Catalyst component for olefin polymerization, and catalyst and use thereof

Abstract

The present application provides a catalyst component for olefin polymerization, and a catalyst and a use thereof. The catalyst component comprises Mg, Ti, halogen, and an internal electron donor, and the internal electron donor comprises quercetin and / or a quercetin derivative. The activity of the catalyst component provided by the present application is generally higher than that of a catalyst component which is most commonly used in industry and uses a phthalate or diether compound as an internal electron donor, the catalyst component has good stereoselectivity, and a polymer obtained by catalysis has high isotacticity, regular granularity and high bulk density.

Description

A catalyst component for olefin polymerization, the catalyst, and its application.

[0001] This application claims priority to Chinese Patent Application No. 202410565985.6, filed on May 9, 2024, entitled “A catalyst component for olefin polymerization, a catalyst and its application thereto”, the entire contents of which are incorporated herein by reference. Technical Field

[0002] This application relates to the field of polyolefin catalysts, and more particularly to a catalyst component, catalyst, and its application for olefin polymerization. Background Technology

[0003] Currently, Ziegler-Natta catalysts (ZN catalysts) still dominate the production of polyolefins. Since the advent of the first generation of ZN catalysts, it has been found that the addition of 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) has a significant impact on 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 maximally changing the catalyst's performance. Therefore, the development of novel electron donors has always been a hot topic in the research and development of ZN polypropylene catalysts.

[0004] The most distinctive high-performance internal electron donor compounds in the prior art are: (1) fatty acid esters and aromatic acid esters, mainly represented by phthalate esters; (2) diethers; (3) succinates; (4) diol esters; and (5) compounds with other functional groups. However, in practical applications, the aforementioned compounds all have certain problems as internal electron donors for olefin polymerization catalysts. Catalysts prepared from phthalate compounds have moderate activity, good stereoselectivity, and low price, but phthalate compounds, as commonly used plasticizers, pose significant risks to human reproductive health and the environment. Catalysts using 1,3-diether compounds as internal electron donors have high activity and good hydrogen-modulated sensitivity, but the resulting polypropylene (PP) has a narrow molecular weight distribution, which is not conducive to developing different grades of PP. Succinate compounds as internal electron donors have the advantage of producing PP with a wider molecular weight distribution, but the stereoregularity of PP needs improvement. The activity of glycol ester catalytic systems is generally not as ideal as that of diether systems.

[0005] Application content

[0006] In view of this, this application provides a catalyst component for olefin polymerization, which has high catalytic activity and good stereoselectivity, and produces polymers with high isotacticity, regular particle size, and high bulk density.

[0007] This application also provides a catalyst for olefin polymerization. Because the catalyst includes the above-mentioned catalyst components, it has high catalytic activity and the polymer obtained by catalytic polymerization has excellent overall performance.

[0008] This application also provides an application of the above-mentioned catalyst in olefin polymerization.

[0009] In a first aspect, this application provides a catalyst component for olefin polymerization, comprising: Mg, Ti, halogen, and an internal electron donor, wherein the internal electron donor comprises quercetin and / or quercetin derivatives.

[0010] Preferably, the quercetin derivative has the quercetin ether structure shown in Formula I:

[0011] In Equation I, R 1 To R 5 Each substituent is independently selected from a first heteroatom or a substituent of 20 or fewer carbon atoms; the substituent includes at least one of straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indene, benzyl, haloalkyl, halocycloalkyl, halophenyl, haloalkylphenyl, halophenylalkyl, haloindenyl, halobenzyl, heterocyclic aryl substituent, and optionally contains a second heteroatom; the first heteroatom is at least one of N, O, S, P, Si and halogen, and the second heteroatom is at least one of N, O, S, P, Si.

[0012] Preferably, R 1 To R 5 Each element is independently selected from halogens, 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, and indene; more preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

[0013] Preferably, the quercetin derivative includes at least one of quercetin ethyl ether, quercetin methyl ether, quercetin benzyl ether, and quercetin p-methoxybenzyl ether.

[0014] Preferably, the quercetin derivative has the quercetin ester structure shown in Formula II:

[0015] In Equation II, R 6 To R 10 Each substituent is independently selected from H, a first heteroatom, or a substituent of 20 or fewer carbon atoms; the substituent includes at least one of straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indene, benzyl, haloalkyl, halocycloalkyl, halophenyl, haloalkylphenyl, halophenylalkyl, haloindenyl, halobenzyl, and heterocyclic aryl substituents, and the substituent optionally contains a second heteroatom; the first heteroatom is at least one of N, O, S, P, Si, and halogen, and the second heteroatom is at least one of N, O, S, P, and Si.

[0016] Preferably, R 6 To R 10 Each element is independently selected from halogens, 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, and indene; more preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

[0017] Preferably, the quercetin derivative includes at least one selected from quercetin benzoate, quercetin phenylacetate, quercetin m-chlorobenzoate, quercetin p-methoxybenzoate, quercetin p-nitrobenzoate, quercetin furanoate, quercetin isonicotinate, quercetin cyclohexylcarboxylate, quercetin ethyl ester, quercetin isobutyl ester, and quercetin n-octyl ester.

[0018] Preferably, the catalyst component comprises: a titanium compound, a magnesium compound, and the internal electron donor; the magnesium compound is selected from X. n Mg(OR a ) 2-n MgCl2·mR a OH, R a 2-n MgX nAt least one of the following: a mixture of MgCl2 and SiO2, a mixture of MgCl2 and Al2O3, and a mixture of magnesium halide and titanium alkoxide, wherein 0.1 ≤ m ≤ 6, 0 ≤ n ≤ 2, X is a halogen, and R a For C1-C 20 The hydrocarbon group; and / or, 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 0 ≤ N ≤ 4.

[0019] Preferably, the magnesium compound is an alkoxide of magnesium dihalide, a liquid magnesium compound, or a derivative in which at least one halogen atom in a magnesium dihalide molecule is replaced by an alkyl group or a halogenated alkyl group; preferably, it is an alkyloxy magnesium compound; more preferably, it is alkoxy magnesium and / or aryloxy magnesium.

[0020] Preferably, the titanium compound includes at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and titanium alkoxyhalides; preferably, the titanium alkoxyhalides include at least one of titanium methoxytrichloride, titanium ethoxytrichloride, titanium propoxytrichloride, titanium n-butoxytrichloride, titanium dimethoxydichloride, titanium diethoxydichloride, titanium dipropoxydichloride, titanium dibutoxydichloride, titanium dibutoxydichloride, titanium trimethoxytrichloride, titanium triethoxytrichloride, titanium tripropoxydichloride, and titanium tributoxydichloride; more preferably, the titanium compound is titanium tetrachloride.

[0021] Preferably, the molar ratio of the internal electron donor to the magnesium element in the magnesium compound is 0.01-5.0:1, more preferably 0.05-3.0:1.

[0022] Secondly, this application provides a catalyst for olefin polymerization, the raw material composition of which includes the above-mentioned catalyst components and organoaluminum compounds.

[0023] Preferably, the organoaluminum compound has the general formula AlR c p X (3-p) , where R c It is hydrogen or C1-C 20 The hydrocarbon group, where X is a halogen, 0≤p≤3, and p is an integer;

[0024] Preferably, the organoaluminum compound includes at least one of trialkylaluminum compound, alkylaluminum halide, alkylaluminum hydride, alkylaluminum sesquichloride, and alkylaluminoxane;

[0025] Preferably, the trialkylaluminum compound includes at least one selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and trioctylaluminum; the alkylaluminum halide includes AlEt2Cl; and the alkylaluminum sesquichloride includes Al2Et3Cl3.

[0026] Preferably, the organoaluminum compound is a mixture of AlEt2Cl and Al2Et3Cl3.

[0027] Preferably, the molar ratio of the organoaluminum compound to the titanium element in the catalyst component is 1-1000:1; more preferably, it is 50-800:1.

[0028] Preferably, the raw material composition of the catalyst further includes an external electron donor.

[0029] Preferably, the external electron donor is a siloxane compound.

[0030] Preferably, the general formula of the siloxane compound is R' β Si(OR”) 4-β In this context, R' and R” are each independently selected from C1-C 18 The hydrocarbon group optionally contains heteroatoms, 0 ≤ β ≤ 3, and β is an integer; the heteroatoms include at least one of N, O, S, P, and Si.

[0031] Preferably, the molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100:1, more preferably 0.01-20:1, and even more preferably 0.01-5:1.

[0032] Preferably, the raw material composition of the catalyst further includes an activity modifier; wherein the activity modifier has the molecular structure shown in Formula III:

[0033] In Equation III, R 11 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 Any of the ester groups, optionally containing a third heteroatom, said third heteroatom being at least one of N, O, S, P, and Si.

[0034] Preferably, R 11Selected 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 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, and indene.

[0035] Preferably, the activity modifier includes at least one of 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.

[0036] Preferably, the molar ratio of the active regulator to the external electron donor is 0.02-50:1, more preferably 0.1-10:1.

[0037] Thirdly, this application provides an application of the above-mentioned catalyst in olefin polymerization.

[0038] This application provides a catalyst component with quercetin or its derivatives as internal electron donors. Its activity is generally higher than that of the most commonly used industrial catalysts with phthalate esters or diethers as internal electron donors. It also has good stereoselectivity, and the polymers obtained by catalysis have high isotacticity, regular particle size and high packing density. Detailed Implementation

[0039] To enable those skilled in the art to better understand the solutions of this application, a further detailed description of this application is provided below. The specific embodiments listed below are merely descriptions of the principles and features of this application; the examples are only for explaining this application and are not intended to limit its scope. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without inventive effort are within the scope of protection of this application.

[0040] In this application, the term "and / or" describes the relationship between related objects, indicating that there can be three relationships. For example, A and / or B can mean: A exists alone, A and B exist simultaneously, or B exists alone. A and B can be singular or plural. The character " / " generally indicates that the related objects before and after are in an "or" relationship.

[0041] In this application, the term "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0042] To improve the efficiency of catalytic olefin polymerization and the resulting polymer particle size regularity, bulk density, isotacticity, etc., this application adopts the following technical solution:

[0043] In a first aspect, this application provides a catalyst component for olefin polymerization, comprising: Mg, Ti, halogen, and an internal electron donor, wherein the internal electron donor comprises quercetin and / or quercetin derivatives.

[0044] Quercetin and its derivatives contain multiple oxygen-containing functional groups in the main aromatic ring structure, located at the ortho, meta, and para positions of the aromatic ring, which is conducive to the coordination of the catalytic active center and improves catalytic performance. In addition, the reaction substrate of quercetin ether or quercetin ester is quercetin, a natural flavonoid compound widely found in various plants. It has antioxidant, anticancer, and antiviral biological activities. The raw material is inexpensive and safe, which is beneficial to environmental protection and product cost control.

[0045] Preferably, the quercetin derivative has the quercetin ether structure shown in Formula I:

[0046] In Equation I, R 1 To R 5 Each substituent is independently selected from a first heteroatom or a substituent of 20 or fewer carbon atoms; the substituent includes at least one of straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indene, benzyl, haloalkyl, halocycloalkyl, halophenyl, haloalkylphenyl, halophenylalkyl, haloindenyl, halobenzyl, heterocyclic aryl substituent, and optionally contains a second heteroatom; the first heteroatom is at least one of N, O, S, P, Si and halogen, and the second heteroatom is at least one of N, O, S, P, Si.

[0047] It is understandable that in Equation I, R 1 R 2 R 3 R 4 and R 5 Same or different.

[0048] Preferably, R1 To R 5 Each element is independently selected from halogens, 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, and indene; more preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

[0049] Preferably, the quercetin derivative includes at least one of quercetin ethyl ether, quercetin methyl ether, quercetin benzyl ether, and quercetin p-methoxybenzyl ether.

[0050] Preferably, the quercetin derivative has the quercetin ester structure shown in Formula II:

[0051] In Equation II, R 6 To R 10 Each substituent is independently selected from H, a first heteroatom, or a substituent of 20 or fewer carbon atoms; the substituent includes at least one of straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indene, benzyl, haloalkyl, halocycloalkyl, halophenyl, haloalkylphenyl, halophenylalkyl, haloindenyl, halobenzyl, and heterocyclic aryl substituents, and the substituent optionally contains a second heteroatom; the first heteroatom is at least one of N, O, S, P, Si, and halogen, and the second heteroatom is at least one of N, O, S, P, and Si.

[0052] It is understandable that in Equation II, R 6 R 7 R 8 R 9 and R 10 Same or different.

[0053] Preferably, R 6 To R 10 Each element is independently selected from halogens, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20The 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, and indene; more preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

[0054] Preferably, the quercetin derivative includes at least one selected from quercetin benzoate, quercetin phenylacetate, quercetin m-chlorobenzoate, quercetin p-methoxybenzoate, quercetin p-nitrobenzoate, quercetin furanoate, quercetin isonicotinate, quercetin cyclohexylcarboxylate, quercetin ethyl ester, quercetin isobutyl ester, and quercetin n-octyl ester.

[0055] It is understood that the Mg, Ti, and halogen in the above-mentioned catalyst components can specifically be compounds including Mg atoms, Ti atoms, and halogens. For example, the catalyst components include: a titanium compound, a magnesium compound, and the internal electron donor; the magnesium compound is selected from X. n Mg(OR a ) 2-n MgCl2·mR a OH, R a 2-n MgX n At least one of the following: a mixture of MgCl2 and SiO2, a mixture of MgCl2 and Al2O3, and a mixture of magnesium halide and titanium alkoxide, wherein 0.1 ≤ m ≤ 6, 0 ≤ n ≤ 2, X is a halogen, and R a For C1-C 20 The hydrocarbon group; and / or, 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 0 ≤ N ≤ 4.

[0056] Preferably, the magnesium compound is an alkoxide of magnesium dihalide, a liquid magnesium compound (a magnesium compound dissolved in a liquid), or a derivative of magnesium dihalide in which at least one halogen atom is replaced by a hydrocarbon or halohydroxyl group; preferably a hydrocarbon-oxygenated magnesium compound; more preferably alkoxymagnesium and / or aryloxymagnesium.

[0057] Preferably, the titanium compound includes at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and titanium alkoxyhalides; preferably, the titanium alkoxyhalides include at least one of titanium methoxytrichloride, titanium ethoxytrichloride, titanium propoxytrichloride, titanium n-butoxytrichloride, titanium dimethoxydichloride, titanium diethoxydichloride, titanium dipropoxydichloride, titanium dibutoxydichloride, titanium dibutoxydichloride, titanium trimethoxytrichloride, titanium triethoxytrichloride, titanium tripropoxydichloride, and titanium tributoxydichloride; more preferably, the titanium compound is titanium tetrachloride.

[0058] Regarding the preparation method of the aforementioned internal electron donor, those skilled in the art can prepare it according to existing conventional methods. For example, the compound shown in Formula I can be prepared by, but is not limited to, the reaction shown in Formula I (R... 1 To R 5 When they are the same, and both are represented as R in reaction I. 1 Synthetic preparation method: Quercetin is reacted with alcohol or haloalkanes in one step to obtain quercetin ether.

[0059] Reaction I:

[0060] The compound represented by formula II can be reacted by, but is not limited to, the following reactions shown in formula II (R). 6 To R 10 When they are the same, and both are represented as R in reaction formula II. 2 Synthesis of substituted quercetin ester by reacting quercetin with acyl chloride in one step.

[0061] Reaction II:

[0062] This application does not specifically limit the preparation method of the above-mentioned catalyst components. For example, magnesium compounds and titanium compounds can be contacted with at least one of the above-mentioned internal electron donors to obtain the catalyst.

[0063] In detail, the following methods can be used:

[0064] 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, 0≤N≤4; preferably TiCl4) and the general formula MgCl2·mR a The adduct of OH (where 0.1≤m≤6, preferably 2≤m≤4, and R) a For C1-C 20Catalyst components are prepared by reacting hydrocarbon groups and internal electron donors.

[0065] The general formula is MgCl2·mR a OH adducts can be suitably prepared into spherical form by mixing an alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, followed by rapid quenching of the emulsion, thereby solidifying the adduct into spherical particles (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 further reaction; for example, MgCl2·mR a The OH adduct or dealcohol adduct is suspended in cold TiCl4 (generally -25℃ to 0℃) to react with the titanium compound. The mixture is heated to 80℃-130℃ and held at this temperature for 0.5-2 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.

[0066] 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-donating compound to load the compound 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).

[0067] 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 to 0 °C, and halogenate at 80 °C to 130 °C. This treatment with the TiCl4 aromatic hydrocarbon solution can be repeated once or multiple times, and an internal electron donor compound can be added once or in batches during multiple such treatments. For example, it can be prepared according to the preparation method of titanium-containing solid catalyst components disclosed in US5077357: ethoxymagnesium, tetraethoxytitanium, o-cresol, ethanol, and chlorobenzene are added sequentially and stirred; a TiCl4 / chlorobenzene solution is quickly added to the above liquid, and the temperature is raised until completely dissolved, and then the temperature is continued to rise to a specific temperature; the ethanol reactants are removed by bubbling with N2, and the mixture is stirred for a certain period of time, then washed once with hot chlorobenzene, washed twice with isooctane, and then dried with N2 to obtain the support. Alternatively, follow another example: add TiCl4, tetraethoxytitanium, ethoxymagnesium, and o-cresol to chlorobenzene in sequence and stir; add ethanol, and continue stirring for 3 hours after the ethoxymagnesium dissolves at high temperature; filter while hot, then wash once with warm chlorobenzene, wash once with isooctane, and finally dry with N2.

[0068] Method 4: Pre-activate magnesium dichloride using existing methods, then treat it with excess TiCl4 at approximately 80°C-135°C, where the solution contains an internal electron donor. Treat the solid with TiCl4 multiple times and wash it with hexane to remove any unreacted TiCl4.

[0069] Method 5: The preparation method of titanium-containing solid catalyst components disclosed in CN1208045 is followed: First, liquid magnesium compound and liquid titanium compound are contacted at low temperature in the presence of a compound selected from alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and esters to precipitate solids. The contact temperature is generally -70℃ to 200℃, preferably -30℃ to 130℃. An internal electron donor is used during the contact process.

[0070] Method Six: Anhydrous magnesium chloride and an internal electron donor compound are co-milled 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°C-130°C, followed by washing with a hydrocarbon solvent until chloride ions are removed. A more detailed method is as follows: The product obtained by co-milling anhydrous magnesium dichloride, a titanium compound, and an internal electron donor compound is treated with a haloalkane such as 1,2-dichloroethane, chlorobenzene, or dichloromethane. This treatment is carried out at a temperature between 40°C and the boiling point of the haloalkane for 1-4 hours, followed by washing with an inert hydrocarbon solvent such as hexane.

[0071] Method 7: Magnesium compounds supported on inorganic oxides such as SiO2, alumina, or porous silica gel are used as supports 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℃. During the treatment process, an internal electron donor compound is added.

[0072] Typical crystalline magnesium halides have a regular structure and can only support a very small amount of Ti, resulting in low catalytic activity. To prepare highly active magnesium halide supported catalysts, the magnesium halides must undergo activation treatment. Activation treatment generally involves using physical and / or chemical methods to prepare them into microcrystals, allowing more active centers to be loaded onto the surface, edges, and defects of the magnesium halide. These treated magnesium halide microcrystals suitable for Ti loading are called "activated magnesium halides." The catalyst component preparation methods described above can lead to the formation of magnesium halides in an active form. Besides these reactions, other methods are known in the literature to form active magnesium halides from starting materials different from magnesium halides.

[0073] In any of the above-described or other existing methods for preparing catalyst components, the internal electron donor can be added directly or through other alternative methods, such as in situ preparation using a suitable internal electron donor precursor that can be converted in an ideal internal electron donor compound, for example by known chemical reactions such as esterification or transesterification.

[0074] Preferably, the molar ratio of the internal electron donor to magnesium in the magnesium compound is 0.01-5.0:1, more preferably 0.05-3.0:1. Furthermore, the internal electron donor can be added simultaneously or separately during the preparation process in batches or in any order and combination.

[0075] Secondly, this application provides a catalyst for olefin polymerization, the raw material composition of which includes the above-mentioned catalyst components and organoaluminum compounds.

[0076] Preferably, the organoaluminum compound has the general formula AlR c p X (3-p) , where R c It is hydrogen or C1-C 20 The hydrocarbon group, where X is a halogen, 0≤p≤3, and p is an integer;

[0077] Preferably, the organoaluminum compound includes at least one of trialkylaluminum compound, alkylaluminum halide, alkylaluminum hydride, alkylaluminum sesquichloride, and alkylaluminoxane;

[0078] Preferably, the trialkylaluminum compound includes at least one selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and trioctylaluminum; the alkylaluminum halide includes AlEt2Cl; and the alkylaluminum sesquichloride includes Al2Et3Cl3.

[0079] Preferably, the organoaluminum compound is a mixture of AlEt2Cl and Al2Et3Cl3.

[0080] Preferably, the molar ratio of the organoaluminum compound to the titanium element in the catalyst component is 1-1000:1, more preferably 50-800:1.

[0081] Preferably, the raw material composition of the catalyst further includes an external electron donor.

[0082] Preferably, the external electron donor is a siloxane compound.

[0083] Preferably, the general formula of the siloxane compound is R' β Si(OR”) 4-β In this context, R' and R” are each independently selected from C1-C 18 The hydrocarbon group optionally contains heteroatoms, 0 ≤ β ≤ 3, and β is an integer; the heteroatoms include at least one of N, O, S, P, and Si.

[0084] For example, 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-n-butyldiethoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldiethoxysilane, di-n-butyldiethoxysilane, and n-butylmethyl Dimethoxysilane, di(2-ethylhexyl)dimethoxysilane, di(2-ethylhexyl)diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldiethoxysilane, cyclopentylisopropyldiethoxysilane, cyclopentylisobutyldimethoxysilane, cyclohexyl-n-propyldimethoxysilane, cyclohexyl-n-propyldiethoxysilane, cyclohexyl-n-butyldiethoxysilane, pentylmethyldimethoxysilane, pentylmethyldiethoxysilane oxysilanes, pentylethyl dimethoxysilane, pentylethyl diethoxysilane, cyclohexyl dimethylmethoxysilane, cyclohexyl diethylmethoxysilane, cyclohexyl diethylmethoxysilane, cyclohexyl diethylethoxysilane, 2-ethylhexyl trimethoxysilane, cyclohexyl dimethoxysilane, cyclohexyl diethoxysilane, 2-ethylhexyl triethoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane, n-propyl trimethoxysilane, n-propyl triethoxysilane, isopropyl trimethoxysilane, isopropyl triethoxysilane, n-butyl trimethoxysilane, isobutyl trimethoxysilane, tert-butyl trimethoxysilane, n-butyl triethoxysilane, cyclohexyl trimethoxysilane, cyclohexyl triethoxysilane, cyclopentyl trimethoxysilane, cyclohexyl trimethoxysilane, cyclohexyl trieth ... Pentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, di(3-methylcyclohexyl)dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, di(4-methylcyclohexyl)dimethoxysilane, 3,One or more of the following: 5-dimethylcyclohexylcyclohexyldimethoxysilane, bis(3,5-dimethylcyclohexyl)dimethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

[0085] In detail, the siloxane compound includes 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.

[0086] 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.

[0087] Preferably, the molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100:1, more preferably 0.01-20:1, and even more preferably 0.01-5:1.

[0088] Preferably, the raw material composition of the catalyst further includes an activity modifier; wherein the activity modifier has the molecular structure shown in Formula III:

[0089] In Equation III, R 11 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 -C20 Fused ring aryl, C 10 -C 20 Any of the ester groups, optionally containing a third heteroatom, said third heteroatom being at least one of N, O, S, P, and Si.

[0090] In this application, if piperate ester is added to the above catalyst components as an activity regulator, the temperature fluctuation in the polymerization reactor can be slowed down by suppressing the initial burst of catalyst activity, so that the polymerization reaction can proceed more smoothly, which is beneficial to industrial production.

[0091] Preferably, R 11 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 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, and indene.

[0092] Preferably, the activity modifier includes at least one of 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.

[0093] Preferably, the molar ratio of the active regulator to the external electron donor is 0.02-50:1, more preferably 0.1-10:1.

[0094] Thirdly, this application provides an application of the above-mentioned catalyst in olefin polymerization.

[0095] Optionally, the olefin includes straight-chain or branched olefins, such as 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.

[0096] According to a specific embodiment of this application, the polymerization includes ethylene and / or propylene polymerization.

[0097] According to a specific implementation of this application, the polymerization includes homopolymerization or copolymerization.

[0098] According to the specific implementation scheme of this application, the order of adding catalyst components during the catalytic process is arbitrary, but it is preferable to add the organoaluminum compound first to the polymerization system, followed by the external electron donor and the activity regulator, and finally the catalyst components.

[0099] The olefin polymerization process can be carried out with or without solvent; the olefin monomer can be in the gas phase or liquid phase; preferably, hydrogen can be added as a molecular weight regulator (polymerization can also be carried out without a molecular weight regulator); continuous polymerization or batch polymerization processes can be applied, and the polymerization reaction can be carried out in one, two, or multiple steps.

[0100] For example, 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.

[0101] The present application will be further described below with reference to specific embodiments:

[0102] In the following experiment, the isotacticity of the polymer 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.

[0103] The bulk density of the polymer was determined using the method specified in JB / T 2412-2008.

[0104] Example of internal electron donor preparation

[0105] Synthesis of quercetin ether derivatives as shown in Formula I

[0106] Quercetin ether derivatives a1-a4 (substituents summarized in Table 1) are synthesized using the methods described in Tetrahedron Letters, Volume 54, Issue 47, November 2013, Pages 6345-6348. Quercetin ethers with other substituents are synthesized using the methods described in the aforementioned literature, selecting halogenated derivatives with the corresponding substituents.

[0107] Table 1: Quercetin ether derivatives represented by Formula I

[0108] Synthesis of quercetin ester derivatives shown in Formula II

[0109] Quercetin benzoate derivatives a5-a15 (substituents summarized in Table 2) were synthesized using the methods described in Molecules 2010, vol 15, #7, pp. 4722-4736. Quercetin ester derivatives with other substituents were synthesized using the methods described in the aforementioned literature, selecting the corresponding acyl chlorides for synthesis.

[0110] Table 2: Quercetin ester compounds represented by Formula II

[0111] Catalyst component preparation example

[0112] Example 1

[0113] This embodiment provides a catalyst component comprising: Mg, Ti, halogen, and quercetin diethyl ether as shown in a1, and its preparation method is as follows:

[0114] In a 500 mL stirred flask fully purged with nitrogen, 10 g of MgCl2·2.5C2H5OH microspheres and 150 mL of titanium tetrachloride were added to prepare a suspension. The suspension was then maintained at -10 °C for 1 hour, slowly heated to 90 °C, and α1-quercetin ether (2.6 g, 6 mmol) 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 catalyst component C1. The titanium content, internal electron donor content, and polymerization data of this catalyst component are shown in Table 3.

[0115] Example 2-15

[0116] Examples 2-15 each provide a catalyst component C2-C15, the preparation process of which is as shown in Example 1, except that quercetin ether is replaced in sequence with 6 mmol of compounds a2-a15 in Tables 1 and 2 respectively.

[0117] Examples 16-18

[0118] Examples 16-18 each provide a catalyst component C16-C18, the preparation process of which is as shown in Example 5, except that 6 mmol of quercetin benzoate is replaced with 4 mmol, 8 mmol and 10 mmol of quercetin benzoate in sequence.

[0119] Example 19

[0120] This embodiment provides a catalyst component comprising: Mg, Ti, halogen, and a5-quercetin benzoate, and its preparation method is as follows:

[0121] 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. 6 mmol of quercetin benzoate 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, catalyst component C19 was obtained. The titanium content, internal electron donor content, and polymerization data of the catalyst components are shown in Table 3.

[0122] Example 20

[0123] This embodiment provides a catalyst component C20, comprising: Mg, Ti, halogens, and a5-quercetin benzoate, and its preparation method is as follows:

[0124] 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 6 mmol of quercetin benzoate was added. The temperature was further raised to 110 °C and held constant for 2 hours. The liquid was then filtered off. 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 filtered off and dried to obtain catalyst component C20. The titanium content, internal electron donor content, and polymerization data of this catalyst component are shown in Table 3.

[0125] Comparative Example 1

[0126] This comparative example provides a catalyst component D1, the preparation process of which is the same as in Example 1, except that quercetin ether is replaced with 6 mmol of di-n-butyl phthalate (DN).

[0127] Comparative Example 2

[0128] This comparative example provides a catalyst component D2, which is prepared in the same manner as in Example 1, except that quercetin ether is replaced with 6 mmol of 9,9-dimethoxymethylfluorene (FLU).

[0129] Example 1 of Aggregation

[0130] The catalyst components obtained above were used as raw materials for olefin polymerization catalysts for polymerization evaluation:

[0131] After the 5L stainless steel reactor was fully purged with nitrogen, 5mL of 0.5mol / L triethylaluminum hexane solution, 1mL of 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 refined propylene. The reaction was prepolymerized at 25℃ for 5 minutes, then the temperature was raised to 70℃ and polymerized 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 3.

[0132] Table 3

[0133] As can be seen from Table 3, under the same preparation conditions, the catalyst components of Examples 1-18 have higher activity than the phthalate internal electron donor catalyst of Comparative Example 1, and higher activity than the diether catalyst of Comparative Example 2. They also have better stereoselectivity, higher isotacticity of the obtained polymer, more regular polymer particle size, and higher packing density.

[0134] Example 2 of Aggregation

[0135] Evaluation of olefin polymerization using catalyst components C7 and C17 as constituent raw materials for olefin polymerization catalysts:

[0136] After the 5L stainless steel reactor was fully purged with nitrogen, 5mL of 0.5mol / L triethylaluminum hexane solution, 1mL of 0.1mol / L methylcyclohexyldimethoxysilane hexane solution, the activity modifier of the types and amounts described in Table 4 (hexane solution of 0.1mol / L activity modifier), 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 refined propylene. The reaction was controlled at 25℃ for prepolymerization for 5 minutes, then the temperature was raised to 70℃ and polymerized 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 temperature fluctuations in the reactor and the polymerization data of the polymer during the polymerization reaction are shown in Table 4.

[0137] Table 4 Note: In Table 4, a represents ethyl piperate; b represents isopropyl piperate; c represents n-octyl piperate; and d represents phenyl piperate.

[0138] As shown in Table 4, when catalyst components C7 and C17 were polymerized without the addition of an activity regulator, the temperature fluctuation inside the reactor was within ±3℃. After the addition of the activity regulator, the temperature fluctuation was significantly reduced, and the resulting polypropylene still maintained a high level of isotacticity and bulk density. The catalytic activity was slightly reduced, but it was still significantly higher than that of comparative examples 1 and 2. Therefore, adding an activity regulator to the catalyst components is more suitable for meeting the requirements of stable operation of industrial plants.

[0139] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

Claims

1. A catalyst component for olefin polymerization, characterized in that, Its composition includes: Mg, Ti, halogens and internal electron donors, wherein the internal electron donors include quercetin and / or quercetin derivatives.

2. The catalyst component according to claim 1, characterized in that, The quercetin derivatives include the quercetin ether structures shown in Formula I: In Equation I, R 1 To R 5 Each substituent is independently selected from a first heteroatom or a substituent of 20 or fewer carbon atoms; the substituent includes at least one of straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indene, benzyl, haloalkyl, halocycloalkyl, halophenyl, haloalkylphenyl, halophenylalkyl, haloindenyl, halobenzyl, heterocyclic aryl substituent, and optionally contains a second heteroatom; the first heteroatom is at least one of N, O, S, P, Si and halogen, and the second heteroatom is at least one of N, O, S, P, Si.

3. The catalyst component according to claim 2, characterized in that, R 1 To R 5 Each of the following substituents, independently selected from halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C11-C20 straight-chain or branched alkyl groups, and having 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, and indene; more preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

4. The catalyst component according to claim 2, characterized in that, The quercetin derivatives include at least one of quercetin ethyl ether, quercetin methyl ether, quercetin benzyl ether, and quercetin p-methoxybenzyl ether.

5. The catalyst component according to any one of claims 1-4, characterized in that, The quercetin derivatives include the quercetin ester structures shown in Formula II: In Equation II, R 6 To R 10 Each substituent is independently selected from H, a first heteroatom, or a substituent with up to 20 carbon atoms; the substituent includes at least one of straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indene, benzyl, haloalkyl, halocycloalkyl, halophenyl, haloalkylphenyl, halophenylalkyl, haloindenyl, halobenzyl, heterocyclic aryl substituent, and optionally contains a second heteroatom; the first heteroatom is at least one of N, O, S, P, Si, and halogen, and the second heteroatom is at least one of N, O, S, P, Si.

6. The catalyst component according to claim 5, characterized in that, R 6 To R 10 Each of the following substituents, independently selected from halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C11-C20 straight-chain or branched alkyl groups, and having 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, and indene; more preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

7. The catalyst component according to claim 6, characterized in that, The quercetin derivatives include at least one of quercetin benzoate, quercetin phenylacetate, quercetin m-chlorobenzoate, quercetin p-methoxybenzoate, quercetin p-nitrobenzoate, quercetin furanoate, quercetin isonicotinate, quercetin cyclohexylcarboxylate, quercetin ethyl ester, quercetin isobutyl ester, and quercetin n-octyl ester.

8. The catalyst component according to claim 1, characterized in that, The catalyst component comprises: a titanium compound, a magnesium compound, and the internal electron donor; the magnesium compound is selected from X. n Mg(OR a ) 2-n MgCl2·mR a OH, R a 2-n MgX n At least one of the following: a mixture of MgCl2 and SiO2, a mixture of MgCl2 and Al2O3, and a mixture of magnesium halide and titanium alkoxide, wherein 0.1 ≤ m ≤ 6, 0 ≤ n ≤ 2, X is a halogen, and R a For C1-C 20 hydrocarbon group; And / or, 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 0 ≤ N ≤ 4.

9. The catalyst component according to claim 8, characterized in that, The magnesium compound is an alkoxide of magnesium dihalide, a liquid magnesium compound, or a derivative in which at least one halogen atom in a magnesium dihalide molecule is replaced by a hydrocarbon or halohydroxyl group; preferably a hydrocarbon-oxygenated magnesium compound; more preferably alkoxymagnesium and / or aryloxymagnesium.

10. The catalyst component according to claim 8, characterized in that, The titanium compound includes at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and titanium alkoxyhalides; preferably, the titanium alkoxyhalides include at least one of titanium methoxytrichloride, titanium ethoxytrichloride, titanium propoxytrichloride, titanium n-butoxytrichloride, titanium dimethoxydichloride, titanium diethoxydichloride, titanium dipropoxydichloride, titanium dibutoxydichloride, titanium dibutoxydichloride, titanium trimethoxytrichloride, titanium triethoxytrichloride, titanium tripropoxytrichloride, and titanium tributoxydichloride.

11. The catalyst component according to claim 8, characterized in that, The molar ratio of the internal electron donor to the magnesium element in the magnesium compound is 0.01-5.0:1, preferably 0.05-3.0:

1.

12. A catalyst for olefin polymerization, characterized in that, Its raw material composition includes the catalyst component as described in any one of claims 1-11 and an organoaluminum compound.

13. The catalyst according to claim 12, 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, 0≤p≤3, and p is an integer; Preferably, the organoaluminum compound includes at least one of trialkylaluminum compound, alkylaluminum halide, alkylaluminum hydride, alkylaluminum sesquichloride, and alkylaluminoxane; Preferably, the trialkylaluminum compound includes at least one selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and trioctylaluminum; the alkylaluminum halide includes AlEt2Cl; and the alkylaluminum sesquichloride includes Al2Et3Cl3. Preferably, the organoaluminum compound is a mixture of AlEt2Cl and Al2Et3Cl3.

14. The catalyst according to claim 12, characterized in that, The molar ratio of the organoaluminum compound to the titanium element in the catalyst component is 1-1000:1, preferably 50-800:

1.

15. The catalyst according to claim 12, characterized in that, The catalyst's feedstock composition also includes an external electron donor.

16. The catalyst according to claim 15, characterized in that, The external electron donor is a siloxane compound.

17. The catalyst according to claim 16, characterized in that, The general formula of the siloxane compound is R' β Si(OR”) 4-β In this context, R' and R” are each independently selected from C1-C 18 The hydrocarbon group optionally contains heteroatoms, 0 ≤ β ≤ 3, and β is an integer; the heteroatoms include at least one of N, O, S, P, and Si.

18. The catalyst according to claim 16 or 17, characterized in that, The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100:1; preferably 0.01-20:1; more preferably 0.01-5:

1.

19. The catalyst according to claim 15, characterized in that, The catalyst's raw material composition further includes an activity modifier; wherein the activity modifier has the molecular structure shown in Formula III: In Equation III, R 11 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 Any of the ester groups, optionally containing a third heteroatom, said third heteroatom being at least one of N, O, S, P, and Si.

20. The catalyst according to claim 19, characterized in that, R 11 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 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, and indene.

21. The catalyst according to claim 19, characterized in that, The active modifier includes at least one of 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.

22. The catalyst according to any one of claims 19-21, characterized in that, The molar ratio of the active modifier to the external electron donor is 0.02-50:1, preferably 0.1-10:

1.

23. The use of the catalyst according to any one of claims 12-22 in olefin polymerization.

Images