0035] In the olefin polymerization catalyst component according to the present invention, the organosilicon compound containing Si-H functional groups can be polymer a1 represented by formula II. Preferably, R... 1 It is an alkyl group with 1-6 carbon atoms, a cycloalkyl group with 3-6 carbon atoms, or an aromatic group with 6-20 carbon atoms, R 2 -R 7 The compound is methyl. In preferred embodiments, examples of compounds represented by Formula II include 1,1,1,3,5,7,7,7-octamethyltetrasiloxane (n=2), polymethylhydrosiloxane, polyethylhydrosiloxane, polyphenylhydrosiloxane, and polycyclohexylhydrosiloxane. The aforementioned polymethylhydrosiloxanes, also known as hydrosilicone oils, have different number-average molecular weights and viscosities due to differences in their average degree of polymerization (n value), but all possess the functions and effects described in this invention and are preferred polymers a1 in this invention. For example, polymethylhydrosiloxanes with a number-average molecular weight Mn=1700-3200 (n=29-55, viscosity 12-45 cSt, Sigma-Aldrich) and Mn≈390 (n≈6, Sigma-Aldrich) are preferred polymers a1 in this invention.

[0036] In the olefin polymerization catalyst component according to the present invention, the organosilicon compound containing Si-H functional groups can be compound a2 as shown in Formula III, without particular limitation. In Formula III, R 8Preferably, the alkyl group has 1-12 carbon atoms, for example, an alkyl group has 1-5 carbon atoms; preferably, n is an integer from 3 to 8. In a preferred case, examples of compounds represented by Formula III may be selected from tetraethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, pentamethylcyclopentasiloxane, etc.

[0037] The polymers a1 or a2 described above can be used alone or in combination. The compounds represented by formula II or III used in this invention are commercially available or can be prepared from corresponding precursor compounds through chemical reactions such as alkylation and condensation.

[0038] According to an embodiment of the present invention, in B), the molar ratio of the organosilicon compound containing Si-H functional groups in a) to the magnesium in the alkoxy magnesium particles is (0.01-5):1, preferably (0.02-2):1.

[0039] According to an embodiment of the present invention, in B), the diether compound b) is selected from 1,3-diether compounds as shown in Formula IV.

[0040]

[0041] In Equation IV, R 1 'and R 2 'Same or different, each being an alkyl group having 1-10 carbon atoms; R 4 'and R 5 'Same or different, each selected from one of the following: alkyl, cycloalkyl, substituted or unsubstituted aryl and alkylaryl groups having 1-20 carbon atoms; R 3 'and R 6 'Same or different, each being one of hydrogen and one of alkyl groups having 1-10 carbon atoms.'

[0042] In B), the diether compounds in b) such as general formula IV include, but are not limited to: 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl -1,3-Dimethoxypropane, 2,2-Dicyclopentyl-1,3-Dimethoxypropane, 2,2-Diethyl-1,3-Dimethoxypropane, 2,2-Dipropyl-1,3-Dimethoxypropane, 2,2-Diisopropyl-1,3-Dimethoxypropane, 2,2-Dibutyl-1,3-Dimethoxypropane, 2-Methyl-2-propyl-1,3-Dimethoxypropane, 2-Methyl-2-benzyl-1,3-Dimethoxypropane, 2-Methyl-2-ethyl-1,3-Dimethoxypropane, 2-Methyl-2-isopropyl-1,3-Dimethoxypropane, 2-Methyl-2-phenyl-1,3-Dimethoxypropane, 2-Methyl-2-cyclohexyl-1,3-Dimethoxypropane -Dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl- 1,3-Dimethoxypropane, 2-Pheny-2-isopropyl-1,3-dimethoxypropane, 2-Pheny-2-sec-butyl-1,3-dimethoxypropane, 2-Benzyl-2-isopropyl-1,3-dimethoxypropane, 2-Cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-Cyclopentyl-2-sec-butyl-1,3-dimethoxypropane, 2-Cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-Cyclohexyl-2-sec-butyl-1,3-dimethoxypropane, 2-Isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2-Cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 9,9-Dimethoxymethylfluorene.Preferred compounds include 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 9,9-di(methoxymethyl)fluorene, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyldimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, and 2,2-diisobutyl-1,3-dimethoxypropane. These compounds can be used alone or in combination of two or more. Most preferably, at least one of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and / or 9,9-di(methoxymethyl)fluorene is preferred.

[0043] According to an embodiment of the present invention, in B), the molar ratio of the diether compound in b) to magnesium in the alkoxy magnesium particles is (0.01-5):1, preferably (0.02-2):1.

[0044] According to embodiments of the present invention, the other types of internal electron-donating compounds in B) c) can be selected from C2 carboxylic acid esters, preferably from benzoic acid monoesters or phthalic acid esters as shown in Formula V.

[0045]

[0046] In formula V, R1 and R2 are independently selected from substituted or unsubstituted C1-C8 alkyl groups, C3-C6 alkyl groups, and C4-C6 alkyl groups. 10 cycloalkyl or C6-C 20 The aromatic group; R3-R6 are independently selected from hydrogen, halogen, C1-C4 alkyl or C1-C4 alkoxy groups, preferably, at least three of R3-R6 are hydrogens, more preferably, the carboxylic acid ester compound is selected from ethyl benzoate, propyl benzoate, butyl benzoate, amyl benzoate, hexyl benzoate, heptyl benzoate, octyl benzoate, nonyl benzoate, decyl benzoate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, phthalic acid ester, etc. Dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dinonyl phthalate, didecyl phthalate, methyl ethyl phthalate, methyl propyl phthalate, methyl butyl phthalate, methyl pentyl phthalate, ethyl propyl phthalate, ethyl butyl phthalate, ethyl pentyl phthalate, ethyl hexyl phthalate, propyl butyl phthalate, propyl pentyl phthalate, propyl hexyl phthalate, butyl pentyl phthalate, butyl hexyl phthalate, butyl pentyl phthalate, and at least one isomer of the above substances.

[0047] According to embodiments of the present invention, in B) c) other types of internal electron-donating compounds, the compounds can be selected from C2 polyol esters, and are preferably selected from diol esters of formula VI.

[0048]

[0049] In formula VI, R1-R2 may be the same or different, and each represents a substituted or unsubstituted linear C1-C1 bond. 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 or substituted or unsubstituted C 10 -C 20 Fused ring aryl group; R3-R8 may be the same or different, each being hydrogen, halogen, substituted or unsubstituted, straight-chain C1-C. 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 or substituted or unsubstituted C 10 -C 20 A fused-ring aryl group; or at least one of R3-R6 forming a ring with at least one of R7-R8.

[0050] According to embodiments of the present invention, the C2 polyol ester 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, or 2,4-pentanediol dibenzoate. It contains at least one of the following: ester, 2-methyl-1,3-pentanediol benzoic acid cinnamate, 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.

[0051] According to an embodiment of the present invention, the other types of internal electron donor compounds in B) c) can be selected from C3 cyanosuccinate compounds, as shown in Formula VII.

[0052]

[0053] In formula VII, R1' and R2' may be the same or different, and each is independently selected from hydrogen, C1-C 14 Straight-chain alkyl, C3-C 10 Branched alkyl, C3-C 10 cycloalkyl, C6-C 10 Aryl, C7-C 10 Alkyl and C7-C 10 Aryl alkyl group; R3' and R4' may be the same or different, and each is independently selected from C1-C2. 14 Straight-chain alkyl, C3-C 10 Branched alkyl, C3-C 10 cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl and C7-C 20 Aryl groups;

[0054] Preferably, R1' and R2' are each independently selected from hydrogen, C1-C8 straight-chain alkyl, and C3-C8 branched alkyl.

[0055] Preferably, R3' and R4' are each independently selected from C1-C6 straight-chain alkyl and C3-C6 branched alkyl.

[0056] The C3 cyanosuccinate compounds can be dimethyl 2-cyano-2,3-diisopropylsuccinate, diethyl 2-cyano-2,3-diisopropylsuccinate, diethyl 2-cyano-2,3-dimethylsuccinate, diethyl 2-cyano-2,3-diethylsuccinate, diethyl 2-cyano-2,3-di-n-propylsuccinate, diethyl 2-cyano-2,3-di-n-butylsuccinate, diethyl 2-cyano-2,3-di-n-pentylsuccinate, diethyl 2-cyano-2,3-diisopentylsuccinate, diethyl 2-cyano-2,3-di-n-hexylsuccinate, diethyl 2-cyano-2,3-diisohexylsuccinate, diethyl 2-cyano-2,3-diisopropylsuccinate, di-n-propyl 2-cyano- Diisopropyl 2,3-diisopropylsuccinate, di-n-butyl 2-cyano-2,3-diisopropylsuccinate, diisobutyl 2-cyano-2,3-diisopropylsuccinate, 1-methyl-4-ethyl 2-cyano-2,3-diisopropylsuccinate (R4 = methyl, R3 = ethyl), 1-ethyl-4-methyl 2-cyano-2,3-diisopropylsuccinate (R4 = ethyl, R3 = methyl), 1-n-butyl-4-ethyl 2-cyano-2,3-diisopropylsuccinate (R4 = n-butyl, R3 = ethyl), 1-ethyl-4-butyl 2-cyano-2,3-diisopropylsuccinate (R4 = ethyl, R3 = n-butyl), dimethyl 2-cyano-2,3-diisobutylsuccinate Ester, diethyl 2-cyano-2,3-diisobutylsuccinate, di-n-propyl 2-cyano-2,3-diisobutylsuccinate, diisopropyl 2-cyano-2,3-diisobutylsuccinate, di-n-butyl 2-cyano-2,3-diisobutylsuccinate, diisobutyl 2-cyano-2,3-diisobutylsuccinate, 1-methyl-4-ethyl 2-cyano-2,3-diisobutylsuccinate (R4 = methyl, R3 = ethyl), 1-ethyl-4-methyl 2-isobutyl-2,3-diisobutylsuccinate (R4 = ethyl, R3 = methyl), 1-n-butyl-4-ethyl 2-cyano-2,3-diisobutylsuccinate (R4 = n-butyl, R3 = ethyl), 2-cyano-2,3-diisobutylsuccinate 1-Ethyl-4-butyl cyanobutyl succinate (R4 = ethyl, R3 = n-butyl), dimethyl 2-cyano-2,3-disec-butylsuccinate, diethyl 2-cyano-2,3-disec-butylsuccinate, di-n-propyl 2-cyano-2,3-disec-butylsuccinate, diisopropyl 2-cyano-2,3-disec-butylsuccinate, di-n-butyl 2-cyano-2,3-disec-butylsuccinate, diisobutyl 2-cyano-2,3-disec-butylsuccinate, 1-methyl-4-ethyl 2-cyano-2,3-disec-butylsuccinate (R4 = methyl, R3 = ethyl), 1-ethyl-4-methyl 2-cyano-2,3-disec-butylsuccinate (R4 = ethyl, R3 = methyl), 2-cyano-2...3-Di-sec-butylsuccinate-1-n-butyl-4-ethyl ester (R4 = n-butyl, R3 = ethyl), 2-cyano-2,3-di-sec-butylsuccinate-1-ethyl-4-n-butyl ester (R4 = ethyl, R3 = n-butyl), dimethyl 2-cyano-2,3-dicyclopentylsuccinate, diethyl 2-cyano-2,3-dicyclopentylsuccinate, di-n-propyl 2-cyano-2,3-dicyclopentylsuccinate, diisopropyl 2-cyano-2,3-dicyclopentylsuccinate, 2-cyano Di-n-butyl 2,3-dicyclopentylsuccinate, diisobutyl 2-cyano-2,3-dicyclopentylsuccinate, 1-methyl-4-ethyl 2-cyano-2,3-dicyclopentylsuccinate (R4 = methyl, R3 = ethyl), 1-ethyl-4-methyl 2-cyano-2,3-dicyclopentylsuccinate (R4 = ethyl, R3 = methyl), 1-n-butyl-4-ethyl 2-cyano-2,3-dicyclopentylsuccinate (R4 = n-butyl, R3 = ethyl), 2-cyano -2,3-Dicyclopentylsuccinic acid-1-ethyl 4-n-butyl ester (R4 = ethyl, R3 = n-butyl), 2-cyano-2,3-dicyclohexylsuccinic acid dimethyl ester, 2-cyano-2,3-dicyclohexylsuccinic acid diethyl ester, 2-cyano-2,3-dicyclohexylsuccinic acid di-n-propyl ester, 2-cyano-2,3-dicyclohexylsuccinic acid diisopropyl ester, 2-cyano-2,3-dicyclohexylsuccinic acid di-n-butyl ester, 2-cyano-2,3-dicyclohexylsuccinic acid diisobutyl ester, 2 2-Cyano-2,3-dicyclohexylsuccinic acid-1-methyl-4-ethyl ester (R4 = methyl, R3 = ethyl), 2-cyano-2,3-dicyclohexylsuccinic acid-1-ethyl-4-methyl ester (R4 = ethyl, R3 = methyl), 2-cyano-2,3-monocyclohexylsuccinic acid-1-n-butyl-4-ethyl ester (R4 = n-butyl, R3 = ethyl), 2-cyano-2,3-dicyclohexylsuccinic acid-1-ethyl-4-n-butyl ester (R4 = ethyl, R3 = n-butyl);

[0057] Diethyl 2-cyano-2-methyl-3-ethyl succinate, diethyl 2-cyano-2-methyl-3-n-propyl succinate, diethyl 2-cyano-2-methyl-3-isopropyl succinate, diethyl 2-cyano-2-methyl-3-n-butyl succinate, diethyl 2-cyano-2-methyl-3-isobutyl succinate, diethyl 2-cyano-2-methyl-3-n-pentyl succinate, diethyl 2-cyano-2-methyl-3-isopentyl succinate, diethyl 2-cyano-2-methyl-3-cyclopentyl succinate, diethyl 2-cyano-2-methyl-3-n-hexyl succinate, diethyl 2-cyano-2-methyl-3-isohexyl succinate;

[0058] Diethyl 2-cyano-2-ethyl-3-methylsuccinate, diethyl 2-cyano-2-ethyl-3-n-propylsuccinate, diethyl 2-cyano-2-ethyl-3-isopropylsuccinate, ethyl 2-cyano-2-ethyl-3-n-butylsuccinate, diethyl 2-cyano-2-ethyl-3-isobutylsuccinate, diethyl 2-cyano-2-ethyl-3-n-pentylsuccinate, diethyl 2-cyano-2-ethyl-3-isopentylsuccinate, diethyl 2-cyano-2-ethyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-ethyl-3-n-hexylsuccinate, diethyl 2-cyano-2-ethyl-3-isohexylsuccinate;

[0059] Diethyl 2-cyano-2-n-propyl-3-methylsuccinate, diethyl 2-cyano-2-n-propyl-3-ethylsuccinate, diethyl 2-cyano-2-n-propyl-3-isopropylsuccinate, diethyl 2-cyano-2-n-propyl-3-n-butylsuccinate, diethyl 2-cyano-2-n-propyl-3-isobutylsuccinate, diethyl 2-cyano-2-n-propyl-3-n-pentylsuccinate, diethyl 2-cyano-2-n-propyl-3-isopentylsuccinate, diethyl 2-cyano-2-n-propyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-n-propyl-3-n-hexylsuccinate, diethyl 2-cyano-2-n-propyl-3-isohexylsuccinate;

[0060] Diethyl 2-cyano-2-isopropyl-3-methylsuccinate, ethyl 2-cyano-2-isopropyl-3-ethylsuccinate, diethyl 2-cyano-2-isopropyl-3-n-propylsuccinate, diethyl 2-cyano-2-isopropyl-3-n-butylsuccinate, diethyl 2-cyano-2-isopropyl-3-isobutylsuccinate, diethyl 2-cyano-2-isopropyl-3-n-pentylsuccinate, diethyl 2-cyano-2-isopropyl-3-isopentylsuccinate, diethyl 2-cyano-2-isopropyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-isopropyl-3-n-hexylsuccinate, diethyl 2-cyano-2-isopropyl-3-isohexylsuccinate;

[0061] Diethyl 2-cyano-2-n-butyl-3-methylsuccinate, diethyl 2-cyano-2-n-butyl-3-ethylsuccinate, diethyl 2-cyano-2-n-butyl-3-n-propylsuccinate, diethyl 2-cyano-2-n-butyl-3-isopropylsuccinate, diethyl 2-cyano-2-n-butyl-3-isobutylsuccinate, diethyl 2-cyano-2-n-butyl-3-n-pentylsuccinate, diethyl 2-cyano-2-n-butyl-3-isopentylsuccinate, diethyl 2-cyano-2-n-butyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-n-butyl-3-n-hexylsuccinate, diethyl 2-cyano-2-n-butyl-3-isohexylsuccinate;

[0062] Diethyl 2-cyano-2-isobutyl-3-methylsuccinate, diethyl 2-cyano-2-isobutyl-3-ethylsuccinate, monoethyl 2-yl-2-isobutyl-3-n-propylsuccinate, diethyl 2-cyano-2-isobutyl-3-isopropylsuccinate, diethyl 2-cyano-2-isobutyl-3-n-butylsuccinate, diethyl 2-cyano-2-isobutyl-3-n-pentylsuccinate, diethyl 2-cyano-2-isobutyl-3-isopentylsuccinate, diethyl 2-cyano-2-isobutyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-isobutyl-3-n-hexylsuccinate, diethyl 2-cyano-2-isobutyl-3-isohexylsuccinate;

[0063] Diethyl 2-cyano-2-n-pentyl-3-methylsuccinate, ethyl 2-cyano-2-n-pentyl-3-ethylsuccinate, diethyl 2-cyano-2-n-pentyl-3-n-propylsuccinate, diethyl 2-cyano-2-n-pentyl-3-isopropylsuccinate, diethyl 2-cyano-2-n-pentyl-3-n-butylsuccinate, diethyl 2-cyano-2-n-pentyl-3-isobutylsuccinate, diethyl 2-cyano-2-n-pentyl-3-isopentylsuccinate, diethyl 2-cyano-2-n-pentyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-n-pentyl-3-hexylsuccinate, diethyl 2-cyano-2-n-pentyl-3-isohexylsuccinate;

[0064] Diethyl 2-cyano-2-isopentyl-3-methylsuccinate, diethyl 2-cyano-2-isopentyl-3-ethylsuccinate, diethyl 2-cyano-2-isopentyl-3-n-propylsuccinate, diethyl 2-cyano-2-isopentyl-3-isopropylsuccinate, diethyl 2-cyano-2-isopentyl-3-n-butylsuccinate, diethyl 2-cyano-2-isopentyl-3-n-butylsuccinate, diethyl 2-cyano-2-isopentyl-3-n-pentylsuccinate, diethyl 2-cyano-2-isopentyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-isopentyl-3-n-hexylsuccinate, diethyl 2-cyano-2-isopentyl-3-isohexylsuccinate;

[0065] Diethyl 2-cyano-2-cyclopentyl-3-methylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-ethylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-n-propylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-isopropylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-n-butylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-n-isobutylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-n-pentylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-isopentylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-n-hexylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-isohexylsuccinate;

[0066] Diethyl 2-cyano-2-n-hexyl-3-methylsuccinate, diethyl 2-cyano-2-n-hexyl-3-ethylsuccinate, diethyl 2-cyano-2-n-hexyl-3-n-propylsuccinate, diethyl 2-cyano-2-n-hexyl-3-isopropylsuccinate, diethyl 2-cyano-2-n-hexyl-3-n-butylsuccinate, diethyl 2-cyano-2-n-hexyl-3-isobutylsuccinate, diethyl 2-cyano-2-n-hexyl-3-n-pentylsuccinate, diethyl 2-cyano-2-n-hexyl-3-isopentylsuccinate, diethyl 2-cyano-2-n-hexyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-n-hexyl-3-isohexylsuccinate;

[0067] At least one of the following: 2-cyano-2-isohexyl-3-methylsuccinate, 2-cyano-2-isohexyl-3-ethylsuccinate, 2-cyano-2-isohexyl-3-n-propylsuccinate, 2-cyano-2-isohexyl-3-isopropylsuccinate, 2-cyano-2-isohexyl-3-n-butylsuccinate, 2-cyano-2-isohexyl-3-isobutylsuccinate, 2-cyano-2-isohexyl-3-n-pentylsuccinate, 2-cyano-2-isohexyl-3-isopentylsuccinate, 2-cyano-2-isohexyl-3-cyclopentylsuccinate, and 2-cyano-2-isohexyl-3-n-hexylsuccinate;

[0068] According to an embodiment of the present invention, the other type of internal electron donor compound in c) may be selected from one or more of the above-mentioned c1, c2 and c3 compounds, but is not limited to the above-mentioned types of compounds, and the total amount of c) and the molar ratio of magnesium in the alkoxy magnesium particles is (0.01-5):1, preferably (0.02-2):1.

[0069] In B), the contact temperature of a), b) and c) is -40-200℃, preferably -20-150℃, and the reaction time is 1min-20h, preferably 5min-8h.

[0070] According to an embodiment of the present invention, the titanium-containing halide C) is as shown in Formula VIII:

[0071] TiX n (OR7) 4-n Formula VIII

[0072] In Formula VIII, X is a halogen, and R7 is a C1-C halogen. 20 The preferred hydrocarbon group is C1-C. 10 Alkyl groups, where n is an integer from 0 to 4.

[0073] According to an embodiment of the present invention, the molar ratio of the titanium-containing halide to the alkoxymagnesium particles is (0.5-100):1, preferably (1-50):1.

[0074] According to an embodiment of the present invention, the reaction temperature is -40-200℃, preferably -20-150℃, and the reaction time is 1min-20h, preferably 5min-8h.

[0075] In this invention, the catalyst component can be prepared using conventional methods for preparing olefin catalyst components in the art; preferably, the solid catalyst component of this invention is prepared by the following method. An alkoxymagnesium compound is suspended in an inert diluent to form a suspension, which is then mixed and contacted with the aforementioned titanium compound and an internal electron donor to obtain a solid dispersion system, commonly referred to as the mother liquor. The mother liquor is filtered, and the resulting solid material is suspended in a solution containing titanium tetrachloride for contact treatment, commonly referred to as titanium treatment; then, after filtration, washing, and drying, the solid component of this invention is obtained.

[0076] The inert diluent used in the formation of the mother liquor in the above method can be at least one selected from hexane, heptane, octane, decane, benzene, toluene, and xylene. The amount of each component used in the formation of the mother liquor, particularly the amount of the inert diluent, is typically 0.5-100 mol, preferably 1-50 mol. The contact temperature is typically -40 to 200°C, preferably -20 to 150°C; the contact time is typically 1 minute to 20 hours, preferably 5 minutes to 8 hours.

[0077] In the titanium treatment process described above, an inert diluent, such as at least one selected from hexane, heptane, octane, decane, benzene, toluene, and xylene, may be selectively added to the titanium tetrachloride-containing solution. The amount of each component in the titanium tetrachloride-containing solution, calculated per mole of magnesium, is 0.5-100 moles of titanium compound, preferably 1-50 moles; the amount of inert diluent is typically 0-100 moles, preferably 0-50 moles. The number of titanium treatments is 0-10 times, preferably 1-5 times.

[0078] During the titanium treatment process, the aforementioned electron donor compound may be selectively added, wherein the amount of internal electron donor is typically 0.005-10 mol, preferably 0.01-1 mol. The titanium treatment temperature is typically 0-200℃, preferably 30-150℃; the contact time is typically 1 minute-20 hours, preferably 5 minutes-6 hours.

[0079] According to the catalyst component a of the present invention, the content of titanium atoms is 1.0-8.0 wt%, preferably 1.6-6.0 wt%; the content of magnesium atoms is preferably 10-70 wt%, preferably 15-40 wt%; the content of halogen atoms is 20-86 wt%, preferably 36-80%; and the total content of internal electron donor compounds is 2-30 wt%, preferably 3-20 wt%.

[0080] Another object of the present invention is to provide a catalyst for olefin polymerization, said catalyst comprising the reaction product of the following components:

[0081] (1) The aforementioned catalyst components;

[0082] (2) Organoaluminum compounds;

[0083] (3)Optionally, external electron-donating compounds.

[0084] According to an embodiment of the present invention, the organoaluminum compound is of formula AlR' m X' 3-m The organoaluminum compound shown, wherein R' is selected from hydrogen, C1-C 20 Alkyl and C6-C 20 Any of the aryl groups; X' is a halogen, and m is an integer from 1 to 3.

[0085] According to an embodiment of the present invention, the external electron donor compound is of formula R. 4 p R 5 q Si(OR 6 ) 4-p-q The organosilicon compound shown, wherein R 4 and R 5 Independently selected from halogens, hydrogen atoms, C1-C 20 Alkyl, C3-C 20 cycloalkyl, C6-C 20 aryl and C1-C 20 Any one of the haloalkyl groups, R 6 Selected from C1-C 20 Alkyl, C3-C 20 cycloalkyl, C6-C 20 aryl and C1-C 20 Any one of the haloalkyl groups; p and q are integers from 0 to 3, and p + q < 4.

[0086] According to an embodiment of the present invention, the molar ratio of aluminum in the organoaluminum compound to titanium in the catalyst component is (5-5000):1, preferably (20-1000):1, more preferably (50-500):1; the molar ratio of aluminum in the organoaluminum compound to the external electron donor compound is (0.1-500):1, preferably (1-300):1, more preferably (3-100):1.

[0087] The present invention also provides a method for olefin polymerization, comprising contacting an olefin with the catalyst under olefin polymerization conditions. Preferably, at least one of the olefins is represented by the general formula CH2=CHR, wherein R is any one of hydrogen and C1-C6 alkyl groups.

[0088] The olefin polymerization method of the present invention can be used for homopolymerization of olefins, and can also be used for copolymerization of multiple olefins. Specific examples of α-olefins represented by the general formula CH2=CHR include ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene, and 4-methyl-1-pentene. More preferably, the olefin represented by the general formula CH2=CHR is selected from at least one of ethylene, propylene, and 1-butene.

[0089] According to an embodiment of the present invention, the olefin polymerization conditions are: temperature 0-150℃, preferably 60-130℃; time 0.1-5h, preferably 0.5-4h; pressure 0.01-10MPa, preferably 0.5-5MPa.

[0090] The beneficial effects of this invention are:

[0091] This invention uses a mixture of small amounts of halogenated substances as a halogenating agent. When titanate compounds are added during the reaction, the reaction is easier to control and the particle morphology is better maintained.

[0092] Using alkoxymagnesium particles as a support, and then employing organosilicon compounds a containing Si-H functional groups, diether compounds b, and one or more other types of compounds c as internal electron donors, the prepared catalyst component exhibits high polymerization activity and a high polymer isotactic index during the polymerization of α-olefins. The resulting catalyst exhibits high activity, good hydrogen sensitivity, and a high isotactic index. It is particularly suitable for developing high-rigidity, high-flowability, and low-ash polyolefin resins. Detailed Implementation

[0093] The present invention will be described in detail below with reference to the embodiments, but the present invention is not limited to the following embodiments.

[0094] It should be noted that the evaluation of the alkoxymagnesium particles and polyolefins prepared in the embodiments of the present invention was carried out using the following methods:

[0095] 1. The particle size and particle size distribution of magnesium dialkoxy and catalyst were measured using the Malvern Mastersizer™ 2000 hexane dispersant laser diffraction method, where SPAN = (D90-D10) / D50.

[0096] 2. The content of internal electron donors in the olefin polymerization catalyst components was determined by gas chromatography.

[0097] 3. The activity of the polymer is calculated by dividing the weight of the final polymer by the weight of the initially added catalyst components.

[0098] 4. Determination of polymer melt index: determined according to GB / T3682-2000.

[0099] 5. The isotactic index (II) of polypropylene is tested as follows: 2 grams of dry polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours. The residue is then dried to constant weight, and the isotacticity is calculated using the following formula:

[0100] Isotacticity II = Mass of extracted polymer / 2 × 100%.

[0101] 6. The isotactic index (II) of polybutene-1 is tested as follows: 3 grams of the sample is dried in a vacuum oven at 75-75°C for 60 minutes. The polybutene-1 sample is then moistened with ether in an extractor and extracted with ether by boiling for 12 hours. The residue is then dried to constant weight, and the isotacticity is calculated using the following formula:

[0102] Isotacticity II = mass of polybutene-1 after extraction / 3 × 100%.

[0103] 7. Propylene Polymerization: In a 5-liter high-pressure reactor, nitrogen gas was used to purge the mixture at 70°C for 1 hour. Then, at room temperature, 5 mL of a triethylaluminum solution in hexane (0.5 mmol / mL), 1 mL of a cyclohexylmethyldimethoxysilane (CHMMS) solution in hexane (0.10 mmol / mL), 10 mL of anhydrous hexane, and 10 mg of solid catalyst were introduced into the nitrogen gas stream. The high-pressure reactor was closed, and 4.5 L (under standard conditions) of hydrogen and 2.0 L of liquid propylene were introduced. The temperature was raised to 70°C within 10 minutes with stirring. After polymerization at 70°C for 2 hours, stirring was stopped, unpolymerized propylene monomers were removed, and the polymer was collected for testing.

[0104] 8. Butene-1 Polymerization: Use a 5L high-pressure polymerization reactor. After pressurizing and leak testing, and verifying that the reactor is airtight, start the reactor stirrer and adjust the speed to 100rpm. Heat the polymerization reactor to 70℃~75℃, use a vacuum pump to statically evacuate for at least 2 minutes, and fully purge the reactor with nitrogen at least 5 times. Then, purge the reactor with nitrogen to 0.05MPa~0.10MPa.

[0105] Under nitrogen protection, the prepared triisobutylaluminum solution and dicyclopentyldimethoxysilane solution were added to the feeder. Using a syringe containing a catalyst sample (mass m0), the mixture in the feeder was drawn up and added to the mixture. The feed valve between the polymerization reactor and the feeder was opened, and the mixture containing the catalyst was added to the reactor. The syringe was rinsed with 5 mL of hexane and added to the polymerization reactor. The feed valve and vent valve were then closed. The hydrogen valve was opened, and 0.85 L (under standard conditions) of hydrogen was added. The hydrogen valve was then closed. The liquid butene-1 feed valve was opened, and 2.3 L of liquid butene-1 was added. The feed valve was then closed. The stirring speed was adjusted to 300 rpm, and the reactor was heated using the temperature-regulating water system. Timing was started when the reactor temperature reached 70°C, and the reaction was carried out for 1 hour. The reactor temperature was maintained between 70°C and 71°C using the temperature-regulating water system.

[0106] Preparation Examples 1-9

[0107] Preparation of alkoxymagnesium particles: In a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a burette were installed. After thorough purging with nitrogen, ethanol with a water content of less than 200 ppm and a small amount of isooctanol with a water content of less than 200 ppm were added to the reactor. Iodine and magnesium chloride were added to dissolve them. Then, 32 g of magnesium powder (less than 360 μm) was added. A certain amount of titanate ester compound was added to the reaction solution to initiate the reaction. After stirring, the temperature was increased until the reflux temperature of the reaction system was reached. The reaction was continued until completion, i.e., no more hydrogen was emitted. Then, washing, separation, and drying were performed. The specific amounts of each raw material added and the results are shown in Table 1.

[0108] Comparative Examples 1-3

[0109] Preparation of alkoxymagnesium support: In a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a burette were installed. After thorough purging with nitrogen, ethanol and a small amount of isooctanol were added to the reactor, followed by the addition of elemental iodine and magnesium chloride to dissolve them. Then, magnesium powder and toluene were added. A titanate compound with a specific structure was added to the reaction solution to initiate the reaction. After stirring, the temperature was increased until the reflux temperature of the reaction system was reached, and the reaction was continued until completion, i.e., no more hydrogen gas was emitted. Then, washing, separation, and drying were performed. The specific amounts of each raw material added and the results are shown in Table 1.

[0110] Table 1 Test data of the preparation example

[0111]

[0112] Example 1

[0113] In a 100 mL reactor that has been fully purged with high-purity nitrogen, 10 g of magnesium alkoxy particles from Preparation Example 1, 50 mL of toluene, 3 mL of polymethylhydrosiloxane (n≈35), and 4.0 mL of di-n-butyl phthalate (DNBP) were added. The mixture was heated to 80 °C and held at that temperature for 2 hours to obtain suspension X1. Simultaneously, in a 300 mL reactor that has been fully purged with high-purity nitrogen, 10 mL of toluene and 90 mL of titanium tetrachloride were added. The mixture was heated to 80 °C, and then suspension X1 was added. The temperature was slowly increased to 115 °C. During the heating process, 1.0 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was added. The mixture was held at that temperature for 2 hours, and then the liquid was filtered clean. Then, a mixture of 30 ml titanium tetrachloride and 120 ml toluene was added, heated to 110°C, and held at that temperature for 1 hour. The liquid was then filtered clean. Next, a mixture of 120 ml titanium tetrachloride and 30 ml toluene was added, heated to 110°C, and stirred for 1 hour. This process was repeated twice. The liquid was then filtered off, and the resulting solid was washed four times with 150 ml of hexane at 60°C. The liquid was then filtered off and the solid powder was dried, yielding the solid catalyst component, which contained 0.056 wt% silicon atoms. Test data are shown in Table 2.

[0114] Example 2

[0115] The solid catalyst component was prepared according to the method of Example 1, except that alkoxymagnesium particles from Preparation Example 2 were added. The silicon atom content in the catalyst component was 0.052 wt%, and other test data are shown in Table 2.

[0116] Example 3

[0117] The solid catalyst component was prepared according to the method of Example 1, except that alkoxymagnesium particles from Preparation Example 3 were added. The silicon atom content in the catalyst component was 0.050 wt%, and other test data are shown in Table 2.

[0118] Example 4

[0119] The solid catalyst component was prepared according to the method of Example 1, except that alkoxymagnesium particles from Preparation Example 4 were added. The silicon atom content in the catalyst component was 0.055 wt%, and other test data are shown in Table 2.

[0120] Example 5

[0121] The solid catalyst component was prepared according to the method of Example 1, except that alkoxymagnesium particles from Preparation Example 7 were added. The silicon atom content in the catalyst component was 0.057 wt%, and other test data are shown in Table 2.

[0122] Example 6

[0123] The solid catalyst component was prepared according to the method in Example 1, except that 1.0 g of 9,9-di(methoxymethyl)fluorene was added instead of 1.0 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane. The silicon atom content in the catalyst component was 0.060 wt%. Other test data are shown in Table 2.

[0124] Example 7

[0125] The solid catalyst component was prepared according to the method in Example 1, except that 3.0 ml of diethyl phthalate (DEP) was added instead of 4.0 ml of di-n-butyl phthalate (DNBP). The silicon content in the catalyst component was 0.061 wt%. Other test data are shown in Table 2.

[0126] Example 8

[0127] The solid catalyst component was prepared according to the method in Example 1, except that diisobutyl phthalate (DIBP) was added instead of di-n-butyl phthalate (DNBP). The silicon atom content in the catalyst component was 0.053 wt%, and other test data are shown in Table 2.

[0128] Example 9

[0129] The solid catalyst component was prepared according to the method in Example 1, except that 3,5-heptanediol dibenzoate was added instead of di-n-butyl phthalate (DNBP). The silicon content in the catalyst component was 0.059 wt%, and other test data are shown in Table 2.

[0130] Example 10

[0131] The solid catalyst component was prepared according to the method of Example 1, except that 2,4-pentanediol dibenzoate was added instead of di-n-butyl phthalate (DNBP). The silicon content in the catalyst component was 0.061 wt%, and other test data are shown in Table 2.

[0132] Example 11

[0133] The solid catalyst component was prepared according to the method in Example 1, except that diethyl 2-cyano-2,3-diisopropylsuccinate was added instead of di-n-butyl phthalate (DNBP). The silicon content in the catalyst component was 0.054 wt%, and other test data are shown in Table 2.

[0134] Example 12

[0135] The solid catalyst component was prepared according to the method in Example 1, except that 3.0 ml of polymethylhydrosiloxane (n≈6) was added instead of 3.0 ml of polymethylhydrosiloxane (n≈35). The silicon atom content in the catalyst component was 0.067 wt%. Other test data are shown in Table 2.

[0136] Example 13

[0137] The solid catalyst component was prepared according to the method in Example 1, except that 3.0 ml of tetramethylcyclotetrasiloxane was added instead of 3.0 ml of polymethylhydrosiloxane (n≈35). The silicon atom content in the catalyst component was 0.071 wt%. Other test data are shown in Table 2.

[0138] Comparative Example 1

[0139] The solid catalyst component was prepared according to the method of Example 1, except that alkoxymagnesium particles from Comparative Preparation Example 1 were added. The silicon atom content in the catalyst component was 0.055 wt%, and other test data are shown in Table 2.

[0140] Comparative Example 2

[0141] The solid catalyst component was prepared according to the method of Example 1, except that alkoxy magnesium particles from Comparative Preparation Example 2 were added, but polymethylhydrosiloxane (n≈35) was not added. The test data are shown in Table 2.

[0142] Comparative Example 3

[0143] The solid catalyst component was prepared according to the method in Example 1, except that polymethylhydrosiloxane (n≈35) was not added, and during the heating process, 1.0 ml of di-n-butyl phthalate (DNBP) was added instead of 1.0 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane. The test data are shown in Table 2.

[0144] Table 2 Test data from the embodiments

[0145]

[0146] As can be seen from the data of the nine preparation examples and two comparative preparation examples in Table 1, the spherical alkoxy magnesium solid particles prepared by reacting metallic magnesium with mixed alcohols, halogenating agents and crosslinking agents provided by the present invention have uniform particle size and stable performance, and are suitable for use as a support for preparing polyolefin catalyst components.

[0147] As can be seen from the data of the 13 examples and 3 comparative examples in Table 2, the catalyst composition prepared by the present invention using organosilicon compound a containing Si-H functional groups, diether compound b, and one or more other types of internal electron donor compounds c exhibits high polymerization activity, good hydrogen regulation sensitivity, and high isotactic index when performing propylene polymerization and butene-1 polymerization. It is suitable for the development of high-performance polyolefin grades and has broad application prospects.

[0148] Although the present invention has been described above with reference to some embodiments, various modifications can be made thereto without departing from the scope of the invention, and equivalent substitutions can be made for the substances therein. The features in the various embodiments disclosed herein can be combined with each other in any manner; the lack of an exhaustive description of these combinations in this specification is merely for the purpose of saving space and resources. Therefore, the present invention is not limited to the specific embodiments disclosed herein, but rather to all technical solutions falling within the scope of the claims.

Claims

1. An olefin polymerization catalyst component comprising the reaction product of the following components: A) Alkoxymagnesium particles; the alkoxymagnesium particles comprise the reaction product of the following components: 1) magnesium powder, 2) mixed alcohol, 3) halogenating agent and 4) crosslinking agent, wherein, The crosslinking agent is a titanate compound; the weight ratio of the titanate compound to magnesium powder is (0.05-2):1; the molar ratio of the mixed alcohol to magnesium powder is (2.5-18):1; and the molar ratio of the halogenating agent to magnesium powder is (0.0025-0.05):

1. B) Internal electron donor compounds, including a) organosilicon compounds containing Si-H functional groups, b) diether compounds and c) other types of internal electron donor compounds; C) Titanium-containing halides; The organosilicon compounds containing Si-H functional groups are selected from organosilicon compounds as shown in Formula II and Formula III. Formula II In formula II, R 1 -R 7 The same or different, is one of the following: alkyl with 1-12 carbon atoms, cycloalkyl with 3-10 carbon atoms, alkylaryl with 6-20 carbon atoms, or substituted or unsubstituted aromatic group with 6-20 carbon atoms; the degree of polymerization n is an integer from 2 to 100; Formula III In Formula III, R 8 It is one of the following: alkyl with 1-12 carbon atoms, cycloalkyl with 3-10 carbon atoms, alkylaryl with 6-20 carbon atoms, or substituted or unsubstituted aromatic group with 6-20 carbon atoms; the degree of polymerization n is an integer from 3 to 20; The diether compounds are selected from 1,3-diether compounds as shown in Formula IV. Formula IV In Equation IV, R 1 'and R 2 'Same or different, each being an alkyl group having 1-10 carbon atoms; R 4 'and R 5 'Same or different, each selected from alkyl, cycloalkyl, substituted or unsubstituted aryl and alkylaryl groups having 1-20 carbon atoms; R 3 'and R 6 'Same or different, each selected from hydrogen and alkyl groups having 1-10 carbon atoms;' The other types of internal electron-donating compounds are selected from one or more of aromatic carboxylic acid esters, polyol esters, and cyanosuccinates.

2. The catalyst component according to claim 1, characterized in that, The aromatic carboxylic acid esters are selected from benzoic acid monoesters or phthalic acid esters as shown in Formula V. Formula V In formula V, R1 and R2 are independently selected from substituted or unsubstituted C1-C8 alkyl groups, C3-C6 alkyl groups, and C4-C6 alkyl groups. 10 cycloalkyl or C6-C 20 The aromatic group; R3-R6 are independently selected from hydrogen, halogen, C1-C4 alkyl or C1-C4 alkoxy.

3. The catalyst component according to claim 1, characterized in that, The polyol ester compounds are selected from the diol ester compounds shown in Formula VI. Formula VI In formula VI, R1-R2 may be the same or different, and each represents a substituted or unsubstituted linear C1-C1 bond. 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 or substituted or unsubstituted C 10 -C 20 Fused ring aryl group; R3-R8 may be the same or different, each being hydrogen, halogen, substituted or unsubstituted, straight-chain C1-C. 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 or substituted or unsubstituted C 10 -C 20 A fused aryl group; or at least one of R3-R6 forming a ring with at least one of R7-R8.

4. The catalyst component according to claim 1, characterized in that, The cyanosuccinate compounds are shown in Formula VII. Formula VII In formula VII, R1' and R2' may be the same or different, and each is independently selected from hydrogen, C1-C 14 Straight-chain alkyl, C3-C 10 Branched alkyl, C3-C 10 cycloalkyl, C6-C 10 Aryl, C7-C 10 Alkyl and C7-C 10 Aryl alkyl group; R3' and R4' may be the same or different, and each is independently selected from C1-C2. 14 Straight-chain alkyl, C3-C 10 Branched alkyl, C3-C 10 cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl and C7-C 20 Aryl group.

5. The catalyst component according to claim 1, characterized in that, The titanium-containing halide described in C) is as shown in Formula VIII: TiX n (OR7) 4-n Formula VIII In Formula VIII, X is a halogen, and R7 is a C1-C halogen. 20 The hydrocarbon group, where n is an integer from 0 to 4.

6. The catalyst component according to claim 5, characterized in that, In Equation VIII, R7 is C1-C 10 Alkyl groups.

7. The catalyst component according to any one of claims 1-6, characterized in that, The molar ratio of the Si-H functional group-containing organosilicon compound to magnesium in the alkoxy magnesium particles is (0.01-5):1; and / or the molar ratio of the diether compound to magnesium in the alkoxy magnesium particles is (0.01-5):1; and / or the total amount of the other types of internal electron donor compounds to magnesium in the alkoxy magnesium particles is (0.01-5):1; and / or the molar ratio of the titanium-containing halide to the alkoxy magnesium particles is (0.5-100):1; and / or the reaction temperature is -40-200℃, and the reaction time is 1 min-20 h.

8. The catalyst component according to claim 5, characterized in that, The molar ratio of the Si-H functional group-containing organosilicon compound to magnesium in the alkoxy magnesium particles is (0.02-2):1; and / or the molar ratio of the diether compound to magnesium in the alkoxy magnesium particles is (0.02-2):1; and / or the total amount of the other types of internal electron donor compounds to magnesium in the alkoxy magnesium particles is (0.02-2):1; and / or the molar ratio of the titanium-containing halide to the alkoxy magnesium particles is (1-50):1; and / or the reaction temperature is -20-150℃, and the reaction time is 5 min-8 h.

9. The catalyst component according to any one of claims 1-6, characterized in that, The structure of the titanate compound is shown in Formula I: (R 1 O) a Ti(OR 2 ) b (OR 3 ) c X d Formula I In Equation I, R 1 R 2 and R 3 The same or different, selected from H and alkyl, X selected from alkoxy, carboxyl, chlorine, sulfonic acid, phosphoric acid and sulfate, a, b, c and d are independent integers from 0 to 4, and a+b+c+d=4.

10. The catalyst component according to claim 9, characterized in that, In Equation I, R 1 R 2 and R 3 Same or different, selected from H and C1-C10 alkyl groups.

11. The catalyst component according to claim 9, characterized in that, The titanate compounds are selected from at least one of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, tetrapentyl titanate, tetrahexyl titanate, tetraheptyl titanate, tetraisooctyl titanate, tetranonyl titanate, tetradecyl titanate, and their isomers.

12. The catalyst component according to any one of claims 1-6, characterized in that, The mixed alcohol is a straight-chain or branched monohydric alcohol or a polyhydric alcohol.

13. The catalyst component according to claim 12, characterized in that, The mixed alcohol is C1-C 10 A mixture of alcohols.

14. The catalyst component according to claim 12, characterized in that, The mixed alcohol is a mixture of ethanol and isooctyl alcohol.

15. The catalyst component according to claim 14, characterized in that, In the mixed alcohol, ethanol accounts for 80-99 wt% and isooctyl alcohol accounts for 1-20 wt%.

16. The catalyst component according to any one of claims 1-6, characterized in that, The halogenating agent is an elemental halogen and / or an inorganic halide.

17. The catalyst component according to claim 16, characterized in that, The halogenating agent is selected from at least one of elemental iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, mercuric chloride, mercuric bromide, mercuric iodide, and alkoxymagnesium halide.

18. The catalyst component according to claim 17, characterized in that, The halogenating agent is selected from at least one of elemental iodine, magnesium iodide, magnesium chloride, and magnesium alkoxyhalides.

19. The catalyst component according to claim 18, characterized in that, The halogenating agent is a mixture of elemental iodine and magnesium chloride.

20. A catalyst for olefin polymerization, comprising a reaction product of the following components: (1) The catalyst component according to any one of claims 1-19; (2) Organoaluminum compounds; (3)Optionally, external electron donor compounds.

21. An olefin polymerization method comprising contacting an olefin with the catalyst of claim 20 under olefin polymerization conditions.

22. The olefin polymerization method according to claim 21, characterized in that, At least one of the olefins is represented by the general formula CH2=CHR, where R is hydrogen or a C1-C6 alkyl group.

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