Catalyst component for olefin polymerization, catalyst and application thereof

Abstract

The invention provides a catalyst component for olefin polymerization, a catalyst and application thereof, the catalyst component comprises Mg, Ti, halogen and an internal electron donor, and the internal electron donor comprises methyl gallate and / or a methyl gallate derivative. The invention provides the catalyst component taking the methyl gallate and / or the derivative thereof as the internal electron donor, the activity of the catalyst component is generally higher than that of the most commonly used catalysts of phthalate and diether internal electron donors in the industry, the stereoselectivity is good, and a polymer obtained by catalysis is high in isotacticity, regular in particle size and high in bulk density.

Description

Technical Field

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

[0002] Currently, the main catalysts for producing polyolefins are the Ziegler-Natta (ZN) catalytic system, characterized by high activity, high stereoregularity, long lifespan, and customizable product structure. 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) to the ZN catalyst can significantly influence the polymerization behavior and polymer properties of olefins. Therefore, by altering the internal electron donor in the catalyst, the properties of the active center can be changed to the greatest extent possible, thereby maximizing the modification of the catalyst's performance.

[0003] The high-performance internal electron donor compounds with distinctive features in the existing technology mainly include: (1) fatty acid esters and aromatic acid esters, mainly represented by phthalate esters; (2) diethers; (3) succinates; (4) glycol esters; (5) compounds with other functional groups. However, in practical applications, the above compounds have certain problems as internal electron donors for olefin polymerization catalysts. Catalysts prepared with phthalate esters have moderate activity, good stereoselectivity, and low price, but phthalate esters are commonly used plasticizers and have great harm to human reproductive health and the environment. Although the catalysts using 1,3-diethers as internal electron donors have improved activity compared with phthalate esters, there is still room for improvement. The advantage of using succinates as internal electron donors is that the synthesized PP has a wider relative molecular mass distribution, but the disadvantage is that the stereoregularity of PP needs to be improved. The overall activity of glycol ester catalytic systems is not as ideal as that of diether systems. Summary of the Invention

[0004] This invention provides a catalyst component for olefin polymerization. This catalyst component has high catalytic activity and good stereoselectivity, and the polymer obtained by catalytic polymerization has high isotacticity, regular particle size, and high bulk density.

[0005] The present invention 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.

[0006] The present invention also provides an application of the above-mentioned catalyst in olefin polymerization.

[0007] In a first aspect, the present invention provides a catalyst component for olefin polymerization, comprising: Mg, Ti, halogen and an internal electron donor, wherein the internal electron donor comprises methyl gallate and / or methyl gallate derivatives.

[0008] In a preferred embodiment, the methyl gallate derivative comprises the molecular structure shown in Formula I:

[0009]

[0010] In Equation I, R 1 To R 3 Each substituent is independently selected from a first heteroatom or a substituent of up to 20 carbon atoms; the substituent is selected from at least one of straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, fused-ring aryl, benzyl, haloalkyl, halocycloalkyl, halophenyl, haloalkylphenyl, halophenylalkyl, halofused-ring aryl, halobenzyl, heterocyclic aryl substituent, 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, Si.

[0011] In a preferred embodiment, R 1 To R 3 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 fused-ring aryl; more preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

[0012] In a preferred embodiment, the methyl gallate derivative includes at least one of methyl gallate trimethyl ether, methyl gallate triethyl ether, methyl gallate tri-n-propyl ether, methyl gallate tri-n-butyl ether, methyl gallate tri-n-pentyl ether, methyl gallate tri-n-octyl ether, methyl gallate tribenzyl ether, and methyl gallate trifuran methyl ether.

[0013] In a preferred embodiment, the methyl gallate derivative comprises the molecular structure shown in Formula II:

[0014]

[0015] In Equation II, R 4 To R 6 Each substituent is independently selected from H, a first heteroatom, and a substituent with up to 20 carbon atoms; the substituent is selected from at least one of straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, fused-ring aryl, benzyl, haloalkyl, halocycloalkyl, halophenyl, haloalkylphenyl, halophenylalkyl, halofused-ring aryl, 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 a halogen, and the second heteroatom is at least one of N, O, S, P, and Si.

[0016] In a preferred embodiment, R 4 To R 6 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 fused-ring aryl; more preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

[0017] In a preferred embodiment, the methyl gallate derivative includes methyl gallate triacetylphenol ester, methyl gallate tripropanoic acid ester, methyl gallate tributanoic acid ester, methyl gallate trivalerate ester, methyl gallate trihexanoic acid ester, methyl gallate triheptanoic acid ester, methyl gallate trioctanoic acid ester, methyl gallate trinonanoic acid ester, methyl gallate trilauric acid ester, methyl gallate tribenzoylphenol ester, and methyl gallate triphenylethylphenol ester. The first of the following: methyl gallate, methyl gallate trichlorobenzoylphenol ester, methyl gallate triisonicotinic phenol ester, methyl gallate tri-p-butylbenzoylphenol ester, methyl gallate tri-p-cyanobenzoylphenol ester, methyl gallate tri-o-acetylsalicylic acid benzoylphenol ester, methyl gallate tri-p-methoxybenzoylphenol ester, methyl gallate tri-p-methylbenzoylphenol ester, methyl gallate tri-p-nitrobenzoylphenol ester, and methyl gallate tri-pentafluorobenzoylphenol ester.

[0018] In a preferred embodiment, the methyl gallate derivative comprises a mixture of compounds with molecular structures shown in Formula I and Formula II, wherein the molar ratio of the compounds with molecular structures shown in Formula I and Formula II is 1-9:1-9.

[0019] In a preferred embodiment, 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;

[0020] 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.

[0021] In a preferred embodiment, 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.

[0022] In a preferred embodiment, 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.

[0023] In a preferred embodiment, 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.

[0024] Secondly, the present invention provides a catalyst for olefin polymerization, the raw material composition of which includes the above-mentioned catalyst components and organoaluminum compounds.

[0025] In a preferred embodiment, the organoaluminum compound has the general formula AlR c p X (3-p) , where Rc It is hydrogen or C1-C 20 The hydrocarbon group, X is a halogen, 0≤p≤3, and p is an integer.

[0026] In a preferred embodiment, the organoaluminum compound includes at least one of trialkylaluminum compounds, alkylaluminum halides, alkylaluminum hydrides, alkylaluminum sesquichlorides, and alkylaluminoxanes.

[0027] In a preferred embodiment, 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.

[0028] In a preferred embodiment, the organoaluminum compound is a mixture of AlEt2Cl and Al2Et3Cl3.

[0029] In a preferred embodiment, the molar ratio of the organoaluminum compound to the titanium element in the catalyst component is 1-1000:1, preferably 50-800:1.

[0030] In a preferred embodiment, the catalyst's feedstock composition further includes an external electron donor.

[0031] In a preferred embodiment, the external electron donor is a siloxane compound.

[0032] In a preferred embodiment, 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.

[0033] In a preferred embodiment, 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.

[0034] In a preferred embodiment, the raw material composition of the catalyst further includes an activity modifier; wherein the activity modifier includes piperate derivatives and / or paeonol derivatives.

[0035] In a preferred embodiment, the piperitate derivative has the molecular structure shown in Formula III:

[0036]

[0037] In Equation III, R 7 Selected from C1-C 20 Straight-chain or branched alkyl groups and their derivatives, C3-C 20 cycloalkyl, C6-C 20 aryl and its derivatives, C 7- C 20 Araneyl groups and their derivatives, C2-C 10 olefin group, C 10 -C 20 Fused ring aryl, C 10 -C 20 One of the ester groups, optionally containing a third heteroatom, said third heteroatom being at least one of N, O, S, P, and Si.

[0038] In a preferred embodiment, R 7 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: 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 fused-ring aryl.

[0039] In a preferred embodiment, the piperate ester derivative is selected from 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.

[0040] In a preferred embodiment, the paeonol derivative has the molecular structure shown in Formula IV:

[0041]

[0042] In equation IV, R 8 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 20One of the ester groups, optionally containing a third heteroatom, said third heteroatom being at least one of N, O, S, P, and Si.

[0043] In a preferred embodiment, R 8 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: 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 fused-ring aryl.

[0044] In a preferred embodiment, the paeonol derivative includes 2-methyl ether-4-methoxyacetophenone, 2-ethyl ether-4-methoxyacetophenone, 2-propyl ether-4-methoxyacetophenone, 2-butyl ether-4-methoxyacetophenone, 2-anisole-4-methoxyacetophenone, 2-acetylphenol ester-4-methoxyacetophenone, 2-propionylphenol ester-4-methoxyacetophenone, 2-butyrylphenol ester-4-methoxyacetophenone, and 2-pentanoylphenol ester. At least one of the following: 4-methoxyacetophenone, 2-hexanoylphenol ester-4-methoxyacetophenone, 2-benzoylphenol ester-4-methoxyacetophenone, 2-phenylacetylphenol ester-4-methoxyacetophenone, 2-m-chlorobenzoylphenol ester-4-methoxyacetophenone, 2-p-chlorobenzoylphenol ester-4-methoxyacetophenone, 2-p-methoxybenzoylphenol ester-4-methoxyacetophenone, and 2-p-nitrobenzoylphenol ester-4-methoxyacetophenone.

[0045] In a preferred embodiment, the activity regulator comprises piperate derivative and paeonol derivative, wherein the molar ratio of piperate derivative and paeonol derivative is 0.02-50, preferably 0.05-20, and more preferably 0.1-10.

[0046] In a preferred embodiment, the molar ratio of the active modifier to the external electron donor is 0.02-50:1, preferably 0.1-10:1.

[0047] Thirdly, the present invention provides an application of the catalyst described in the second aspect above in olefin polymerization.

[0048] This invention provides a catalyst component with methyl gallate and / or its derivatives as internal electron donors. Its activity is generally higher than that of the most commonly used phthalate and diether internal electron donor catalysts in industry. It also has good stereoselectivity and produces polymers with high isotacticity, regular particle size, and high packing density. Detailed Implementation

[0049] To enable those skilled in the art to better understand the present invention, the present invention will be further described in detail below. The specific embodiments listed below are merely descriptions of the principles and features of the present invention, and the examples are only for explaining the present invention and are not intended to limit the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0050] 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.

[0051] 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.

[0052] Low catalyst activity in olefin polymerization increases production costs, increases product ash content, affects product quality, and reduces the competitiveness of polyolefin products. Therefore, it is necessary to improve catalyst activity to meet production requirements. To address this, the present invention adopts the following technical solution:

[0053] In a first aspect, the present invention provides a catalyst component for olefin polymerization, comprising: Mg, Ti, halogen and an internal electron donor, wherein the internal electron donor comprises methyl gallate and / or methyl gallate derivatives.

[0054] Among them, methyl gallate and / or methyl gallate derivatives contain multiple oxygen-containing functional groups in the main aromatic ring structure, which are 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 the catalytic performance. In addition, the reaction substrates of methyl gallate and / or methyl gallate derivatives are gallic acid or methyl gallate, which are inexpensive, readily available, safe and environmentally friendly, which is beneficial to environmental protection and product cost control.

[0055] Preferably, the methyl gallate derivative comprises the molecular structure shown in Formula I:

[0056]

[0057] In Equation I, R 1 To R 3 Each substituent is independently selected from a first heteroatom or a substituent of up to 20 carbon atoms; the substituent is selected from at least one of straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, fused-ring aryl, benzyl, haloalkyl, halocycloalkyl, halophenyl, haloalkylphenyl, halophenylalkyl, halofused-ring aryl, halobenzyl, heterocyclic aryl substituent, 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, Si.

[0058] It is understandable that in Equation I, R 1 R 2 R 3 Same or different.

[0059] Preferably, R 1 To R 3 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 fused-ring aryl; more preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

[0060] Preferably, the methyl gallate derivative includes at least one of methyl gallate trimethyl ether, methyl gallate triethyl ether, methyl gallate tri-n-propyl ether, methyl gallate tri-n-butyl ether, methyl gallate tri-n-pentyl ether, methyl gallate tri-n-octyl ether, methyl gallate tribenzyl ether, and methyl gallate trifuran methyl ether.

[0061] In a preferred embodiment, the methyl gallate derivative comprises the molecular structure shown in Formula II:

[0062]

[0063] In Equation II, R 4 To R 6Each substituent is independently selected from H, a first heteroatom, and a substituent with up to 20 carbon atoms; the substituent is selected from at least one of straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, fused-ring aryl, benzyl, haloalkyl, halocycloalkyl, halophenyl, haloalkylphenyl, halophenylalkyl, halofused-ring aryl, 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 a halogen, and the second heteroatom is at least one of N, O, S, P, and Si.

[0064] It is understandable that in Equation II, R 4 R 5 R 6 Same or different.

[0065] Preferably, R 4 To R 6 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 fused-ring aryl; more preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

[0066] Preferably, the methyl gallate derivatives include methyl gallate triacetylphenol ester, methyl gallate tripropanoic acid ester, methyl gallate tributanoic acid ester, methyl gallate trivalerate ester, methyl gallate trihexanoic acid ester, methyl gallate triheptanoic acid ester, methyl gallate trioctanoic acid ester, methyl gallate trinonanoic acid ester, methyl gallate trilauric acid ester, methyl gallate tribenzoylphenol ester, and methyl gallate triphenylacetic acid ester. The ester, at least one of the following: methyl gallate trichlorobenzoylphenol ester, methyl gallate triisonicotinic phenol ester, methyl gallate tri-p-butylbenzoylphenol ester, methyl gallate tri-p-cyanobenzoylphenol ester, methyl gallate tri-o-acetylsalicylic acid benzoylphenol ester, methyl gallate tri-p-methoxybenzoylphenol ester, methyl gallate tri-p-methylbenzoylphenol ester, methyl gallate tri-p-nitrobenzoylphenol ester, and methyl gallate tri-pentafluorobenzoylphenol ester.

[0067] Preferably, the methyl gallate derivative comprises a mixture of compounds with molecular structures shown in Formula I and Formula II, wherein the molar ratio of the compounds with molecular structures shown in Formula I and Formula II is 1-9:1-9.

[0068] 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 hydrocarbon group;

[0069] 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.

[0070] 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.

[0071] 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 tripropoxytrichloride, and titanium dibutoxydichloride.

[0072] 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.

[0073] Preferably, the internal electron donor comprises a mixture of compounds with molecular structures shown in Formula I and Formula II, wherein the molar ratio of the compounds with molecular structures shown in Formula I and Formula II is 1-9:1-9.

[0074] For example, the internal electron donor is a mixture of the compound of Formula I and the compound of Formula II, wherein the molar ratio of the compound of Formula I to the compound of Formula II is 1:9; preferably, the molar ratio of the compound of Formula I to the compound of Formula II is 3:7; the molar ratio of the compound of Formula I to the compound of Formula II is 5:5; the molar ratio of the compound of Formula I to the compound of Formula II is 7:3; or the molar ratio of the compound of Formula I to the compound of Formula II is 9:1.

[0075] 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 with the molecular structure shown in Formula I can be prepared using at least three equivalents of a single alcohol or haloalkane to obtain R. 1 -R 3 The same product, R 1 -R 3 Different products can be produced by using different alcohols or haloalkanes as starting materials, either added in batches or simultaneously to the reaction.

[0076] In detail, R 1 To R 3 At the same time, it can be achieved through reactions including but not limited to those shown in Formula I below (where substituents are all represented as R in Formula I). 1 The preparation method of ) is used for synthesis.

[0077] Reaction I:

[0078]

[0079] Compounds with the molecular structure shown in Formula II can be synthesized by methods including, but not limited to, the following: methyl gallate reacts with an acyl chloride in one step to obtain methyl gallate phenolate; R can be obtained using at least three equivalents of a single acyl chloride. 4 -R 6 The same product, R 4 -R 6 Different products can be produced by using different acyl chlorides as starting materials, either added in batches or simultaneously to the reaction.

[0080] In detail, R 4 -R 6 At the same time, it can be achieved through reactions including but not limited to those shown in Formula II below (where substituents are all represented as R in Formula II). 4 The preparation method of ) is used for synthesis.

[0081] Reaction II:

[0082]

[0083] The present invention 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.

[0084] In detail, it can be done in the following ways:

[0085] 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 20 Catalyst components are prepared by reacting hydrocarbon groups and internal electron donors.

[0086] 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.

[0087] 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).

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] In the preparation methods exemplified above or any other existing catalyst components, the internal electron donor can be added directly or through other optional 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. Furthermore, the internal electron donor can be added simultaneously or separately during the preparation process, in batches or in any order and combination.

[0095] Secondly, the present invention provides a catalyst for olefin polymerization, the raw material composition of which includes the above-mentioned catalyst components and organoaluminum compounds.

[0096] 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, 0≤p≤3, and p is an integer.

[0097] Preferably, the organoaluminum compound includes at least one of trialkylaluminum compounds, alkylaluminum halides, alkylaluminum hydrides, alkylaluminum sesquichlorides, and alkylaluminoxanes.

[0098] 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.

[0099] Preferably, the organoaluminum compound is a mixture of AlEt2Cl and Al2Et3Cl3.

[0100] 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.

[0101] Preferably, the raw material composition of the catalyst further includes an external electron donor.

[0102] Preferably, the external electron donor is a siloxane compound.

[0103] 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.

[0104] 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 combinations of 5-dimethylcyclohexylcyclohexyldimethoxysilane, bis(3,5-dimethylcyclohexyl)dimethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] Preferably, the raw material composition of the catalyst further includes an activity modifier; wherein the activity modifier includes piperate derivatives and / or paeonol derivatives.

[0109] Low catalyst activity reduces the competitiveness of polyolefin products. However, when high-activity catalysts are used in polyolefin plants, the polymerization temperature often fluctuates greatly due to uneven active centers, excessively high initial reaction rates, and large activity fluctuations, affecting stable production and product quality. In this invention, if the above-mentioned activity regulator is added to the catalyst components, the temperature fluctuation in the polymerization reactor can be slowed down by suppressing the initial catalyst activity burst, making the polymerization reaction more stable and beneficial to industrial production.

[0110] Preferably, the piperate derivative comprises the molecular structure shown in Formula III:

[0111]

[0112] In Equation III, R 7 Selected from C1-C 20 Straight-chain or branched alkyl groups and their derivatives, C3-C 20 cycloalkyl, C6-C 20 aryl and its derivatives, C 7- C 20 Araneyl groups and their derivatives, C2-C 10 olefin group, C 10 -C 20 Fused ring aryl, C 10 -C 20 One of the ester groups, optionally containing a third heteroatom, said third heteroatom being at least one of N, O, S, P, and Si.

[0113] Preferably, R 7 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: 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 fused-ring aryl.

[0114] Preferably, the piperate ester derivative is selected from 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.

[0115] Preferably, the paeonol derivative comprises the molecular structure shown in Formula IV:

[0116]

[0117] In equation IV, R 8 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 20Araneyl groups and their derivatives, C2-C 10 olefin group, C 10 -C 20 Fused ring aryl, C 10 -C 20 One of the ester groups, optionally containing a third heteroatom, said third heteroatom being at least one of N, O, S, P, and Si.

[0118] Preferably, R 8 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: 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 fused-ring aryl.

[0119] Preferably, the paeonol derivatives include 2-methyl ether-4-methoxyacetophenone, 2-ethyl ether-4-methoxyacetophenone, 2-propyl ether-4-methoxyacetophenone, 2-butyl ether-4-methoxyacetophenone, 2-anisole-4-methoxyacetophenone, 2-acetylphenol ester-4-methoxyacetophenone, 2-propanoylphenol ester-4-methoxyacetophenone, 2-butanoylphenol ester-4-methoxyacetophenone, 2-pentanoylphenol ester-4- At least one of the following: methoxyacetophenone, 2-hexanoylphenol ester-4-methoxyacetophenone, 2-benzoylphenol ester-4-methoxyacetophenone, 2-phenylacetylphenol ester-4-methoxyacetophenone, 2-m-chlorobenzoylphenol ester-4-methoxyacetophenone, 2-p-chlorobenzoylphenol ester-4-methoxyacetophenone, 2-p-methoxybenzoylphenol ester-4-methoxyacetophenone, and 2-p-nitrobenzoylphenol ester-4-methoxyacetophenone.

[0120] Preferably, the active regulator comprises piperate ester derivatives and paeonol derivatives, and the molar ratio of piperate ester derivatives to paeonol derivatives is 0.02-50, preferably 0.05-20, and more preferably 0.1-10.

[0121] Preferably, the molar ratio of the active regulator to the external electron donor is 0.02-50:1, more preferably 0.1-10:1.

[0122] Thirdly, the present invention provides an application of the catalyst described in the second aspect above in olefin polymerization.

[0123] 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.

[0124] According to a specific embodiment of the present invention, the polymerization includes ethylene and / or propylene polymerization.

[0125] According to a specific embodiment of the present invention, the polymerization includes homopolymerization or copolymerization.

[0126] According to a specific embodiment of the present invention, 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.

[0127] 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.

[0128] 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.

[0129] The present invention will be further described below with reference to specific embodiments:

[0130] 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.

[0131] The bulk density of the polymer was determined using the method specified in JB / T 2412-2008.

[0132] Example of internal electron donor preparation

[0133] Synthesis of compounds with the molecular structure shown in Formula I

[0134] 0.1 mol of methyl gallate was dissolved in acetonitrile. 0.33 mol of potassium carbonate and 0.33 mol of iodomethane were added to the solution, and the mixture was heated under reflux for 24 hours. The mixture was filtered, and the residue was washed with dichlorohexane and dried under rotary evaporation. 200 mL of water and 300 mL of dichloromethane were added, and the aqueous phase was extracted with 300 mL of dichloromethane. This process was repeated twice. The organic phases were combined and washed with 100 mL of saturated brine. The organic phase was dried with anhydrous sodium sulfate, filtered, dried under rotary evaporation, and vacuum dried (60 °C) overnight to obtain product a1.

[0135] a2-a5 were synthesized using the route described above, the only difference being the selection of halogenated derivatives with corresponding substituents for synthesis. The structures and NMR results are shown in Table 1.

[0136]

[0137] Table 1 shows the compounds with molecular structures represented by Formula I.

[0138]

[0139]

[0140] Synthesis of compounds with the molecular structure shown in Formula II

[0141] Under nitrogen protection, 10 g of methyl gallate was dissolved in 300 mL of anhydrous tetrahydrofuran in a dry 500 mL Schlenk flask, 20 mL of pyridine was added, followed by 24 mL of benzoyl chloride, and the mixture was heated under reflux overnight. After cooling to room temperature, the mixture was washed with brine and extracted with ethyl acetate to obtain the organic phase. The organic phase was dried and concentrated to obtain the crude product, which could be directly recrystallized from hexane and ethyl acetate to obtain product a6.

[0142] a7-a18 were synthesized using the route described above, the only difference being the selection of acyl chlorides with corresponding substituents for synthesis. The structures and NMR results are shown in Table 2.

[0143]

[0144] Compounds with molecular structures shown in Formula II in Table 2

[0145]

[0146]

[0147] Catalyst component preparation example

[0148] Example 1

[0149] This embodiment provides a catalyst component, comprising Mg, Ti, halogen, and compound a1. The preparation method of the catalyst component is as follows:

[0150] In a 500 mL stirred flask fully purged with nitrogen, 10 g of MgCl2·2.5C2H5OH microspheres and 150 mL of titanium tetrachloride were added to prepare a suspension. The suspension was then maintained at -15 °C for 1 hour, slowly heated to 80 °C, and 10 mmol of trimethyl gallate (a1) was added. The temperature was further increased to 110 °C and held 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, and 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.

[0151] Example 2-18

[0152] Examples 2-18 provide catalyst components including catalyst components C2-C15 respectively. The preparation process of the catalyst components is as shown in Example 1, except that trimethyl gallate methyl ether (a1) is replaced with 10 mmol of compounds a2-a18 in Table 1 and Table 2 respectively.

[0153] Example 19

[0154] This embodiment provides a catalyst component including catalyst component C19. The preparation process of the catalyst component is as shown in Example 1, except that 10 mmol of methyl gallate trimethyl ether (a1) is replaced with 1 mmol of methyl gallate trimethyl ether (a1) and 9 mmol of methyl gallate tribenzoate (a6).

[0155] Example 20

[0156] This embodiment provides a catalyst component including catalyst component C20. The preparation method of the catalyst component is as shown in Example 1, except that 10 mmol of methyl gallate trimethyl ether (a1) is replaced with 3 mmol of methyl gallate trimethyl ether (a1) and 7 mmol of methyl gallate tribenzoate (a6).

[0157] Example 21

[0158] This embodiment provides a catalyst component including catalyst component C21. The preparation method of the catalyst component is as shown in Example 1, except that 10 mmol of methyl gallate trimethyl ether (a1) is replaced with 5 mmol of methyl gallate trimethyl ether (a1) and 5 mmol of methyl gallate tribenzoate (a6).

[0159] Example 22

[0160] This embodiment provides a catalyst component including catalyst component C22. The preparation method of the catalyst component is as shown in Example 1, except that 10 mmol of methyl gallate trimethyl ether (a1) is replaced with 7 mmol of methyl gallate trimethyl ether (a1) and 3 mmol of methyl gallate tribenzoate (a6).

[0161] Example 23

[0162] This embodiment provides a catalyst component including catalyst component C23. The preparation method of the catalyst component is as shown in Example 1, except that 10 mmol of methyl gallate trimethyl ether (a1) is replaced with 9 mmol of methyl gallate trimethyl ether (a1) and 1 mmol of methyl gallate tribenzoate (a6).

[0163] Example 24

[0164] This embodiment provides a catalyst component including catalyst component C24. The preparation method of the catalyst component is as follows:

[0165] 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. 10 mmol of trimethyl gallate (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, catalyst component C24 was obtained. The titanium content, internal electron donor content, and polymerization data of the catalyst components are shown in Table 3.

[0166] Example 25

[0167] This embodiment provides a catalyst component including catalyst component C25, and the preparation method of the catalyst component is as follows:

[0168] 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 10 mmol of trimethyl gallate (a1) 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 C25. The titanium content, internal electron donor content, and polymerization data of this catalyst component are shown in Table 3.

[0169] Example 26

[0170] This embodiment provides a catalyst component including catalyst component C26, and the preparation method of the catalyst component is as follows:

[0171] 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. 10 mmol of methyl gallate and tribenzoic acid ester (a6) were 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 C26 was obtained. The titanium content, internal electron donor content, and polymerization data of the catalyst components are shown in Table 3.

[0172] Example 27

[0173] This embodiment provides a catalyst component including catalyst component C27, and the preparation method of the catalyst component is as follows:

[0174] 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 10 mmol of methyl gallate and phenolic tribenzoate (a6) were 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 C27. The titanium content, internal electron donor content, and polymerization data of this catalyst component are shown in Table 3.

[0175] Comparative Example 1

[0176] This comparative example provides a catalyst component, including catalyst component D1, which is prepared in the same manner as in Example 1, except that a1 is replaced with 10 mmol of di-n-butyl phthalate (DN).

[0177] Comparative Example 2

[0178] This comparative example provides a catalyst component, including catalyst component D2, which is prepared in the same manner as in Example 1, except that a1 is replaced with 10 mmol of 9,9-dimethoxymethylfluorene (FLU).

[0179] Example 1 of Aggregation

[0180] Evaluation of olefin polymerization using catalysts containing the above-mentioned catalyst components:

[0181] 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.

[0182] Table 3

[0183]

[0184]

[0185] As can be seen from Table 3, the catalyst components of Examples 1-27, under the same preparation conditions, have significantly higher activity than the phthalate internal electron donor catalyst of Comparative Example 1 and the diether catalyst of Comparative Example 2, and the isotacticity and packing density of the resulting polymers are also maintained in a high range.

[0186] Example 2 of Aggregation

[0187] Evaluation of olefin polymerization using catalysts that include C6 catalyst component:

[0188] 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 type and amount of activity modifier listed in Table 4 (0.1 mol / L hexane solution of the activity modifier), 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.

[0189] Table 4

[0190]

[0191]

[0192] Note: b1: Isopropyl piperate, b2: n-Amyl piperate, b3: Isooctyl piperate, b4: Phenyl piperate, b5: 2-methyl ether-4-methoxyacetophenone, b6: 2-butyrophenol ester-4-methoxyacetophenone, b7: 2-benzoylphenol ester-4-methoxyacetophenone.

[0193] As shown in Table 4, when no activity regulator is added during the polymerization of the catalyst components, the temperature fluctuation inside the reactor is within ±3℃. After adding the activity regulator, the temperature fluctuation is significantly reduced, and the obtained polypropylene still maintains a high level of isotacticity and bulk density. The catalytic activity is slightly reduced, but it is still significantly higher than that of Comparative Example 1. Therefore, adding an activity regulator to the catalyst components is more suitable for meeting the requirements of stable operation of industrial plants.

[0194] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention 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; and these 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 the present invention.

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 methyl gallate and / or methyl gallate derivatives.

2. The catalyst component according to claim 1, characterized in that, The methyl gallate derivative comprises the molecular structure shown in Formula I: In Equation I, R 1 To R 3 Each substituent is independently selected from a first heteroatom or a substituent of up to 20 carbon atoms; the substituent is selected from at least one of straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, fused-ring aryl, benzyl, haloalkyl, halocycloalkyl, halophenyl, haloalkylphenyl, halophenylalkyl, halofused-ring aryl, halobenzyl, heterocyclic aryl substituent, 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, Si.

3. The catalyst component according to claim 2, characterized in that, R 1 To R 3 Each of the following substituents, 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, 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 fused-ring aryl; more preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

4. The catalyst component according to claim 2, characterized in that, The methyl gallate derivatives include at least one of the following: methyl gallate trimethyl ether, methyl gallate triethyl ether, methyl gallate tri-n-propyl ether, methyl gallate tri-n-butyl ether, methyl gallate tri-n-pentyl ether, methyl gallate tri-n-octyl ether, methyl gallate tribenzyl ether, and methyl gallate trifuran methyl ether.

5. The catalyst component according to any one of claims 1-4, characterized in that, The methyl gallate derivative comprises the molecular structure shown in Formula II: In Equation II, R 4 To R 6 Each substituent is independently selected from H, a first heteroatom, and a substituent with up to 20 carbon atoms; the substituent is selected from at least one of straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, fused-ring aryl, benzyl, haloalkyl, halocycloalkyl, halophenyl, haloalkylphenyl, halophenylalkyl, halofused-ring aryl, 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 a halogen, and the second heteroatom is at least one of N, O, S, P, and Si.

6. The catalyst component according to claim 5, characterized in that, R 4 To R 6 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 fused-ring aryl; more preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

7. The catalyst component according to claim 5, characterized in that, The methyl gallate derivatives include methyl gallate triacetylphenol ester, methyl gallate tripropanoic acid ester, methyl gallate tributanoic acid ester, methyl gallate trivalerate ester, methyl gallate trihexanoic acid ester, methyl gallate triheptanoic acid ester, methyl gallate trioctanoic acid ester, methyl gallate trinonanoic acid ester, methyl gallate trilauric acid ester, methyl gallate tribenzoylphenol ester, and methyl gallate triphenylacetic acid ester. At least one of the following: methyl gallate trichlorobenzoylphenol ester, methyl gallate triisonicotinic phenol ester, methyl gallate tri-p-butylbenzoylphenol ester, methyl gallate tri-p-cyanobenzoylphenol ester, methyl gallate tri-o-acetylsalicylic acid benzoylphenol ester, methyl gallate tri-p-methoxybenzoylphenol ester, methyl gallate tri-p-methylbenzoylphenol ester, methyl gallate tri-p-nitrobenzoylphenol ester, and methyl gallate tripentafluorobenzoylphenol ester.

8. The catalyst component according to claim 5, characterized in that, The methyl gallate derivative comprises a mixture of compounds with molecular structures shown in Formula I and Formula II, wherein the molar ratio of the compounds with molecular structures shown in Formula I and Formula II is 1:9 to 9:

1.

9. 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.

10. The catalyst component according to claim 9, 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.

11. The catalyst component according to claim 9, 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.

12. The catalyst component according to claim 9, 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.

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

14. The catalyst according to claim 13, 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.

15. The catalyst according to claim 13, 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.

16. The catalyst according to claim 13, characterized in that, The catalyst's feedstock composition also includes an external electron donor.

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

18. The catalyst according to claim 17, 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.

19. The catalyst according to claim 17 or 18, 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.

20. The catalyst according to claim 16, characterized in that, The catalyst's raw material composition also includes an activity modifier; wherein the activity modifier includes piperate derivatives and / or paeonol derivatives.

21. The catalyst according to claim 20, characterized in that, The piperate derivative has the molecular structure shown in Formula III: In Equation III, R 7 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 One of the ester groups, optionally containing a third heteroatom, said third heteroatom being at least one of N, O, S, P, and Si.

22. The catalyst according to claim 21, characterized in that, R 7 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: 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 fused-ring aryl.

23. The catalyst according to claim 22, characterized in that, The piperate ester derivative is selected from 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.

24. The catalyst according to claim 20, characterized in that, The paeonol derivative has the molecular structure shown in Formula IV: In equation IV, R 8 Selected from C1-C 20 Straight-chain or branched alkyl groups and their derivatives, C3-C20 cycloalkyl groups, 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 One of the ester groups, optionally containing a third heteroatom, said third heteroatom being at least one of N, O, S, P, and Si.

25. The catalyst according to claim 24, characterized in that, R 8 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: 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 fused-ring aryl.

26. The catalyst according to claim 25, characterized in that, The paeonol derivatives include 2-methyl ether-4-methoxyacetophenone, 2-ethyl ether-4-methoxyacetophenone, 2-propyl ether-4-methoxyacetophenone, 2-butyl ether-4-methoxyacetophenone, 2-anisole-4-methoxyacetophenone, 2-acetylphenol ester-4-methoxyacetophenone, 2-propionylphenol ester-4-methoxyacetophenone, 2-butyrylphenol ester-4-methoxyacetophenone, and 2-pentanoylphenol ester-4-methoxyacetophenone. At least one of the following: 2-hexanoylphenol ester-4-methoxyacetophenone, 2-benzoylphenol ester-4-methoxyacetophenone, 2-phenylacetylphenol ester-4-methoxyacetophenone, 2-m-chlorobenzoylphenol ester-4-methoxyacetophenone, 2-p-chlorobenzoylphenol ester-4-methoxyacetophenone, 2-p-methoxybenzoylphenol ester-4-methoxyacetophenone, and 2-p-nitrobenzoylphenol ester-4-methoxyacetophenone.

27. The catalyst according to claim 20, characterized in that, The active regulator includes piperate ester derivatives and paeonol derivatives, wherein the molar ratio of piperate ester derivatives and paeonol derivatives is 0.02-50, preferably 0.05-20, and more preferably 0.1-10.

28. The catalyst according to any one of claims 20-27, 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.

29. The use of a catalyst according to any one of claims 13-28 in olefin polymerization.

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