Internal electron donor regulator, solid catalyst component as well as preparation method and application of solid catalyst component

Abstract

The invention discloses an internal electron donor regulator, a solid catalyst component and a preparation method and application thereof. The internal electron donor regulator comprises at least one of compounds with a structure as shown in the following formula (I), r1 and R1'are the same or different, and are respectively and independently one of hydrogen, halogen, hydroxyl, C1-C30 straight-chain alkyl containing or not containing a substituent group, C3-C30 branched-chain alkyl containing or not containing a substituent group, C2-C30 alkenyl containing or not containing a substituent group, C2-C30 ester group containing or not containing a substituent group, C6-C30 aryl containing or not containing a substituent group, and C3-C30 cycloalkyl or heterocyclic radical containing or not containing a substituent group; r1 and R1'can form a ring at will; r < 2 >, R < 3 >, R < 4 >, R < 5 >, R < 2 '>, R < 3' >, R < 4 '> and R < 5' > are the same or different and are respectively and independently one of hydrogen, halogen, hydroxyl, nitryl, amino, C1-C30 linear alkyl containing or not containing substituent groups, C3-C30 branched alkyl containing or not containing substituent groups, C2-C30 alkenyl containing or not containing substituent groups, C6-C30 aryl containing or not containing substituent groups, and C3-C30 cycloalkyl or heterocyclic radical containing or not containing substituent groups; any two of R2, R3, R4, R5, R2 ', R3', R4 'and R5' can form a ring at will; a is selected from one of alkylene, arylene, heteroarylene, alkyl arylene and aryl alkylene which contain or do not contain substituent groups. When the compound with the structure as shown in the formula (I) and the existing internal electron donor compound are used together, the performance of the internal electron donor can be effectively improved, and the obtained catalyst has higher catalytic activity and orientation capability, and can adjust the molecular weight distribution of a polymer to obtain a polyolefin product with moderate molecular weight distribution.

Description

An internal electron donor modifier, a solid catalyst component, its preparation method and application Technical Field

[0001] This invention relates to the field of olefin polymerization technology, specifically to an internal electron donor regulator, a solid catalyst component, its preparation method, and its application. Background Technology

[0002] A crucial aspect of the development direction of the polyolefin industry is the development of catalysts. Through continuous improvements in catalysts, including enhanced activity, improved orientation capabilities, and strengthened (co)polymerization abilities, the polyolefin industry has become a relatively mature technological field. Simultaneously, advancements in catalyst technology have driven continuous progress in polyolefin processing technology, and improvements in processing technology have also promoted the continuous improvement and development of catalysts.

[0003] Currently, Ziegler-Natta catalysts, or ZN-type catalysts, are still commonly used in the polyolefin industry. The main characteristics of these catalysts are high activity and strong orientation. Common ZN catalyst systems mainly consist of three parts: a catalyst component with titanium active centers supported on a magnesium chloride crystal structure, an alkylaluminum co-catalyst, and a silane-based external electron donor to improve the catalyst's orientation. During the catalyst component preparation process, electron-donating compounds are usually added, such as phthalates, succinates, 1,3-diethers, and glycol esters. The addition of these compounds significantly improves the catalyst's performance, and the catalyst exhibits different polymerization properties depending on the type of electron donor used. In existing technologies, catalysts using phthalates as internal electron donors exhibit high activity and strong orientation; catalysts using succinates can broaden the molecular weight distribution of polypropylene products and greatly improve the polymer's processing performance; catalysts using 1,3-diethers have excellent hydrogen sensitivity and can effectively control the molecular weight of propylene polymers in the reactor. Furthermore, existing technologies also employ compounds containing imine-like structures as internal electron donors in olefin polymerization catalysts. These compounds are characterized by retaining carbon-nitrogen double bonds in their structure. When used in combination with different types of internal electron donors, they can effectively improve the polymerization performance of the catalyst. The characteristics of the catalyst vary depending on the structure of the carbon-nitrogen double-bond-containing compound. For example, catalysts prepared using compounds containing one carbon-nitrogen double bond, as described in Chinese Patent CN105085730A, as internal electron donors result in polymers with high melt index, wide molecular weight distribution, and high isotacticity. When using compounds containing two carbon-nitrogen double bonds, as described in Chinese Patent CN105085731A, the catalyst exhibits slow activity decay, and the resulting polypropylene product has a wide molecular weight distribution. When using compounds containing two carbon-nitrogen double bonds and (heterocyclic) aryl functional groups, as described in Chinese Patent CN105085746A, the catalyst's activity and orientation ability are improved, and the resulting polypropylene product has a wide molecular weight distribution. The common characteristic of the aforementioned carbon-nitrogen double bond compounds is that when the catalysts prepared are used for propylene polymerization, the resulting polypropylene products have a wide molecular weight distribution. Generally speaking, a wider molecular weight distribution is beneficial to improving the processing performance of the polymer. However, if the molecular weight distribution is too wide, defective products are more likely to occur during processing, leading to a decrease in production efficiency, especially when producing synthetic fiber products or filament products.

[0004] Therefore, there is still a need in the field to improve and adjust the Ziegler-Natta catalyst and its components to give them higher catalytic activity and orientation ability, and to make appropriate adjustments to the molecular weight distribution to meet the requirements of fiber materials or drawing materials where the molecular weight distribution cannot be too wide. Summary of the Invention

[0005] To address the problems existing in the prior art, this invention provides an internal electron donor modifier, a solid catalyst component, its preparation method, and its application. Through experimental research and exploration, the inventors unexpectedly discovered that when a compound with the structure shown in formula (I) is used in the preparation process of a polyolefin catalyst, it can act as an internal electron donor modifier. Specifically, when this type of compound is used in conjunction with existing internal electron donor compounds, it can effectively improve the performance of the internal electron donor. The resulting catalyst exhibits high catalytic activity and orientation ability, and can regulate the molecular weight distribution of the polymer, yielding a polyolefin product with a suitable molecular weight distribution.

[0006] One object of the present invention is to provide an internal electron donor modifier comprising at least one of the compounds with the structure shown in formula (I):

[0007]

[0008] Among them, R1 and R1 ’ Whether identical or different, each independently comprises one of the following: hydrogen, halogen, hydroxyl, C1-C30 straight-chain alkyl with or without substituents, C3-C30 branched alkyl with or without substituents, C2-C30 alkenyl with or without substituents, C2-C30 ester with or without substituents, C6-C30 aryl with or without substituents, or C3-C30 cycloalkyl or heterocyclic with or without substituents, and R1 and R1 ’ It can form any ring (R1 and R1) ’ (Can be bridged or connected into a ring); R2, R3, R4, R5, R2 ’ R3 ’ R4 ’ and R5 ’ Whether identical or different, each is independently one of hydrogen, halogen, hydroxyl, nitro, amino, C1-C30 straight-chain alkyl with or without substituents, C3-C30 branched alkyl with or without substituents, C2-C30 alkenyl with or without substituents, C6-C30 aryl with or without substituents, or C3-C30 cycloalkyl or heterocyclic with or without substituents, and R2, R3, R4, R5, R2 ’ R3 ’ R4 ’ and R5 ’ Any two groups in it can form a ring (R2, R3, R4, R5, R2). ’ R3 ’ R4 ’ and R5 ’(Any two groups in the given form can be bridged or linked to form a ring at any position); A is selected from alkylene, arylene, heteroarylene, alkylarylene, and arylalkylene, with or without substituents. When A is one or more substituted alkylene groups, the substituted atom is oxygen, sulfur, nitrogen, boron, silicon, phosphorus, or a halogen atom; when A is a heteroarylene, the heteroatom is oxygen, sulfur, nitrogen, boron, silicon, phosphorus, or a halogen atom.

[0009] In a preferred embodiment of the present invention,

[0010] R1 and R1 ’ They are either the same or different, and are independently one of the following: hydrogen, halogen, hydroxyl, C1-C10 straight-chain alkyl with or without substituents, C3-C10 branched alkyl with or without substituents, C2-C10 alkenyl with or without substituents, C2-C10 ester with or without substituents, or C6-C30 aryl with or without substituents, and R1 and R1 ’ The rings can be formed arbitrarily; the C6-C30 aryl groups include C6-C15 non-fused-ring aryl groups and C10-C30 fused-ring aryl groups; preferably, R1 and R1 ’ Each of the following is independently one of hydrogen, halogen, hydroxyl, C1-C5 straight-chain alkyl with or without substituents, and C3-C5 branched alkyl with or without substituents, and R1 and R1 ’ It can form any ring; and / or,

[0011] R2, R3, R4, R5, R2 ’ R3 ’ R4 ’ and R5 ’ Whether identical or different, each is independently one of hydrogen, halogen, hydroxyl, nitro, amino, C1-C10 straight-chain alkyl with or without substituents, C3-C10 branched-chain alkyl with or without substituents, C6-C30 aryl with or without substituents, C6-C15 cycloalkyl or heterocyclic with or without substituents, and R2, R3, R4, R5, R2 ’ R3 ’ R4 ’ and R5 ’ Any two groups in the group can form a ring; preferably, R2, R3, R4, R5, and R2... ’ R3 ’ R4 ’ and R5 ’Each of the following is independently one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, methoxy, isopropyl ether, tert-butyl ether, phenyl, halophenyl, naphthyl, biphenyl, nitro, amino, pyridyl, thiophene, and quinolinyl, and R2, R3, R4, R5, and R2 are respectively... ’ R3 ’ R4 ’ and R5 ’ Any two groups in the compound can form a ring; and / or,

[0012] A is selected from one of the following: C1-C20 alkylene groups with or without substituents; C6-C20 aryl groups with or without substituents; C5-C20 heteroaryl groups with or without substituents; C7-C20 alkylaryl groups with or without substituents; and C7-C20 arylalkylene groups with or without substituents; preferably one of the following: C1-C10 alkylene groups with or without substituents; more preferably one of the following: C1-C5 alkylene groups; wherein the C6-C20 arylene groups include C6-C20 non-fused-ring arylene groups and C10-C20 fused-ring arylene groups.

[0013] A second objective of this invention is to provide a method for preparing an internal electron donor modifier, as described in one of the objectives of this invention, comprising the step of performing a condensation reaction between a diamine compound and a halomethylpyridine compound to obtain the internal electron donor modifier; preferably,

[0014] The diamine compound has the structure shown in formula (ⅠⅠ):

[0015]

[0016] In equation (ⅠⅠ), R1 and R1 ’ Whether identical or different, each independently comprises one of the following: hydrogen, halogen, hydroxyl, C1-C30 straight-chain alkyl with or without substituents, C3-C30 branched alkyl with or without substituents, C2-C30 alkenyl with or without substituents, C2-C30 ester with or without substituents, C6-C30 aryl with or without substituents, or C3-C30 cycloalkyl or heterocyclic with or without substituents, and R1 and R1 ’ It can be formed into any ring; preferably, R1 and R1 ’ They are either the same or different, and are independently one of the following: hydrogen, halogen, hydroxyl, C1-C10 straight-chain alkyl with or without substituents, C3-C10 branched alkyl with or without substituents, C2-C10 alkenyl with or without substituents, C2-C10 ester with or without substituents, or C6-C30 aryl with or without substituents, and R1 and R1 ’It can be arbitrarily cyclic; the C6-C30 aryl group includes C6-C15 non-fused-ring aryl group and C10-C30 fused-ring aryl group; more preferably, R1 and R1 ’ Each of the following is independently one of hydrogen, halogen, hydroxyl, C1-C5 straight-chain alkyl with or without substituents, and C3-C5 branched alkyl with or without substituents, and R1 and R1 ’ It can be cyclically formed in any way; A is selected from one of alkylene, arylene, heteroarylene, alkylarylene, and arylalkylene, with or without substituents; preferably, A is selected from one of C1-C20 alkylene, C6-C20 arylene, C5-C20 heteroaryl, C7-C20 alkylaryl, and C7-C20 arylalkylene, with or without substituents; more preferably, it is selected from one of C1-C10 alkylene, and even more preferably, it is selected from one of C1-C5 alkylene; the C6-C20 arylene includes C6-C20 non-fused-ring arylene and C10-C20 fused-ring arylene; and / or,

[0017] The halomethylpyridine compound has the structure shown in formula (ⅠⅠⅠ):

[0018]

[0019] In formula (ⅠⅠⅠ), X is a halogen, and R2, R3, R4, and R5 may be the same or different, and are independently one of hydrogen, halogen, hydroxyl, nitro, amino, C1-C30 straight-chain alkyl with or without substituents, C3-C30 branched alkyl with or without substituents, C2-C30 alkenyl with or without substituents, C6-C30 aryl with or without substituents, C3-C30 cycloalkyl or heterocyclic with or without substituents, and any two groups among R2, R3, R4, and R5 may be arbitrarily cyclic; preferably, R2, R3, R4, R5, and R2 ’ R3 ’ R4 ’ and R5 ’ Whether identical or different, each is independently one of hydrogen, halogen, hydroxyl, nitro, amino, C1-C10 straight-chain alkyl with or without substituents, C3-C10 branched-chain alkyl with or without substituents, C6-C30 aryl with or without substituents, C6-C15 cycloalkyl or heterocyclic with or without substituents, and R2, R3, R4, R5, R2 ’ R3 ’ R4 ’ and R5 ’Any two groups in it can form a ring; more preferably, R2, R3, R4, R5, and R2 ’ R3 ’ R4 ’ and R5 ’ Each of the following is independently one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, methoxy, isopropyl ether, tert-butyl ether, phenyl, halophenyl, naphthyl, biphenyl, nitro, amino, pyridyl, thiophene, and quinolinyl, and R2, R3, R4, R5, and R2 are respectively... ’ R3 ’ R4 ’ and R5 ’ Any two groups in it can form a ring.

[0020] In this invention, C1 to C30 can be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, and C30. C2 to C30 can be C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, and C20. 7. C28, C29, C30. C3 to C30 can be C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30. C6 to C30 can be C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30.

[0021] The substituents described in this invention can be any substituents in the chemical field, such as halogens, hydroxyl groups, nitro groups, amino groups, C1-C30 straight-chain alkyl groups, C3-C30 branched alkyl groups, C2-C30 alkenyl groups, C6-C30 aryl groups, C3-C30 cycloalkyl groups or heterocyclic groups, etc., and no special restrictions are imposed in this invention.

[0022] In a preferred embodiment of the present invention,

[0023] The molar ratio of the amino group in the diamine compound to the halomethyl group in the halomethylpyridine compound is 1:(0.1–10), preferably 1:(0.5–2), more preferably 1:(1–2); and / or,

[0024] The reaction temperature is 10–280°C, preferably 20–150°C; and / or the reaction time is 1 min–168 h, preferably 4 h–72 h, more preferably 24 h–60 h.

[0025] In a preferred embodiment of the present invention,

[0026] The diamine compound and the halomethylpyridine compound are reacted in a solvent in the presence of a basic reagent to obtain the internal electron donor modifier; the condensation reaction removes hydrogen halide, which is acidic, and the addition of a basic reagent promotes the condensation reaction; preferably...

[0027] The alkaline reagent is selected from at least one of the following: hydroxides of alkali metals or alkaline earth metals, bicarbonates of alkali metals or alkaline earth metals, carbonates of alkali metals or alkaline earth metals, stearates of alkali metals or alkaline earth metals, amine compounds, nitrogen-containing heterocyclic compounds, alkali metal salts of alcohols, alkyllithium reagents, Grignard reagents, and quaternary ammonium compounds; and / or,

[0028] The solvent is selected from at least one of polar solvents, preferably from at least one of formamide, acetonitrile, methanol, ethanol, propanol, acetone, dioxane, tetrahydrofuran, methyl ethyl ketone, n-butanol, ethyl acetate, diethyl ether, isopropyl ether, dichloromethane, chloroform, bromoethane, benzene, and carbon tetrachloride, more preferably from dichloromethane and / or chloroform; more preferably,

[0029] The molar ratio of the diamine compound, the alkaline reagent, and the solvent is 100:(0.1-50):(1-50000), preferably 100:(0.5-5):(100-3000), wherein the diamine compound is expressed in terms of the number of moles of amino groups.

[0030] The preparation method of the internal electron donor modifier described in this invention can adopt the following specific technical solutions:

[0031] (1) Pretreatment: First, disperse the diamine compound in a solvent, stir thoroughly and dissolve it, wherein the dissolution temperature is preferably -35℃~10℃, more preferably -10℃~5℃;

[0032] (2) Synthesis: Add halomethylpyridine compound to it, stir and heat it, add basic reagent and continue to stir thoroughly to carry out the reaction;

[0033] (3) Post-treatment: After the reaction is completed, the product is washed with deionized water, and the volatile solvent is removed by rotary evaporation or under reduced pressure to obtain a solid. The final product is purified by recrystallization with an inert solvent. The inert solvent is preferably an inert alkane reagent, and more preferably n-hexane and / or n-pentane.

[0034] A third objective of this invention is to provide a solid catalyst component for olefin polymerization, comprising a mixture of magnesium compounds, titanium compounds, internal electron donor compounds, and an internal electron donor modifier according to one objective of this invention or an internal electron donor modifier obtained by the preparation method according to another objective of this invention, and / or reaction products.

[0035] In a preferred embodiment of the present invention,

[0036] The magnesium compound is selected from the general formula MgX. m (OR 1 ) 2-m At least one of the compounds shown, wherein repeated R 1 Each is independently a hydrocarbon group from C1 to C20, preferably a hydrocarbon group from C1 to C10, where X is a halogen and m = 0 to 2; preferably, the magnesium compound is selected from R. 1 Magnesium halide and magnesium alkoxy are at least one of C1-C10 alkyl groups, preferably at least one of magnesium dichloride, magnesium dibromide, magnesium diiodide, magnesium methoxychloride, magnesium ethoxychloride, magnesium propoxychloride, and magnesium butoxychloride; and / or,

[0037] The titanium compound is selected from the general formula TiX. n (OR 2 ) 4-n At least one of the compounds shown, wherein repeated R 2 Each is independently a hydrocarbon group from C1 to C20, preferably a hydrocarbon group from C1 to C10, where X is a halogen and n = 0 to 4; preferably, the titanium compound is selected from titanium halides, R 2 At least one of C1-C10 alkyl titanate esters, preferably at least one of titanium tetrachloride, n-butyl titanate, isobutyl titanate, and 2-ethylhexyl titanate; and / or,

[0038] The internal electron donor compound includes any known compound that can be used as an internal electron donor, and since it is well known to those skilled in the art, it will not be described in detail here. In this invention, the internal electron donor compound preferably includes at least one of mono- or poly-ester compounds, mono- or poly-ol acid compounds, di- or poly-ol ester compounds, imine compounds, and ether compounds, and more preferably at least one of succinate compounds, diol ester compounds, iminoalkane compounds, and ether compounds.

[0039] In a preferred embodiment of the present invention,

[0040] The catalyst component comprises, in part, 0.5–6.0 wt% titanium, 10.0–60.0 wt% magnesium, 20.0–80.0 wt% halogen, 4.0–40.0 wt% internal electron donor compound, and 0–32.0 wt% internal electron donor modifier, preferably not 0 wt% based on 100 wt% of the catalyst component; preferably,

[0041] The catalyst component comprises, in part, 1.0–4.0 wt% titanium, 15.0–35.0 wt% magnesium, 30.0–55.0 wt% halogen, 6.0–20.0 wt% internal electron donor compound, and 0.01–18.0 wt% internal electron donor modifier, preferably 0.1–1.0 wt% based on 100 wt% of the catalyst component; more preferably,

[0042] In the catalyst composition, the molar ratio of the internal electron donor compound and the internal electron donor modifier is 1:(0-3), preferably 1:(0-1), and more preferably 1:(0.05-0.8).

[0043] A fourth objective of this invention is to provide a method for preparing a solid catalyst component for olefin polymerization, as described in objective three of this invention, comprising the steps of mixing and / or reacting raw materials including a magnesium compound, a titanium compound, an internal electron donor compound, and an internal electron donor modifier as described in objective one of this invention or an internal electron donor modifier obtained by the preparation method described in objective two of this invention; preferably,

[0044] The preparation method of the catalyst component includes:

[0045] (1) Dissolve the magnesium compound in a solvent system containing organic alcohol solvent and / or inert hydrocarbon reagent;

[0046] (2) Add the internal electron donor regulator to the solution obtained in step (1) and mix and react;

[0047] (3) Add the solution obtained in step (2) to the titanium compound to carry out the reaction;

[0048] (4) Add an internal electron donor compound to the reaction solution obtained in step (3) and react to obtain the solid catalyst component.

[0049] In step (2), a titanium compound may be added optionally.

[0050] In step (4), the precipitate obtained by adding an internal electron donor compound to the reaction solution obtained in step (3) is optionally treated with titanium compound, washed and dried to obtain the solid catalyst component.

[0051] The preparation method of the solid catalyst component for olefin polymerization of the present invention can adopt the following specific technical solutions:

[0052] 1) Mix magnesium compounds, organic alcohol solvents and inert hydrocarbon reagents, stir thoroughly at a high temperature of 110-160°C to dissolve them, forming a transparent or translucent mixed solution, and then cool down to 60-100°C;

[0053] 2) Dissolve the internal electron donor modifier and optional titanium compound in an inert hydrocarbon reagent, and add them to the solution from step 1) and mix thoroughly;

[0054] 3) Cool the solution obtained in step 2) to -10 to 40°C, slowly transfer it to a reaction flask containing a titanium compound pre-cooled to -25°C, and maintain it at -25±10°C, preferably -25±5°C, throughout the entire dropwise addition process;

[0055] 4) The solution obtained in step 3) is heated in a programmed manner while being stirred thoroughly. When the temperature reaches 40-100°C, an internal electron donor compound is added, and the temperature is continued to rise until it reaches 110-130°C.

[0056] 5) Continue stirring for 0.5 to 5 hours under the above temperature conditions and cool. Let the mixed solution stand and slowly precipitate. After removing the upper filtrate, add titanium compound again for titanium treatment. Repeat the above steps once or multiple times. After removing the upper filtrate for the last titanium treatment, it is not necessary to add titanium compound again.

[0057] 6) After completing step 5), wash the precipitate once or multiple times with an inert solvent, and after drying, obtain the solid catalyst component for olefin polymerization.

[0058] In a preferred embodiment of the present invention,

[0059] In step 1),

[0060] The organic alcohol solvent is a conventional organic alcohol solvent in the art, and can be at least one of alcohols containing C2-C20 alkyl, C3-C20 cycloalkyl, or C6-C20 aryl groups, preferably at least one of ethanol, isopropanol, butanol, 2-ethylhexanol, heptanol, isooctanol, and phenol, more preferably isooctanol; and / or,

[0061] The inert hydrocarbon reagent is a conventional inert hydrocarbon reagent in the art, and may be at least one of C5-C20 alkanes, C5-C20 cycloalkanes, and C6-C20 aromatics, preferably at least one of hexane, heptane, octane, decane, cyclohexane, benzene, toluene, xylene, or their derivatives, more preferably at least one of hexane and n-decane; and / or,

[0062] The mixing temperature is 0–40°C, and the mixture needs to be heated to a higher temperature to achieve full dissolution. This higher dissolution temperature depends on the organic alcohol and inert hydrocarbon solvent used. The preferred high-temperature dissolution temperature is 110–160°C.

[0063] In this invention, there are no special restrictions on the amount of organic alcohol solvent and inert hydrocarbon reagent. Those skilled in the art can adjust them according to the actual situation. For example, the ratio of organic alcohol solvent (calculated by the number of moles of hydroxide ions): inert hydrocarbon reagent (calculated by the number of moles of the relative molecular mass of the inert hydrocarbon molecular formula): magnesium compound (calculated by the number of moles of magnesium element) can be (0.1-20):(0.1-500):1.

[0064] In step 2),

[0065] The internal electron donor modifier (in moles based on the relative molecular mass of the compound used): titanium compound (in moles of titanium): magnesium compound (in moles of magnesium) = (0.01–1):(0–2):1, preferably = (0.01–0.2):(0–0.5):1; and / or,

[0066] The mixing conditions include (temperature and time depend on the amount of reactants added): preferably a temperature of 10–100°C and a time of 10 seconds–2 hours; and / or,

[0067] In step 3),

[0068] Cool the reaction solution obtained in step 2) to -10 to 40°C and then add it dropwise to the low-temperature titanium compound; and / or,

[0069] The temperature of the low-temperature titanium compound is -40 to -10°C; preferably,

[0070] During the dropwise addition process, the system temperature is maintained at –25±20℃, preferably –25±5℃; and / or,

[0071] In step 4),

[0072] The temperature at which the internal electron-donating compound is added is 40–100°C, preferably 60–80°C; and / or,

[0073] The amount of the internal electron-donating compound added per mole of magnesium is 0.01 to 0.2 moles, preferably 0.05 to 0.2 moles; as a specific embodiment of the present invention, the amount of the internal electron-donating regulator in the above steps should not exceed the amount of the internal electron-donating compound; and / or,

[0074] The reaction temperature is 110–130°C, and / or the reaction time is 1–8 hours; and / or,

[0075] In step 5),

[0076] The titanium compound (calculated as a molar ratio of titanium): magnesium compound (calculated as a molar ratio of magnesium) = (1~100):1; and / or,

[0077] The titanium treatment temperature is 110–130°C, and / or the titanium treatment time is 1–8 hours; preferably,

[0078] The titanium treatment is performed 1-5 times; and / or,

[0079] In step 6), the washing temperature is preferably 30-80°C, and the inert solvent is preferably hexane and / or pentane.

[0080] A fifth objective of this invention is to provide a catalyst for olefin polymerization, comprising a reaction product containing the following components:

[0081] a) the solid catalyst component of objective three of the present invention or the solid catalyst component obtained by the preparation method of objective four of the present invention, b) alkylaluminum compounds and optionally c) organosilicon compounds; preferably,

[0082] The general formula of the alkylaluminum compound is AlR f q X 3-q , where the repeated R f Each is independently hydrogen or a C1-C20 hydrocarbon group, preferably hydrogen or a C1-C20 alkyl group, where X is a halogen, and 1 ≤ q ≤ 3; preferably, the alkylaluminum compound is selected from one or more of trialkylaluminum, dialkylaluminum chloride, alkylaluminum chloride, and alkylaluminoxane, and more preferably from one or two of triethylaluminum and triisobutylaluminum; and / or,

[0083] The general formula of the organosilicon compound is R A t Si(OR B ) 4-t Where t is an integer, and 0 ≤ t ≤ 3, and the repeated R AEach group is independently selected from alkyl, cycloalkyl, aryl, haloalkyl, amino, halogen, or hydrogen atoms, preferably from C1-C10 alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C1-C10 haloalkyl, amino, halogen, or hydrogen atoms, with repeated R. B The organosilicon compounds are independently selected from alkyl, cycloalkyl, aryl, haloalkyl, or amino groups, preferably from C1-C10 alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C1-C10 haloalkyl, or amino groups; preferably, the organosilicon compounds are selected from at least one of cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, and diisopropyldimethoxysilane.

[0084] In a preferred embodiment of the present invention,

[0085] In the catalyst for olefin polymerization, the solid catalyst components a), alkyl aluminum compound b), and organosilicon compound c) are added in a certain proportion during the olefin polymerization process. The relevant proportions are well known to those skilled in the art. As a specific embodiment of the present invention, preferably, the proportion is calculated as a) based on Ti active centers, b) based on aluminum, and c) based on silicon molar ratios of a):b):c) = 1:(10~2000):(0~500), preferably 1:(10~1000):(0~200).

[0086] A sixth objective of this invention is to provide a method for olefin polymerization, comprising the step of polymerizing an olefin in the presence of a solid catalyst component according to a third objective of this invention, a solid catalyst component obtained by a preparation method according to a fourth objective of this invention, or a catalyst for olefin polymerization according to a fifth objective of this invention; preferably,

[0087] The olefin is selected from at least one of compounds with the general formula CH2=CHR, wherein R is hydrogen, a C1-C12 alkyl group or a C6-C12 aryl group, and preferably the olefin is at least one of ethylene, propylene, butene-1, 4-methyl-1-pentene, and 1-hexene.

[0088] In the olefin polymerization process, hydrogen can be optionally added as a chain transfer agent, and the olefin monomers undergo coordination polymerization under certain conditions by increasing the temperature and pressure. The olefin polymerization reaction can be continuous or intermittent, and the polymerization process or method can follow known polymerization methods, suitable for gas-phase, liquid-phase, or gas-liquid combined, bulk, or slurry reactions. As a specific embodiment of the present invention, preferably, the olefin is propylene, and the polymerization temperature is 0–150°C, more preferably 60–90°C.

[0089] As a specific embodiment of the present invention, when using the olefin polymerization catalyst described in the present invention for propylene polymerization, the melt index of the resin product is adjusted by changing the amount of hydrogen added. When producing polypropylene products with a melt index of 25-55 g / 10 min that can be used for fiber materials and polypropylene products with a melt index of 0-10 g / 10 min that can be used for drawing materials, the product processing performance is good and the performance of downstream products is significantly improved.

[0090] This invention has the following advantages:

[0091] 1. The internal electron donor regulator of the present invention has not been reported in the literature for use in supported Ziegler-Natta olefin polymerization catalysts and olefin polymerization reactions.

[0092] 2. In the internal electron donor regulator of the present invention, the nitrogen atom forms a delocalized π bond in the pyridine structure as a carbon-nitrogen double bond, and the nitrogen atom is connected to the carbon atom in sp3 hybridization, and the nitrogen atom contains a pair of unpaired lone pairs of electrons. Compared with imine compounds with a single sp2 hybridized carbon-nitrogen double bond, the nitrogen atom in the internal electron donor regulator of the present invention has the combined effect of electron delocalization and lone pairs of electrons. Therefore, its addition during the preparation process can further and effectively reduce the bonding energy between the internal electron donor and the metal during the formation of the catalyst, and significantly improve the electron-donating effect of the electron donor.

[0093] 3. In the preparation of supported ZN catalysts, the internal electron donor is usually added after the titanium active center is loaded onto the magnesium chloride support. However, the internal electron donor regulator of this invention is added before the titanium active center is loaded onto the magnesium chloride support. That is, it is pre-contacted with the titanium compound before the titanium is loaded. This is obviously different from the role of the internal electron donor compound.

[0094] 4. As an internal electron donor regulator, when used in conjunction with existing internal electron donors to prepare olefin polymerization catalysts, the catalyst activity is improved, the orientation ability is well maintained, and the molecular weight distribution is moderate. It has obvious advantages when used in the production of products such as fiber materials and drawing materials that require a relatively narrow molecular weight distribution of polypropylene raw materials.

[0095] In summary, the solid catalyst components provided by this invention, as well as the solid catalyst components and / or catalysts prepared by the preparation method described in this invention, are suitable for the field of olefin polymerization, especially propylene polymerization. When the catalysts described in this invention are used in olefin polymerization reactions, they exhibit high catalytic activity and stereospecific orientation, resulting in a satisfactory molecular weight distribution. They are particularly suitable for preparing fiber products and filament products, effectively improving the processing properties of polymers and enhancing the performance of downstream products. Detailed Implementation

[0096] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0097] Unless otherwise specified, the raw materials used in the embodiments and comparative examples of this invention are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0098] Test method:

[0099] 1. Polymer melt index (MI): Determined according to GB / T 3682.1-2018;

[0100] 2. Isotacticity index (II) of propylene polymer: determined by n-heptane extraction method: 2g of dry polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours. After drying the residue to constant weight, the ratio of the polymer weight (g) to 2 (g) is the isotacticity index of propylene polymer.

[0101] 3. Polymer molecular weight distribution (MWD = Mw / Mn): The molecular weight distribution was determined using a Waters PL-GPC220 gel permeation chromatography system with trichlorobenzene as solvent at 150°C (standard: polystyrene, flow rate: 1.0 mL / min, column: 3xPlgel 10 μm MlxED-B300x7.5 nm).

[0102] 4. Activity calculation: Catalyst activity = (mass of prepared polyolefin) / (mass of solid catalyst component) kg / g.

[0103] 5. Compound NMR (nuclear magnetic resonance) 1 H-NMR: Measured using a Bruker nuclear magnetic resonance spectrometer at a test temperature of 298K.

[0104] 6. Elongation at break of polymer products: expressed as the nominal strain at tensile break of plastic products, and determined in accordance with GB / T 1040.2-2022.

[0105] Preparation of internal electron donor modifier

[0106] Example 1: N,N'-Dimethyl-N,N'-bis(2-pyridylmethyl)-1,2-ethylenediamine Preparation

[0107] 3 g (0.034 mol) of N,N'-dimethylethylenediamine was dispersed in 50 mL of dichloromethane and cooled to 0 °C. 12.3 g (0.075 mol) of 2-chloromethylpyridine hydrochloride was slowly added, and the mixture was stirred for 30 min. The temperature was then raised to 30 °C, and 0.15 mL of triethylamine was added using a dropper. The reaction was continued at 30 °C with stirring for 40 h. The supernatant was poured off, and the mixture was washed with a small amount of deionized water to remove volatile solvents, yielding a yellow solid. Recrystallization from hexane yielded 4.6 g of the product (50% yield). NMR analysis confirmed the product as N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)-1,2-ethylenediamine. The 1H NMR data are as follows: 1 ¹H-NMR (d6-DMSO, 500MHz): δ 8.34 (dd, 2H), 7.65 (td, 2H), 7.48 (dt, 2H), 7.32 (dd, J = 7.8, 2H), 3.65 (s, 4H), 2.71 (s, 4H), 2.37 (s, 4H), 1.67 (s, 6H). Based on the chemical reaction principle and the above NMR data, the structure of N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)-1,2-ethylenediamine prepared in Example 1 is as follows:

[0108] Example 2: 1,4-bis(2-pyridylmethyl)-1,4-diazacycloheptane Preparation

[0109] Similar to Example 1, except that 0.034 mol of N,N'-dimethylethylenediamine was replaced with 0.034 mol of piperazine, and the solvent was changed from dichloromethane to acetonitrile. The reaction temperature was changed to reflux, and the yield was 33%. The obtained product was confirmed by NMR analysis to be 1,4-bis(2-pyridylmethyl)-1,4-diazacycloheptane. The 1H NMR data are as follows: 1 ¹H NMR (d6-DMSO, 500MHz) δ 8.13 (dd, 2H), 7.53 (td, 2H), 7.43 (dt, 2H), 7.16 (dd, 2H), 3.62 (s, 4H), 2.61–2.54 (m, 4H), 2.41–2.34 (m, 4H), 1.88 (penta, 2H). Based on the chemical reaction principle and the above NMR data, the structure of 1,4-bis(2-pyridylmethyl)-1,4-diazacycloheptane prepared in Example 2 is as follows:

[0110] Example 3: 1,4-bis(2-quinolinemethyl)-1,4-diazacycloheptane Preparation

[0111] Similar to Example 2, only 0.075 mol of 2-chloromethylpyridine hydrochloride was replaced with 0.075 mol of 2-chloromethylquinoline, resulting in a yield of 39%. The obtained product was confirmed by NMR analysis to be 1,4-bis(2-quinolinemethyl)-1,4-diazacycloheptane, and the 1H NMR data are as follows: 1 ¹H NMR (d6-DMSO, 500MHz) δ 8.18 (d, 2H), 8.04–7.89 (m, 2H), 7.75–7.68 (m, 4H), 7.58–7.50 (m, 2H), 7.41–7.34 (m, 2H), 3.70 (s, 4H), 2.66–2.59 (m, 4H), 2.51–2.38 (s, 4H), 1.89–1.74 (m, 1H). Based on the chemical reaction principle and the above NMR data, the structure of 1,4-bis(2-quinolinemethyl)-1,4-diazacycloheptane prepared in Example 3 is as follows:

[0112] Preparation of solid catalyst components for olefin polymerization:

[0113] Example 4

[0114] Under nitrogen protection, 4.8 g of anhydrous magnesium chloride, 19.5 g of isooctanol, and 19.5 g of decane solvent were added to a 500 ml reactor equipped with a stirrer. After thorough mixing at 30°C, the mixture was heated to 130°C and reacted for 1.5 hours until the magnesium chloride was completely dissolved. The solution was then cooled to 90°C. 10 mL of decane containing 0.003 mol of the compound prepared in Example 1 and 0.005 mol of tetrabutyl titanate was transferred to the solution using a stainless steel double-ended needle and stirred thoroughly for 1 hour. The solution was further cooled to 25°C. Under high-purity nitrogen protection, the cooled solution was slowly transferred to 80 ml of titanium tetrachloride solution pre-cooled to -25°C using a pressure differential. During the reaction... Maintain a constant temperature; after the transfer is complete, slowly heat the above mixed solution to 80°C, add 0.006 mol of the internal electron donor compound 2,4-pentanediol dibenzoate, and continue heating to 110°C for 2 hours; after the time is up, let the mixture stand for 30 minutes, remove the upper filtrate, add 120 mL of titanium tetrachloride again, and heat to 110°C for 2 hours. Repeat this operation twice; wash the solid precipitate four times with 100 mL of hexane, and after vacuum drying, obtain 5.5 g of solid catalyst component, of which Ti: 1.9 wt%, Mg: 23.2 wt%, Cl: 40.2 wt%, internal electron donor compound: 9.6 wt%, and internal electron donor regulator: 2.1 wt%.

[0115] Example 5

[0116] Same as Example 4, except that the compound prepared in Example 1 was replaced with an equimolar amount of the compound prepared in Example 2. After vacuum drying, 6.7 g of solid catalyst component was obtained, wherein Ti: 2.4 wt%, Mg: 24.7 wt%, Cl: 38.9 wt%, internal electron donor compound: 11.3 wt%, and internal electron donor modifier: 1.8 wt%.

[0117] Example 6

[0118] Same as Example 4, except that the compound prepared in Example 1 was replaced with an equimolar amount of the compound prepared in Example 3. After vacuum drying, 5.8 g of solid catalyst component was obtained, wherein Ti: 2.0 wt%, Mg: 21.6 wt%, Cl: 41.5 wt%, internal electron donor compound: 10.1 wt%, and internal electron donor modifier: 0.9 wt%.

[0119] Example 7

[0120] Same as Example 4, except that the internal electron donor compound was replaced with an equimolar amount of diethyl 2,3-diisopropylsuccinate. After vacuum drying, 5.2 g of solid catalyst component was obtained, wherein Ti: 1.4 wt%, Mg: 28.9 wt%, Cl: 33.5 wt%, internal electron donor compound: 7.8 wt%, and internal electron donor modifier: 2.7 wt%.

[0121] Example 8

[0122] Same as Example 4, except that the internal electron donor compound was replaced with an equimolar amount of ethyl benzoate. After vacuum drying, 4.4 g of solid catalyst component was obtained, wherein Ti: 2.3 wt%, Mg: 25.8 wt%, Cl: 39.4 wt%, internal electron donor compound: 15.8 wt%, and internal electron donor modifier: 6.4 wt%.

[0123] Example 9

[0124] Same as Example 4, except that the internal electron donor compound was replaced with an equimolar amount of di-n-butyl phthalate. After vacuum drying, 5.9 g of solid catalyst component was obtained, wherein Ti: 2.7 wt%, Mg: 24.5 wt%, Cl: 44.3 wt%, internal electron donor compound: 8.6 wt%, and internal electron donor modifier: 1.3 wt%.

[0125] Example 10

[0126] Same as Example 4, except that the internal electron donor compound was replaced with an equimolar amount of 9,9-di(methoxymethyl)fluorene. After vacuum drying, 7.1 g of solid catalyst component was obtained, wherein Ti: 1.7 wt%, Mg: 26.1 wt%, Cl: 44.1 wt%, internal electron donor compound: 10.4 wt%, and internal electron donor modifier: 2.0 wt%.

[0127] Example 11

[0128] Same as Example 4, except that the internal electron donor compound was replaced with an equimolar amount of 5-tert-butyl-3-methyl-1,2-phenylene dibenzoate. After vacuum drying, 6.9 g of solid catalyst component was obtained, wherein Ti: 2.7 wt%, Mg: 28.3 wt%, Cl: 41.2 wt%, internal electron donor compound: 8.8 wt%, and internal electron donor modifier: 3.5 wt%.

[0129] Comparative Example 1 did not contain the internal electron donor modifier described in this invention.

[0130] Under nitrogen protection, 4.8 g of anhydrous magnesium chloride, 19.5 g of isooctanol, and 19.5 g of decane solvent were added to a 500 ml reactor equipped with a stirrer. After thorough mixing at 30 °C, the mixture was heated to 130 °C and reacted for 1.5 hours until the magnesium chloride was completely dissolved. 10 mL of decane containing 0.005 mol tetrabutyl titanate was transferred to the above solution using a stainless steel double-ended needle, and the reaction was continued at 130 °C for 1 hour. The mixture was cooled to room temperature, and under nitrogen protection, the above alcohol was added dropwise. Add the solution to 80 mL of titanium tetrachloride solution pre-cooled to -25 °C, keep the temperature constant, slowly raise the temperature to 80 °C, add 0.006 mol of 2,4-pentanediol dibenzoate, continue to raise the temperature to 110 °C and maintain for 2 hours. After the time is up, let the mixture stand for 30 min, remove the upper filtrate, add 120 mL of titanium tetrachloride again, raise the temperature to 110 °C and maintain for 2 hours, and repeat this operation twice. Wash the solid precipitate four times with 100 mL of hexane, and after vacuum drying, obtain 4.8 g of solid catalyst component.

[0131] Comparative Example 2: The internal electron donor modifier described in this invention is added post-electron donor.

[0132] Under nitrogen protection, 4.8 g of anhydrous magnesium chloride, 19.5 g of isooctanol, and 19.5 g of decane solvent were added to a 500 ml reactor equipped with a stirrer. After thorough mixing at 30 °C, the mixture was heated to 130 °C and reacted for 1.5 hours until the magnesium chloride was completely dissolved. The reaction was then continued at 130 °C for another hour. The mixture was cooled to room temperature, and under nitrogen protection, the alcohol was added dropwise to 80 ml of titanium tetrachloride solution pre-cooled to -25 °C. The temperature was kept constant and the mixture was slowly heated. At 80°C, 0.006 mol of 2,4-pentanediol dibenzoate and 0.003 mol of the internal electron donor regulator prepared in Example 1 were added. The temperature was then raised to 110°C and maintained for 2 hours. After the time was up, the mixture was allowed to stand for 30 minutes. The upper filtrate was removed, and 120 mL of titanium tetrachloride was added again. The temperature was raised to 110°C and maintained for 2 hours. This operation was repeated twice. The solid precipitate was washed four times with 100 mL of hexane and dried under vacuum to obtain 5.7 g of solid catalyst component.

[0133] Comparative Example 3

[0134] Similar to Comparative Example 1, except that the internal electron donor compound was replaced with an equimolar amount of diethyl 2,3-diisopropylsuccinate.

[0135] Comparative Example 4

[0136] Similar to Comparative Example 1, except that the internal electron donor compound was replaced with an equimolar amount of ethyl benzoate.

[0137] Comparative Example 5

[0138] Similar to Comparative Example 1, except that the internal electron donor compound was replaced with an equimolar amount of di-n-butyl phthalate.

[0139] Comparative Example 6

[0140] Similar to Comparative Example 1, except that the internal electron donor compound was replaced with an equimolar amount of 9,9-di(methoxymethyl)fluorene.

[0141] Comparative Example 7

[0142] Similar to Comparative Example 1, except that the internal electron donor compound was replaced with an equimolar amount of 5-tert-butyl-3-methyl-1,2-phenylene dibenzoate.

[0143] Aggregate evaluation method:

[0144] The polymerization evaluation of the catalyst can be carried out according to the following steps: 1.8 L of propylene, 10 mg of the catalyst component prepared in the examples and comparative examples, 5 mmol of triethylaluminum, 1 mmol of cyclohexylmethyldimethoxysilane, and 0.8 g of hydrogen are added to a 5 L stainless steel high-pressure reactor that has been thoroughly purged with nitrogen. The temperature is raised to 70 °C and maintained for 1 hour. After the reaction is completed, the temperature is lowered and the pressure is released to obtain powdered polypropylene granules. The relevant results are summarized in Table 1.

[0145] Table 1. Evaluation Results of Catalyst Polymerization

[0146]

[0147] Note: *Polymers numbered 9 and 12 used 4.8g of hydrogen gas, the rest are the same.

[0148] The test results of polymers 1-9 and 10-17 show that when the catalysts obtained by the compounds and preparation methods described in this invention are used in the propylene polymerization reaction, the catalysts can achieve an overall improvement in activity, and the overall orientation ability of the catalysts is well maintained. In addition, the catalysts show a significant effect in regulating the molecular weight distribution, and the molecular weight distribution of the obtained polymers is in the range of 4.8-6.4, which is moderate.

[0149] By adding only 1% (relative to the weight of the polypropylene powder) of antioxidant 1010 to the polypropylene powder with the corresponding polymerization number, granulating the powder, adding it to the extruder and preparing the specimens, the tensile breaking properties of the specimens were measured, and the relevant results are summarized in Table 2.

[0150] Table 2 Results of tensile elongation at break test

[0151]

[0152] Comparing the nominal strain analysis results of samples a to h, it can be seen that the polypropylene product prepared using the catalyst method described in this invention exhibits significant advantages in nominal strain at break within both high melt index (analysis results of sample e compared to sample g) and low melt index (analysis results of samples a, b, c, d compared to samples f, h). This demonstrates that the polypropylene product prepared using the catalyst described in this invention exhibits a significantly increased nominal strain at break, indicating that the product is less prone to breakage during processing into fiber or filament materials, thus greatly improving its processing performance. Therefore, it is particularly suitable for application in fiber and filament products.

[0153] Any numerical value mentioned in this invention, if there is only a two-unit interval between any minimum and any maximum value, includes all values ​​that increase by one unit each time from the minimum to the maximum value. For example, if the amount of a component, or the value of a process variable such as temperature, pressure, or time, is stated as 50-90, in this specification it means specifically listing values ​​such as 51-89, 52-88… and 69-71 and 70-71, etc. For non-integer values, it may be appropriately considered that a unit is 0.1, 0.01, 0.001, or 0.0001. These are merely some specifically specified examples. In this application, in a similar manner, all possible combinations of numerical values ​​between the listed minimum and maximum values ​​are considered to have been disclosed.

[0154] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. An internal electron donor modifier, comprising at least one of compounds with the structure shown in formula (I): in, R1 and R1 ’ Whether identical or different, each independently comprises one of the following: hydrogen, halogen, hydroxyl, C1-C30 straight-chain alkyl with or without substituents, C3-C30 branched alkyl with or without substituents, C2-C30 alkenyl with or without substituents, C2-C30 ester with or without substituents, C6-C30 aryl with or without substituents, or C3-C30 cycloalkyl or heterocyclic with or without substituents, and R1 and R1 ’ They can form any ring; R2, R3, R4, R5, R2 ’ R3 ’ R4 ’ and R5 ’ Whether identical or different, each is independently one of hydrogen, halogen, hydroxyl, nitro, amino, C1-C30 straight-chain alkyl with or without substituents, C3-C30 branched alkyl with or without substituents, C2-C30 alkenyl with or without substituents, C6-C30 aryl with or without substituents, or C3-C30 cycloalkyl or heterocyclic with or without substituents, and R2, R3, R4, R5, R2 ’ R3 ’ R4 ’ and R5 ’ Any two groups in can form a ring; A is selected from one of the following: alkylene, arylene, heteroarylene, alkylarylene, and arylalkylene, with or without substituents.

2. The internal electron donor modifier as described in claim 1, characterized in that: R1 and R1 ’ They are either the same or different, and are independently one of the following: hydrogen, halogen, hydroxyl, C1-C10 straight-chain alkyl with or without substituents, C3-C10 branched alkyl with or without substituents, C2-C10 alkenyl with or without substituents, C2-C10 ester with or without substituents, or C6-C30 aryl with or without substituents, and R1 and R1 ’ They can form any ring; and / or, R2, R3, R4, R5, R2 ’ R3 ’ R4 ’ and R5 ’ Whether identical or different, each is independently one of hydrogen, halogen, hydroxyl, nitro, amino, C1-C10 straight-chain alkyl with or without substituents, C3-C10 branched-chain alkyl with or without substituents, C6-C30 aryl with or without substituents, C6-C15 cycloalkyl or heterocyclic with or without substituents, and R2, R3, R4, R5, R2 ’ R3 ’ R4 ’ and R5 ’ Any two groups in the compound can form a ring; preferably, R2, R3, R4, R5, and R2... ’ R3 ’ R4 ’ and R5 ’ Each of the following is independently one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, methoxy, isopropyl ether, tert-butyl ether, phenyl, halophenyl, naphthyl, biphenyl, nitro, amino, pyridyl, thiophene, and quinolinyl, and R2, R3, R4, R5, and R2 are respectively... ’ R3 ’ R4 ’ and R5 ’ Any two groups in the cyclic compound can be formed arbitrarily; and / or, A is selected from one of the following: C1-C20 alkylene, C6-C20 arylene, C5-C20 heteroarylene, C7-C20 alkylarylene, and C7-C20 arylalkylene, with or without substituents.

3. A method for preparing an internal electron donor modifier as described in any one of claims 1-2, comprising the step of performing a condensation reaction of a diamine compound with a halomethylpyridine compound to obtain the internal electron donor modifier; preferably, the diamine compound has the structure shown in formula (ⅠⅠ): In equation (ⅠⅠ), R1 and R1 ’ Whether identical or different, each independently comprises one of the following: hydrogen, halogen, hydroxyl, C1-C30 straight-chain alkyl with or without substituents, C3-C30 branched alkyl with or without substituents, C2-C30 alkenyl with or without substituents, C2-C30 ester with or without substituents, C6-C30 aryl with or without substituents, or C3-C30 cycloalkyl or heterocyclic with or without substituents, and R1 and R1 ’ It can form rings in any way; A is selected from one of alkylene, arylene, heteroarylene, alkylarylene, and arylalkylene, with or without substituents; and / or, the halomethylpyridine compound has the structure shown in formula (ⅠⅠⅠ): In formula (ⅠⅠⅠ), X is a halogen, and R2, R3, R4 and R5 may be the same or different, and are independently one of hydrogen, halogen, hydroxyl, nitro, amino, C1-C30 straight-chain alkyl with or without substituents, C3-C30 branched alkyl with or without substituents, C2-C30 alkenyl with or without substituents, C6-C30 aryl with or without substituents, C3-C30 cycloalkyl or heterocyclic with or without substituents, and any two groups among R2, R3, R4 and R5 may be cyclic in any way.

4. The preparation method according to claim 3, characterized in that: The molar ratio of the amino group in the diamine compound to the halomethyl group in the halomethylpyridine compound is 1:(0.1-10), preferably 1:(0.5-2); and / or the reaction temperature is 10-280°C, preferably 20-150°C; and / or the reaction time is 1 min-168 h, preferably 4 h-72 h.

5. The preparation method according to claim 3, characterized in that: The diamine compound and the halomethylpyridine compound are reacted in a solvent in the presence of a basic reagent to obtain the internal electron donor modifier; preferably, the basic reagent is selected from at least one of alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal bicarbonates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal stearates, amine compounds, nitrogen-containing heterocyclic compounds, alkali metal salts of alcohols, alkyllithium reagents, Grignard reagents, and quaternary ammonium compounds; and / or, the solvent is selected from polar solvents. At least one of the following, preferably at least one of formamide, acetonitrile, methanol, ethanol, propanol, acetone, dioxane, tetrahydrofuran, methyl ethyl ketone, n-butanol, ethyl acetate, diethyl ether, isopropyl ether, dichloromethane, chloroform, bromoethane, benzene, and carbon tetrachloride; more preferably, the molar ratio of the diamine compound, the basic reagent, and the solvent is 100:(0.1-50):(1-50000), preferably 100:(0.5-5):(100-3000), wherein the diamine compound is calculated based on the molar number of amino groups.

6. A solid catalyst component for olefin polymerization, comprising a magnesium compound, a titanium compound, an internal electron donor compound, and a mixture of the internal electron donor modifier as described in any one of claims 1-2 or the internal electron donor modifier obtained by any one of the preparation methods described in claims 3-5 and / or reaction products.

7. The solid catalyst component as described in claim 6, characterized in that: The magnesium compound is selected from the general formula MgX. m (OR 1 ) 2-m At least one of the compounds shown, wherein repeated R 1 Each is independently a hydrocarbon group from C1 to C20, preferably a hydrocarbon group from C1 to C10, where X is a halogen and m = 0 to 2; preferably, the magnesium compound is selected from R. 1 The titanium compound is at least one of C1-C10 alkyl magnesium halide and alkoxy magnesium, preferably at least one of magnesium dichloride, magnesium dibromide, magnesium diiodide, methoxy magnesium chloride, ethoxy magnesium chloride, propoxy magnesium chloride, and butoxy magnesium chloride; and / or, the titanium compound is selected from the general formula TiX. n (OR 2 ) 4-n At least one of the compounds shown, wherein repeated R 2 Each is independently a hydrocarbon group from C1 to C20, preferably a hydrocarbon group from C1 to C10, where X is a halogen and n = 0 to 4; preferably, the titanium compound is selected from titanium halides, R 2 It is at least one of C1 to C10 alkyl titanate esters, preferably at least one of titanium tetrachloride, n-butyl titanate, isobutyl titanate, and 2-ethylhexyl titanate; and / or, the internal electron donor compound includes at least one of mono- or poly-ester compounds, mono- or poly-ol acid compounds, di- or poly-ol ester compounds, imine compounds, and ether compounds, preferably at least one of succinate compounds, diol ester compounds, iminoalkane compounds, and ether compounds.

8. The solid catalyst component as described in claim 6, characterized in that: The catalyst composition comprises 0.5–6.0 wt% titanium, 10.0–60.0 wt% magnesium, 20.0–80.0 wt% halogen, 4.0–40.0 wt% internal electron donor compound, and 0–32.0 wt% internal electron donor modifier; preferably, the catalyst composition comprises 1.0–4.0 wt% titanium, 15.0–35.0 wt% magnesium, 30.0–55.0 wt% halogen, 6.0–20.0 wt% internal electron donor compound, and 0.01–18.0 wt% internal electron donor modifier.

9. A method for preparing a solid catalyst component as described in any one of claims 6-8, comprising the steps of mixing and / or reacting raw materials including a magnesium compound, a titanium compound, an internal electron donor compound, and an internal electron donor modifier as described in any one of claims 1-2 or an internal electron donor modifier obtained by the preparation method of any one of claims 3-5; preferably, the method for preparing the catalyst component comprises: (1) Dissolve the magnesium compound in a solvent system containing organic alcohol solvent and / or inert hydrocarbon reagent; (2) Add the internal electron donor regulator to the solution obtained in step (1) and mix and react; (3) Add the solution obtained in step (2) to the titanium compound and react; (4) Add the internal electron donor compound to the reaction solution obtained in step (3) and react to obtain the solid catalyst component.

10. A catalyst for olefin polymerization, comprising a reaction product containing: a) a solid catalyst component according to any one of claims 6-8 or a solid catalyst component obtained by the preparation method according to claim 9; b) an alkylaluminum compound; and optionally c) an organosilicon compound; preferably, the alkylaluminum compound has the general formula AlR f q X 3-q ,in, Repeated R f Each of the following is independently a hydrogen or C1-C20 hydrocarbon group, preferably a hydrogen or C1-C20 alkyl group, where X is a halogen, and 1 ≤ q ≤ 3; preferably, the alkylaluminum compound is selected from one or more of trialkylaluminum, dialkylaluminum chloride, alkylaluminum chloride, and alkylaluminoxane; and / or, the organosilicon compound has the general formula R. A t Si(OR B ) 4-t Where t is an integer, and 0 ≤ t ≤ 3, and the repeated R A Each group is independently selected from alkyl, cycloalkyl, aryl, haloalkyl, amino, halogen, or hydrogen atoms, preferably from C1-C10 alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C1-C10 haloalkyl, amino, halogen, or hydrogen atoms, with repeated R. B The organosilicon compounds are independently selected from alkyl, cycloalkyl, aryl, haloalkyl, or amino groups, preferably from C1-C10 alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C1-C10 haloalkyl, or amino groups; preferably, the organosilicon compounds are selected from at least one of cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, and diisopropyldimethoxysilane.

11. The catalyst for olefin polymerization as described in claim 10, characterized in that: The molar ratio of components a), b), and c) is 1:(10-2000):(0-500) based on titanium:aluminum:silicon, preferably 1:(10-1000):(0-200).

12. A method for olefin polymerization, comprising the step of polymerizing an olefin in the presence of a solid catalyst component according to any one of claims 5-7, a solid catalyst component obtained by any one of the preparation methods according to claims 8-9, or a catalyst for olefin polymerization according to any one of claims 10-11; preferably, the olefin is selected from at least one compound of the general formula CH2=CHR, wherein, R is hydrogen, a C1-C12 alkyl group, or a C6-C12 aryl group, and preferably the olefin is at least one selected from ethylene, propylene, butene-1, 4-methyl-1-pentene, and 1-hexene.

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