Olefin polymerization catalyst

Abstract

The invention discloses a catalyst component for olefin polymerization and a catalyst containing the catalyst component. The catalyst component comprises Mg, Ti, halogen and a substituted maltol derivative internal electron donor, wherein the substituted maltol derivative internal electron donor is a substituted maltol ether internal electron donor and has a substituted maltol ether structure as shown in a formula I, and in the formula I, R1 and R2 are the same or different and are respectively and independently selected from H, halogen and C1-C20 alkyl. The invention provides a catalyst component taking a substituted maltol derivative as an internal electron donor, a preferred internal electron donor is a substituted maltol ester compound, each oxygen atom of the internal electron donor contained in the catalyst component is special in position on a carbon skeleton, the coordination ability is stronger, and the catalytic activity is higher. And oxygen-containing functional groups can participate in the formation of an active center.

Description

Technical Field

[0001] This invention relates to a solid catalyst component for olefin polymerization, a catalyst containing the same, and its applications, belonging to the field of polyolefin catalysts. Background Technology

[0002] Currently, Ziegler-Natta catalysts (ZN catalysts) still dominate the production of polyolefins. Most ZN catalyst development focuses on developing highly active and stereoregularly oriented catalysts and improving their copolymerization capabilities. Traditional ZN catalysts (transition metal compounds such as titanium chemically bonded to a magnesium support) offer high catalytic efficiency, produce polymers with good overall performance, and are low-cost. Therefore, the vast majority of catalysts used in polypropylene production worldwide are still based on ZN catalytic systems, characterized by high activity, high stereoregularity, long lifespan, and customizable product structures. The development of ZN catalysts shows that, as early as the advent of the first generation of catalysts, it was discovered that adding a third component (mostly an electron donor, also known as a Lewis base; those added during catalyst preparation are called internal electron donors, while those added during polymerization are called external electron donors) significantly impacts olefin polymerization behavior and polymer properties. Changing the internal electron donor in the catalyst can maximally alter the properties of the catalyst's active center, thereby maximizing the change in catalyst performance. Therefore, the development of novel electron donors has always been a hot topic in ZN polypropylene catalyst research and development.

[0003] The high-performance internal electron donor compounds with distinctive features in the prior art mainly include: (1) fatty acid esters and aromatic esters, mainly phthalate esters; (2) diethers (e.g., compounds disclosed in EP0361493 and EP0728724); (3) succinates (e.g., compounds disclosed in WO9856834, WO0063261 and WO03022894); (4) glycol esters (e.g., compounds disclosed in WO9856834, WO0063261 and WO03022894); and (5) compounds with other functional groups (compounds disclosed in CN1105671, CN1242780 and US20060128558), etc. However, in practical applications, the above-mentioned compounds all have certain problems as internal electron donors for olefin polymerization catalysts. Although catalysts using 1,3-diether compounds as internal electron donors have high activity and good hydrogen-modulated sensitivity, the relative molecular mass distribution of the synthesized PP is narrow, which is not conducive to the development of different grades of PP. Succinate compounds as internal electron donors have the advantage of producing PP with a wider relative molecular mass distribution, but the stereoregularity of PP and the hydrogen-modulated sensitivity of the catalyst need to be improved. The activity of glycol ester catalytic systems is generally not as ideal as that of diether systems.

[0004] Currently, phthalate compounds are the most widely used internal electron donors in polyolefin industry. Catalysts prepared from phthalates exhibit moderate activity, good stereoselectivity, and low cost. However, as commonly used plasticizers, phthalates pose significant risks to human reproductive health and the environment, creating a substantial demand for alternatives. The use of most phthalate compounds has already been restricted. Therefore, developing novel electron donors with excellent activity, good stereoselectivity, superior overall performance, and low cost to replace the widely used phthalate electron donor compounds and applying them to the preparation of highly efficient Ziegler-Natta catalysts has been a common research goal in the field of polyolefin catalysts in recent years. Summary of the Invention

[0005] To address the aforementioned problems, the present invention aims to provide a catalyst component, catalyst, and its application for olefin polymerization. This catalyst component and catalyst exhibit high catalytic activity, generally exceeding that of commonly used phthalate and diether internal electron-donating catalysts in industry. Furthermore, the polymer obtained from the catalytic polymerization has regular particle size, high packing density, and high isotacticity.

[0006] To achieve the above objectives, the present invention provides a catalyst component for olefin polymerization, the catalyst component comprising: Mg, Ti, halogen, and a substituted maltol derivative internal electron donor; wherein the substituted maltol derivative internal electron donor is a substituted maltol ether internal electron donor having the substituted maltol ether structure shown in Formula I:

[0007] In formula I, R 1 and R 2 Whether the elements are the same or different, they are each independently selected from H, halogens, and C1-C. 20 The hydrocarbon group; preferably, R 1 and R 2 Each contains heteroatoms selected from one or more combinations of N, O, S, P, Si, and halogens.

[0008] According to a specific embodiment of the present invention, preferably, in formula I, R 1 and R 2Each of the following substituents, independently selected from H, halogens, and up to 20 carbon atoms, includes: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indene, benzyl, haloalkyl, heteroatom-containing alkyl, halocycloalkyl, heteroatom-containing cycloalkyl, halophenyl, heteroatom-containing phenyl, haloalkylphenyl, heteroatom-containing alkylphenyl, halophenylalkyl, heteroatom-containing phenylalkyl, haloindenyl, heteroatom-containing indene, halobenzyl, heteroatom-containing benzyl, heterocyclic aryl substituents; wherein the heteroatom includes one or more combinations of N, O, S, P, and Si.

[0009] According to a specific embodiment of the present invention, preferably, in formula I, R 1 and R 2 Each is independently selected from H, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20 The following substituents with 20 or fewer carbon atoms, whether linear or branched alkyl groups: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, benzyl and its derivatives, phenethyl and its derivatives, furanyl, pyrroleyl, thiophenyl, indene; more preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

[0010] According to a specific embodiment of the present invention, preferably, the electron donor in the substituted maltol ether class includes methyl maltol methyl ether, methyl maltol ethyl ether, methyl maltol n-propyl ether, methyl maltol n-butyl ether, methyl maltol n-pentyl ether, methyl maltol n-hexyl ether, methyl maltol cyclohexyl ether, methyl maltol n-heptyl ether, methyl maltol n-octyl ether, methyl maltol n-nonyl ether, methyl maltol n-decyl ether, methyl maltol dodecyl ether, methyl maltol tetradecyl ether, methyl maltol hexadecyl ether, methyl maltol octadecyl ether, methyl maltol phenyl ether, methyl maltol benzyl ether, methyl maltol m-chloroanisole, methyl maltol o-chloroanisole, methyl maltol p-chloroanisole, methyl maltol p-methoxyanisole, methyl maltol p-methylanisole, methyl maltol p-nitroanisole, methyl maltol (α-furanyl) ether, and methyl maltol (α-thiophenyl) methyl ether. The following are one or more combinations of methyl maltol propenyl ether, ethyl maltol methyl ether, ethyl maltol ethyl ether, ethyl maltol n-propyl ether, ethyl maltol n-butyl ether, ethyl maltol n-pentyl ether, ethyl maltol n-hexyl ether, ethyl maltol n-heptyl ether, ethyl maltol n-octyl ether, ethyl maltol n-nonyl ether, ethyl maltol n-decyl ether, ethyl maltol dodecyl ether, ethyl maltol tetradecyl ether, ethyl maltol hexadecyl ether, ethyl maltol octadecyl ether, ethyl maltol phenyl ether, ethyl maltol benzyl ether, ethyl maltol m-chloroanisole, ethyl maltol o-chloroanisole, ethyl maltol p-chloroanisole, ethyl maltol p-methoxyanisole, ethyl maltol p-methylanisole, ethyl maltol p-nitroanisole, ethyl maltol (α-furanyl) ether, ethyl maltol (α-thiophenyl) methyl ether, and ethyl maltol propenyl ether.

[0011] According to a specific embodiment of the present invention, preferably, the internal electron donor of the substituted maltol derivative is an internal electron donor of a substituted maltol ester, which has the substituted maltol ester structure shown in Formula II:

[0012]

[0013] In Equation II, R 3 and R 4 Whether the elements are the same or different, they are each independently selected from H, halogens, and C1-C. 20 The hydrocarbon group; preferably, R 3 and R 4 Each contains heteroatoms selected from one or more combinations of N, O, S, P, Si, and halogens.

[0014] According to a specific embodiment of the present invention, preferably, in formula II, R 3 and R 4Each of the following substituents, independently selected from H, halogens, and up to 20 carbon atoms, includes: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indene, benzyl, haloalkyl, heteroatom-containing alkyl, halocycloalkyl, heteroatom-containing cycloalkyl, halophenyl, heteroatom-containing phenyl, haloalkylphenyl, heteroatom-containing alkylphenyl, halophenylalkyl, heteroatom-containing phenylalkyl, haloindenyl, heteroatom-containing indene, halobenzyl, heteroatom-containing benzyl, heterocyclic aryl substituents; wherein the heteroatom includes one or more combinations of N, O, S, P, and Si.

[0015] According to a specific embodiment of the present invention, preferably, in formula II, R 3 and R 4 Each is independently selected from H, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20 The following substituents with 20 or fewer carbon atoms, whether linear or branched alkyl groups: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, benzyl and its derivatives, phenethyl and its derivatives, furanyl, pyrroleyl, thiophenyl, indene; more preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

[0016] According to a specific embodiment of the present invention, preferably, the electron donor in the substituted maltol ester class includes methyl maltol acetate, methyl maltol propionate, methyl maltol butyrate, methyl maltol isobutyrate, methyl maltol valerate, methyl maltol isovalerate, methyl maltol hexanoate, methyl maltol heptanoate, methyl maltol cyclohexanoate, methyl maltol octanoate, methyl maltol nonanoate, methyl maltol decanoate, methyl maltol laurate, methyl maltol myristate, methyl maltol palmitate, methyl maltol stearate, methyl maltol benzoate, methyl maltol m-chlorobenzoate, methyl maltol o-chlorobenzoate, methyl maltol p-chlorobenzoate, methyl maltol p-methoxybenzoate, methyl maltol p-methylbenzoate, and methyl maltol p-nitrobenzoate. The following are one or more combinations of methyl maltol benzoate, ethyl maltol acetate, ethyl maltol propionate, ethyl maltol butyrate, ethyl maltol isobutyrate, ethyl maltol valerate, ethyl maltol isovalerate, ethyl maltol hexanoate, ethyl maltol heptanoate, ethyl maltol cyclohexanoate, ethyl maltol octanoate, ethyl maltol nonanoate, ethyl maltol decanoate, ethyl maltol laurate, ethyl maltol myristate, ethyl maltol palmitate, ethyl maltol stearate, ethyl maltol benzoate, ethyl maltol m-chlorobenzoate, ethyl maltol o-chlorobenzoate, ethyl maltol p-chlorobenzoate, ethyl maltol p-methoxybenzoate, ethyl maltol p-methylbenzoate, and ethyl maltol p-nitrobenzoate.

[0017] According to specific embodiments of the present invention, preferably, the molar ratio of the substituted maltol ether of Formula I to the substituted maltol ester of Formula II is ≥1:9; preferably, the molar ratio of the substituted maltol ether of Formula I to the substituted maltol ester of Formula II is ≥3:7; the molar ratio of the substituted maltol ether of Formula I to the substituted maltol ester of Formula II is ≥5:5; the molar ratio of the substituted maltol ether of Formula I to the substituted maltol ester of Formula II is ≥7:3; the molar ratio of the substituted maltol ether of Formula I to the substituted maltol ester of Formula II is ≥9:1.

[0018] The substituted maltol ethers shown in Formula I can be synthesized by methods including but not limited to the following reaction formula 1: substituted maltol reacts with alcohols or haloalkanes in one step to obtain substituted maltol ethers;

[0019] Reaction 1:

[0020]

[0021] The substituted maltol esters shown in Formula II can be synthesized by methods including but not limited to the following reaction formula 2: substituted maltol reacts with acyl chloride in one step to obtain substituted maltol esters;

[0022] Reaction 2:

[0023]

[0024] According to a specific embodiment of the present invention, preferably, the catalyst component comprises a titanium compound, a magnesium compound, and an internal electron donor as shown in Formula I and / or Formula II; the precursor of the magnesium compound is selected from X. n Mg(OR a ) 2-n MgCl2·mR a OH, R a 2-n MgX n One or more combinations of MgCl2 / SiO2, MgCl2 / Al2O3, magnesium halides, and titanium alkoxides, wherein m is 0.1-6, 0≤n≤2, X is a halogen, and R a For C1-C 20 The hydrocarbon group; the general formula of the titanium compound is TiX. N (OR b ) 4-N , where R b For C1-C 20 The hydrocarbon group, where X is a halogen and N is 1-4.

[0025] According to a specific embodiment of the present invention, preferably, the magnesium compound is an alkoxide of magnesium dihalide; or, the magnesium compound is a liquid magnesium compound (a magnesium compound dissolved in a liquid); or, the magnesium compound is a derivative in which at least one halogen atom in a magnesium dihalide molecule is replaced by an alkyl group or a haloalkyl group; preferably, it is an alkyloxy magnesium compound; more preferably, it is an alkoxy magnesium and / or an aryloxy magnesium.

[0026] According to a specific embodiment of the present invention, preferably, the titanium compound includes one or a combination of two or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and titanium alkoxyhalides.

[0027] According to a specific embodiment of the present invention, preferably, the alkyl titanium halide includes one or a combination of two or more of methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, and tri-n-butoxy titanium chloride.

[0028] According to a specific embodiment of the present invention, preferably, the titanium compound is titanium tetrachloride.

[0029] According to a specific embodiment of the present invention, preferably, the molar ratio of the internal electron donor shown in Formula I to the magnesium compound calculated in terms of magnesium element is 0.01-5.0, more preferably 0.05-3.0.

[0030] The present invention does not specifically limit the preparation method of the above-mentioned solid catalyst components, which can be carried out according to the following listed methods:

[0031] Method 1: A magnesium alkoxide or magnesium chloride alkoxide, excess TiCl4, and an internal electron donor are reacted at a temperature of 80℃-135℃; preferably, a general formula TiX can be used. N (OR b ) 4-N Titanium compounds (where R) b For C1-C 20 The hydrocarbon group, where X is a halogen and N = 1-4; preferably TiCl4) and the general formula MgCl2·mR a The adduct of OH (where m is a number from 0.1 to 6, preferably 2 to 4, and R) a For C1-C 20 Solid catalyst components are prepared by reacting hydrocarbon groups (or internal electron donors) with adducts of the general formula MgCl2·mRaOH. The adducts can be suitably prepared into spherical shapes by mixing an alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, followed by rapid cooling of the emulsion, thereby solidifying the adduct into spherical particles (see disclosures in US4399054 and US4469648). The spherical adducts obtained by this method can react directly with titanium compounds, or they can be pre-treated with a thermally controlled dealcoholization process (80°C-130°C) to obtain a dealcoholization adduct (wherein the molar number of the alcohol is generally less than 3, preferably between 0.1 and 2.5), before proceeding with subsequent reactions.

[0032] For example, the adduct or dealcohol adduct is suspended in cold TiCl4 (typically -25°C to 0°C) to react with a titanium compound, and the mixture is heated to 80°C to 130°C and held at this temperature for 0.5 to 2 hours. The treatment with TiCl4 can be performed once or multiple times, and an internal electron donor can be added during the TiCl4 treatment. This treatment can be repeated once or multiple times.

[0033] Method 2: A magnesium compound is dissolved in a solvent system consisting of an organic epoxy compound, an organophosphorus compound, and an inert diluent to form a homogeneous solution. This solution is then mixed with a titanium compound, and a solid is precipitated in the presence of a precipitation aid. This solid is treated with an internal electron donor to load the electron donor onto the solid. If necessary, further treatment with titanium tetrahalide and an inert diluent is performed. The precipitation aid is one of organic anhydrides, organic acids, ethers, or ketones. The components, per mole of magnesium halide, are: organic epoxy compound 0.2-10 mol, organophosphorus compound 0.1-3 mol, precipitation aid 0-1.0 mol, and Ti compound 0.5-150 mol (based on moles of titanium).

[0034] Method 3: React a TiCl4 or hydroxyl-titanium aromatic hydrocarbon solution (e.g., toluene, xylene, etc.) with a dialkoxymagnesium compound such as magnesium (preferably diethoxymagnesium) or diaryloxymagnesium at -25-0°C, and halogenate at 80-130°C. This treatment with the TiCl4 aromatic hydrocarbon solution can be repeated once or multiple times, and an internal electron donor is added once or in batches during multiple such treatments. For example, the preparation method of the titanium-containing solid catalyst component disclosed in US5077357 can be used as follows: Add magnesium ethoxy, tetraethoxytitanium, o-cresol, ethanol, and chlorobenzene sequentially, and stir; quickly add a TiCl4 / chlorobenzene solution to the above liquid, heat until completely dissolved, and continue heating to a specific temperature; use N2 bubbling to remove the ethanol reactants, and continue stirring for a certain period of time, then wash once with hot chlorobenzene, wash twice with isooctane, and then dry with N2 to obtain the support. Alternatively, as in another example: TiCl4, tetraethoxytitanium, ethoxymagnesium and o-cresol are added to chlorobenzene in sequence and stirred; ethanol is added, and after the ethoxymagnesium dissolves at high temperature, stirring is continued for 3 hours; the mixture is filtered while hot, then washed once with warm chlorobenzene, once with isooctane, and finally dried with N2.

[0035] Method 4: Magnesium dichloride is pre-activated using existing methods, and then treated with excess TiCl4 at approximately 80℃-135℃, wherein the solution contains an internal electron donor. The solid is treated with TiCl4 multiple times and washed with hexane to remove any unreacted TiCl4.

[0036] Method 5: Prepare the titanium-containing solid catalyst component according to the preparation method disclosed in CN1208045: First, contact the liquid magnesium compound and the liquid titanium compound at low temperature in the presence of a compound selected from alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and esters to precipitate a solid. The contact temperature is generally -70℃ to 200℃, preferably -30℃ to 130℃. An internal electron donor is used during the contact process.

[0037] Method Six: Anhydrous magnesium chloride and an internal electron donor are ground together under conditions where magnesium dichloride is activated. The resulting product can be treated once or multiple times with excess TiCl4 at a temperature of 80℃-130℃, followed by washing with a hydrocarbon solvent until no chloride ions are present. A more detailed method is as follows: The product obtained by co-grinding anhydrous magnesium dichloride, a titanium compound, and an internal electron donor is treated with a haloalkane such as 1,2-dichloroethane, chlorobenzene, or dichloromethane. This treatment is carried out at a temperature between 40℃ and the boiling point of the haloalkane for 1-4 hours, followed by washing with an inert hydrocarbon solvent such as hexane.

[0038] Method 7: Magnesium compounds supported on inorganic oxides such as SiO2, alumina, or porous silica gel are used as carriers for preparation. The mixture is then activated using well-known methods and treated with an excess of TiCl4 at a temperature of approximately 80℃-135℃. An internal electron donor is added during the treatment process.

[0039] The reaction of the above-mentioned catalyst components leads to the formation of magnesium halides in an active form. Typical crystalline magnesium halides have a regular structure and can support very little Ti, resulting in low catalytic activity. To prepare highly active supported catalysts, magnesium halides must undergo activation treatment. Activation methods include using physical and / or chemical methods to prepare them into microcrystals so that active centers are supported on the surface, edges, and defects of the magnesium halide. These treated magnesium halide microcrystals suitable for supporting Ti are called "activated magnesium halides." Besides these reactions, other methods are known in the literature to form magnesium halides in an active form from starting materials different from magnesium halides.

[0040] In any method for preparing the catalyst component, the aforementioned internal electron donor can be added directly or optionally obtained in situ using a suitable precursor that can be converted in the desired internal electron donor via known chemical reactions such as esterification or transesterification. Typically, the internal electron donor is used at a molar ratio of 0.01-5, preferably 0.05-3.0, relative to the molar number of MgCl2. Furthermore, the internal electron donor can be added simultaneously or separately during the preparation process, either in batches or in any order and combination.

[0041] The present invention also provides an olefin polymerization catalyst, the catalyst comprising the above-described catalyst components and an organoaluminum compound.

[0042] According to a specific embodiment of the present invention, preferably, the organoaluminum compound has the general formula AlR c p X (3-p) , where R c It is hydrogen or C1-C 20The hydrocarbon group, X is a halogen, and p is an integer 0 ≤ p ≤ 3.

[0043] According to a specific embodiment of the present invention, preferably, the organoaluminum compound includes one or more of the following: trialkylaluminum compound, alkylaluminum halide, alkylaluminum hydride, alkylaluminum sesquichloride, and alkylaluminoxane.

[0044] According to a specific embodiment of the present invention, preferably, the trialkylaluminum compound includes one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and trioctylaluminum; the alkylaluminum halide includes AlEt2Cl; the alkylaluminum sesquichloride includes Al2Et3Cl3; more preferably, the organoaluminum compound is a mixture of AlEt2Cl and Al2Et3Cl3.

[0045] According to a specific embodiment of the present invention, preferably, the molar ratio of the organoaluminum compound to the titanium atoms in the catalyst component is 1-1000:1, more preferably 50-800.

[0046] According to a specific embodiment of the present invention, preferably, the catalyst further includes an external electron donor.

[0047] According to a specific embodiment of the present invention, preferably, the external electron donor is a siloxane compound.

[0048] According to a specific embodiment of the present invention, preferably, the general formula of the siloxane compound is R'. t Si(OR”) 4-t In this context, R' and R” are each independently selected from C1-C 18 The hydrocarbon group, where t is an integer 0 ≤ t ≤ 3.

[0049] According to a specific embodiment of the present invention, preferably, R' and R” each contain heteroatoms.

[0050] According to a specific embodiment of the present invention, preferably, the heteroatom includes one or more combinations of N, O, S, P, and Si.

[0051] According to a specific embodiment of the present invention, preferably, the siloxane compound includes trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, triisobutylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldiethoxysilane. Di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, di(2-ethylhexyl)dimethoxysilane, di(2-ethylhexyl)diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylethyldiethoxysilane, cyclopentylisopropyldiethoxysilane, cyclopentylisobutyldimethoxysilane, cyclohexyl-n-propyldimethoxysilane Cyclohexyl-n-propyldiethoxysilane, cyclohexyl-n-butyldiethoxysilane, pentylmethyldimethoxysilane, diphenyldimethoxysilane, pentylmethyldiethoxysilane, pentylethyldimethoxysilane, pentylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane, cyclohexyldimethoxysilane, cyclohexyldiethoxysilane, 2-ethylhexyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, isobutyl Trimethoxysilane, tert-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclopentyldimethoxysilane, 3,The following are included in the list of one or more of the following: 5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, di(3-methylcyclohexyl)dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, di(4-methylcyclohexyl)dimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, di(3,5-dimethylcyclohexyl)dimethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyl tert-butyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, and (1,1,1-trifluoro-2-propyl)-methylmethoxysilane.

[0052] According to a specific embodiment of the present invention, preferably, the siloxane compound includes di-n-propyl dimethoxysilane, diisopropyl dimethoxysilane, di-n-butyl dimethoxysilane, diisobutyl dimethoxysilane, di-tert-butyl dimethoxysilane, di-n-butyl diethoxysilane, tert-butyl trimethoxysilane, dicyclohexyl dimethoxysilane, dicyclohexyl diethoxysilane, cyclohexylmethyl dimethoxysilane, and cyclohexylethyl diethoxysilane. One or more combinations of cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, and 3,5-dimethylcyclopentyldimethoxysilane.

[0053] According to a specific embodiment of the present invention, preferably, the siloxane compound includes one or more combinations of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, methyl tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane, cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane, and tert-hexyltrimethoxysilane.

[0054] According to a specific embodiment of the present invention, preferably, the molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100, more preferably 0.01-20, and even more preferably 0.01-5.

[0055] Preferably, the catalyst further includes an activity modifier.

[0056] According to a specific embodiment of the present invention, preferably, the activity modifier is a piper ester represented by Formula III:

[0057]

[0058] In Equation III, R 5 Selected from C1-C 20 Straight-chain or branched alkyl groups and their derivatives, C3-C 20 cycloalkyl, C6-C 20 aryl groups and their derivatives, C7-C 20 Araneyl groups and their derivatives, C2-C 10 olefin group, C 10 -C 20 Fused ring aryl, C 10 -C 20 The ester group; preferably, R 5 It also contains heteroatoms, which include one or more combinations of N, O, S, P, and Si.

[0059] According to a specific embodiment of the present invention, preferably, in formula III, R 5 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20 Straight-chain or branched alkyl groups, and the following substituents with 20 or fewer carbon atoms: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, benzyl and its derivatives, phenethyl and its derivatives, furanyl, pyrroleyl, thiophenyl, indene.

[0060] According to a specific embodiment of the present invention, preferably, the piperate ester includes one or more of the following: methyl piperate, ethyl piperate, n-propyl piperate, isopropyl piperate, n-butyl piperate, isobutyl piperate, n-pentyl piperate, isopentyl piperate, n-octyl piperate, isooctyl piperate, cyclohexyl piperate, and phenyl piperate.

[0061] According to a specific embodiment of the present invention, preferably, the molar ratio of the piperic acid ester to the external electron donor is (0.02-50):1, more preferably (0.1-10):1.

[0062] The present invention also provides the application of the above-mentioned catalyst in olefin polymerization.

[0063] According to a specific embodiment of the present invention, preferably, the olefin comprises a straight-chain or branched olefin, more preferably one or a combination of two or more of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, butadiene, vinylcyclopentene, and vinylcyclohexene.

[0064] According to a specific embodiment of the present invention, preferably, the polymerization includes ethylene and / or propylene polymerization.

[0065] According to a specific embodiment of the present invention, preferably, the polymerization includes homopolymerization or copolymerization.

[0066] According to a specific embodiment of the present invention, preferably, during the catalytic process, the order in which the components of the catalyst are added is arbitrary, with the organoaluminum compound being added to the polymerization system first, followed by the external electron donor, and finally the catalyst components.

[0067] According to a specific embodiment of the present invention, preferably, the polymerization can be carried out with or without a solvent; the olefin can be in the gas phase or the liquid phase; more preferably, hydrogen can be further added as a molecular weight regulator (polymerization can also be carried out without a molecular weight regulator); the polymerization is a continuous polymerization or a batch polymerization, and the polymerization can be carried out in one step, two steps or multiple steps.

[0068] According to a specific embodiment of the present invention, preferably, the polymerization temperature is ≤200℃, more preferably 20-100℃, and even more preferably 40-80℃; the polymerization pressure is ≤10MPa, more preferably 0.3-5MPa.

[0069] This invention provides a catalyst component using substituted maltol derivatives as internal electron donors. A preferred type of internal electron donor is a substituted maltol ester compound. The oxygen atoms of the internal electron donor in this catalyst component are strategically positioned on the carbon skeleton, exhibiting stronger coordination ability and facilitating the participation of oxygen-containing functional groups in the formation of active centers. Catalysts prepared using the internal electron donors of this invention generally exhibit higher activity than industrially most commonly used phthalate-based internal electron donor catalysts, and also higher activity than highly active diether catalysts. Furthermore, they demonstrate good stereoselectivity, resulting in polymers with high isotacticity. In addition, some maltol derivative compounds are commercially available raw materials, simplifying the preparation route. The substituted maltol is a widely used flavoring agent and food additive both domestically and internationally, ensuring the raw material's safety and low cost, thus reducing catalyst production costs. Detailed Implementation

[0070] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0071] The isotacticity of polymers was determined by the heptane extraction method (boiling heptane extraction for 6 hours): two grams of dry polymer sample were placed in an extractor and extracted with boiling heptane for 6 hours. The residue was then dried to constant weight. The ratio of the obtained polymer weight (g) to 2 is the isotacticity.

[0072] The bulk density of the polymer was determined using the method specified in JB / T 2412-2008.

[0073] Preparation example: Synthesis of internal electron donors of substituted maltol ethers represented by Formula I

[0074] 1. The synthesis of methyl maltol methyl ether (a1) is carried out through the following steps:

[0075] 100 mL of toluene, 0.2 mmol of tetra-n-butylammonium bisulfate, 10 mmol of methyl maltol, and 15 mmol of 50% NaOH aqueous solution were added to a 250 mL three-necked flask. The mixture was cooled to 0 °C, and dimethyl sulfate / toluene (1.6 g / 10 mL) was added dropwise over 0.5 h. The temperature was then raised to 10 °C and stirred for 5 h. The mixture was then heated to room temperature and stirred overnight. Water (80 mL) was added, and the mixture was stirred for 20 min. The extract was then separated. The organic phase was washed with water for two years and then evaporated to dryness. Column chromatography yielded methyl maltol methyl ether (a1). Its NMR data are shown in Table 1.

[0076] 2. Other substituted maltol ethers (a2-a9) were synthesized using the reaction route of reaction formula I. The structures and NMR results are shown in Table 1.

[0077]

[0078]

[0079] Table 1 shows the internal electron donors of substituted maltol ethers according to Formula I.

[0080]

[0081]

[0082] Preparation example: Synthesis of the internal electron donor of the substituted maltol esters shown in Formula II

[0083] 1. The synthesis of methyl maltol propionate (a10) follows these steps:

[0084] 0.5 g of dimethylpyridine, 100 mL of dichloromethane, 10 mmol of methyl maltol, and 3 mL of triethylamine were added to a 250 mL three-necked flask. While stirring, a solution of 10 mmol of propionyl chloride in dichloromethane (10 mL) was added dropwise, and the mixture was stirred overnight at room temperature. The solution was filtered, washed with 100 mL of saturated sodium bicarbonate solution and 100 mL of saturated saline solution, and separated. The organic phase was dried over anhydrous Na₂SO₄, filtered, rotary evaporated, and separated by column chromatography to obtain liquid methyl maltol propionate (a). Its NMR data are shown in Table 2.

[0085] 2. Other substituted maltol esters (a11-a21) were synthesized using the above route. The structures and NMR results are shown in Table 2.

[0086]

[0087] Table 2 shows the internal electron donors of substituted maltol esters (Formula II).

[0088]

[0089]

[0090]

[0091]

[0092] Preparation of catalyst components

[0093] Example 1

[0094] This embodiment provides a catalyst component, the preparation method of which is as follows:

[0095] In a 500 mL stirred flask equipped with a stirrer and fully purged with nitrogen, 10 g of MgCl2·2.5C2H5OH microspheres and 150 mL of titanium tetrachloride were added to prepare a suspension. The suspension was then maintained at -15 °C for 1 hour, slowly heated to 80 °C, and 15 mmol of methyl maltol methyl ether was added. The temperature was further increased to 110 °C and held constant for 1 hour. The liquid was then filtered off, and the resulting solid was washed three times with 120 mL of titanium tetrachloride at 125 °C. It was then washed four times with 150 mL of hexane at 60 °C. Finally, the liquid was filtered off and dried to obtain solid catalyst component C1. The titanium content, internal electron donor content, and polymerization data of this solid catalyst component are shown in Table 3.

[0096] Example 2-Example 21

[0097] Catalyst components C2-C21 in Examples 2-21 were prepared as in Example 1, except that methyl maltol methyl ether (a1) was replaced with 15 mmol of compounds a2-a21 in Tables 1 and 2 respectively.

[0098] Example 22

[0099] The catalyst preparation process in this embodiment is the same as that in Example 1, except that 15 mmol of methyl maltol methyl ether (a1) is replaced with 12 mmol of methyl maltol methyl ether (a1) and 3 mmol of methyl maltol benzoate (a15).

[0100] Example 23

[0101] The catalyst preparation process in this embodiment is the same as that in Example 1, except that 15 mmol of methyl maltol methyl ether (a1) is replaced with 9 mmol of methyl maltol methyl ether (a1) and 6 mmol of methyl maltol benzoate (a15).

[0102] Example 24

[0103] The catalyst preparation process in this embodiment is the same as that in Example 1, except that 15 mmol of methyl maltol methyl ether (a1) is replaced with 7 mmol of methyl maltol methyl ether (a1) and 8 mmol of methyl maltol benzoate (a15).

[0104] Example 25

[0105] The catalyst preparation process in this embodiment is the same as that in Example 1, except that 15 mmol of methyl maltol methyl ether (a1) is replaced with 3 mmol of methyl maltol methyl ether (a1) and 12 mmol of methyl maltol benzoate (a15).

[0106] Example 26

[0107] The catalyst preparation process in this embodiment is the same as in Example 1, except that 15 mmol of methyl maltol methyl ether (a1) is replaced with 7 mmol of methyl maltol methyl ether (a1) and 8 mmol of methyl maltol isobutyrate (a12).

[0108] Example 27

[0109] The catalyst preparation process in this embodiment is the same as that in Example 1, except that 15 mmol of methyl maltol methyl ether (a1) is replaced with 5 mmol of methyl maltol methyl ether (a1) and 10 mmol of methyl maltol isobutyrate (a12).

[0110] Example 28

[0111] This embodiment provides a catalyst component, the preparation method of which is as follows:

[0112] In a 500 mL stirred flask equipped with a stirrer and fully purged with nitrogen, 10 g of anhydrous magnesium chloride, 150 mL of toluene, 17 mL of epichlorohydrin, and 16 mL of tributyl phosphate were added at room temperature. The mixture was heated to 50 °C with stirring and maintained for 2 hours until the solid was completely dissolved. Then, 2.40 g of phthalic anhydride was added and the mixture was maintained for another hour. The solution was cooled to -25 °C, and 110 mL of titanium tetrachloride was added dropwise over 1 hour. The temperature was slowly raised to 80 °C, and the solid was gradually washed out during the heating process. 15 mmol of methyl maltol methyl ether (a1) was added and the mixture was maintained at 80 °C for 1 hour. After filtration, the solution was washed twice with 200 mL of toluene. Then, 120 mL of toluene and 80 mL of titanium tetrachloride were added, and the temperature was raised to 110 °C and maintained for 2 hours. The liquid was then filtered clean, and the process was repeated once more. The liquid was filtered off, and the resulting solid was washed once with 100 mL of dichloroethane and four times with hexane. After drying, solid catalyst component C28 was obtained. The titanium content, internal electron donor content, and polymerization data of the solid catalyst components are shown in Table 3.

[0113] Example 29

[0114] This embodiment provides a catalyst component, the preparation method of which is as follows:

[0115] In a 500 mL stirred flask fully purged with nitrogen, 8 g of magnesium diethoxy and 100 mL of toluene were added to prepare a suspension. 25 mL of titanium tetrachloride was added dropwise at -15 °C. After the addition was complete, the temperature was slowly raised to 0 °C, and then 50 mL of titanium tetrachloride was added dropwise. The temperature was then slowly raised to 80 °C, and 15 mmol of methyl maltol methyl ether (a1) was added. The temperature was further raised to 110 °C and held constant for 2 hours. The liquid was then filtered clean, and the solid was washed three times with 100 mL of titanium tetrachloride at 125 °C, and then four times with 120 mL of hexane at 60 °C. The liquid was filtered off and dried to obtain solid catalyst component C29. The titanium content, internal electron donor content, and polymerization data of this solid catalyst component are shown in Table 3.

[0116] Example 30

[0117] This embodiment provides a catalyst component, the preparation method of which is as follows:

[0118] In a 500 mL stirred flask equipped with a stirrer and fully purged with nitrogen, 10 g of anhydrous magnesium chloride, 150 mL of toluene, 17 mL of epichlorohydrin, and 16 mL of tributyl phosphate were added at room temperature. The mixture was heated to 50 °C with stirring and maintained for 2 hours until the solid was completely dissolved. Then, 2.40 g of phthalic anhydride was added and the mixture was maintained for another hour. The solution was cooled to -25 °C, and 110 mL of titanium tetrachloride was added dropwise over 1 hour. The temperature was slowly raised to 80 °C, and the solid was gradually washed out during the heating process. 15 mmol of methyl maltol benzoate (a15) was added and the mixture was maintained at 80 °C for 1 hour. After filtration, the solution was washed twice with 200 mL of toluene. Then, 120 mL of toluene and 80 mL of titanium tetrachloride were added, and the temperature was raised to 110 °C and maintained for 2 hours. The liquid was then filtered clean, and the process was repeated once more. The liquid was filtered off, and the resulting solid was washed once with 100 mL of dichloroethane and four times with hexane. After drying, the solid catalyst component C30 was obtained. The titanium content, internal electron donor content, and polymerization data of the solid catalyst components are shown in Table 3.

[0119] Example 31

[0120] This embodiment provides a catalyst component, the preparation method of which is as follows:

[0121] In a 500 mL stirred flask equipped with nitrogen purging, 8 g of magnesium diethoxy and 100 mL of toluene were added to prepare a suspension. 25 mL of titanium tetrachloride was added dropwise at -15 °C. After the addition was complete, the temperature was slowly raised to 0 °C, and then 50 mL of titanium tetrachloride was added dropwise. The temperature was then slowly raised to 80 °C, and 15 mmol of methyl maltol benzoate (a15) was added. The temperature was further raised to 110 °C and held constant for 2 hours. The liquid was then filtered clean, and the liquid was discarded. The resulting solid was washed three times with 100 mL of titanium tetrachloride at 125 °C, and then four times with 120 mL of hexane at 60 °C. The liquid was then filtered off and dried to obtain solid catalyst component C31. The titanium content, internal electron donor content, and polymerization data of this solid catalyst component are shown in Table 3.

[0122] Comparative Example 1

[0123] This comparative example provides a catalyst component D1, which is prepared in the same manner as in Example 1, except that 2,6-dimethoxymethyl-4-pyranone is replaced with 15 mmol of di-n-butyl phthalate (DN).

[0124] Comparative Example 2

[0125] This comparative example provides a catalyst component D2, which is prepared in the same manner as in Example 1, except that 2,6-dimethoxymethyl-4-pyranone is replaced with 15 mmol of 9,9-dimethoxyfluorene (FLU).

[0126] Aggregation 1

[0127] The catalyst components obtained above were used as components of olefin polymerization catalysts for polymerization evaluation:

[0128] After purging the 5L stainless steel reactor with nitrogen, 5mL of a 0.5mol / L triethylaluminum hexane solution, 1mL of a 0.1mol / L methylcyclohexyldimethoxysilane hexane solution, and 10mg of the prepared catalyst component were added. Then, 10mL of hexane was added to flush the feed line, followed by 2L (under standard conditions) of hydrogen and 2.5L of purified propylene. The reaction was prepolymerized at 25℃ for 5 minutes, then the temperature was raised to 70℃, and polymerization was carried out at this temperature for 1 hour. After the reaction was completed, the reactor was cooled and stirring was stopped. The reaction product was discharged and dried to obtain the polymer. Polymerization data are shown in Table 3.

[0129] Table 3

[0130]

[0131]

[0132] As shown in Table 3, the catalysts with substituted maltol ethers and / or substituted maltol esters as internal electron donors in Examples 1-31, under the same preparation conditions, exhibited higher activity than the phthalate-based internal electron donor catalysts of Comparative Example 1, and higher activity than the diether catalysts of Comparative Example 2. Furthermore, they showed good stereoselectivity and produced polymers with high isotacticity. The catalysts also exhibited regular particle size and high packing density.

[0133] Aggregation 2

[0134] The polymerization evaluation was conducted using C16 catalyst component as a component of the olefin polymerization catalyst.

[0135] After the 5L stainless steel reactor was fully purged with nitrogen, 5 mL of a 0.5 mol / L triethylaluminum hexane solution, 1 mL of a 0.1 mol / L methylcyclohexyldimethoxysilane hexane solution, the activity modifier (0.1 mol / L hexane solution) of the types and amounts described in Table 4, and 10 mg of the prepared catalyst component were added. Then, 10 mL of hexane was added to flush the feed line, followed by 2 L (under standard conditions) of hydrogen and 2.5 L of purified propylene. The reaction was prepolymerized at 25°C for 5 minutes, then the temperature was raised to 70°C, and polymerization was carried out at this temperature for 1 hour. After the reaction was completed, the reactor was cooled and stirring was stopped. The reaction product was discharged and dried to obtain the polymer. The polymerization data are shown in Table 4.

[0136] Table 4

[0137]

[0138] Activity regulators: a: ethyl piperate; b: isopropyl piperate; c: n-octyl piperate; d: phenyl piperate.

[0139] As shown in Table 4, when catalyst component C16 was polymerized without the addition of an activity regulator, the temperature fluctuation inside the reactor was within ±3℃. After the addition of piperate ester, the temperature fluctuation was significantly reduced, and the resulting polypropylene still maintained a high level of isotacticity and packing density. The catalytic activity was slightly reduced, but it was still significantly higher than that of comparative examples 1 and 2, making it more suitable for meeting the requirements of stable operation of industrial plants.

[0140] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the present invention.

Claims

1. A catalyst component for olefin polymerization, characterized in that, Contains: Mg, Ti, halogens, and substituted maltol derivative internal electron donors; wherein, the substituted maltol derivative internal electron donor is a substituted maltol ether internal electron donor having the substituted maltol ether structure shown in Formula I: In formula I, R 1 and R 2 Whether the elements are the same or different, they are each independently selected from H, halogens, and C1-C. 20 Hydrocarbon group.

2. The catalyst component for olefin polymerization according to claim 1, characterized in that, R 1 and R 2 Each contains heteroatoms selected from one or more combinations of N, O, S, P, Si and halogens.

3. The catalyst component for olefin polymerization according to claim 1, characterized in that, In formula I, R 1 and R 2 Each of the following substituents, independently selected from H, halogens, and up to 20 carbon atoms, includes: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indene, benzyl, haloalkyl, heteroatom-containing alkyl, halocycloalkyl, heteroatom-containing cycloalkyl, halophenyl, heteroatom-containing phenyl, haloalkylphenyl, heteroatom-containing alkylphenyl, halophenylalkyl, heteroatom-containing phenylalkyl, haloindenyl, heteroatom-containing indene, halobenzyl, heteroatom-containing benzyl, heterocyclic aryl substituents; wherein the heteroatom includes one or more combinations of N, O, S, P, and Si.

4. The catalyst component for olefin polymerization according to claim 1, characterized in that, In formula I, R 1 and R 2 Each is independently selected from H, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20 The following substituents with 20 or fewer carbon atoms, either straight-chain or branched alkyl groups: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, benzyl and its derivatives, phenethyl and its derivatives, furanyl, pyrroleyl, thiophenyl, indene; preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

5. The catalyst component for olefin polymerization according to claim 1, characterized in that, The substituted maltol ethers include electron donors such as methyl maltol methyl ether, methyl maltol ethyl ether, methyl maltol n-propyl ether, methyl maltol n-butyl ether, methyl maltol n-pentyl ether, methyl maltol n-hexyl ether, methyl maltol cyclohexyl ether, methyl maltol n-heptyl ether, methyl maltol n-octyl ether, methyl maltol n-nonyl ether, methyl maltol n-decyl ether, methyl maltol dodecyl ether, methyl maltol tetradecyl ether, methyl maltol hexadecyl ether, methyl maltol octadecyl ether, methyl maltol phenyl ether, methyl maltol benzyl ether, methyl maltol m-chloroanisole, methyl maltol o-chloroanisole, methyl maltol p-chloroanisole, methyl maltol p-methoxyanisole, methyl maltol p-methylanisole, methyl maltol p-nitroanisole, methyl maltol (α-furanyl) ether, methyl maltol (α-thienyl) methyl ether, and methyl maltol propenyl. The following are one or more combinations of ethers, ethyl maltol methyl ether, ethyl maltol ethyl ether, ethyl maltol n-propyl ether, ethyl maltol n-butyl ether, ethyl maltol n-pentyl ether, ethyl maltol n-hexyl ether, ethyl maltol n-heptyl ether, ethyl maltol n-octyl ether, ethyl maltol n-nonyl ether, ethyl maltol n-decyl ether, ethyl maltol dodecyl ether, ethyl maltol tetradecyl ether, ethyl maltol hexadecyl ether, ethyl maltol octadecyl ether, ethyl maltol phenyl ether, ethyl maltol benzyl ether, ethyl maltol m-chloroanisole, ethyl maltol o-chloroanisole, ethyl maltol p-chloroanisole, ethyl maltol p-methoxyanisole, ethyl maltol p-methylanisole, ethyl maltol p-nitroanisole, ethyl maltol (α-furanyl) ether, ethyl maltol (α-thienyl) methyl ether, and ethyl maltol propenyl ether.

6. The catalyst component for olefin polymerization according to claim 1, characterized in that, The internal electron donor of the substituted maltol derivative is an internal electron donor of a substituted maltol ester, which has the substituted maltol ester structure shown in Formula II: In Equation II, R 3 and R 4 Whether the elements are the same or different, they are each independently selected from H, halogens, and C1-C. 20 hydrocarbon group; Preferably, R 3 and R 4 Each contains heteroatoms selected from one or more combinations of N, O, S, P, Si and halogens; Preferably, in formula II, R 3 and R 4 Each of the following substituents, independently selected from H, halogens, and having 20 or fewer carbon atoms, includes: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indene, benzyl, haloalkyl, heteroatom-containing alkyl, halocycloalkyl, heteroatom-containing cycloalkyl, halophenyl, heteroatom-containing phenyl, haloalkylphenyl, heteroatom-containing alkylphenyl, halophenylalkyl, heteroatom-containing phenylalkyl, haloindenyl, heteroatom-containing indene, halobenzyl, heteroatom-containing benzyl, and heterocyclic aryl substituents; wherein the heteroatom comprises one or more combinations of N, O, S, P, and Si; Preferably, in formula II, R 3 and R 4 Each is independently selected from H, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20 The following substituents with 20 or fewer carbon atoms, whether linear or branched alkyl groups: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, benzyl and its derivatives, phenethyl and its derivatives, furanyl, pyrroleyl, thiophenyl, indene; more preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

7. The catalyst component for olefin polymerization according to claim 6, characterized in that, The substituted maltol esters include methyl maltol acetate, methyl maltol propionate, methyl maltol butyrate, methyl maltol isobutyrate, methyl maltol valerate, methyl maltol isovalerate, methyl maltol hexanoate, methyl maltol heptanoate, methyl maltol cyclohexanoate, methyl maltol octanoate, methyl maltol nonanoate, methyl maltol decanoate, methyl maltol laurate, methyl maltol myristate, methyl maltol palmitate, methyl maltol stearate, methyl maltol benzoate, methyl maltol m-chlorobenzoate, methyl maltol o-chlorobenzoate, methyl maltol p-chlorobenzoate, methyl maltol p-methoxybenzoate, methyl maltol p-methylbenzoate, and methyl maltol p-nitrobenzoate. Ester, ethyl maltol acetate, ethyl maltol propionate, ethyl maltol butyrate, ethyl maltol isobutyrate, ethyl maltol valerate, ethyl maltol isovalerate, ethyl maltol hexanoate, ethyl maltol heptanoate, ethyl maltol cyclohexanoate, ethyl maltol octanoate, ethyl maltol nonanoate, ethyl maltol decanoate, ethyl maltol laurate, ethyl maltol myristate, ethyl maltol palmitate, ethyl maltol stearate, ethyl maltol benzoate, ethyl maltol m-chlorobenzoate, ethyl maltol o-chlorobenzoate, ethyl maltol p-chlorobenzoate, ethyl maltol p-methoxybenzoate, ethyl maltol p-methylbenzoate, and ethyl maltol p-nitrobenzoate are all listed in one or more combinations.

8. The catalyst component for olefin polymerization according to claim 6, characterized in that, The molar ratio of the substituted maltol ether of Formula I to the substituted maltol ester of Formula II is ≥1:

9. Preferably, the molar ratio of the substituted maltol ether of Formula I to the substituted maltol ester of Formula II is ≥3:

7. Preferably, the molar ratio of the substituted maltol ether of Formula I to the substituted maltol ester of Formula II is ≥5:

5. Preferably, the molar ratio of the substituted maltol ether of Formula I to the substituted maltol ester of Formula II is ≥7:

3. Preferably, the molar ratio of the substituted maltol ether of Formula I to the substituted maltol ester of Formula II is ≥9:

1.

9. The catalyst component for olefin polymerization according to claim 1, characterized in that, The catalyst component comprises titanium compounds, magnesium compounds, and internal electron donors as shown in Formula I and / or Formula II; Preferably, the precursor of the magnesium compound is selected from X. n Mg(OR a ) 2-n MgCl2·mR a OH, R a 2-n MgX n One or more combinations of MgCl2 / SiO2, MgCl2 / Al2O3, magnesium halides, and titanium alkoxides, wherein m is 0.1-6, 0≤n≤2, X is a halogen, and R a For C1-C 20 The hydrocarbon group; the general formula of the titanium compound is TiX. N (OR b ) 4-N , where R b For C1-C 20 The hydrocarbon group, where X is a halogen and N is 1-4; Preferably, the magnesium compound is an alkoxide of magnesium dihalide; or, the magnesium compound is a liquid magnesium compound; or, the magnesium compound is a derivative in which at least one halogen atom in a magnesium dihalide molecule is replaced by an alkyl group or a haloalkyl group; preferably, it is an alkyloxy magnesium compound; more preferably, it is an alkoxy magnesium and / or an aryloxy magnesium compound. Preferably, the titanium compound includes one or a combination of two or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and titanium alkoxyhalides; Preferably, the alkyl titanium halide comprises one or a combination of two or more of the following: titanium methoxytrichloride, titanium ethoxytrichloride, titanium propoxytrichloride, titanium n-butoxytrichloride, titanium dimethoxydichloride, titanium diethoxydichloride, titanium dipropoxydichloride, titanium di n-butoxydichloride, titanium trimethoxytrichloride, titanium triethoxytrichloride, titanium tripropoxytrichloride, and titanium tri n-butoxytrichloride. Preferably, the titanium compound is titanium tetrachloride.

10. The catalyst component for olefin polymerization according to claim 1, characterized in that, The molar ratio of the internal electron donor shown in Formula I to the magnesium compound calculated in terms of magnesium element is 0.01-5.0, preferably 0.05-3.

0.

11. An olefin polymerization catalyst, characterized in that, Includes the catalyst component and organoaluminum compound as described in any one of claims 1-0.

12. The olefin polymerization catalyst according to claim 11, characterized in that, The general formula of the organoaluminum compound is AlR c p X (3-p) , where R c It is hydrogen or C1-C 20 The hydrocarbon group, where X is a halogen and p is an integer 0 ≤ p ≤ 3; Preferably, the organoaluminum compound includes one or more of the following: trialkylaluminum compounds, alkylaluminum halides, alkylaluminum hydrides, alkylaluminum sesquichlorides, and alkylaluminoxanes. Preferably, the trialkylaluminum compound includes one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and trioctylaluminum; the alkylaluminum halide includes AlEt2Cl; the alkylaluminum sesquichloride includes Al2Et3Cl3; more preferably, the organoaluminum compound is a mixture of AlEt2Cl and Al2Et3Cl3.

13. The olefin polymerization catalyst according to claim 11, characterized in that, The molar ratio of the organoaluminum compound to the titanium atoms in the catalyst component is 1-1000:1, preferably 50-800.

14. The olefin polymerization catalyst according to claim 11, characterized in that, The catalyst also includes an external electron donor; Preferably, the external electron donor is a siloxane compound; Preferably, the general formula of the siloxane compound is R' t Si(OR”) 4-t In this context, R' and R” are each independently selected from C1-C 18 The hydrocarbon group, where t is an integer 0 ≤ t ≤ 3; Preferably, R' and R” each contain heteroatoms; Preferably, the heteroatom comprises one or more combinations of N, O, S, P, and Si; Preferably, the siloxane compound includes trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, triisobutylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldiethoxysilane, di-n-butyldiethoxysilane. Alkane, n-Butylmethyldimethoxysilane, Di(2-ethylhexyl)dimethoxysilane, Di(2-ethylhexyl)diethoxysilane, Dicyclohexyldimethoxysilane, Dicyclohexyldiethoxysilane, Dicyclopentyldimethoxysilane, Dicyclopentyldiethoxysilane, Cyclohexylmethyldimethoxysilane, Cyclohexylmethyldiethoxysilane, Cyclohexylethyldimethoxysilane, Cyclohexylisopropyldimethoxysilane, Cyclohexylethyldiethoxysilane, Cyclopentylmethyldimethoxysilane, Cyclopentylmethyldiethoxysilane, Cyclopentylethyldimethoxysilane, Cyclopentylethyldiethoxysilane, Cyclopentylisopropyldiethoxysilane, Cyclopentylisobutyldimethoxysilane, Cyclohexyln-propyldimethoxysilane, Cyclohexyln-propyl Cyclohexyl-n-butyldiethoxysilane, pentylmethyldimethoxysilane, diphenyldimethoxysilane, pentylmethyldiethoxysilane, pentylethyldimethoxysilane, pentylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane, cyclohexyldimethoxysilane, cyclohexyldiethoxysilane, 2-ethylhexyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane Cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclopentyldimethoxysilane, 3,The following are included in the list of one or more of the following: 5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, di(3-methylcyclohexyl)dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, di(4-methylcyclohexyl)dimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, di(3,5-dimethylcyclohexyl)dimethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyl tert-butyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, and (1,1,1-trifluoro-2-propyl)-methylmethoxysilane.

15. The olefin polymerization catalyst according to claim 14, characterized in that, The siloxane compounds include one or more combinations of di-n-propyl dimethoxysilane, diisopropyl dimethoxysilane, di-n-butyl dimethoxysilane, diisobutyl dimethoxysilane, di-tert-butyl dimethoxysilane, di-n-butyl diethoxysilane, tert-butyl trimethoxysilane, dicyclohexyl dimethoxysilane, dicyclohexyl diethoxysilane, cyclohexylmethyl dimethoxysilane, cyclohexylethyl diethoxysilane, cyclohexylethyl dimethoxysilane, cyclohexylethyl diethoxysilane, cyclopentylmethyl dimethoxysilane, cyclopentylmethyl diethoxysilane, cyclopentylethyl dimethoxysilane, cyclohexylcyclopentyl dimethoxysilane, cyclohexylcyclopentyl diethoxysilane, 3-methylcyclohexylcyclopentyl dimethoxysilane, 4-methylcyclohexylcyclopentyl dimethoxysilane, and 3,5-dimethylcyclopentyl dimethoxysilane.

16. The olefin polymerization catalyst according to claim 14, characterized in that, The siloxane compounds include one or more of the following: cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, methyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane, cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane, and tert-hexyltrimethoxysilane.

17. The olefin polymerization catalyst according to claim 14, characterized in that, The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100, preferably 0.01-20, and more preferably 0.01-5.

18. The olefin polymerization catalyst according to claim 14, characterized in that, The catalyst also includes an activity modifier; Preferably, the activity modifier is a piperitate ester represented by Formula III: In Equation III, R 5 Selected from C1-C 20 Straight-chain or branched alkyl groups and their derivatives, C3-C 20 cycloalkyl, C6-C 20 aryl groups and their derivatives, C7-C 20 Araneyl groups and their derivatives, C2-C 10 olefin group, C 10 -C 20 Fused ring aryl, C 10 -C 20 The ester group; preferably, R 5 It also contains heteroatoms, which include one or more combinations of N, O, S, P, and Si; Preferably, in formula III, R 5 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20 Straight-chain or branched alkyl groups, and the following substituents with 20 or fewer carbon atoms: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, benzyl and its derivatives, phenethyl and its derivatives, furanyl, pyrroleyl, thiophenyl, indene; Preferably, the piperate ester includes one or more of the following: methyl piperate, ethyl piperate, n-propyl piperate, isopropyl piperate, n-butyl piperate, isobutyl piperate, n-pentyl piperate, isopentyl piperate, n-octyl piperate, isooctyl piperate, cyclohexyl piperate, and phenyl piperate.

19. The olefin polymerization catalyst according to claim 18, characterized in that, The molar ratio of the piperidine ester to the external electron donor is (0.02-50):1, preferably (0.1-10):

1.

20. The use of the catalyst according to any one of claims 11-19 in olefin polymerization.

21. The application according to claim 20, characterized in that, The olefins include straight-chain or branched olefins, preferably one or more combinations of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, butadiene, vinylcyclopentene, and vinylcyclohexene.

22. The application according to claim 20, characterized in that, The polymerization includes the polymerization of ethylene and / or propylene.

23. The application according to claim 20, characterized in that, The polymerization includes homopolymerization or copolymerization.

24. The application according to claim 20, characterized in that, During the catalytic process, the order in which the components of the catalyst are added is arbitrary; Preferably, the organoaluminum compound is added to the polymerization system first, followed by the external electron donor, and finally the catalyst component.

25. The application according to claim 20, characterized in that, The polymerization is carried out with or without a solvent; the olefin is in the gas phase or liquid phase; preferably, hydrogen is added or not added as a molecular weight regulator; the polymerization is a continuous polymerization or a batch polymerization, and the polymerization is carried out in one step, two steps or more steps.

26. The application according to claim 20, characterized in that, The polymerization temperature is ≤200℃, preferably 20-100℃, and more preferably 40-80℃; the polymerization pressure is ≤10MPa, preferably 0.3-5MPa.

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