Catalyst system, prepolymerization catalyst composition, and olefin polymerization process

Abstract

The invention belongs to the field of petrochemical engineering, and particularly relates to a catalyst system, a prepolymerization catalyst composition and an olefin polymerization reaction method. The catalyst system comprises a component A and / or a reaction product of the component A; the component A comprises a main catalyst component, a co-catalysis component and an external electron donor; the main catalyst component comprises a magnesium element, a titanium element, halogen and an internal electron donor; the internal electron donor comprises an alcohol ester compound I; the co-catalysis component is selected from an aluminum alkyl compound; and the external electron donor contains a 3-pyrroline-1-formate compound. According to the invention, the 3-pyrroline-1-formate compound is used as an external electron donor, the aluminum alkyl is used as a cocatalyst and is matched with the main catalyst component for use, so that the catalyst system can improve the stereospecificity and hydrogen regulation sensitivity of the catalyst system under the conditions of keeping relatively high activity and wide molecular weight distribution of a polymerization product; and high-isotactic low-molecular-weight polyolefin products can be prepared.

Description

Technical Field

[0001] The invention belongs to the field of petrochemical industry, and specifically relates to a catalyst system, a prepolymerization catalyst composition and an olefin polymerization reaction method. Background Art

[0002] As we all know, in order to meet the needs of industrial production and produce products with excellent performance, the stereospecificity of Ziegler-Natta polyolefin catalysts, the molecular weight and molecular weight distribution of polymers are all important technical parameters. Catalysts with excellent comprehensive performance have always been the goal pursued by polyolefin resin manufacturers and R&D institutions.

[0003] As the core of polyolefin technology, Ziegler-Natta catalyst mainly includes magnesium / titanium / internal electron donor. The catalyst is often used together with alkyl aluminum and external electron donor to form a complete catalyst system. External electron donors have the remarkable characteristics of rich variety, flexible and controllable addition, and great influence on various properties of catalysts. Therefore, it is an important direction of catalyst research and development to regulate the overall performance of the catalyst by selecting appropriate external electron donors.

[0004] The catalyst system containing alcohol ester compounds as internal electron donors has the characteristics of good stereospecificity and wide molecular weight distribution of polymerization products. The industrial production of polyolefins requires the development of a catalyst system that can further improve the stereospecificity and hydrogen regulation sensitivity while maintaining the wide molecular weight distribution and easy processing of the polymerization products. Summary of the invention

[0005] In view of the problems existing in the above-mentioned prior art, one of the objects of the present invention is to provide a catalyst system for olefin polymerization. When a 3-pyrroline-1-carboxylate compound is added as an external electron donor to a Ziegler-Natta type polyolefin catalyst system in which an internal electron donor includes an alcohol ester compound, the polymerization product maintains the characteristics of a wide molecular weight distribution, the isotactic index is increased, and the molecular weight becomes lower. The polymerization system has better stereospecificity and hydrogen modulation sensitivity.

[0006] On the one hand, the present invention provides a catalyst system, comprising component A and / or the reaction product of component A; the catalyst system comprises component A and / or the reaction product of component A; the component A comprises a main catalyst component (which is usually solid), a co-catalyst component and an external electron donor; the main catalyst component comprises magnesium, titanium, a halogen and an internal electron donor; the internal electron donor comprises an alcohol ester compound I; the co-catalyst component is selected from an alkyl aluminum compound; the external electron donor comprises a 3-pyrroline-1-carboxylate compound.

[0007] As a preferred embodiment, the 3-pyrroline-1-carboxylate is selected from the structure shown in formula (a),

[0008]

[0009] In formula (a), M1 and M2 are the same or different and are independently selected from hydrogen, C1-C 20 Alkyl, keto, halogen, substituted or unsubstituted phenyl; preferably, M1 and M2 are each independently selected from C1-C 10 Alkyl, keto, halogen, substituted or unsubstituted phenyl; preferably, M1 and M2 are each independently selected from methyl, ethyl, isopropyl, n-butyl, tert-butyl, isobutyl, pentyl, hexyl, keto, halogen, C1-C6 alkyl substituted phenyl;

[0010] M3 and M4 are the same or different and are independently selected from hydrogen and halogen;

[0011] M1, M2, M3, and M4 optionally contain a substituent a1 selected from hydroxyl, halogen, cyano, nitro, amino, mono-C1-C 10 Alkylamino, di-C1-C 10 One or more of an alkylamino group, an aldehyde group, a carboxyl group and a heteroatom;

[0012] R is selected from C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, C3-C 12 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Arylalkyl, 4-12 membered heterocycloalkyl and C5-C 20 Heteroaryl, R optionally contains a substituent a2; the substituent a2 is selected from hydroxyl, halogen, cyano, nitro, amino, mono-C1-C 10 Alkylamino, di-C1-C 10 One or more of an alkylamino group, an aldehyde group, a carboxyl group and a heteroatom.

[0013] As a preferred embodiment, the 3-pyrroline-1-carboxylate compound can be specifically selected from 3-pyrroline-1-carboxylic acid benzyl ester, 3-pyrroline-1-carboxylic acid tert-butyl ester, 3-pyrroline-1-carboxylic acid ethyl ester, 3-pyrroline-1-carboxylic acid propyl ester, 3-pyrroline-1-carboxylic acid pentyl ester, 2,5-dioxopyrroline-1-carboxylic acid methyl ester, 2,5-dioxopyrroline-1-carboxylic acid ethyl ester, 2,5-dioxopyrroline-1-carboxylic acid tert-butyl ester, 2,5-dioxopyrroline-1-carboxylic acid heptyl ester, 2- ...propyl ester, 2,5-dioxopyrroline-1-carboxylic acid pentyl ester, 2,5-dioxopyrroline-1-carboxylic acid methyl ester, 2,5-dioxopyrroline-1-carboxylic acid ethyl ester, 2,5-dioxopyrroline-1-carboxylic acid tert-butyl ester, 2,5-dioxopyrroline-1-carboxylic acid heptyl ester, 2,5-dioxopyrroline-1-carboxylic acid propyl At least one of tert-butyl 2-pyrroline-1-carboxylate, 2-oxo-3-pyrroline-1-carboxylate, methyl 2-oxo-3-pyrroline-1-carboxylate, ethyl 2-chloro-3-pyrroline-1-carboxylate, methyl 2-bromo-3-pyrroline-1-carboxylate, tert-butyl 2,5-dichloro-3-pyrroline-1-carboxylate, ethyl 2,3-dichloro-3-pyrroline-1-carboxylate, ethyl 2-methyl-3-pyrroline-1-carboxylate and tert-butyl 3-methyl-3-pyrroline-1-carboxylate.

[0014] The inventors of the present application have discovered through research that by introducing a 3-pyrroline-1-carboxylate compound shown in formula (a) as an external electron donor into a Ziegler-Natta type polyolefin catalyst system in which the internal electron donor includes an alcohol ester, the isotactic index of the polymerization product is increased, the molecular weight becomes lower, and the molecular weight distribution becomes wider. The polymerization system has good stereospecificity and hydrogen modulation sensitivity, and the product processing performance is improved.

[0015] Preferably, the weight ratio of the titanium element, the magnesium element and the internal electron donor in the main catalyst component is 1:(5-25):(2-15).

[0016] Preferably, the molar ratio of the 3-pyrroline-1-carboxylate compound to the main catalyst component calculated as titanium element is (0.1-1000):1, preferably (1-200):1, and more preferably (1-80):1.

[0017] Preferably, the molar ratio of the main catalyst component calculated as titanium element to the alkyl aluminum compound calculated as aluminum element is 1:(5-5000), preferably 1:(20-2000).

[0018] Preferably, the molar ratio of the external electron donor to the aluminum element in the alkyl aluminum compound is 1:(0.1-1000), preferably 1:(1-500).

[0019] Preferably, the molar ratio of the external electron donor to the titanium element in the main catalyst component is (0-500):1, preferably (0.01-200):1, and more preferably (0.1-100):1.

[0020] The preparation method of the main catalyst component in the present invention includes but is not limited to the following method:

[0021] Method 1: A magnesium compound is added to an inert solvent, and then an organic epoxy compound and an organic phosphorus compound are added, and after dissolving, a precipitation aid and a titanium compound are added to precipitate a solid; an internal electron donor is added to be carried on the solid, and then treated with titanium tetrahalide and an inert diluent to obtain a solid;

[0022] Method 2: In an inert solvent such as decane or toluene, a solid magnesium compound is dissolved in an organic alcohol compound such as 2-ethylhexanol, and after dissolution, a precipitation aid and a titanium compound are added to precipitate a solid; an internal electron donor is added to be carried on the solid, and then treated with a titanium compound and an inert diluent to obtain;

[0023] Method 3: dispersing the magnesium halide alcoholate into a low temperature (e.g., below -5°C) titanium compound, then heating it to a high temperature (e.g., above 50°C), adding an internal electron donor compound during the heating process, filtering, treating the obtained precipitate with a titanium compound, washing the precipitate, and obtaining the main catalyst component;

[0024] Method 4: preparing an alkoxy magnesium carrier and an inert diluent into a suspension, then reacting the suspension with a mixture of a titanium compound and an inert diluent, filtering the suspension, contacting the obtained precipitate with the titanium compound and an internal electron donor compound, washing the precipitate, and obtaining the main catalyst component;

[0025] Method 5: In an inert solvent such as toluene, a solid magnesium compound, an organic alcohol compound, and a precipitation aid are reacted at high temperature for 5 hours, and then an internal electron donor is added to continue the reaction for one hour, and then cooled to room temperature to obtain a stable and uniform alcoholate solution. After the above-prepared alcoholate uniform solution is contacted with a titanium compound at low temperature for 4 hours, the temperature is raised to 60°C, an internal electron donor is added and filtered, and the obtained precipitate is treated with a titanium compound, and the precipitate is washed to obtain the main catalyst component.

[0026] According to a preferred embodiment of the present invention, a titanium compound or a mixture of a titanium compound and an inert solvent (an inert solvent such as hexane, heptane, octane, decane, toluene, etc.) precooled to -15°C to -40°C is mixed with a magnesium compound, and the temperature of the mixture is raised to 90-110°C in stages and maintained for 0.1-2 hours, and an internal electron donor is added during the heating process. Then the solid-liquid separation is performed, and the obtained solid phase is treated at least twice with the titanium compound again, washed with a solvent, and finally vacuum dried to obtain the main catalyst component.

[0027] According to the present invention, the magnesium compound can be various magnesium compounds conventionally used in the preparation of olefin polymerization catalysts in the art, for example, the magnesium compound can be selected from at least one of magnesium dihalide, alkoxymagnesium, alkylmagnesium, hydrates of magnesium dihalide, alcoholates of magnesium dihalide, and derivatives in which one halogen atom in the magnesium dihalide molecule is replaced by a hydrocarbonoxy group or a halogenated hydrocarbonoxy group. According to a preferred embodiment of the present invention, the magnesium compound is an alcoholate of magnesium dihalide.

[0028] According to a preferred embodiment of the present invention, the alcoholate of magnesium dihalide has a spherical magnesium alcoholate represented by formula (VIII),

[0029] MgX2·m(R'OH)·nE·qH2O Formula (VIII)

[0030] In formula (VIII): X is chlorine or bromine; R' is a C1-C4 alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl), m is 0.5-4.0; E is an ether or ester electron donor compound, n is 0-1.0, wherein the ether or ester can be an ether or ester that can be used as an electron donor as known in the art, and can also be an internal electron donor and / or external electron donor used in the present invention; q is 0-0.8.

[0031] According to a preferred embodiment of the present invention, in formula (VIII), X is chlorine or bromine; R' is a C1-C4 alkyl group, m is 1.5 to 3.5; and n and q are both 0.

[0032] According to a preferred embodiment of the present invention, the magnesium compound is MgCl2·m(CH3CH2OH), where m is 1.5 to 3.5.

[0033] According to some embodiments of the present invention, the preparation method of the alcoholate of magnesium dihalide can be prepared according to methods known in the art, for example, it can be prepared by referring to the method disclosed in CN1330086A.

[0034] According to a preferred embodiment of the present invention, the preparation method of the alcoholate of magnesium dihalide comprises: (1) mixing anhydrous magnesium dihalide with an alcohol compound (R'OH), and reacting at 90-140°C to obtain an alcoholate of magnesium halide; (2) shearing the alcoholate of magnesium halide in a dispersion medium, and cooling in an inert medium after shearing to obtain the alcoholate of spherical magnesium halide. Wherein, the ratio of the anhydrous magnesium dihalide and the alcohol compound can be determined according to the actual need to load the alcohol compound in the anhydrous magnesium dihalide. Wherein, the dispersion medium can be a hydrocarbon inert solvent, such as kerosene, white oil, silicone oil, paraffin oil, vaseline oil, etc. The inert medium can be selected from pentane, hexane, heptane, petroleum ether, raffinate oil, etc. The shearing refers to shearing the magnesium halide alcoholate by external shear force, for example, high-speed stirring method (such as CN1330086A), spray method (such as US6020279A), high-gravity rotating bed (such as CN1580136A) and emulsifier method (CN1463990A).

[0035] According to a preferred embodiment of the present invention, in order to further improve the purity of the magnesium compound, the obtained spherical magnesium halide alcoholate is further subjected to washing and drying steps.

[0036] According to the present invention, the alkoxy magnesium is prepared by reacting metal magnesium, ethanol, isooctyl alcohol (2-ethylhexanol) and a mixed halogenating agent under an inert atmosphere. The mixed halogenating agent is a combination of halogens and halogen compounds, and the non-limiting selection of the halogens and halogen compounds is: iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, potassium chloride, potassium bromide, potassium iodide, calcium chloride, calcium bromide, calcium iodide, mercuric chloride, mercuric bromide, mercuric iodide, ethoxymagnesium iodide, methoxymagnesium iodide, isopropylmagnesium iodide, hydrogen chloride, chloroacetyl chloride, etc.

[0037] According to the present invention, the titanium compound may be any titanium compound conventionally used in the preparation of olefin polymerization catalysts in the art.

[0038] According to a preferred embodiment of the present invention, the titanium compound has a structure shown in formula (IX),

[0039] Ti(OR”) 4-k X k Formula (c)

[0040] In formula (c), R" is a C1-C20 alkyl group, X is F, Cl or Br; and k is an integer from 0 to 4.

[0041] According to a preferred embodiment of the present invention, in formula (c): R" is a C1-C10 alkyl group.

[0042] According to a preferred embodiment of the present invention, in formula (c): R" is a C1-C5 alkyl group.

[0043] According to a preferred embodiment of the present invention, for example, in formula (c): R" is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, or neopentyl.

[0044] According to a preferred embodiment of the present invention, in formula (c): X is Cl.

[0045] According to a preferred embodiment of the present invention, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, monochlorotributoxytitanium, dichlorodibutoxytitanium, trichloromonobutoxytitanium, monochlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium and titanium trichloride.

[0046] According to a preferred embodiment of the present invention, the titanium compound is titanium tetrachloride.

[0047] According to some embodiments of the present invention, the weight ratio of the titanium element, the magnesium element, and the internal electron donor in the main catalyst component is 1:(5-25):(2-15).

[0048] In some preferred embodiments of the present invention, the alkyl aluminum compound is selected from the compound represented by formula (e),

[0049] AlR3 Formula (e),

[0050] In formula (e), R is a C1-C 20 The alkyl group is preferably a C1-C6 alkyl group which may be substituted by a halogen atom.

[0051] In some preferred embodiments of the present invention, the alkyl aluminum compound is selected from triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum dichloride, Al(n-C6H 13 )3 and Al(n-C8H 17 )3 or more.

[0052] In some preferred embodiments of the present invention, the molar ratio of the external electron donor to the aluminum element in the alkyl aluminum compound is 1:(0.1-1000), preferably 1:(1-500).

[0053] According to the present invention, in the catalyst system, the molar ratio of the main catalyst component calculated as titanium element to the alkyl aluminum compound calculated as aluminum element is 1:(5-5000), preferably 1:(20-2000).

[0054] As a preferred embodiment, the alcohol ester compound I is selected from the diol ester compound represented by formula (I),

[0055]

[0056] In formula (I), R 1 and R 2 The same or different, each independently selected from C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl, C7-C 20 Arylalkyl or C 10 -C 20 Preferably, R 1 and R 2 The same or different, each independently selected from C1-C 10 Alkyl, C2-C 10 Alkenyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Alkyl, C7-C 10 Aralkyl and C 10 -C 15 Fused ring aromatic groups;

[0057] M is a divalent linking group selected from C1-C 20 Alkylene, C3-C 20 Cycloalkylene or C6-C 20 Arylene.

[0058] As a preferred embodiment, R 1 , R 2 Optionally, it contains a substituent I, which is selected from at least one of a hydroxyl group, a halogen atom, a cyano group, a nitro group, an amino group, a mono-C1-C6 alkylamino group, a di-C1-C6 alkylamino group, an aldehyde group, a carboxyl group and a heteroatom.

[0059] As a preferred embodiment, M optionally contains a substituent II, wherein the substituent II is selected from nitrogen, oxygen, sulfur, silicon, phosphorus, halogen atoms and C1-C 20 At least one of the alkyl groups, when the substituent II is a plurality of C1-C 20 In the case of alkyl groups, the substituents are optionally bonded to form one or more rings.

[0060] As a preferred embodiment, the alcohol ester compound I is selected from the diol ester compound represented by formula (II),

[0061]

[0062] In formula (II),

[0063] The brackets indicate that there are n carbon atoms bonded in sequence, and each carbon atom is also bonded to two substituents, that is, there are n carbon atoms and R' in the brackets. 1 , R' 2 , R' 3 …R' 2n etc. 2n substituents;

[0064] R'1 and R'2 are the same or different and are independently selected from C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Arylalkyl and C7-C 20 Alkaryl; preferably selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Arylalkyl and C7-C 10 Alkaryl;

[0065] R'3, R'4, R'5, R'6 and R' 1 , R' 2 -R' 2n (In the present invention, R' 2 -R' 2n refers to R' 2 , R' 3 , R' 4 ……R' 2n ) are the same or different and are independently selected from hydrogen, halogen, C1-C 20 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl, C7-C 20 Aralkyl and C 10 -C 20 Condensed ring aromatic group; preferably selected from C1-C 10 Alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10Alkyl, C7-C 10 Aralkyl and C 10 -C 15 Fused ring aromatic groups;

[0066] R'1, R'2, R'3, R'4, R'5, R'6, R' 1 , R' 2 -R' 2n The present invention optionally contains a substituent III; the substituent III is selected from at least one of halogen, C1-C6 alkyl and C1-C6 alkoxy;

[0067] R'3, R'4, R'5, R'6, R' 1 , R' 2 -R' 2n Optionally contain heteroatoms, the heteroatoms are one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus; or, R'3, R'4, R'5, R'6, R' 1 , R' 2 -R' 2n Two or more of the substituents R'3 and R'4 are bonded to each other to form a saturated or unsaturated monocyclic ring or a saturated or unsaturated polycyclic ring; wherein n is an integer of 0 to 10, preferably an integer of 1 to 8, and more preferably an integer of 2 to 6. When n is 0, the carbon atoms of the substituents R'3 and R'4 are bonded to the carbon atoms of the substituents R'5 and R'6.

[0068] As a preferred embodiment, the diol ester compound represented by formula (I) or the diol ester compound represented by formula (II) is selected from 2,4-pentanediol dibenzoate, 3-methyl-2,4-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 3,5-heptanediol di-p-methylbenzoate, 3,5-heptanediol di-o-methylbenzoate, 3,5-heptanediol di-p-chlorobenzoate, 3,5-heptanediol di-o-chlorobenzoate, 3,5-heptanediol di-p-methoxybenzoate, 3,5-heptanediol di-o-methoxybenzoate, 3,5-heptanediol di-m-methoxybenzoate, 2-methyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-heptanediol dibenzoate. Acid esters, 6-methyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 5-ethyl-3,5-heptanediol dibenzoate, 4-propyl-3,5-heptanediol dibenzoate, 4-butyl-3,5-heptanediol dibenzoate, 2,4-dimethyl-3,5-heptanediol dibenzoate, 2,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 4,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 2-methyl-4-ethyl -3,5-heptanediol dibenzoate, 4-methyl-4-ethyl-3,5-heptanediol dibenzoate, 2-methyl-4-propyl-3,5-heptanediol dibenzoate, 4-methyl-4-propyl-3,5-heptanediol dibenzoate, 6-methyl-2,4-heptanediol di(p-chlorobenzoate), 6-methyl-2,4-heptanediol di(p-methylbenzoate), 6-methyl-2,4-heptanediol di(m-methylbenzoate), 2,2,6,6-tetramethyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-octanediol dibenzoate, 4-ethyl-3,5-octanediol dibenzoate, 4-propyl-3,5-octanediol dibenzoate, 4-butyl-3,5-octanediol dibenzoate, ,4-dimethyl-3,5-octanediol dibenzoate, 4-methyl-4-ethyl-3,5-octanediol dibenzoate, 2-methyl-4-ethyl-3,5-octanediol dibenzoate, 2-methyl-6-ethyl-3,5-octanediol dibenzoate, 5-methyl-4,6-nonanediol dibenzoate, 5-ethyl-4,6-nonanediol dibenzoate, 5-propyl-4,6-nonanediol dibenzoate, 5-butyl-4,6-nonanediol dibenzoate, 5,5-dimethyl-4,6-nonanediol dibenzoate, 5-methyl-4-ethyl-4,6-nonanediol dibenzoate, 5-phenyl-4,6-nonanediol dibenzoate, 4,6-nonanediol dibenzoate and 4-butyl-3,5-heptanediol dibenzoate, 1,2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1,2-phenylene dibenzoate, 3,5-diisopropyl-1,2-phenylene dibenzoate, 3,6-dimethyl-1,2-phenylene dibenzoate, 4-tert-butyl-1,2-phenylene dibenzoate, 1,2-naphthalene dibenzoate, 2,3-naphthalene dibenzoate, 1,8-naphthyl dibenzoate, 1,8-naphthyl dibenzoate, 1,8-naphthyl dibenzoate, 1,8-naphthyl dibenzoate, 1,8-naphthyl dibenzoate, 1,8-naphthyl dibenzoate, 1,8-naphthyl dibenzoate, 1,8-naphthyl dibenzoate, ester, di-4-ethylbenzoic acid-1,8-naphthyl ester, di-4-n-propylbenzoic acid-1,8-naphthyl ester, di-4-isopropylbenzoic acid-1,8-naphthyl ester, di-4-n-butylbenzoic acid-1,8-naphthyl ester, di-4-isobutylbenzoic acid-1,8-naphthyl ester, di-4-tert-butylbenzoic acid-1,8-naphthyl ester, di-4-phenylbenzoic acid-1,8-naphthyl ester, di-4-fluorobenzoic acid-1,8-naphthyl ester, di-3-fluorobenzoic acid-1,8-naphthyl ester and di-2-fluorobenzoic acid-1,8-naphthyl ester.

[0069] As a preferred embodiment, the internal electron donor further includes a second internal electron donor, and the second internal electron donor is selected from at least one of a diether compound I, a succinate compound I, and an aromatic carboxylate compound I; the molar ratio of the first internal electron donor to the second internal electron donor is (100-1): (1-100).

[0070] More preferably, the catalyst system further comprises a second external electron donor, which is selected from one or more of silane compounds, diether compounds II, alcohol ester compounds II, aromatic carboxylic acid ester compounds II and succinate compounds II; the molar ratio of the first external electron donor to the second external electron donor is (100-1): (1-100).

[0071] The alcohol ester compound II is selected from any one of the diol ester compounds represented by formula (I) or formula (II);

[0072] As a preferred embodiment, the diether compound I and the diether compound II are each independently selected from the diether compound represented by formula (III);

[0073]

[0074] In formula (III),

[0075] R Ⅰ , R Ⅱ , R Ⅲ , R Ⅳ , R Ⅴ and R Ⅵ are the same or different, each independently selected from hydrogen, halogen, C1-C20 Alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Arylalkyl and C7-C 20 Alkaryl; preferably, C1-C 18 Alkyl, C3-C 18 Cycloalkyl, C6-C 18 Aryl, C7-C 18 Arylalkyl and C7-C 18 Alkaryl; more preferably, C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Arylalkyl and C7-C 10 Alkaryl;

[0076] R Ⅶ and R Ⅷ The same or different, each independently selected from C1-C 20 Alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Arylalkyl and C7-C 20 Alkaryl, preferably C1-C 18 Alkyl, C3-C 18 Cycloalkyl, C6-C 18 Aryl, C7-C 18 Arylalkyl and C7-C 18 Alkaryl; more preferably, C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Arylalkyl and C7-C 10 Alkyl.

[0077] As a preferred embodiment, R Ⅶ and R Ⅷ Optionally, it has a substituent IV, which is selected from C1-C 10 Alkyl, C1-C 10 Alkoxy, hydroxy, halogen, cyano, nitro, amino, mono-C1-C 10 Alkylamino, di-C1-C 10 Alkylamino, aldehyde, carboxyl and heteroatoms.

[0078] As a preferred embodiment, the R Ⅰ , R Ⅱ , R Ⅲ , R Ⅳ , R Ⅴand R Ⅵ Two or more of the fluorene rings are bonded to each other to form a saturated or unsaturated monocyclic or polycyclic ring, such as a fluorene ring;

[0079] As a preferred embodiment, R Ⅲ and R Ⅳ They are bonded to each other to form a saturated or unsaturated monocyclic or polycyclic ring.

[0080] As a preferred embodiment, the diether compound represented by formula (III) is selected from 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2-(1-naphthyl)-1,3-dimethoxypropane )-1,3-dimethoxypropane, 2-(2-fluorophenyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3 -dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-isopropyl 3-dimethoxypropane, 2-(1-methylbutyl)-2-sec-butyl-1,3-dimethoxypropane, 2,2-di-sec-butyl-1,3-dimethoxypropane, 2,2-di-tert-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-isopropyl-2-phenyl-1,3-dimethoxypropane, 2-phenyl-2-sec-butyl-1,3-dimethoxypropane, 2-isopropyl-2-benzyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-sec-butyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 1,1-bis(methoxymethyl)-cyclopentadiene, 1,1-bis(methoxymethyl)-2,3,4,5,-tetramethylcyclopentadiene, 1,1-bis(methoxymethyl)-2,3,4,5,-tetramethylcyclopentadiene, 1,1-bis(methoxymethyl)-2,3,4,5,-tetraphenylcyclopentadiene, 1,1-bis(methoxymethyl)-2,3,4,5,-tetrafluorocyclopentadiene, 1,1-bis(methoxymethyl)-3,4-dicyclopentylcyclopentadiene, 1,1-bis(methoxymethyl)indene, 1,1-bis(methoxymethyl)-2,3-dimethoxyindene, 1,1-bis(methoxymethyl)-2,3,6,7-tetrafluoroindene, 1,1-bis(methoxymethyl)-4,5,6,7-tetrafluoroindene, 1,1-bis(methoxymethyl)-4,7-dimethylindene, 1,1-bis(methoxymethyl)-3,6-dimethylindene, 1,1-bis(methoxymethyl)-4-phenylindene, 1,1-bis(methoxymethyl)-4-phenyl-2-methylindene, 1,1-bis(methoxymethyl)-4-tetracyclohexylindene, 1,1-bis(methoxymethyl)-7-(3,3,3-trifluoropropyl)phenylindene, 1,1-bis(methoxymethyl)-7-cyclopentyl Indene, 1,1-bis(methoxymethyl)-7-isopropylindene, 1,1-bis(methoxymethyl)-7-cyclohexylindene, 1,1-bis(methoxymethyl)-7-tert-butylindene, 1,1-bis(methoxymethyl)-7-tert-butyl-2-methylindene, 1,1-bis(methoxymethyl)-7-phenylindene, 1,1-bis(methoxymethyl)-2-phenylindene, 9,9-bis(methoxymethyl)fluorene, 9,9-bis(methoxymethyl)-2,7-dicyclopentylfluorene, 9,9-bis(methoxymethyl)-1,8-dichlorofluorene, 9,9-bis(methoxymethyl)-1,8-difluorofluorene, 9,9-bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene, 9,9-bis(methoxymethyl) -4-tert-butylfluorene, 1,1-bis-(methoxymethyl)-2,5-cyclohexadiene, 1,1-bis-(methoxymethyl)-benzonaphthalene, 7,7-bis-(methoxymethyl)-2,5-norbornadiene, 9,9-bis-(methoxymethyl)-1,4-methanedihydronaphthalene, 9,9-bis-(methoxymethyl)-1,4-methanedihydroanthracene, 4,4-bis-(methoxymethyl)-1-phenyl-1,4-dihydronaphthalene, 4,4-bis-(methoxymethyl)-1-phenyl-3,4-dihydronaphthalene, 5,5-bis-(methoxymethyl)-1,3,6-cycloheptatriene and 1-methoxymethyl-1-(1'-methoxyethyl)-2,3,4,5-tetramethylcyclopentadiene. ,

[0081] The succinate compound I and the succinate compound II are each independently selected from the compound represented by formula (d),

[0082]

[0083] In formula (d),

[0084] R"1, R"2, R"3, R"4, R"5 and R"6 are the same or different and are each independently selected from C1-C 20 Alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Arylalkyl or C7-C 20 Alkaryl, R"1, R"2, R"3, R"4, R"5 and R"6 optionally contain halogen or heteroatom;

[0085] Preferably, two or more of R"3, R"4, R"5 and R"6 are bonded to each other to form a saturated or unsaturated monocyclic ring or a saturated or unsaturated polycyclic ring;

[0086] Preferably, the compound represented by formula (d) is selected from 2,3-bis(2-ethylbutyl)succinic acid diethyl ester, 2,3-diethyl-2-isopropylsuccinic acid diethyl ester, 2,3-diisopropylsuccinic acid diethyl ester, 2,3-di-tert-butylsuccinic acid diethyl ester, 2,3-diisobutylsuccinic acid diethyl ester, 2,3-(bistrimethylsilyl)succinic acid diethyl ester, 2-(3,3,3-trifluoropropyl)-3-methylsuccinic acid diethyl ester, 2,3-dineopentylsuccinic acid diethyl ester, 2,3-diisopentylsuccinic acid diethyl ester, 2,3-(1-trifluoromethyl-ethyl)succinic acid diethyl ester, 2-isopropyl-3-isobutylsuccinate, 2-tert-butyl-3-isopropylsuccinate, 2-isopropyl-3-cyclohexylsuccinate, 2-isopentyl-3-cyclohexylsuccinate, 2,2,3,3-tetramethylsuccinate, 2,2,3,3-tetraethylsuccinate, 2,2,3,3-tetrapropylsuccinate, 2,3-diethyl-2,3-diisopropyldisuccinate, 2,3-bis(2-ethylbutyl)succinate, 2,3-diethyl-2-isopropylsuccinate, 2,3 -Diisobutyl diisopropylsuccinate, diisobutyl 2,3-di-tert-butylsuccinate, diisobutyl 2,3-diisobutylsuccinate, diisobutyl 2,3-(bistrimethylsilyl)succinate, diisobutyl 2-(3,3,3-trifluoropropyl)-3-methylsuccinate, diisobutyl 2,3-dineopentylsuccinate, diisobutyl 2,3-diisopentylsuccinate, diisobutyl 2,3-(1-trifluoromethyl-ethyl)succinate, diisobutyl 2-isopropyl-3-isobutylsuccinate, diisobutyl 2-tert-butyl-3-isopropylsuccinate, diisobutyl 2-isopropyl-3-cyclohexylsuccinate diisobutyl amber, diethyl 2,3-diisopropyl 2-cyanosuccinate, diisobutyl 2-isopentyl-3-cyclohexyl succinate, diisobutyl 2,2,3,3-tetramethyl succinate, diisobutyl 2,2,3,3-tetraethyl succinate, diisobutyl 2,2,3,3-tetrapropyl succinate, diisobutyl 2,3-diethyl-2,3-diisopropyl disuccinate; preferably one or more selected from diethyl 2,3-diisopropyl succinate, diethyl 2,3-di-tert-butyl succinate, diethyl 2,3-diisobutyl succinate and diisobutyl 2,3-diisopropyl succinate;

[0087] The aromatic carboxylic acid ester compound I and the aromatic carboxylic acid ester compound II are each independently selected from the compound represented by formula (VI),

[0088]

[0089] In formula (VI), R 3The same or different, each independently selected from C1-C8 alkyl, C5-C 10 Cycloalkyl, C6-C 15 Aryl, C7-C 15 Alkyl or C7-C 15 Aralkyl; R 3 optionally having a substituent V;

[0090] R 4 , R 5 , R 6 , R 7 may be the same or different, and are independently selected from hydrogen, halogen, C1-C8 alkyl, C5-C 10 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl or C7-C 20 Aralkyl; R 4 , R 5 , R 6 , R 7 optionally having a substituent VI;

[0091] The substituent V and substituent VI are each independently selected from a C1-C6 alkyl group or a halogen atom;

[0092] The compound represented by formula (VI) is preferably a phthalic acid ester; more preferably, the aromatic carboxylic acid ester compound is at least one selected from diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate and dioctyl phthalate;

[0093] The silane compound has a structure shown in formula (b):

[0094]

[0095] In formula (b), R1, R2, R3, and R4 are the same or different and are independently selected from hydrogen, C1-C 10 Alkyl, C2-C 10 Alkenyl, C1-C 10 Alkoxy, C2-C 10 Alkenyloxy, C2-C 10 Alkynyl, C2-C 10 Alkynyloxy, C3-C 10 Cycloalkyl, C6-C 15 At least one of aryl and amino, preferably C1-C6 alkyl, C3-C6 cycloalkyl, C6-C 10Aryl and amino, R1, R2, R3, R4 optionally contain a substituent IX, the substituent IX is selected from halogen, C1-C6 alkyl, C3-C6 cycloalkyl, C6-C 10 at least one of an aryl group and an amino group;

[0096] Preferably, the silane compound is selected from tetramethoxysilane, tetraethoxysilane, diisopropyldimethoxysilane, isopropyltrimethoxysilane, di-n-propyldimethoxysilane, n-propyltrimethoxysilane, di-n-butyldimethoxysilane, di-tert-butyldimethoxysilane, diisobutyldimethoxysilane, cyclopentyltrimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyldimethoxysilane, cyclohexylethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, vinylmethoxysilane, vinylethoxysilane, vinylpropoxysilane, vinyldimethoxysilane, vinyldiethoxysilane, vinyldipropoxysilane, vinyltrimethoxysilane, vinyl at least one of triethoxysilane, vinyltripropoxysilane, allylmethoxysilane, allylethoxysilane, allylpropoxysilane, allyldimethoxysilane, allyldiethoxysilane, allyldipropoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltripropoxysilane, aminotrimethylsilane, aminotriethylsilane, aminotripropylsilane, aminotri-n-butylsilane, aminotriisobutylsilane, methylaminotrimethylsilane, methylaminotriethylsilane, methylaminotripropylsilane, methylaminotri-n-butylsilane, methylaminotriisobutylsilane, ethylaminotrimethylsilane, ethylaminotriethylsilane, ethylaminotripropylsilane, ethylaminotri-n-butylsilane and ethylaminotriisobutylsilane;

[0097] Since the present invention improves the performance of olefin polymerization catalyst by changing the external electron donor, the method for preparing the main catalyst component (usually a solid catalyst) in the present invention can be carried out according to the conventional method used in the art, for example, reference can be made to the methods disclosed in CN1506384A, CN1091748A, CN85100997A, CN102399326A, US4540679A, CN109096415B, etc., and the present invention incorporates their disclosed contents herein by reference.

[0098] In a second aspect, the present invention provides a prepolymerized catalyst composition, comprising a prepolymer obtained by polymerizing an olefin using the catalyst system described in the first aspect of the present invention.

[0099] In some preferred embodiments of the present invention, the prepolymerization multiple of the prepolymer is 0.1-1000 g prepolymer / g main catalyst component, preferably 0.2-500 g prepolymer / g main catalyst component, and more preferably 0.5-20 g prepolymer / g main catalyst component.

[0100] According to the present invention, the term "prepolymerized catalyst" refers to a catalyst which has been subjected to a polymerization step at a relatively low conversion degree. In the present invention, the prepolymerization may be carried out using the same olefin as the olefin used for the polymerization.

[0101] According to some preferred embodiments of the present invention, the general formula of the olefin is CH2=CHR, wherein R is hydrogen or a C1-C7 alkyl group.

[0102] According to some preferred embodiments of the present invention, the olefin to be prepolymerized is propylene.

[0103] According to some preferred embodiments of the present invention, propylene or a mixture thereof with up to 20% by mole of one or more α-olefins is used for prepolymerization.

[0104] According to some embodiments of the present invention, the temperature of the prepolymerization reaction is -20 to 80° C., and the polymerization pressure is preferably 0 to 5 MPa.

[0105] According to some preferred embodiments of the present invention, the temperature of the prepolymerization reaction is 0-50°C.

[0106] According to some embodiments of the present invention, the prepolymerization reaction is carried out in liquid or gas phase.

[0107] According to some embodiments of the present invention, the prepolymerization step can be performed in-line as part of a continuous polymerization process, or independently in a batch operation.

[0108] According to some preferred embodiments of the present invention, to prepare 0.1-1000 g olefin prepolymer / g polymer of the main catalyst component, the prepolymerization of the catalyst of the present invention and olefin is independently carried out in a batch operation at a polymerization pressure of 0-5 MPa.

[0109] In a third aspect, the present invention provides an olefin polymerization method, in which olefins are polymerized in any one of the above-mentioned catalyst systems.

[0110] The olefin polymerization may be homopolymerization of a single olefin or copolymerization of a plurality of olefins, or may be a combination of homopolymerization of a single olefin and copolymerization of a plurality of olefins.

[0111] According to some preferred embodiments of the present invention, the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene.

[0112] According to some preferred embodiments of the present invention, the olefin is ethylene, propylene and / or 1-butene.

[0113] In some preferred embodiments of the present invention, the polymerization reaction conditions include: temperature of 0°C to 150°C, preferably 50°C to 90°C; pressure of 0.01MPa to 10MPa, preferably 0.1MPa to 5MPa; time of 0.1h to 5h, preferably 0.2h to 3h.

[0114] According to some embodiments of the present invention, both the catalyst system and the prepolymerized catalyst composition can be used for the polymerization reaction of olefins.

[0115] According to some preferred embodiments of the present invention, the catalyst system and the prepolymerized catalyst composition can be used in homopolymerization of propylene or copolymerization with other olefins.

[0116] According to the present invention, the catalyst system of the present invention can be directly added to the reactor for use in the polymerization process, or the catalyst system and the prepolymerized catalyst composition obtained by prepolymerizing olefins can be added to the reactor for polymerization reaction.

[0117] According to the present invention, the olefin polymerization reaction can be carried out according to a known polymerization method, can be carried out in liquid phase or gas phase, can also be carried out in a combination of liquid phase and gas phase polymerization stages, and can also adopt conventional techniques such as slurry process, gas phase fluidized bed, etc.

[0118] According to the present invention, the polymerization can be carried out in the presence of a solvent. Wherein, based on the titanium element in the main catalyst component, the concentration of the catalyst system in the solvent can be 0.1×10 -5 -5×10 -5 mol / L.

[0119] According to some preferred embodiments of the present invention, the concentration of the catalyst system in the solvent can be 0.2×10 -5 -2×10 -5 mol / L.

[0120] In the present invention, the hydrocarbon group may be selected from an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group and an alkaryl group.

[0121] In the present invention, alkyl refers to a straight chain alkyl or a branched chain alkyl, and non-limiting examples thereof include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, tetrahydrogeranyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, n-nonadecyl and n-eicosyl.

[0122] In the present invention, examples of alkenyl may include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, and octenyl.

[0123] In the present invention, examples of the alkynyl group may include, but are not limited to, ethynyl and propargyl.

[0124] In the present invention, examples of cycloalkyl may include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloundecyl, and cyclododecyl.

[0125] In the present invention, examples of halogen include, but are not limited to, fluorine, chlorine, bromine and iodine.

[0126] In the present invention, examples of aryl groups may include, but are not limited to, phenyl, methylphenyl, ethylphenyl, 4-tert-butylphenyl, and naphthyl.

[0127] In the present invention, aralkyl refers to an alkyl group having an aryl substituent, and examples may include, but are not limited to, phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-t-butyl, and phenyl-isopropyl.

[0128] In the present invention, the alkylaryl group refers to an aryl group having 7 to 20 carbon atoms and having an alkyl substituent, and examples thereof may include but are not limited to: methylphenyl and ethylphenyl.

[0129] In the present invention, examples of alkoxy groups may include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentyl, tert-pentyloxy and hexyloxy.

[0130] In the present invention, the heteroatom refers to an atom usually contained in a molecular structure except a halogen atom, a carbon atom and a hydrogen atom, such as O, N, S, P, Si and B.

[0131] The present invention adopts 3-pyrroline-1-carboxylate compound as an external electron donor and alkyl aluminum as a co-catalyst component, which are used in combination with a main catalyst component. This catalyst system can improve the stereospecificity and hydrogen adjustment sensitivity of the catalyst system while maintaining high activity and a wide molecular weight distribution of the polymer product, and can prepare high isotactic low molecular weight polyolefin products. DETAILED DESCRIPTION

[0132] According to an embodiment of the present invention, the main catalyst component includes titanium element, magnesium element and an internal electron donor, and is a reaction product of a titanium compound, a magnesium compound and an internal electron donor.

[0133] The present invention is described in detail below by way of examples, but the protection scope of the present invention is not limited to the following description.

[0134] In the examples and comparative examples, the titanium content of the catalyst was measured colorimetrically using a UV-Visible Spectrophotometer Model 722.

[0135] The performance test of the polymer prepared in the embodiment and comparative example is as follows:

[0136] 1. Determination method of polymer weight average molecular weight and molecular weight distribution: high temperature gel permeation chromatography, measured in accordance with standard GB / T 36214.4-2018.

[0137] 2. Determination method of isotactic index of polymer: refer to standard GB / T 2412-2008.

[0138] Preparation Example 1

[0139] This preparation example is used to illustrate the preparation of a magnesium compound.

[0140] Anhydrous magnesium chloride and ethanol are mixed in a molar ratio of 1:2.6, and the temperature is raised to 120° C. to react to generate a magnesium chloride alcoholate melt for 2 to 4 hours. The magnesium chloride alcoholate melt is stirred at high speed in a dispersion medium of white oil and silicone oil and then placed in cooled hexane to form spherical magnesium chloride alcoholate particles, which are washed and dried to obtain a spherical carrier.

[0141] Preparation Example 2

[0142] This preparation example is used to illustrate the preparation of the main catalyst component.

[0143] In a 300ml stirred glass reaction bottle fully replaced with high-purity nitrogen, add 100ml of titanium tetrachloride, cool to -20°C, add 8g of the spherical carrier prepared in Preparation Example 1, slowly heat to 110°C, add 3mmol of 2,4-pentanediol dibenzoate and 3mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane as internal electron donors during the heating process, keep constant temperature at 110°C for 0.5h to obtain a solid-liquid mixture, filter out the liquid, mix and filter the solid with titanium tetrachloride twice, then wash five times with hexane, and obtain a titanium-containing solid catalyst component Z1 after vacuum drying. The titanium content in Z1 is 2.7wt%.

[0144] Preparation Example 3

[0145] This preparation example is used to illustrate the preparation of the main catalyst component.

[0146] In a reactor fully replaced with high-purity nitrogen, add 6.0g of magnesium chloride, 119ml of toluene, 5ml of epichlorohydrin, and 15.6ml of tributyl phosphate (TBP) in sequence, and heat to 50°C under stirring, and maintain for 2.5 hours until the solid is completely dissolved; add 1.7g of phthalic anhydride and continue to maintain for 1 hour; cool the solution to below -25°C, add 70ml of TiCl4 dropwise within 1 hour, and slowly heat to 80°C. Solids are gradually precipitated during the heating process; add 6mmol of 3-methyl-2,4-pentanediol dibenzoate as an internal electron donor, maintain the temperature for 1 hour, filter, add 80ml of toluene, wash twice, and obtain a solid precipitate. Then add 60ml of toluene and 40ml of TiCl4, raise the temperature to 100°C, treat for 2 hours, drain the filtrate, add 60ml of toluene and 40ml of TiCl4, raise the temperature to 100°C, treat for 2 hours, and drain the filtrate; add 60ml of toluene, wash three times in a boiling state, then add 60ml of hexane, wash twice in a boiling state, add 60ml of hexane, wash twice at room temperature, and obtain a titanium-containing solid catalyst component Z2, the titanium content of Z2 is 2.6wt%.

[0147] Preparation Example 4

[0148] This preparation example is used to illustrate the preparation of the main catalyst component.

[0149] In a 300mL stirred glass reaction bottle fully replaced with high-purity nitrogen, add 100mL of titanium tetrachloride, cool to -20°C, add 8g of the spherical carrier prepared in Preparation Example 1, slowly heat to 110°C, add 6mmol of 2,3-diisopropylsuccinic acid diethyl ester as an internal electron donor during the heating process, keep constant temperature at 110°C for 0.5h, filter out the liquid, treat with titanium tetrachloride twice, then wash with hexane five times, and obtain titanium-containing solid catalyst component Z3 after vacuum drying. The titanium content in Z3 is 4.1wt%.

[0150] Examples 1-9 and Comparative Examples 1-9

[0151] Examples 1-9 and Comparative Examples 1-9 are used to illustrate the catalyst system and application thereof provided by the present invention.

[0152] In a 48-channel parallel pressure reactor (reaction volume 20 mL), a certain amount of hydrogen was filled; propylene gas was filled to about 1 MPa, and 5 mL of liquid propylene was added; triethylaluminum (calculated as aluminum element): external electron donor: solid catalyst component (calculated as titanium element) was added in a molar ratio of 500:20:1 to prepare a mixed solution; a certain amount of the mixed solution (containing 0.02 mg of the solid catalyst component) was injected into the reactor; the reaction was carried out at 70°C for 1 hour to obtain a polymer, and the isotactic index, weight average molecular weight and molecular weight distribution of the polymer were determined. The results are shown in Table 1.

[0153] Table 1

[0154]

[0155] Note: D1: cyclohexylmethyldimethoxysilane;

[0156] D2: 2-isopropyl-2-isopentyl-1,3-dimethoxypropane;

[0157] NE1: benzyl 3-pyrroline-1-carboxylate;

[0158] NE2: tert-butyl 3-pyrroline-1-carboxylate;

[0159] NE3: methyl 2,5-dioxo-3-pyrroline-1-carboxylate;

[0160] NE4: tert-butyl 2-oxo-3-pyrroline-1-carboxylate;

[0161] NE5: 2-chloro-3-pyrroline-1-carboxylic acid ethyl ester;

[0162] NE6: 2-Methyl-3-pyrroline-1-carboxylic acid ethyl ester.

[0163] It can be seen from Examples 1-9 and Comparative Examples 1-7 in Table 1 that when the 3-pyrroline-1-carboxylate compound provided by the present invention is added as an electron donor to an olefin polymerization system in which the internal electron donor contains alcohol ester, the polymerization product maintains the characteristics of a wide molecular weight distribution, the isotactic index is increased, and the molecular weight of the polymer is decreased; the stereospecificity and hydrogen regulation sensitivity are simultaneously increased. And it can be seen from Comparative Examples 8-9 that when the 3-pyrroline-1-carboxylate compound is added as an electron donor to a polymerization system in which the internal electron donor is succinate, the isotactic index of the polymer is decreased, and the molecular weight distribution of the polymer becomes narrower, indicating that the matching of different internal and external electron donors has different effects on the performance of the polymerization product. Therefore, the olefin polymerization system in which the 3-pyrroline-1-carboxylate compound is used as an electron donor and matched with the internal electron donor alcohol ester is an excellent combination, which can produce highly isotactic and low molecular weight products.

[0164] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to 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 words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A catalyst system, characterized in that The catalyst system includes component A and / or a reaction product of component A; The component A comprises a main catalyst component, a co-catalyst component and an external electron donor; The main catalyst component comprises magnesium, titanium, halogen and an internal electron donor; the internal electron donor comprises an alcohol ester compound I; The co-catalytic component is selected from alkyl aluminum compounds; The external electron donor comprises a 3-pyrroline-1-carboxylate compound.

2. The catalyst system according to claim 1, characterized in that The 3-pyrroline-1-carboxylate is selected from the structure shown in formula (a), In formula (a), M1 and M2 are the same or different and are independently selected from hydrogen, C1-C 20 Alkyl, keto, halogen, substituted or unsubstituted phenyl; preferably, M1 and M2 are each independently selected from hydrogen, C1-C 10 Alkyl, keto, halogen, substituted or unsubstituted phenyl; more preferably, M1 and M2 are each independently selected from hydrogen, methyl, ethyl, isopropyl, n-butyl, tert-butyl, isobutyl, pentyl, hexyl, keto, halogen, or C1-C6 alkyl substituted phenyl; M3 and M4 are the same or different and are independently selected from hydrogen and halogen; M1, M2, M3, and M4 optionally contain a substituent a1; R is selected from C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, C3-C 12 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Arylalkyl, 4-12 membered heterocycloalkyl or C5-C 20 Heteroaryl; R optionally contains substituent a2; The substituent a1 and the substituent a2 are each independently selected from hydroxyl, halogen, cyano, nitro, amino, mono-C1-C 10 Alkylamino, di-C1-C 10 At least one of an alkylamino group, an aldehyde group, a carboxyl group, and a heteroatom; Preferably, the 3-pyrroline-1-carboxylate compound is selected from 3-pyrroline-1-carboxylic acid benzyl ester, 3-pyrroline-1-carboxylic acid tert-butyl ester, 3-pyrroline-1-carboxylic acid ethyl ester, 3-pyrroline-1-carboxylic acid propyl ester, 3-pyrroline-1-carboxylic acid pentyl ester, 2,5-dioxopyrroline-1-carboxylic acid methyl ester, 2,5-dioxopyrroline-1-carboxylic acid ethyl ester, 2,5-dioxopyrroline-1-carboxylic acid tert-butyl ester, 2,5-dioxopyrroline-1-carboxylic acid heptyl ester, 2-oxo-3-py ... At least one of tert-butyl pyrroline-1-carboxylate, ethyl 2-oxo-3-pyrroline-1-carboxylate, methyl 2-oxo-3-pyrroline-1-carboxylate, ethyl 2-chloro-3-pyrroline-1-carboxylate, methyl 2-bromo-3-pyrroline-1-carboxylate, tert-butyl 2,5-dichloro-3-pyrroline-1-carboxylate, ethyl 2,3-dichloro-3-pyrroline-1-carboxylate, ethyl 2-methyl-3-pyrroline-1-carboxylate, and tert-butyl 3-methyl-3-pyrroline-1-carboxylate.

3. The catalyst system according to claim 1 or 2, characterized in that The weight ratio of titanium element, magnesium element and internal electron donor in the main catalyst component is 1:(5-25):(2-15); and / or, the molar ratio of the 3-pyrroline-1-carboxylate compound to the main catalyst component calculated as titanium element is (0.1-1000):1, preferably (1-200):1, more preferably (1-80):1; and / or, the molar ratio of the main catalyst component calculated as titanium element to the alkyl aluminum compound calculated as aluminum element is 1:(5-5000), preferably 1:(20-2000); and / or, the molar ratio of the external electron donor to the aluminum element in the alkyl aluminum compound is 1:(0.1-1000), preferably 1:(1-500); and / or, the alkylaluminum compound is selected from triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum dichloride, Al(n-C6H13)3 and Al(n-C8H 17 )3 or more.

4. The catalyst system according to claim 1, 2 or 3, characterized in that The alcohol ester compound I is selected from the diol ester compound represented by formula (I), In formula (I), R 1 and R 2 The same or different, each independently selected from C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl, C7-C 20 Arylalkyl or C 10 -C 20 Preferably, R 1 and R 2 The same or different, each independently selected from C1-C 10 Alkyl, C2-C 10 Alkenyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Alkyl, C7-C 10 Aralkyl and C 10 -C 15 Fused ring aromatic groups; M is a divalent linking group selected from C1-C 20 Alkylene, C3-C 20 Cycloalkylene or C6-C 20 arylene; Preferably, R 1 , R 2 Optionally containing a substituent I, wherein the substituent I is selected from at least one of a hydroxyl group, a halogen atom, a cyano group, a nitro group, an amino group, a mono-C1-C6 alkylamino group, a di-C1-C6 alkylamino group, an aldehyde group, a carboxyl group and a heteroatom; Preferably, M optionally contains a substituent II selected from nitrogen, oxygen, sulfur, silicon, phosphorus, halogen atoms and C1-C 20 At least one of the alkyl groups, when the substituent II is a plurality of C1-C 20 When alkyl, substituent II is optionally bonded to form one or more rings; Alternatively, the alcohol ester compound I is selected from the diol ester compound represented by formula (II), In formula (II), R'1 and R'2 are the same or different and are independently selected from C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Arylalkyl and C7-C 20 Alkaryl; preferably selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Arylalkyl and C7-C 10 Alkaryl; R'3, R'4, R'5, R'6, R' 1 , R' 2 -'R' 2n are the same or different, each independently selected from hydrogen, halogen, C1-C 20 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl, C7-C 20 Aralkyl and C 10 -C 20 Condensed ring aromatic group; preferably selected from C1-C 10 Alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Alkyl, C7-C 10 Aralkyl and C 10 -C 15 Fused ring aromatic groups; R'1, R'2, R'3, R'4, R'5, R'6, R' 1 , R' 2 -R' 2n Optionally containing a substituent III; the substituent III is selected from at least one of halogen, C1-C6 alkyl and C1-C6 alkoxy; R'3, R'4, R'5, R'6, R' 1 , R' 2 -R' 2n Optionally contain heteroatoms, said heteroatoms being one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus; Preferably, R'3, R'4, R'5, R'6 and R' 1 , R' 2 -R' 2n Two or more of them are bonded to each other to form a saturated or unsaturated monocyclic ring or a saturated or unsaturated polycyclic ring; n is an integer of 0 to 10, preferably an integer of 1 to 8, and more preferably an integer of 2 to 6. When n is 0, the carbon atoms of the substituents R'3 and R'4 are bonded to the carbon atoms of the substituents R'5 and R'6.

5. The catalyst system according to claim 4, characterized in that The diol ester compound represented by formula (I) or the diol ester compound represented by formula (II) is selected from 2,4-pentanediol dibenzoate, 3-methyl-2,4-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 3,5-heptanediol di-p-methylbenzoate, 3,5-heptanediol di-o-methylbenzoate, 3,5-heptanediol di-p-chlorobenzoate, 3,5-heptanediol di-o-chlorobenzoate, 3,5-heptanediol di-p-methoxybenzoate, 3,5-heptanediol di-o-methoxybenzoate, 3,5-heptanediol di-m-methoxybenzoate, 2-methyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-heptanediol dibenzoate, 6-methyl- -3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 5-ethyl-3,5-heptanediol dibenzoate, 4-propyl-3,5-heptanediol dibenzoate, 4-butyl-3,5-heptanediol dibenzoate, 2,4-dimethyl-3,5-heptanediol dibenzoate, 2,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 4,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 2-methyl-4-ethyl-3,5- Heptanediol dibenzoate, 4-methyl-4-ethyl-3,5-heptanediol dibenzoate, 2-methyl-4-propyl-3,5-heptanediol dibenzoate, 4-methyl-4-propyl-3,5-heptanediol dibenzoate, 6-methyl-2,4-heptanediol di(p-chlorobenzoate), 6-methyl-2,4-heptanediol di(p-methylbenzoate), 6-methyl-2,4-heptanediol di(m-methylbenzoate), 2,2,6,6-tetramethyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-octanediol dibenzoate, 4-ethyl-3,5-octanediol dibenzoate, 4-propyl-3,5-octanediol dibenzoate, 4-butyl-3,5-octanediol dibenzoate, -Dimethyl-3,5-octanediol dibenzoate, 4-methyl-4-ethyl-3,5-octanediol dibenzoate, 2-methyl-4-ethyl-3,5-octanediol dibenzoate, 2-methyl-6-ethyl-3,5-octanediol dibenzoate, 5-methyl-4,6-nonanediol dibenzoate, 5-ethyl-4,6-nonanediol dibenzoate, 5-propyl-4,6-nonanediol dibenzoate, 5-butyl-4,6-nonanediol dibenzoate, 5,5-dimethyl-4,6-nonanediol dibenzoate, 5-methyl-4-ethyl-4,6-nonanediol dibenzoate, 5-phenyl-4,6-nonanediol dibenzoate, 4,6-nonanediol dibenzoate and 4-butyl-3,5-heptanediol dibenzoate, 1,2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1,2-phenylene dibenzoate, 3,5-diisopropyl-1,2-phenylene dibenzoate, 3,6-dimethyl-1,2-phenylene dibenzoate, 4-tert-butyl-1,2-phenylene dibenzoate, 1,2-naphthalene dibenzoate, 2,3-naphthalene dibenzoate, 1,8-naphthyl dibenzoate, 1,8-naphthyl dibenzoate, 1,8-naphthyl dibenzoate, 1,8-naphthyl dibenzoate, 1,8-naphthyl dibenzoate, 1,8-naphthyl dibenzoate, 1,8-naphthyl dibenzoate, 1,8-naphthyl dibenzoate, ester, di-4-ethylbenzoic acid-1,8-naphthyl ester, di-4-n-propylbenzoic acid-1,8-naphthyl ester, di-4-isopropylbenzoic acid-1,8-naphthyl ester, di-4-n-butylbenzoic acid-1,8-naphthyl ester, di-4-isobutylbenzoic acid-1,8-naphthyl ester, di-4-tert-butylbenzoic acid-1,8-naphthyl ester, di-4-phenylbenzoic acid-1,8-naphthyl ester, di-4-fluorobenzoic acid-1,8-naphthyl ester, di-3-fluorobenzoic acid-1,8-naphthyl ester and di-2-fluorobenzoic acid-1,8-naphthyl ester.

6. The catalyst system according to claim 5, characterized in that The internal electron donor further comprises a second internal electron donor, and the second internal electron donor is selected from at least one of a diether compound I, a succinate compound I, and an aromatic carboxylate compound I; The molar ratio of the first internal electron donor to the second internal electron donor is (100-1):(1-100).

7. The catalyst system according to claim 6, characterized in that The catalyst system further comprises a second external electron donor, which is selected from one or more of a silane compound, a diether compound II, an alcohol ester compound II, an aromatic carboxylic acid ester compound II and a succinate compound II; The molar ratio of the first external electron donor to the second external electron donor is (100-1):(1-100).

8. The catalyst system according to claim 6 or 7, characterized in that The alcohol ester compound II is selected from any one of the diol ester compounds represented by formula (I) or formula (II); the diether compound I and the diether compound II are each independently selected from the diether compound represented by formula (III); In formula (III), R Ⅰ , R Ⅱ , R Ⅲ , R Ⅳ , R Ⅴ and R Ⅵ are the same or different, each independently selected from hydrogen, halogen, C1-C 20 Alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Arylalkyl and C7-C 20 Alkaryl; preferably, C1-C 18 Alkyl, C3-C 18 Cycloalkyl, C6-C 18 Aryl, C7-C 18 Arylalkyl and C7-C 18 Alkaryl; more preferably, C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Arylalkyl and C7-C 10 Alkaryl; R Ⅶ and R Ⅷ The same or different, each independently selected from C1-C 20 Alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Arylalkyl and C7-C 20 Alkaryl, preferably C1-C 18 Alkyl, C3-C 18 Cycloalkyl, C6-C 18 Aryl, C7-C 18 Arylalkyl and C7-C 18 Alkaryl; more preferably, C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Arylalkyl and C7-C 10 Alkaryl; Preferably, R Ⅶ and R Ⅷ Optionally, it has a substituent IV; the substituent IV is selected from C1-C 10 Alkyl, C1-C 10 Alkoxy, hydroxy, halogen, cyano, nitro, amino, mono-C1-C 10 Alkylamino, di-C1-C 10 Alkylamino, aldehyde, carboxyl and heteroatoms; Preferably, the R Ⅰ , R Ⅱ , R Ⅲ , R Ⅳ , R Ⅴ and R Ⅵ Two or more of the are bonded to each other to form a saturated or unsaturated monocyclic or polycyclic ring, preferably a fluorene ring; Preferably, R Ⅲ and R Ⅳ Bonded to each other to form a saturated or unsaturated monocyclic or polycyclic ring; Preferably, the diether compound represented by formula (III) is selected from 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2-(1-naphthyl)-1,3 -dimethoxypropane, 2-(2-fluorophenyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxy 2-Methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-isopropyl- 1,3-dimethoxypropane, 2-(1-methylbutyl)-2-sec-butyl-1,3-dimethoxypropane, 2,2-di-sec-butyl-1,3-dimethoxypropane, 2,2-di-tert-butyl-1,3-dimethoxypropane, 2,2-di-neopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-isopropyl-2-phenyl-1,3-dimethoxypropane, 2-phenyl-2-sec-butyl-1,3-dimethoxypropane, 2-isopropyl-2-benzyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-sec-butyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 1,1-bis(methoxymethyl)-cyclopentadiene, 1,1-bis(methoxymethyl)-2,3,4,5,-tetramethylcyclopentadiene, 1,1-bis(methoxymethyl)-2,3,4,5,-tetramethylcyclopentadiene, 1,1-bis(methoxymethyl)-2,3,4,5,-tetraphenylcyclopentadiene, 1,1-bis(methoxymethyl)-2,3,4,5,-tetrafluorocyclopentadiene, 1,1-bis(methoxymethyl)-3,4-dicyclopentylcyclopentadiene, 1,1-bis(methoxymethyl)indene, 1,1-bis(methoxymethyl)-2,3-dimethoxyindene, 1,1-bis(methoxymethyl)-2,3,6,7-tetrafluoroindene, 1,1-bis(methoxymethyl)-4,5,6,7-tetrafluoroindene, 1,1-bis(methoxymethyl)-4,7-dimethylindene, 1,1-bis(methoxymethyl)-3,6-dimethylindene, 1,1-bis(methoxymethyl)-4-phenylindene, 1,1-bis(methoxymethyl)-4-phenyl-2-methylindene, 1,1-bis(methoxymethyl)-4-tetracyclohexylindene, 1,1-bis(methoxymethyl)-7-(3,3,3-trifluoropropyl)phenylindene, 1,1-bis(methoxymethyl)-7-cyclopentylindene , 1,1-bis(methoxymethyl)-7-isopropylindene, 1,1-bis(methoxymethyl)-7-cyclohexylindene, 1,1-bis(methoxymethyl)-7-tert-butylindene, 1,1-bis(methoxymethyl)-7-tert-butyl-2-methylindene, 1,1-bis(methoxymethyl)-7-phenylindene, 1,1-bis(methoxymethyl)-2-phenylindene, 9,9-bis(methoxymethyl)fluorene, 9,9-bis(methoxymethyl)-2,7-dicyclopentylfluorene, 9,9-bis(methoxymethyl)-1,8-dichlorofluorene, 9,9-bis(methoxymethyl)-1,8-difluorofluorene, 9,9-bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene, 9,9-bis(methoxymethyl)- at least one of 4-tert-butylfluorene, 1,1-bis-(methoxymethyl)-2,5-cyclohexadiene, 1,1-bis-(methoxymethyl)-benzonaphthalene, 7,7-bis-(methoxymethyl)-2,5-norbornadiene, 9,9-bis-(methoxymethyl)-1,4-methanedihydronaphthalene, 9,9-bis-(methoxymethyl)-1,4-methanedihydroanthracene, 4,4-bis-(methoxymethyl)-1-phenyl-1,4-dihydronaphthalene, 4,4-bis-(methoxymethyl)-1-phenyl-3,4-dihydronaphthalene, 5,5-bis-(methoxymethyl)-1,3,6-cycloheptatriene and 1-methoxymethyl-1-(1'-methoxyethyl)-2,3,4,5-tetramethylcyclopentadiene; The succinate compound I and the succinate compound II are each independently selected from the compound represented by formula (d), In formula (d), R"1, R"2, R"3, R"4, R"5 and R"6 are the same or different and are each independently selected from C1-C 20 Alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Arylalkyl or C7-C 20 Alkaryl, R"1, R"2, R"3, R"4, R"5 and R"6 optionally contain halogen or heteroatom; Preferably, two or more of R"3, R"4, R"5 and R"6 are bonded to each other to form a saturated or unsaturated monocyclic ring or a saturated or unsaturated polycyclic ring; Preferably, the compound represented by formula (d) is selected from 2,3-bis(2-ethylbutyl)succinic acid diethyl ester, 2,3-diethyl-2-isopropylsuccinic acid diethyl ester, 2,3-diisopropylsuccinic acid diethyl ester, 2,3-di-tert-butylsuccinic acid diethyl ester, 2,3-diisobutylsuccinic acid diethyl ester, 2,3-(bistrimethylsilyl)succinic acid diethyl ester, 2-(3,3,3-trifluoropropyl)-3-methylsuccinic acid diethyl ester, 2,3-dineopentylsuccinic acid diethyl ester, 2,3-diisopentylsuccinic acid diethyl ester, 2,3-(1-trifluoromethyl-ethyl)succinic acid diethyl ester, 2-isopropyl-3-isobutylsuccinate, 2-tert-butyl-3-isopropylsuccinate, 2-isopropyl-3-cyclohexylsuccinate, 2-isopentyl-3-cyclohexylsuccinate, 2,2,3,3-tetramethylsuccinate, 2,2,3,3-tetraethylsuccinate, 2,2,3,3-tetrapropylsuccinate, 2,3-diethyl-2,3-diisopropyldisuccinate, 2,3-bis(2-ethylbutyl)succinate, 2,3-diethyl-2-isopropylsuccinate, 2,3 -Diisobutyl diisopropylsuccinate, diisobutyl 2,3-di-tert-butylsuccinate, diisobutyl 2,3-diisobutylsuccinate, diisobutyl 2,3-(bistrimethylsilyl)succinate, diisobutyl 2-(3,3,3-trifluoropropyl)-3-methylsuccinate, diisobutyl 2,3-dineopentylsuccinate, diisobutyl 2,3-diisopentylsuccinate, diisobutyl 2,3-(1-trifluoromethyl-ethyl)succinate, diisobutyl 2-isopropyl-3-isobutylsuccinate, diisobutyl 2-tert-butyl-3-isopropylsuccinate, diisobutyl 2-isopropyl-3-cyclohexylsuccinate diisobutyl amber, diethyl 2,3-diisopropyl 2-cyanosuccinate, diisobutyl 2-isopentyl-3-cyclohexyl succinate, diisobutyl 2,2,3,3-tetramethyl succinate, diisobutyl 2,2,3,3-tetraethyl succinate, diisobutyl 2,2,3,3-tetrapropyl succinate, diisobutyl 2,3-diethyl-2,3-diisopropyl disuccinate; preferably one or more selected from diethyl 2,3-diisopropyl succinate, diethyl 2,3-di-tert-butyl succinate, diethyl 2,3-diisobutyl succinate and diisobutyl 2,3-diisopropyl succinate; The aromatic carboxylic acid ester compound I and the aromatic carboxylic acid ester compound II are each independently selected from the compound represented by formula (VI), In formula (VI), R 3 The same or different, each independently selected from C1-C8 alkyl, C5-C 10 Cycloalkyl, C6-C 15 Aryl, C7-C 15 Alkyl or C7-C 15 Aralkyl; R 3 optionally having a substituent V; R 4 , R 5 , R 6 , R 7 may be the same or different, and are independently selected from hydrogen, halogen, C1-C8 alkyl, C5-C 10 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl or C7-C 20 Aralkyl; R 4 , R 5 , R 6 , R 7 optionally having a substituent VI; The substituent V and substituent VI are each independently selected from a C1-C6 alkyl group or a halogen atom; The compound represented by formula (VI) is preferably a phthalic acid ester; more preferably, the aromatic carboxylic acid ester compound is at least one selected from diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate and dioctyl phthalate; The silane compound has a structure shown in formula (b): In formula (b), R1, R2, R3, and R4 are the same or different and are independently selected from hydrogen, C1-C 10 Alkyl, C2-C 10 Alkenyl, C1-C 10 Alkoxy, C2-C 10 Alkenyloxy, C2-C 10 Alkynyl, C2-C 10 Alkynyloxy, C3-C 10 Cycloalkyl, C6-C 15 At least one of aryl and amino, preferably C1-C6 alkyl, C3-C6 cycloalkyl, C6-C 10 Aryl and amino, R1, R2, R3, R4 optionally contain a substituent IX, the substituent IX is selected from halogen, C1-C6 alkyl, C3-C6 cycloalkyl, C6-C 10 at least one of an aryl group and an amino group; Preferably, the silane compound is selected from tetramethoxysilane, tetraethoxysilane, diisopropyldimethoxysilane, isopropyltrimethoxysilane, di-n-propyldimethoxysilane, n-propyltrimethoxysilane, di-n-butyldimethoxysilane, di-tert-butyldimethoxysilane, diisobutyldimethoxysilane, cyclopentyltrimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyldimethoxysilane, cyclohexylethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, vinylmethoxysilane, vinylethoxysilane, vinylpropoxysilane, vinyldimethoxysilane, vinyldiethoxysilane, vinyldipropoxysilane, vinyltrimethoxysilane, vinyl At least one of triethoxysilane, vinyltripropoxysilane, allylmethoxysilane, allylethoxysilane, allylpropoxysilane, allyldimethoxysilane, allyldiethoxysilane, allyldipropoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltripropoxysilane, aminotrimethylsilane, aminotriethylsilane, aminotripropylsilane, aminotri-n-butylsilane, aminotriisobutylsilane, methylaminotrimethylsilane, methylaminotriethylsilane, methylaminotripropylsilane, methylaminotri-n-butylsilane, methylaminotriisobutylsilane, ethylaminotrimethylsilane, ethylaminotriethylsilane, ethylaminotripropylsilane, ethylaminotri-n-butylsilane and ethylaminotriisobutylsilane.

9. A prepolymerized catalyst composition comprising a prepolymer obtained by polymerizing the catalyst system according to any one of claims 1 to 8 with an olefin; The prepolymer has a prepolymer multiple of 0.1 to 1000 g prepolymer / g of the main catalyst component, preferably 0.2 to 500 g prepolymer / g of the main catalyst component, and more preferably 0.5 to 20 g prepolymer / g of the main catalyst component; The general formula of the olefin is CH2=CHR, wherein R is hydrogen or C1-C7 alkyl; The olefin to be prepolymerized is propylene; Prepolymerization with propylene or a mixture thereof with up to 20% by mole of one or more alpha-olefins; The temperature of the prepolymerization reaction is -20 to 80°C, and the polymerization pressure is preferably 0 to 5 MPa; The temperature of the prepolymerization reaction is 0-50°C.

10. An olefin polymerization method, wherein an olefin is polymerized in the catalyst system according to any one of claims 1 to 8; The general formula of the olefin is CH2=CHR, wherein R is hydrogen or a C1-C7 alkyl group, and the olefin polymerization can be a homopolymerization of a single olefin or a copolymerization of multiple olefins, or a combination of a single olefin homopolymerization process and a multiple olefin copolymerization process; The olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene; The polymerization conditions include: The temperature is 0°C to 150°C, preferably 50°C to 90°C; the pressure is 0.01MPa to 10MPa, preferably 0.1MPa to 5MPa; and the time is 0.1h to 5h, preferably 0.2h to 3h.

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