Solid catalyst components for olefin polymerization reactions and process for their preparation and use

Abstract

This invention relates to the field of olefin polymerization technology, and discloses a solid catalyst component for olefin polymerization reactions, its preparation method, and its application. The preparation method includes reacting a magnesium compound and a titanium compound with an internal electron donor, a performance modifier, and a precipitation aid; wherein the internal electron donor is at least one of a main-chain asymmetric diol ester compound; the performance modifier is selected from at least one silane compound; and the precipitation aid is selected from at least one malonate ester compound. The solid catalyst component prepared by this invention, when used in olefin polymerization, especially propylene polymerization, not only improves polymerization activity but also results in polymers with high melt strength and a wide molecular weight distribution, suitable for producing pipes and extruded thick plates.

Description

Technical Field

[0001] This invention relates to the field of olefin polymerization technology, and more specifically to a solid catalyst component for olefin polymerization reactions, its preparation method, and its application. Background Technology

[0002] As is well known, solid titanium catalysts with magnesium, titanium, halogens and electron donors as basic components can be used in olefin polymerization reactions, especially in the polymerization of α-olefins with 3 or more carbon atoms, where polymers with high yields and high stereoregularity can be obtained. Electron donor compounds are an essential component of the catalyst, and the development of internal electron donor compounds has led to the continuous upgrading of polyolefin catalysts. Currently, a large number of electron donor compounds have been disclosed, such as esters, acid anhydrides, ketones, ethers, alcohols, amines and their derivatives.

[0003] Melt strength of polyolefins reflects the resistance of the polyolefin melt to stretching and sag, and is a very important property that determines the processability of the material. In recent years, melt strength has been recognized as one of the important molding parameters in polymer molding processes involving stretching and traction operations, such as melt spinning, blow molding, extrusion coating, blown film, fiber extrusion, and thermoforming. These molding processes are greatly affected by the melt strength of the material.

[0004] CN1169845C discloses a diol ester compound. Using this diol ester compound as an electron donor in olefin polymerization catalysts yields catalysts with excellent overall performance. However, when this catalyst is used to prepare propylene polymers with high melt strength, the melt strength of the resulting polymer needs further improvement, and the molecular weight distribution needs further broadening. Summary of the Invention

[0005] The purpose of this invention is to overcome the problem of low melt strength of olefin polymers in the prior art, and to provide a solid catalyst component for olefin polymerization reaction, its preparation method and application. When used for olefin polymerization, this solid catalyst component has high catalytic activity, and the resulting polymer has a wide molecular weight distribution and high melt strength, making it suitable for the production of pipes and extruded thick plates.

[0006] To achieve the above objectives, the present invention provides a method for preparing a solid catalyst component for olefin polymerization, the method comprising: reacting a magnesium compound, a titanium compound, an internal electron donor, a performance modifier, and a precipitation aid;

[0007] The internal electron donor is selected from at least one of the main-chain asymmetric diol ester compounds; the performance modifier is selected from at least one of the silane compounds; and the precipitation aid is selected from at least one of the malonate compounds.

[0008] A second aspect of the present invention provides a solid catalyst component prepared by the preparation method described above.

[0009] A third aspect of the present invention provides a catalyst for olefin polymerization reactions, the catalyst comprising:

[0010] (1) The solid catalyst components described above;

[0011] (2) Activator;

[0012] (3) Optional external electron donor.

[0013] A fourth aspect of the present invention provides a prepolymerization catalyst composition for olefin polymerization reactions, the prepolymerization catalyst composition comprising a prepolymer obtained by prepolymerization of an olefin using the above-described catalyst.

[0014] The fifth aspect of the present invention provides a method for olefin polymerization, the method comprising: polymerizing olefins in the presence of the solid catalyst component described above or the solid catalyst component prepared by the method described above;

[0015] Alternatively, the olefins may be polymerized in the presence of the catalyst described above;

[0016] Alternatively, the olefins may be polymerized in the presence of the aforementioned prepolymerization catalyst composition.

[0017] This invention employs a main-chain asymmetric glycol ester compound as an internal electron donor, a silane compound as a performance modifier, and a malonic acid ester compound as a precipitation aid in the preparation of the solid catalyst component. The resulting solid catalyst component, when used in olefin polymerization, especially propylene polymerization, not only improves polymerization activity but also produces polymers with high melt strength and a wide molecular weight distribution, making them suitable for producing pipes and extruded thick plates. In a preferred embodiment of this invention, using the silane compound of formula (II) as a performance modifier and the malonic acid ester compound of formula (III) as a precipitation aid further enhances polymerization activity, as well as the polymer's melt strength and molecular weight distribution. Detailed Implementation

[0018] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0019] In this invention, unless otherwise specified, the halogen atom and halogen can be selected from F, Cl, Br, I, etc. C1-C 10 Straight-chain alkyl groups can be selected from C1, C2, C3, C4, C5, C6, C7, C8, C9, ... 10 Straight-chain alkyl groups. C3-C 10 Branched alkyl groups can be selected from C3, C4, C5, C6, C7, C8, C9, C10, C11, C20, C30, C40, C50, C60, C70, C80, C90, C10, C110, C120, C130, C140, C150, C160, C170, C180, C190, C100, C11 10 Branched alkyl groups. C3-C 10 The cycloalkyl group can be selected from C3, C4, C5, C6, C7, C8, C9, C10, C11, C20, C30, C40, C50, C60, C70, C80, C90, C10, C110, C120, C130, C140, C150, C160, C170, C180, C190, C10 ... 10 Cycloalkyl groups. C6-C 15 The aryl group can be selected from C6, C7, C8, C9, ... 10 C 11 C 12 C 13 C 14 C 15 Aryl group. C7-C 15 The alkylaryl group can be selected from C7, C8, C9, C10, C20, C30, C40, C50, C60, C70, C80, C90, C1 ... 10 C 11 C 12 C 13 C 14 C 15 alkylaryl groups. C7-C 15 Aryl alkyl groups can be selected from C7, C8, C9, and C6. 10 C 11 C 12 C 13 C 14 C 15 Aryl groups.

[0020] The first aspect of the present invention provides a method for preparing a solid catalyst component for olefin polymerization reaction, the method comprising: reacting a magnesium compound, a titanium compound with an internal electron donor, a performance modifier and a precipitation aid;

[0021] The internal electron donor is selected from at least one of the main-chain asymmetric diol ester compounds; the performance modifier is selected from at least one of the silane compounds; and the precipitation aid is selected from at least one of the malonate compounds.

[0022] In this invention, the term "main-chain asymmetric diol ester compound" refers to a diol compound used to prepare the diol ester compound that is asymmetric. For example, 2,4-hexanediol dibenzoate is obtained by reacting 1 mol of 2,4-hexanediol with 2 mol of benzoyl chloride, wherein the structure of 2,4-hexanediol is asymmetric.

[0023] According to the present invention, preferably, the internal electron donor is at least one of the main-chain asymmetric diol ester compounds represented by formula (I);

[0024]

[0025] Among them, R1 and R2 may be the same or different, and are each independently selected from halogen atoms, C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C3-C 10 cycloalkyl, C6-C 15 Aryl, C7-C 15 Alkyl or C7-C 15 Aryl groups;

[0026] R3 and R4 may be the same or different, and each is independently selected from hydrogen, halogen atoms, and C1-C atoms. 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C3-C 10 cycloalkyl, C6-C 15 Aryl, C7-C 15 Alkyl or C7-C 15 Aryl groups;

[0027] R5 is selected from hydrogen, halogen atoms, and C1-C atoms. 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C3-C 10 cycloalkyl, C6-C 15 Aryl, C7-C 15 Alkyl or C7-C 15 Aryl group; n is an integer from 1 to 5; where n is the number of substituents on the benzene ring.

[0028] According to the present invention, preferably, R1 and R2 are each independently selected from halogen atoms, C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C3-C 10 Cycloalkyl; more preferably, R1 and R2 are each independently selected from C1-C8 straight-chain alkyl and C3-C8 branched alkyl.

[0029] According to the present invention, preferably, R3 and R4 are each independently selected from hydrogen, halogen atoms, C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C3-C 10 cycloalkyl and C7-C 15 Aryl alkyl group; more preferably, R3 and R4 are each independently selected from hydrogen, C1-C8 straight-chain alkyl, C3-C8 branched alkyl, and C7-C4. 10 Aryl alkyl group.

[0030] According to the present invention, preferably, R5 is selected from hydrogen, halogen atoms, C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl group; n is an integer from 1 to 2; more preferably, R5 is selected from hydrogen, halogen atom, C1-C8 straight-chain alkyl group, C3-C8 branched alkyl group; n is 1. More preferably, when n=1, R5 is an ortho- or para-substituent on the benzene ring.

[0031] According to the present invention, preferably, the internal electron donor is selected from 2,4-hexanediol dibenzoate, 2,4-hexanediol di-o-methylbenzoate, 2,4-hexanediol di-m-methylbenzoate, 2,4-hexanediol di-p-methylbenzoate, 2,4-hexanediol di-m-chlorobenzoate, 2,4-hexanediol di-p-chlorobenzoate, 2,4-hexanediol di-p-ethylbenzoate, 2,4-hexanediol di-p-propylbenzoate, 2,4-hexanediol di-p-butylbenzoate, 2,4-hexanediol di-p-tert-butylbenzoate, 3-methyl-2,4-hexanediol dibenzoate, 3-ethyl-2,4-hexanediol dibenzoate, 3-n-propyl-2,4-hexanediol dibenzoate, 3-benzyl-2,4-hexanediol dibenzoate. Ester, 3-methyl-2,4-hexanediol di-p-methylbenzoate, 3-ethyl-2,4-hexanediol di-p-methylbenzoate, 3-ethyl-2,4-hexanediol di-p-ethylbenzoate, 3-ethyl-2,4-hexanediol di-p-n-propylbenzoate, 3-ethyl-2,4-hexanediol di-p-n-butylbenzoate, 3-ethyl-2,4-hexanediol di-p-tert-butylbenzoate, 3-n-butyl-2,4-hexanediol dibenzoate, 2,4-heptanediol dibenzoate, 2,4-heptanediol di-o-methylbenzoate, 2,4-heptanediol di-m-methylbenzoate, 2,4-heptanediol di-p-methylbenzoate, 2,4-heptanediol di-o-chlorobenzoate, 2,4-heptanediol di-m-chlorobenzoate, 2,4-heptanediol di-o-chlorobenzoate, 2,4-heptanediol di-m-chlorobenzoate, 2,4-heptanediol di-p-methylbenzoate, Dichlorobenzoate, 2,4-heptanediol di-2-ethylbenzoate, 2,4-heptanediol di-2-n-propylbenzoate, 2,4-heptanediol di-2-n-butylbenzoate, 2,4-heptanediol di-2-tert-butylbenzoate, 3-methyl-2,4-heptanediol dibenzoate, 3-ethyl-2,4-heptanediol dibenzoate, 3-n-propyl-2,4-heptanediol dibenzoate, 3-methyl-2,4-heptanediol di-2-methylbenzoate, 3-ethyl-2,4-heptanediol di-2-n-propylbenzoate, 3-ethyl-2,4-heptanediol di-2-n-butylbenzoate, 3-ethyl-2,4-heptanediol di-2-tert-butylbenzoate, 6-methyl-2,4-heptanediol dibenzoate, 6-methyl-2,4-heptanediol dibenzoate, 6-methyl-2,4-heptanediol dibenzoate, 3-ethyl-2,4-heptanediol di-2-tert-butylbenzoate, 3-ethyl-2,4-heptanediol di-2-ethyl-2 ... Diol di-p-methylbenzoate, 6-methyl-2,4-heptanediol di-m-methylbenzoate, 6-methyl-2,4-heptanediol di-o-methylbenzoate, 6-methyl-2,4-heptanediol di-p-ethylbenzoate, 6-methyl-2,4-heptanediol di-p-propylbenzoate, 6-methyl-2,4-heptanediol di-p-butylbenzoate, 6-methyl-2,4-heptanediol di-p-tert-butylbenzoate, 3-ethyl-6-methyl-2,4-heptanediol dibenzoate, 3-ethyl-6-methyl-2,4-heptanediol di-p-propylbenzoate, 3-n-propyl-6-methyl-2,4-heptanediol di-p-butylbenzoate, 3-n-butyl-6-methyl-2,4-heptanediol di-p-tert-butylbenzoate, 2...At least one of the following: 4-octanediol dibenzoate, 3,5-octanediol dibenzoate, 3,5-octanediol di-p-methylbenzoate, 3,5-octanediol di-m-methylbenzoate, 3,5-octanediol di-o-methylbenzoate, 3,5-octanediol di-p-ethylbenzoate, 3,5-octanediol di-p-n-propylbenzoate, 3,5-octanediol di-p-n-butylbenzoate, 3,5-octanediol di-p-tert-butylbenzoate, 4-methyl-3,5-octanediol dibenzoate, 4-ethyl-3,5-octanediol di-p-n-butylbenzoate, and 4-n-propyl-3,5-octanediol dibenzoate.

[0032] According to the present invention, preferably, the performance modifier is selected from at least one of the silane compounds shown in formula (II).

[0033] (R6) y Si(OR7) 4-y (II)

[0034] Among them, R6 is selected from C1-C 10 Straight-chain alkyl or C3-C 10 Branched alkyl groups; R7 is C1-C 10 Straight-chain alkyl; y is an integer from 1 to 3. More preferably, R6 is selected from C1-C8 straight-chain alkyl or C3-C8 branched alkyl; R7 is C1-C6 straight-chain alkyl.

[0035] According to the present invention, preferably, the performance modifier is selected from methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, tetramethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane, triethylmethoxysilane, ethyltriethoxysilane, diethyldiethoxysilane, triethylethoxysilane, tetraethoxysilane, n-propyltrimethoxysilane, di-n-propyldimethoxysilane, tri-n-propylmethoxysilane, n-propyltriethoxysilane, di-n-propyldiethoxysilane, tri-n-propyldiethoxysilane, and tri-n-propyltrimethoxysilane. At least one of propylethoxysilane, isopropyltriethoxysilane, diisopropyldiethoxysilane, triisopropylethoxysilane, isopropyltrimethoxysilane, diisopropyldimethoxysilane, triisopropylmethoxysilane, n-butyltrimethoxysilane, di-n-butyldimethoxysilane, tri-n-butylmethoxysilane, n-butyltriethoxysilane, di-n-butyldiethoxysilane, tri-n-butylethoxysilane, isobutyltriethoxysilane, diisobutyldiethoxysilane, triisobutylethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, and triisobutylmethoxysilane.

[0036] According to the present invention, preferably, the precipitation aid is selected from at least one of the malonate compounds shown in formula (III).

[0037]

[0038] Among them, R8 and R9 may be the same or different, and are independently selected from hydrogen, halogens, and C1-C. 10 Straight-chain alkyl, C2-C 10 Straight-chain alkenyl, C2-C 10 Branched alkenyl, C3-C 10 Branched alkyl, C3-C 12 cycloalkyl, C6-C 15 Aryl, C7-C 15 Alkyl or aryl; more preferably, R8 and R9 are each independently selected from hydrogen, halogen, C1-C8 straight-chain alkyl, C2-C8 straight-chain alkenyl, C2-C8 branched alkenyl, C3-C8 branched alkyl, C3-C 10 cycloalkyl, C6-C 12 Aryl, C7-C 12 alkylaryl or arylalkyl;

[0039] R 10 Selected from C1-C 10 Straight-chain alkyl, C3-C 12 Branched alkyl, C3-C 15 cycloalkyl, C6-C 15 Aryl, C7-C 15 alkylaryl or arylalkyl; more preferably, R 10 Selected from C1-C8 straight-chain alkyl, C3-C8 branched alkyl, C3-C 10 cycloalkyl, C6-C 12 Aryl, C7-C 12 Alkyl or aryl.

[0040] According to the present invention, preferably, the co-precipitant is selected from diisobutylmalonide, di-n-butylmalonide, di-tert-butylmalonide, diisobutylmalonide, di-n-butylmalonide, di-tert-butylmalonide, diisobutylmalonide, di-n-butylmalonide, di-tert-butylmalonide, di-dipentyl diisobutylmalonide, di-n-butylmalonide, di-tert-butylmalonide, di-hexyl diisobutylmalonide, di-n-butylmalonide, di-heptyl diisobutylmalonide, di-n-butylmalonide, di-tert-butylmalonide, di-propyl dipropylmalonide, di-isopentyl dipropylmalonide, di-n-pentyl dipropylmalonide, di-hexyl dipropylmalonide, di-diisopentyl dipropylmalonide, di-di ... Dipropyl phenyl-ethyl malonate, dipropyl phenyl methyl malonate, dipropyl phenyl propionate, dipropyl phenyl-butyl malonate, dipropyl phenyl isobutyl malonate, dipropyl diphenyl malonate, benzyl ethyl malonate, benzyl methyl malonate, benzyl propyl malonate, benzyl-butyl malonate, dipropyl phenyl isopentyl malonate, dipropyl benzyl-butyl malonate, dipropyl benzyl-butyl malonate, dipropyl benzyl ethyl malonate, dibutyl phenyl methyl malonate, dibutyl phenyl propionate, dibutyl phenyl-propyl malonate, dibutyl phenyl-butyl malonate, dibutyl phenyl isobutyl malonate, dibutyl phenyl isopentyl malonate, dibutyl phenyl-butyl malonate, dipropyl benzyl ethyl malonate, dibutyl phenyl methyl malonate, dibutyl phenyl propionate, dibutyl phenyl propionate, dipropyl benzyl ethyl malonate, dipropyl phenyl propionate, dipropyl phenyl isopentyl malonate, dipropyl phenyl isopentyl malonate, dipropyl phenyl propionate, benzyl ethyl malonate, dipropyl phenyl isopentyl ... Dibutyl phenyl ethyl malonate, benzyl methyl malonate, benzyl propyl malonate, benzyl n-butyl malonate, benzyl isobutyl malonate, benzyl isopentyl malonate, benzyl n-pentyl malonate, dibenzyl malonate, phenyl ethyl dipentyl malonate, phenyl methyl dipentyl malonate, phenyl propyl dipentyl malonate, phenyl n-butyl dipentyl malonate, phenyl isobutyl malonate, phenyl isopentyl dipentyl malonate, phenyl n-pentyl malonate, diphenyl malonate, benzyl ethyl dipentyl malonate, benzyl methyl dipentyl malonate, benzyl propyl dipentyl malonate, benzyl n-butyl dipentyl malonate, benzyl isobutyl malonate, benzyl isopentyl dipentyl malonate Ester, benzyl n-pentyl malonate dipentyl ester, phenylethyl dicyclohexyl malonate, phenylmethyl dicyclohexyl malonate, phenylpropyl dicyclohexyl malonate, phenylmethyl diphenyl malonate, phenyl isopentyl diphenyl malonate, phenyl n-pentyl diphenyl malonate, diphenyl diphenyl malonate, benzyl ethyl diphenyl malonate, benzyl methyl diphenyl malonate, benzyl propyl diphenyl malonate, benzyl n-butyl diphenyl malonate, benzyl isobutyl diphenyl malonate, benzyl isopentyl diphenyl malonate, benzyl n-pentyl diphenyl malonate, dibenzyl diphenyl malonate, allyl methyl diphenyl malonate, allyl propyl diphenyl malonate, allyl n-butyl diphenyl malonate, allyl isobutyl diphenyl malonate, allyl isopentyl diphenyl malonateAllyl n-pentyl malonate diphenyl ester, diallyl diphenyl malonate, allyl methyl malonate dimethyl ester, allyl propyl dimethyl malonate, allyl n-butyl malonate dimethyl ester, allyl isobutyl malonate dimethyl ester, allyl isopentyl dimethyl malonate, allyl n-pentyl malonate dimethyl ester, diallyl dimethyl malonate, allyl methyl diethyl malonate, allyl n- Diethyl butyl malonate, allyl isobutyl malonate, allyl isopentyl malonate, allyl n-pentyl malonate, diallyl diethyl malonate, allyl methyl malonate, allyl propyl malonate, allyl n-butyl malonate, allyl isobutyl malonate, allyl isopentyl malonate, allyl n-pentyl malonate, diallyl propyl malonate Dipropyl diacidate, allyl methyl malonate dibutyl ester, allyl propyl malonate dibutyl ester, allyl n-butyl malonate dibutyl ester, allyl isobutyl malonate dibutyl ester, allyl isopentyl malonate dibutyl ester, allyl n-pentyl malonate dibutyl ester, diallyl dibutyl malonate, allyl methyl malonate dipentyl ester, allyl propyl malonate dipentyl ester, allyl n-butyl malonate dipentyl ester, allyl isobutyl malonate dibutyl malonate dibutyl ester At least one of the following: dipentyl isopentyl malonate, dipentyl isopentyl n-pentyl malonate, dipentyl diallyl malonate, dicyclohexyl methyl malonate, dicyclohexyl allylpropyl malonate, dicyclohexyl allyl n-butyl malonate, dicyclohexyl isopentyl malonate, dicyclohexyl isopentyl malonate, dicyclohexyl isopentyl malonate, dicyclohexyl isopentyl malonate, and dicyclohexyl diallyl malonate.

[0041] According to the present invention, preferably, the amount of the co-precipitant added relative to each mole of magnesium compound is 0-1 mole (e.g., 0.01 mole, 0.1 mole, 0.15 mole, 0.2 mole, 0.3 mole, 0.4 mole, 0.5 mole, 0.6 mole, 0.7 mole, 0.8 mole, 0.9 mole, 1 mole, and any two of the above, preferably 0.1-2 moles), and the amount of the internal electron donor added is 0.02-0.4 moles (e.g., 0.02 mole, 0.03 mole, 0.04 mole, 0.05 mole, 0.06 mole, 0.07 mole, 0.08 mole, 0.09 ... The amounts of the performance modifier are 1 mol, 0.15 mol, 0.2 mol, 0.25 mol, 0.3 mol, 0.35 mol, 0.4 mol, and any two of the above, preferably 0.05-0.1 mol), and the amount of the performance modifier added is 0.01-0.3 mol (e.g., 0.01 mol, 0.02 mol, 0.03 mol, 0.04 mol, 0.05 mol, 0.06 mol, 0.07 mol, 0.08 mol, 0.09 mol, 0.1 mol, 0.15 mol, 0.2 mol, 0.25 mol, 0.3 mol, and any two of the above, preferably 0.05-0.1 mol).

[0042] According to the present invention, preferably, the amount of titanium compound added is 0.5-150 moles relative to each mole of magnesium compound (e.g., 0.5 moles, 1 mole, 20 moles, 30 moles, 40 moles, 50 moles, 60 moles, 70 moles, 80 moles, 90 moles, 100 moles, 110 moles, 120 moles, 130 moles, 140 moles, 150 moles, and any range of any two of the above).

[0043] According to the present invention, preferably, the magnesium compound is selected from at least one of magnesium dihalides, magnesium alkoxy compounds, alkyl magnesium compounds, hydrates or alcohols of magnesium dihalides, and derivatives of magnesium dihalides in which the halogen atom is replaced by an alkoxy or haloalkoxy group, more preferably selected from magnesium dihalides and / or magnesium dihalides alcohols; for example, magnesium dichloride, magnesium dibromide, magnesium diiodide, and their alcohols.

[0044] According to the present invention, preferably, the titanium compound has the general formula TiX. m (OR 1) 4-m In the formula R 1 For C1-C 20 The hydrocarbon group, where X is a halogen, 1≤m≤4, more preferably, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloromonoethoxy, and is even more preferably titanium tetrachloride.

[0045] According to a preferred embodiment of the present invention, the preparation method includes: in the presence of a precipitation aid, making a titanium compound into a first contact with a solution containing a magnesium compound and a performance modifier; and making the product of the first contact into a second contact with an internal electron donor.

[0046] According to a preferred embodiment of the present invention, the solution containing the magnesium compound and the performance modifier further includes an organic epoxy compound and an organophosphorus compound. More preferably, the amount of the organic epoxy compound is 0.2-10 moles and the amount of the organophosphorus compound is 0.1-3 moles per mole of magnesium compound.

[0047] According to a preferred embodiment of the present invention, the organic epoxy compound is selected from at least one of aliphatic olefins, dienes, oxides of halogenated aliphatic olefins or dienes, glycidyl ethers and internal ethers having 2-8 carbon atoms; more preferably, the organic epoxy compound is selected from at least one of ethylene oxide, propylene oxide, butane oxide, butadiene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, and tetrahydrofuran.

[0048] According to a preferred embodiment of the present invention, the organophosphorus compound is selected from at least one of the following: a hydrocarbon ester or a halohydrocarbon ester of orthophosphoric acid, a hydrocarbon ester or a halohydrocarbon ester of phosphorous acid. More preferably, the organophosphorus compound is selected from at least one of the following: trimethyl orthophosphoric acid, triethyl orthophosphoric acid, tributyl orthophosphoric acid, triphenyl orthophosphoric acid, trimethyl orthophosphoric acid, triethyl orthophosphoric acid, tributyl orthophosphoric acid, and triphenylmethyl orthophosphoric acid.

[0049] According to a preferred embodiment of the present invention, the solution containing the magnesium compound and the performance regulator further includes an inert diluent. More preferably, the inert diluent is selected from at least one of hexaane, heptane, octane, decane, benzene, toluene, and xylene.

[0050] According to a preferred embodiment of the present invention, the method includes: (1) preparing a solution containing a magnesium compound and a performance modifier: dissolving the magnesium compound in a mixture of a performance modifier, an organic epoxy compound, an organic phosphorus compound, and an inert diluent to form a homogeneous solution; (2) adding a precipitation aid to the solution obtained in step (1), and then adding a titanium compound dropwise to obtain a solid; (3) treating the solid with an internal electron donor. The treatment allows the internal electron donor to be loaded onto the solid; if necessary, the solid is further treated with titanium tetrahalide and an inert diluent.

[0051] According to a preferred embodiment of the present invention, the solution containing magnesium compounds and performance regulators may also include organic alcohol compounds, wherein the organic alcohol compounds may be monohydric alcohols with 2-8 carbon atoms, such as ethanol, propanol, butanol, pentanol, hexanol, octanol, isooctanol, etc., or mixtures thereof.

[0052] According to another preferred embodiment of the present invention, the internal electron donor can also be directly mixed with the magnesium compound and then reacted with the titanium compound. Therefore, the solid catalyst component can also be prepared by the following method: forming an emulsion of magnesium compound, performance modifier and internal electron donor in diluent, then adding titanium compound and precipitation aid to the emulsion to obtain a solid, and then undergoing optional treatment to obtain the solid catalyst component.

[0053] In any preparation method, the desired internal electron donor can be added directly in the form of a compound; or it can be added in other ways, such as by obtaining a suitable precursor of the internal electron donor in situ, which can be converted into the desired internal electron donor through known chemical reactions such as esterification.

[0054] A second aspect of the present invention provides a solid catalyst component prepared by the preparation method described above.

[0055] According to the present invention, preferably, the content of magnesium in the solid catalyst component is 3-25 wt%, the content of titanium is 1-6 wt%, and the content of internal electron donor compound is 1-20 wt%; more preferably, the content of magnesium is 10-20 wt%, the content of titanium is 1-5 wt%, and the content of internal electron donor is 5-15 wt%.

[0056] A third aspect of the present invention provides a catalyst for olefin polymerization reactions, the catalyst comprising:

[0057] (1) The solid catalyst components described above;

[0058] (2) Activator;

[0059] (3) Optional external electron donor.

[0060] According to the present invention, preferably, the amount of alkyl aluminum compound used is 0.01-100 mmol and the amount of external electron donor is 0.001-10 mmol per 100 mg of solid catalyst component.

[0061] According to the present invention, preferably, the activator is at least one of an alkylaluminum compound; the general formula of the alkylaluminum compound may be AlR 2 j X 3-j In the formula R 2The activator can be hydrogen, a hydrocarbon group having 1-20 carbon atoms (preferably a hydrocarbon group having 1-5 carbon atoms), X can be a halogen, and j can be an integer from 1 to 3. More preferably, the activator is selected from at least one of triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, triisooctylaluminum, diethylaluminum hydrogen, diisobutylaluminum hydrogen, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, and diethylaluminum chloride, and even more preferably triethylaluminum and / or triisobutylaluminum.

[0062] According to the present invention, preferably, the external electron donor is at least one of an organosilicon compound. The general formula of the external electron donor can be R0. 3 k Si(OR 4 ) 4-k In the formula, k can be an integer between 0 and 3, and R 3 and R 4 It can be the same or different alkyl, cycloalkyl, aryl, haloalkyl, amino, R 3 It can also be a halogen or a hydrogen atom. More preferably, the external electron donor is selected from trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, etc. The silane is selected from one or more of the following: dipropyltriethoxysilane, dipropyltriethoxysilane, dibutyltriethoxysilane, diisopropyltriethoxysilane, dibutyltriethoxysilane, phenyltriethoxysilane, cyclohexylmethyldimethoxysilane, and methyl tert-butyldimethoxysilane, and is more preferably one or more of the following: dipropyltrimethoxysilane, dibutyltrimethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, and dicyclopentyldimethoxysilane.

[0063] According to the present invention, preferably, the molar ratio of the solid catalyst component based on Ti, the alkyl aluminum compound based on Al, and the external electron donor based on Si is 1:5-1000:0-500, more preferably 1:20-250:1-50.

[0064] The catalyst of the present invention can be directly added to the reactor for the polymerization process, or the catalyst can be prepolymerized before the polymerization process. Therefore, a fourth aspect of the present invention provides a prepolymerization catalyst composition for olefin polymerization, the prepolymerization catalyst composition containing a prepolymer obtained by prepolymerization of the above-described catalyst with an olefin.

[0065] It is understood that the prepolymerization catalyst composition includes the above-mentioned solid catalyst component and the prepolymer obtained by prepolymerization of the solid catalyst component with an olefin.

[0066] In this invention, the term "prepolymerization" refers to polymerization at a lower degree of conversion.

[0067] According to the present invention, preferably, the prepolymerization ratio of the prepolymer is 0.1-1000 g olefin polymer / g solid catalyst component, more preferably 0.2-800 g olefin polymer / g solid catalyst component.

[0068] According to the present invention, preferably, the olefin has the general formula CH2=CHR, where R is hydrogen or C1-C. 12 The olefin is a hydrocarbon or aryl group, and more preferably, the olefin is ethylene or propylene. Particularly preferred is prepolymerization using a mixture of ethylene or propylene and one or more α-olefins in an amount of up to 20 mol%.

[0069] The prepolymerization process can be carried out in a liquid or gas phase at temperatures ranging from -40 to 80°C, preferably from -20 to 50°C. The prepolymerization step can be performed online as part of a continuous polymerization process or independently in a batch operation. For preparing polymers with an olefin polymer content of 0.5-20 g / g solid catalyst component, batch prepolymerization of the catalyst of the present invention with propylene is particularly preferred. The prepolymerization pressure can be 0.01-10 MPa.

[0070] The fifth aspect of the present invention provides a method for olefin polymerization, the method comprising: polymerizing olefins in the presence of the solid catalyst component described above or the solid catalyst component prepared by the method described above;

[0071] Alternatively, the olefins may be polymerized in the presence of the catalyst described above;

[0072] Alternatively, the olefins may be polymerized in the presence of the aforementioned prepolymerization catalyst composition.

[0073] The catalyst of the present invention can be directly added to the reactor for use in the polymerization process, or the catalyst can be added to the reactor after prepolymerization of the catalyst with olefins to obtain a prepolymerized catalyst composition.

[0074] The olefin polymerization reaction of the present invention is carried out according to known polymerization methods, which can be carried out in the liquid phase or gas phase, or in a combination of liquid phase and gas phase polymerization stages. Conventional techniques such as slurry polymerization and gas-phase fluidized bed polymerization are employed. Preferably, the following reaction conditions are used: polymerization temperature 0-150°C, preferably 60-90°C.

[0075] The olefins described in this invention have the general formula CH2=CHR, where R is hydrogen or C1-C. 12 Alkyl or aryl groups. Such as at least one selected from ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. Preferably selected from ethylene and / or propylene. Such as homopolymerization of propylene and copolymerization of propylene with other olefins. The method of the present invention is also applicable to homopolymerization of ethylene or copolymerization of ethylene with α-olefins, such as 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 4-methyl-1-pentene.

[0076] The present invention will be described in detail below through embodiments. In the following embodiments,

[0077] Polymerization activity: The amount of polymer obtained within a certain time (in kg) divided by the amount of solid catalyst component added (in g).

[0078] Examples 1-4

[0079] In a reactor fully purged with high-purity nitrogen, 6.0 g of magnesium chloride, 120 mL of toluene, 5 mL of epichlorohydrin, 15.6 mL of tributyl phosphate (TBP), and 6 mmol of the performance modifier silane compound (II) from Table 1 were added sequentially. The mixture was heated to 50 °C with stirring and maintained for 2.5 hours until the solid completely dissolved. Then, 10 mmol of the precipitation aid from Table 1 was added, and the temperature was maintained for another hour. The solution was cooled to below -25 °C, and 70 mL of TiCl4 was added dropwise over one hour. The temperature was slowly increased to 80 °C, and a solid gradually precipitated during the heating process. 6 mmol of the internal electron donor compound (I) from Table 1 was added, and the temperature was maintained for another hour. After filtration, 80 mL of toluene was added, and the mixture was washed twice to obtain a solid precipitate.

[0080] Then add 60 mL of toluene and 40 mL of TiCl4, heat to 110 °C, treat for 2 hours, remove the filtrate, add another 60 mL of toluene and 40 mL of TiCl4, heat to 110 °C, treat for 2 hours, remove the filtrate; add 60 mL of toluene, wash once in boiling state, add 60 mL of hexane, wash twice in boiling state, add 60 mL of hexane, wash twice at room temperature, and obtain the solid catalyst component.

[0081] Comparative Example 1

[0082] The procedure was carried out according to Example 4, except that the performance modifier silane compound was not added, and the precipitation aid was replaced with an equimolar amount of phthalic anhydride (i.e., phthalic anhydride).

[0083] Comparative Example 2

[0084] The procedure was carried out according to Example 4, except that the internal electron donor compound was replaced with an equimolar amount of 3-ethyl-2,4-pentanediol dibenzoate.

[0085] Test Example 1

[0086] The solid catalyst components of the above examples and comparative examples were subjected to propylene polymerization. The propylene polymerization procedure was as follows: In a 5L stainless steel reactor, after complete purging with gaseous propylene, 2.5 mmol of AlEt3 and 0.1 mmol of methylcyclohexyldimethoxysilane were added, followed by 8-10 mg of the above-mentioned solid catalyst component and 1.2L of hydrogen gas. 2.3L of liquid propylene was then introduced, and the temperature was raised to 70°C and maintained for 1 hour. The reactor was then cooled and depressurized to obtain PP powder. The polymerization activity results are shown in Table 1.

[0087] Table 1

[0088]

[0089] ID1: 2,4-Heptanediol di(4-n-Butylbenzoate)

[0090] ID2: 2,4-Octadiol dibenzoate

[0091] ID3: 2,4-Hexanediol di(4-n-propylbenzoate)

[0092] ID4: 3-Ethyl-2,4-hexanediol dibenzoate

[0093] ID5: 3-Ethyl-2,4-pentanediol dibenzoate

[0094] Test Example 2

[0095] The PP powder prepared in Test Example 1 was tested, and the results are shown in Table 2. The test methods are as follows:

[0096] (1) Polymer isotactic index (TII): The isotactic index is determined by the heptane extraction method (boiling heptane extraction for 6 hours). 2g of dry polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours. The residue is dried to constant weight. The ratio of the polymer weight (g) to 2g is the isotactic index.

[0097] (2) Melt index (MI) of polymer: determined according to test standard GB / T 3682—2000.

[0098] (3) Polymer molecular weight distribution MWD (MWD = M w / M n Gel permeation chromatography was used, with trichlorobenzene as solvent in a PL-GPC220 column at 150℃ (standard was polystyrene, flow rate was 1.0 mL / min, column was 3xPlgel 10um M1xED-B 300x7.5nm).

[0099] (4) Melt strength: The Rheoten melt strength tester is used. After the polymer is melted and plasticized by a single screw extruder, it is extruded through a 90° rotating round die and held between two rollers for uniaxial stretching in a constant acceleration manner. The stretching force is measured by a force measuring element. The maximum force value measured from the start of stretching to the melt fracture is the melt strength.

[0100] Table 2

[0101]

[0102] As can be seen from Tables 1 and 2, Examples 1-4 show that the synergistic effect of the electron donor in the main chain asymmetric glycol ester compound with the performance modifier silane compound and the precipitation aid malonate compound can improve the melt strength and molecular weight distribution of the polymer.

[0103] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing a solid catalyst component for olefin polymerization, characterized in that, The preparation method includes: reacting magnesium compounds, titanium compounds with an internal electron donor, a performance modifier, and a precipitation aid; The precipitation aid is selected from at least one of malonate compounds; The internal electron donor is at least one of the main-chain asymmetric diol ester compounds represented by formula (Ⅰ); （Ⅰ） Among them, R1 and R2 may be the same or different, and are each independently selected from halogen atoms, C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C3-C 10 cycloalkyl, C6-C 15 Aryl, C7-C 15 Alkyl or C7-C 15 Aryl alkyl groups; R3 and R4 may be the same or different, and each is independently selected from hydrogen, halogen atoms, and C1-C atoms. 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C3-C 10 cycloalkyl, C6-C 15 Aryl, C7-C 15 Alkyl or C7-C 15 Aryl alkyl groups; R5 is selected from hydrogen, halogen atoms, and C1-C atoms. 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C3-C 10 cycloalkyl, C6-C 15 Aryl, C7-C 15 Alkyl or C7-C 15 Aryl group; n is an integer from 1 to 5; where n is the number of substituents on the benzene ring; The performance modifier is selected from at least one of the silane compounds shown in formula (II). (R6) y Si(OR7) 4-y (II) Among them, R6 is selected from C1-C 10 Straight-chain alkyl or C3-C 10 Branched alkyl groups; R7 is C1-C 10 Straight-chain alkyl; y is an integer from 1 to 3.

2. The preparation method according to claim 1, wherein, R5 is selected from hydrogen, halogen atoms, and C1-C atoms. 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C3-C 10 cycloalkyl, C6-C 15 Aryl, C7-C 15 Alkyl or C7-C 15 Aryl group; n is an integer from 1 to 2; where n is the number of substituents on the benzene ring.

3. The preparation method according to claim 1, wherein, R1 and R2 are each independently selected from C1-C8 straight-chain alkyl groups and C3-C8 branched alkyl groups.

4. The preparation method according to claim 1, wherein, R3 and R4 are each independently selected from hydrogen, C1-C8 straight-chain alkyl, C3-C8 branched alkyl, and C7-C4. 10 Aryl alkyl group.

5. The preparation method according to claim 1, wherein, R5 is selected from hydrogen, halogen atoms, C1-C8 straight-chain alkyl, and C3-C8 branched alkyl; n is 1.

6. The preparation method according to claim 1, wherein, The internal electron donor is selected from 2,4-hexanediol dibenzoate, 2,4-hexanediol di-o-methylbenzoate, 2,4-hexanediol di-m-methylbenzoate, 2,4-hexanediol di-p-methylbenzoate, 2,4-hexanediol di-m-chlorobenzoate, 2,4-hexanediol di-p-chlorobenzoate, 2,4-hexanediol di-p-ethylbenzoate, 2,4-hexanediol di-p-propylbenzoate, 2,4-hexanediol di-p-butylbenzoate, 2,4-hexanediol di-p-tert-butylbenzoate, 3-methyl-2,4-hexanediol dibenzoate, 3-ethyl-2,4-hexanediol dibenzoate, 3-n-propyl-2,4-hexanediol dibenzoate, 3-benzyl-2,4-hexanediol dibenzoate, 3-methyl ...benzyl-2,4-hexanediol dibenzoate, 3-methyl-2,4-hexanediol dibenzoate, 3-benzyl-2,4-hexanediol dibenzoate, 3-benzyl-2,4-hexanediol dibenzoate, 3-benzyl-2,4-hexanediol dibenzoate, 3-benzyl-2,4-hexanediol dibenzoate, Hexanediol di-p-methylbenzoate, 3-ethyl-2,4-hexanediol di-p-methylbenzoate, 3-ethyl-2,4-hexanediol di-p-ethylbenzoate, 3-ethyl-2,4-hexanediol di-p-n-propylbenzoate, 3-ethyl-2,4-hexanediol di-p-n-butylbenzoate, 3-ethyl-2,4-hexanediol di-p-tert-butylbenzoate, 3-n-butyl-2,4-hexanediol dibenzoate, 2,4-heptanediol dibenzoate, 2,4-heptanediol di-o-methylbenzoate, 2,4-heptanediol di-m-methylbenzoate, 2,4-heptanediol di-p-methylbenzoate, 2,4-heptanediol di-o-chlorobenzoate, 2,4-heptanediol di-m-chlorobenzoate, 2,4-heptanediol di-p-chlorobenzoate, 2, 4-Heptanediol di-p-ethylbenzoate, 2,4-Heptanediol di-p-propylbenzoate, 2,4-Heptanediol di-p-butylbenzoate, 2,4-Heptanediol di-p-tert-butylbenzoate, 3-methyl-2,4-Heptanediol dibenzoate, 3-ethyl-2,4-Heptanediol dibenzoate, 3-n-propyl-2,4-Heptanediol dibenzoate, 3-methyl-2,4-Heptanediol di-p-methylbenzoate, 3-ethyl-2,4-Heptanediol di-p-propylbenzoate, 3-ethyl-2,4-Heptanediol di-p-butylbenzoate, 3-ethyl-2,4-Heptanediol di-p-tert-butylbenzoate, 6-methyl-2,4-Heptanediol dibenzoate, 6-methyl-2,4-Heptanediol di-p-methylbenzoate, 6- Methyl-2,4-heptanediol di-m-methylbenzoate, 6-methyl-2,4-heptanediol di-o-methylbenzoate, 6-methyl-2,4-heptanediol di-p-ethylbenzoate, 6-methyl-2,4-heptanediol di-p-propylbenzoate, 6-methyl-2,4-heptanediol di-p-butylbenzoate, 6-methyl-2,4-heptanediol di-p-tert-butylbenzoate, 3-ethyl-6-methyl-2,4-heptanediol dibenzoate, 3-ethyl-6-methyl-2,4-heptanediol di-p-propylbenzoate, 3-n-propyl-6-methyl-2,4-heptanediol di-p-butylbenzoate, 3-n-butyl-6-methyl-2,4-heptanediol di-p-tert-butylbenzoate, 2,4-octanediol dibenzoate, 3...At least one of the following: 5-octanediol dibenzoate, 3,5-octanediol di-p-methylbenzoate, 3,5-octanediol di-m-methylbenzoate, 3,5-octanediol di-o-methylbenzoate, 3,5-octanediol di-p-ethylbenzoate, 3,5-octanediol di-p-n-propylbenzoate, 3,5-octanediol di-p-n-butylbenzoate, 3,5-octanediol di-p-tert-butylbenzoate, 4-methyl-3,5-octanediol dibenzoate, 4-ethyl-3,5-octanediol di-p-n-butylbenzoate, and 4-n-propyl-3,5-octanediol dibenzoate.

7. The preparation method according to claim 1, wherein, R6 is selected from C1-C8 straight-chain alkyl or C3-C8 branched alkyl; R7 is C1-C6 straight-chain alkyl.

8. The preparation method according to claim 1, wherein, The performance modifier is selected from methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, tetramethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane, triethylmethoxysilane, ethyltriethoxysilane, diethyldiethoxysilane, triethylethoxysilane, tetraethoxysilane, n-propyltrimethoxysilane, di-n-propyldimethoxysilane, tri-n-propylmethoxysilane, n-propyltriethoxysilane, di-n-propyldiethoxysilane, tri-n-propylethoxysilane, and tri-n-propylethoxysilane. At least one of silane, isopropyltriethoxysilane, diisopropyldiethoxysilane, triisopropylethoxysilane, isopropyltrimethoxysilane, diisopropyldimethoxysilane, triisopropylmethoxysilane, n-butyltrimethoxysilane, di-n-butyldimethoxysilane, tri-n-butylmethoxysilane, n-butyltriethoxysilane, di-n-butyldiethoxysilane, tri-n-butylethoxysilane, isobutyltriethoxysilane, diisobutyldiethoxysilane, triisobutylethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, and triisobutylmethoxysilane.

9. The preparation method according to claim 1, wherein, The precipitation aid is selected from at least one of the malonate compounds shown in formula (III). （Ⅲ） Among them, R8 and R9 may be the same or different, and are independently selected from hydrogen, halogens, and C1-C. 10 Straight-chain alkyl, C2-C 10 Straight-chain alkenyl, C2-C 10 Branched alkenyl, C3-C 10 Branched alkyl, C3-C 12 cycloalkyl, C6-C 15 Aryl, C7-C 15 alkylaryl or arylalkyl; R 10 Selected from C1-C 10 Straight-chain alkyl, C3-C 12 Branched alkyl, C3-C 15 cycloalkyl, C6-C 15 Aryl, C7-C 15 Alkyl or aryl.

10. The preparation method according to claim 9, wherein, R8 and R9 may be the same or different, and are each independently selected from hydrogen, halogen, C1-C8 straight-chain alkyl, C2-C8 straight-chain alkenyl, C2-C8 branched alkenyl, C3-C8 branched alkyl, C3-C 10 cycloalkyl, C6-C 12 Aryl, C7-C 12 alkylaryl or arylalkyl; R 10 Selected from C1-C8 straight-chain alkyl, C3-C8 branched alkyl, C3-C 10 cycloalkyl, C6-C 12 Aryl, C7-C 12 Alkyl or aryl.

11. The preparation method according to claim 1, wherein, The precipitation aid is selected from diisobutylmalonide, di-n-butylmalonide, di-tert-butylmalonide, diisobutylmalonide, di-n-butylmalonide, di-tert-butylmalonide, diisobutylmalonide, di-n-butylmalonide, di-tert-butylmalonide, di-di-tert-butylmalonide, diisobutylmalonide, di-n-butylmalonide, di-tert-butylmalonide, diisobutylmalonide, di-n-butylmalonide, di-dimethylolpropionate, di-n-butylmalonide. Dipentyl di-tert-butylmalonate, di-tert-butyl dihexyl di-isobutylmalonate, di-n-butylmalonate, di-hepta-diisobutylmalonate, di-n-butylmalonate, di-thirt-butylmalonate, di-propyl di-propionate, di-isopentyl di-propionate, di-n-pentyl di-propionate, di-hexyl di-propionate, di-n-pentyl di-propionate, benzene Dipropyl phenyl ethyl malonate, dipropyl phenyl methyl malonate, dipropyl phenyl propyl malonate, dipropyl phenyl n-butyl malonate, dipropyl phenyl isobutyl malonate, dipropyl phenyl malonate, benzyl ethyl malonate, dipropyl phenyl methyl malonate, dipropyl phenyl propyl malonate, dipropyl phenyl n-butyl malonate, dipropyl phenyl isopentyl malonate, dipropyl phenyl n-butyl malonate, dipropyl phenyl isobutyl malonate, dibutyl phenyl isopentyl malonate, dibutyl phenyl n-butyl malonate, dibutyl phenyl isopentyl malonate, dibutyl phenyl n-butyl malonate, dibutyl phenyl ethyl malonate, benzyl Dibutyl methyl malonate, benzylpropyl dibutyl malonate, benzyl n-butyl malonate, benzyl isobutyl malonate, benzyl isopentyl malonate, benzyl n-pentyl malonate, dibenzyl malonate, phenylethyl dipentyl malonate, phenylmethyl dipentyl malonate, phenylpropyl dipentyl malonate, phenyl n-butyl dipentyl malonate, phenyl isobutyl malonate, phenyl isopentyl dipentyl malonate, phenyl n-pentyl malonate, diphenyl dipentyl malonate, benzyl ethyl dipentyl malonate, benzyl methyl dipentyl malonate, benzylpropyl dipentyl malonate, benzyl n-butyl malonate, benzyl isobutyl malonate, benzyl isopentyl malonate, benzyl n-pentyl malonate Dicyclohexyl phenylethyl malonate, dicyclohexyl phenylmethyl malonate, dicyclohexyl phenylpropyl malonate, diphenyl methyl malonate, diphenyl isopentyl malonate, diphenyl n-pentyl malonate, diphenyl phenyl malonate, benzyl ethyl malonate, benzyl methyl malonate, benzyl propyl malonate, benzyl n-butyl malonate, benzyl isobutyl malonate, benzyl isopentyl malonate, benzyl n-pentyl malonate, dibenzyl malonate, allyl methyl malonate, allyl propyl malonate, allyl n-butyl malonate, allyl isobutyl malonate, allyl isopentyl malonate, allyl n-pentyl malonateDiallyl diphenyl malonate, allyl methyl malonate, allyl propyl dimethyl malonate, allyl n-butyl dimethyl malonate, allyl isobutyl malonate, allyl isopentyl dimethyl malonate, allyl n-pentyl dimethyl malonate, diallyl dimethyl malonate, allyl methyl diethyl malonate, allyl propyl diethyl malonate, allyl n-butyl diethyl malonate, allyl Diethyl propyl isobutyl malonate, diethyl allyl isopentyl malonate, diethyl allyl n-pentyl malonate, diallyl diethyl malonate, dipropyl allyl methyl malonate, dipropyl allyl malonate, dipropyl allyl n-butyl malonate, dipropyl allyl isobutyl malonate, dipropyl allyl isopentyl malonate, dipropyl allyl n-pentyl malonate, diallyl diethyl malonate, allyl Dibutyl propyl methyl malonate, allyl propyl dibutyl malonate, allyl n-butyl malonate, allyl isobutyl malonate, allyl isopentyl dibutyl malonate, allyl n-pentyl malonate, diallyl dibutyl malonate, allyl methyl dipentyl malonate, allyl propyl dipentyl malonate, allyl n-butyl dipentyl malonate, allyl isobutyl dipentyl malonate At least one of the following: allyl isopentyl dipentyl malonate, allyl n-pentyl dipentyl malonate, diallyl dipentyl malonate, allyl methyl dicyclohexyl malonate, allyl propyl dicyclohexyl malonate, allyl n-butyl dicyclohexyl malonate, allyl isobutyl dicyclohexyl malonate, allyl isopentyl dicyclohexyl malonate, allyl n-pentyl dicyclohexyl malonate, and diallyl dicyclohexyl malonate.

12. The preparation method according to claim 1, wherein, For each mole of magnesium compound, the amount of precipitation aid is 0-1 mole, the amount of titanium compound is 0.5-150 moles, the amount of internal electron donor is 0.02-0.4 moles, and the amount of performance modifier is 0.01-0.3 moles.

13. The solid catalyst component prepared by the preparation method according to any one of claims 1-12.

14. A catalyst for olefin polymerization, characterized in that, The catalyst contains: (1) The solid catalyst component prepared by the method of any one of claims 1-12 or the solid catalyst component of claim 13; (2) Activator; (3) Optional external electron donor.

15. The catalyst according to claim 14, wherein, The activator is at least one of alkylaluminum compounds.

16. The catalyst according to claim 14, wherein, The external electron donor is at least one of organosilicon compounds.

17. The catalyst according to claim 14, wherein, The molar ratio of solid catalyst component (calculated as Ti), alkylaluminum compound (calculated as Al), and external electron donor (calculated as Si) is 1:5-1000:0-500.

18. A prepolymerization catalyst composition for olefin polymerization, characterized in that, The prepolymer catalyst composition contains a prepolymer obtained by prepolymerization of an olefin using the catalyst according to any one of claims 14-17.

19. The prepolymerization catalyst composition according to claim 18, wherein, The prepolymerization ratio of the prepolymer is 0.1-1000g olefin polymer / g solid catalyst component.

20. The prepolymerization catalyst composition according to claim 18, wherein, The olefin has the general formula CH2=CHR, where R is hydrogen or C1-C. 12 Hydrocarbon or aryl groups.

21. The prepolymerization catalyst composition according to claim 20, wherein, The olefin is ethylene or propylene.

22. A method for olefin polymerization, characterized in that, The method includes: polymerizing olefins in the presence of a solid catalyst component prepared by the method of any one of claims 1-12 or the solid catalyst component of claim 13; Alternatively, the olefin may be polymerized in the presence of the catalyst described in any one of claims 14-17; Alternatively, the olefin may be polymerized in the presence of the prepolymerization catalyst composition according to any one of claims 18-21.

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