Catalyst component and catalyst for olefin polymerization, application of catalyst component and catalyst and olefin polymerization method

Abstract

The invention provides a catalyst component for olefin polymerization, a catalyst, application of the catalyst and an olefin polymerization method, the catalyst component comprises magnesium, titanium, halogen and internal electron donor compounds, and the internal electron donor compounds comprise a first internal electron donor compound as shown in a general formula (I) and a second internal electron donor compound as shown in a general formula (II); wherein the molar ratio of the first internal electron donor compound to the second internal electron donor compound is 1: (0.01-100); the prepared catalyst component and the catalyst have high hydrogen regulation sensitivity when being used for olefin polymerization, the obtained polyolefin product has high melt index and isotactic index, and subsequent processing and product development are facilitated.

Description

Technical Field

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

[0002] Common industrial polyolefin catalysts include Ziegler-Natta catalysts, which are based on magnesium, titanium, halogens, and electron donors, and single-center catalysts, which are based on transition metal complexes as the main active components. For Ziegler-Natta catalysts, electron donor compounds are essential components, playing a crucial role in regulating catalyst activity, orientation ability, kinetic behavior, hydrogen sensitivity, molecular weight distribution, and copolymerization performance. Electron donor compounds have always been a research hotspot for novel polypropylene catalysts, and their research and development can promote the continuous upgrading of catalysts and the continuous improvement of process technologies. With the development of Ziegler-Natta catalysts, a large number of electron donor compounds have been synthesized and reported. For example, patent document CN85100997A uses di-n-butyl phthalate or diisobutyl phthalate as internal electron donor compounds; patent document CN1453298 uses glycol ester compounds; patent document CN1313869 uses succinate compounds; and patent document EP361494 uses diether compounds as internal electron donors. However, when phthalate compounds are used as internal electron donors in Ziegler-Natta catalysts, the resulting polymers have a low melt index, which is detrimental to the processing and application of the polymers.

[0003] Therefore, it is of great significance to develop a novel internal electron donor compound for olefin polymerization catalysts that can overcome the shortcomings of existing technologies. Summary of the Invention

[0004] To address at least one technical problem existing in the prior art, the present invention provides a catalyst component, a catalyst, its application, and a method for olefin polymerization. The catalyst component and catalyst of the present invention are used to catalyze olefin polymerization and have high hydrogen sensitivity, resulting in a polymer with a high melt index. On the other hand, the catalyst component and catalyst of the present invention have high catalytic activity, and the resulting polymerization product also has a high isotactic index.

[0005] The objective of this invention is mainly achieved through the following technical solutions.

[0006] In a first aspect, the present invention provides a catalyst component for olefin polymerization, the catalyst component comprising magnesium, titanium, halogens and an internal electron donor compound, the internal electron donor compound comprising a first internal electron donor compound represented by general formula (I) and a second internal electron donor compound represented by general formula (II).

[0007] The molar ratio of the first internal electron donor compound to the second internal electron donor compound is 1:0.01-100.

[0008]

[0009] In general formula (I), R1-R4 are each independently selected from hydrogen, C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl, C3-C 12 Cyclic hydrocarbon group, C2-C 12 alkenyl, C2-C 12 alkynyl group, C6-C 20 Aryl, C7-C 20 Hydrocarbon aryl, C7-C 20 Aromatic group, C6-C 20 heteroaryl, C4-C 20 At least one of heterocyclic groups and halogens; for R1-R4, the C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl, C3-C 12 Cyclic hydrocarbon group, C2-C 12 alkenyl, C2-C 12 alkynyl group, C6-C 20 Hydrocarbon aryl, C6-C 20 Aromatic group, C6-C 20 heteroaryl and C4-C 20 The hydrogen atom on the heterocyclic group can be optionally substituted with a substituent.

[0010] R5 and R6 are each independently selected from hydrogen, C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl, C3-C 12 Cyclic hydrocarbon group, C2-C 12 alkenyl, C2-C 12 alkynyl group, C6-C 20 Aryl, C7-C 20 Hydrocarbon aryl, C7-C 20 Aromatic group, C6-C 20 heteroaryl, C4-C 20 At least one of heterocyclic groups and halogens; for R5 and R6, the C1-C 12 Straight-chain alkyl, C3-C 12Branched alkyl, C3-C 12 Cyclic hydrocarbon group, C2-C 12 alkenyl, C2-C 12 alkynyl group, C6-C 20 Hydrocarbon aryl, C6-C 20 Aromatic group, C6-C 20 heteroaryl and C4-C 20 The hydrogen atom on the heterocyclic group can be optionally substituted with a substituent.

[0011] R7 and R8 are each independently selected from C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C3-C 12 Cyclic hydrocarbon group, C2-C 10 alkenyl, C2-C 10 alkynyl group, C6-C 20 Aryl, C7-C 20 Hydrocarbon aryl, C7-C 20 Aromatic group, C6-C 20 heteroaryl and C4-C 15 At least one of the heterocyclic groups; for R7 and R8, the C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C3-C 12 Cyclic hydrocarbon group, C2-C 10 alkenyl, C2-C 10 alkynyl group, C6-C 20 Hydrocarbon aryl, C6-C 20 Aromatic group, C6-C 20 heteroaryl and C4-C 15 The hydrogen atom on the heterocyclic group can be optionally substituted with a substituent.

[0012] n is an integer between 0 and 4.

[0013] In general formula (II), R9 is selected from C2-C8 straight-chain alkyl groups, C3-C6 alkyl groups, and C4-C6 alkyl groups. 10 Branched alkyl, C5-C 10 Cyclic hydrocarbon group, C6-C 15 Aryl, C 7- C 15 Hydrocarbon aryl and C7-C 15 At least one of the aromatic groups;

[0014] R 10 -R 13 Each element is independently selected from hydrogen, halogens, C1-C6 straight-chain alkyl groups, and C3-C4 alkyl groups. 10 Branched alkyl, C5-C 10 Cyclic hydrocarbon group, C6-C 20 Aryl, C7-C 20 Hydrocarbon aryl and C7-C20 At least one of the aromatic groups; for R 10 -R 13 The C1-C6 straight-chain alkyl group, C3-C 10 Branched alkyl, C5-C 10 Cyclic hydrocarbon group, C6-C 20 Aryl, C7-C 20 Hydrocarbon aryl and C7-C 20 The hydrogen atom on the aromatic group can be optionally replaced by a substituent.

[0015] R1-R4, R5-R6, R7-R8 and R 10 -R 13 In this context, each substituent is independently selected from at least one of -OH, -NH2, C1-C6 alkyl-substituted amino, -CHO, -COOH, halogen, C1-C6 alkyl, and C1-C6 alkoxy.

[0016] Preferably, R1-R4 are each independently selected from C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C5-C 10 Cyclic hydrocarbon group, C2-C 10 alkenyl, C2-C 10 alkynyl group, C6-C 18 Aryl, C7-C 18 Hydrocarbon aryl, C7-C 18 Aromatic group, C6-C 18 heteroaryl and C4-C 18 At least one of the heterocyclic groups; preferably, R1-R4 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloheptyl, cyclooctyl, phenyl, naphthyl, 4-methyl The alkylphenyl, 4-ethylphenyl, benzyl, phenethyl, phenyl n-propyl, phenyl n-butyl, phenyl tert-butyl, phenyl isopropyl, phenyl n-pentyl, and phenyl n-butyl are selected from at least one of the following: alkyl, alkyl, branched, alkyl, cycloalkyl, alkenyl, aryl, aryl, alkyl, aryl, and heteroaryl. More preferably, each of R1-R4 is independently selected from at least one of the following: C1-C4 straight-chain alkyl, C3-C4 branched-chain alkyl, C5-C8 cycloalkyl, C2-C5 alkenyl, C6-C9 aryl, C7-C9 aryl, C7-C9 aryl, and C6-C9 heteroaryl.

[0017] Preferably, R5 and R6 are each independently selected from C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C5-C 10 Cyclic hydrocarbon group, C2-C10 alkenyl, C2-C 10 alkynyl group, C6-C 18 Aryl, C7-C 18 Hydrocarbon aryl, C7-C 18 Aromatic group, C6-C 18 heteroaryl and C4-C 18 At least one of the heterocyclic groups; R5 and R6 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloheptyl, cyclooctyl, phenyl, naphthyl, 4-methylbenzene More preferably, R5 and R6 are each independently selected from at least one of C1-C4 straight-chain alkyl, C3-C4 branched-chain alkyl, C5-C8 cyclic hydrocarbon, C2-C5 alkenyl, C6-C9 aryl, C7-C9 hydrocarbon aryl, C7-C9 aromatic hydrocarbon, and C6-C9 heteroaryl.

[0018] Preferably, R7 and R8 are each independently selected from C1-C8 straight-chain alkyl, C3-C8 branched alkyl, and C4-C8 branched alkyl. 10 Cyclic hydrocarbon group, C2-C8 alkenyl group, C2-C8 alkynyl group, C6-C 15 Aryl, C7-C 15 Hydrocarbon aryl, C7-C 15 Aromatic group, C6-C 15 heteroaryl and C4-C 12 At least one of the heterocyclic groups; preferably, R7 and R8 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloheptyl, cyclooctyl, phenyl, naphthyl, 4- At least one of methylphenyl, 4-ethylphenyl, benzyl, phenethyl, phenyl n-propyl, phenyl n-butyl, phenyl tert-butyl, phenyl isopropyl, phenyl n-pentyl, and phenyl n-butyl; more preferably, R7 and R8 are each independently selected from C1-C4 straight-chain alkyl, C3-C4 branched-chain alkyl, C5-C8 cycloalkyl, C2-C5 alkenyl, C6-C9 aryl, C7-C9 aryl, C7-C9 aromatic, C6-C9 heteroaryl, and C4-C 10 At least one of the heterocyclic groups.

[0019] Preferably, R10 -R 13 Each is independently selected from C1-C6 straight-chain alkyl or C3-C8 branched alkyl.

[0020] Preferably, the first internal electron-donating compound is selected from dimethyl 2,2'-(1,3-dioxolane-2,2-diyl)diacetate, dimethyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate, dimethyl 2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate, diethyl 2,2'-(1,3-dioxolane-2,2-diyl)diacetate, diethyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate, diethyl 2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate, di-n-propyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate, and di-n-propyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate. propyl ester, di-n-propyl 2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate, diisopropyl 2,2'-(1,3-dioxolane-2,2-diyl)diacetic acid, diisopropyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate, diisopropyl 2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate, 2, 2'-(1,3-dioxolane-2,2-diyl)diacetic acid di-n-butyl ester, 2,2'-(1,3-dioxolane-2,2-diyl)diacetic acid di-n-butyl ester, 2,2'-(1,3-dioxolane-2,2-diyl)diacetic acid di-n-butyl ester, 2,2'-(1,3-dioxolane-2,2-diyl)diacetic acid diisobutyl ester, 2,2'-(1 Diisobutyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate, diisobutyl 2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate, ditert-butyl 2,2'-(1,3-dioxolane-2,2-diyl)diacetic acid, ditert-butyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate ... Di-tert-butyl di-(1,3-dioxolane-2,2-diyl)dibutyrate, diphenyl 2,2'-(1,3-dioxolane-2,2-diyl)diacetate, diphenyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate, diphenyl 2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate ... Dimethyl 2,2'-(1,3-dioxolane-2,2-diyl)diacetate, dimethyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate, dimethyl 2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate, dimethyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetate, dimethyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate, dimethyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, diethyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetate, diethyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetate, dimethyl ...methyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetate, dimethyl 2,2'-(4,5-diDiethyl 2,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate, diethyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, di-n-propyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetate, di-n-propyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate, di-n-propyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, diisopropyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetate, diisopropyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropion ... Diisopropyl dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetic acid di-n-butyl ester, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate di-n-butyl ester, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate di-n-butyl ester, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetic acid diisobutyl ester, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate ... Diisobutyl butyrate, di-tert-butyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetate, di-tert-butyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate, di-tert-butyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, diphenyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetate, diphenyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate, diphenyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate ... Di(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetate di-p-methylphenyl ester, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate di-p-methylphenyl ester, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate di-p-methyl ester, 2,2'-(1,3-dioxane-2,2-diyl)diacetate dimethyl ester, 2,2'-(1,3-dioxane-2,2-diyl)dipropionate dimethyl ester, 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate dimethyl ester, 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate dimethyl ester, 2,2'-(1,3-dioxane-2,2-diyl)diacetate diethyl ester, 2,2'-(1,3-dioxane-2,2-diyl)dipropionate diethyl ester, 2,Diethyl 2'-(1,3-dioxane-2,2-diyl)dibutyrate, di-n-propyl 2,2'-(1,3-dioxane-2,2-diyl)diacetate, di-n-propyl 2,2'-(1,3-dioxane-2,2-diyl)dipropionate, di-n-propyl 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate, di-n-propyl 2,2'-(1,3-dioxane-2,2-diyl)diacetate, diisopropyl 2,2'-(1,3-dioxane-2,2-diyl)diacetate, di-n- ... Diisopropyl dipropionate, 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate, di-n-butyl diacetate, 2,2'-(1,3-dioxane-2,2-diyl)dipropionate, di-n-butyl dibutyrate, 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate, di-n-butyl dibutyrate, 2,2'-(1,3-dioxane-2,2-diyl)diacetate, diisobutyl diacetate, 2,2'-( Diisobutyl 1,3-dioxane-2,2-diyl)dipropionate, diisobutyl 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate, di-tert-butyl 2,2'-(1,3-dioxane-2,2-diyl)diacetic acid, di-tert-butyl 2,2'-(1,3-dioxane-2,2-diyl)dipropionate, di-tert-butyl 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate, di-tert-butyl 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate, di-tert-butyl 2,2'-(1,3-dioxane-2,2-diyl)dipropionate At least one of the following: diphenyl diacetate, diphenyl 2,2'-(1,3-dioxane-2,2-diyl)dipropionate, diphenyl 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate, di-p-methylphenyl 2,2'-(1,3-dioxane-2,2-diyl)diacetic acid, di-p-methylphenyl 2,2'-(1,3-dioxane-2,2-diyl)dipropionate, and di-p-methylphenyl 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate.

[0021] Preferably, the molar ratio of the first internal electron donor compound to the second internal electron donor compound is 1:0.02-50, more preferably 1:0.05-20, and even more preferably 1:0.2-6.

[0022] Preferably, the magnesium in the catalyst component is derived from a magnesium compound.

[0023] More preferably, the magnesium compound is selected from at least one of magnesium dihalides, magnesium alkoxy compounds, alkyl magnesium compounds, hydrates of magnesium dihalides, alcohols of magnesium dihalides, derivatives of magnesium dihalides in which the halogen atom is substituted with an alkoxy group, and derivatives of magnesium dihalides in which the halogen atom is substituted with a haloalkoxy group.

[0024] More preferably, the alkoxy group in the magnesium dihalide derivative in which the halogen atom is replaced by an alkoxy group is C1-C. 10alkoxy groups.

[0025] Preferably, the magnesium compound includes at least one of magnesium dichloride, magnesium dibromide, magnesium diiodide, an alcoholysis of magnesium dichloride, an alcoholysis of magnesium dibromide, and an alcoholysis of magnesium diiodide.

[0026] Preferably, the titanium in the catalyst component is derived from a titanium compound.

[0027] Preferably, the titanium compound comprises the general formula TiX. m (OR 1 ) 4-m The compound, the TiX m (OR 1 ) 4-m R in 1 For C1-C 20 The hydrocarbon group, where X is a halogen, and 1 ≤ m ≤ 4.

[0028] More preferably, R 1 For C1-C 20 Alkyl groups, preferably C1-C 10 Alkyl, more preferably C1-C6 alkyl.

[0029] 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 trichloroethoxy.

[0030] Preferably, the molar ratio of magnesium, titanium, halogen and electron donor compound is 1:0.5-150:0.1-800:0.02-0.4, more preferably 1:0.5-50:1-200:0.05-0.2.

[0031] In a second aspect, the present invention provides a catalyst for olefin polymerization, the catalyst feedstock comprising the catalyst components described in the first aspect, an organoaluminum compound, and optionally an external electron donor compound.

[0032] The external electron donor compound includes at least one of organosilicon compounds.

[0033] Preferably, the organosilicon compound has the general formula R. 3 kSi(OR 4 ) 4-k 0≤k≤3 is preferably 1≤k≤3.

[0034] R 3 Selected from halogens, hydrogen, C1-C 20 Alkyl, C3-C 20 Cyclic hydrocarbon group, C6-C 20 Aryl, C1-C20 At least one of haloalkyl and amino groups.

[0035] R 4 Selected from C1-C 20 Alkyl, C3-C 20 Cyclic hydrocarbon group, C6-C 20 Aryl, C1-C 20 At least one of haloalkyl and amino groups.

[0036] Preferably, the organosilicon compound is selected from at least one of trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, n-propyltriethoxysilane, isopropyltriethoxysilane, n-butyltriethoxysilane, isobutyltriethoxysilane, phenyltriethoxysilane, cyclohexylmethyldimethoxysilane, and methyltert-butyldimethoxysilane.

[0037] Preferably, the organoaluminum compound is an alkylaluminum compound.

[0038] Preferably, the alkylaluminum compound has the general formula AlR 2 j X 3-j R 2 It is hydrogen or C1-C 20 Hydrocarbon group, X is a halogen, 1≤j≤3.

[0039] More preferably, R 2 It is a C1-C8 alkyl group.

[0040] Preferably, the alkylaluminum compound is selected from at least one of triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, triisooctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloro, diisobutylaluminum monochloro, sesquiethylaluminum chloride, and diethylaluminum dichloro.

[0041] Preferably, the molar ratio of aluminum in the alkylaluminum compound to titanium in the catalyst component is 5-5000:1, more preferably 5-1000:1, and even more preferably 25-100:1.

[0042] Preferably, the molar ratio of silicon in the external electron donor compound to titanium in the catalyst component is 0.1-500:1, more preferably 25-100:1.

[0043] Thirdly, the present invention provides the application of the catalyst component described in the first aspect or the catalyst described in the second aspect in olefin polymerization reactions.

[0044] Fourthly, the present invention provides a method for olefin polymerization, the method comprising: contacting an olefin with the catalyst component described in the first aspect or the catalyst described in the second aspect under olefin polymerization conditions to carry out a polymerization reaction.

[0045] Preferably, the method further includes: prepolymerizing the olefin by contacting the catalyst component or catalyst prior to the polymerization reaction.

[0046] Preferably, the olefin comprises an olefin as shown in the general formula CH2=CHR, wherein R is hydrogen, C1-C2, C2 ... 12 Alkyl or C1-C 12 Aryl groups.

[0047] Preferably, R is a C1-C6 alkyl group.

[0048] Preferably, the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 1-hexene.

[0049] And / or, the conditions for the polymerization reaction include: a temperature of 0 to 150°C, preferably 60 to 90°C; and a pressure of 0.01 to 10 MPa, preferably 0.01 to 6 MPa.

[0050] And / or, the conditions for the prepolymerization reaction include: a temperature of -40 to 80°C, preferably -20 to 50°C; and a pressure of 0.01 to 10 MPa, preferably 0.01 to 6 MPa.

[0051] This invention relates to a catalyst component, catalyst, and its application in olefin polymerization, as well as a method for olefin polymerization. The catalyst component and catalyst prepared by this invention not only exhibit high hydrogen sensitivity and produce a high melt index of the resulting polymer (reaching over 5.3 g / 10 min at 230°C and 2.16 kg load pressure), which is beneficial for subsequent processing and product development, but also possess high catalytic activity (reaching over 25 kg PP / gcat), and the resulting polymerization product also exhibits a high isotactic index (reaching over 96.6%). Detailed Implementation

[0052] The inventors of this invention have discovered through research that using a compound of 1,3-dioxane-2,2-dicarboxylic acid diesters and phthalate esters with specific structures as internal electron donors can effectively improve the hydrogen sensitivity of catalyst components used in olefin polymerization, resulting in a higher melt index of the obtained polymerization product. Furthermore, the catalyst components and catalyst exhibit good polymerization activity and stereotactic orientation, leading to a higher isotactic index of the obtained product.

[0053] In a first aspect, the present invention provides a catalyst component for olefin polymerization, the catalyst component comprising magnesium, titanium, halogen and an internal electron donor compound, wherein the internal electron donor compound comprises a first internal electron donor compound represented by general formula (I) and a second internal electron donor compound represented by general formula (II);

[0054] The molar ratio of the first internal electron donor compound to the second internal electron donor compound is 1:0.01-100;

[0055]

[0056] In general formula (I), R1-R4 are each independently selected from hydrogen, C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl, C3-C 12 Cyclic hydrocarbon group, C2-C 12 alkenyl, C2-C 12 alkynyl group, C6-C 20 Aryl, C7-C 20 Hydrocarbon aryl, C7-C 20 Aromatic group, C6-C 20 heteroaryl, C4-C 20 At least one of heterocyclic groups and halogens; for R1-R4, the C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl, C3-C 12 Cyclic hydrocarbon group, C2-C 12 alkenyl, C2-C 12 alkynyl group, C6-C 20 Hydrocarbon aryl, C6-C 20 Aromatic group, C6-C 20 heteroaryl and C4-C 20 The hydrogen atom on the heterocyclic group may optionally be substituted with a substituent;

[0057] R5 and R6 are each independently selected from hydrogen, C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl, C3-C 12 Cyclic hydrocarbon group, C2-C 12 alkenyl, C2-C 12alkynyl group, C6-C 20 Aryl, C7-C 20 Hydrocarbon aryl, C7-C 20 Aromatic group, C6-C 20 heteroaryl, C4-C 20 At least one of heterocyclic groups and halogens; for R5 and R6, the C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl, C3-C 12 Cyclic hydrocarbon group, C2-C 12 alkenyl, C2-C 12 alkynyl group, C6-C 20 Hydrocarbon aryl, C6-C 20 Aromatic group, C6-C 20 heteroaryl and C4-C 20 The hydrogen atom on the heterocyclic group may optionally be substituted with a substituent;

[0058] R7 and R8 are each independently selected from C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C3-C 12 Cyclic hydrocarbon group, C2-C 10 alkenyl, C2-C 10 alkynyl group, C6-C 20 Aryl, C7-C 20 Hydrocarbon aryl, C7-C 20 Aromatic group, C6-C 20 heteroaryl and C4-C 15 At least one of the heterocyclic groups; for R7 and R8, the C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C3-C 12 Cyclic hydrocarbon group, C2-C 10 alkenyl, C2-C 10 alkynyl group, C6-C 20 Hydrocarbon aryl, C6-C 20 Aromatic group, C6-C 20 heteroaryl and C4-C 15 The hydrogen atom on the heterocyclic group may optionally be substituted with a substituent;

[0059] n is an integer between 0 and 4;

[0060] In general formula (II), R9 is selected from C2-C8 straight-chain alkyl groups, C3-C6 alkyl groups, and C4-C6 alkyl groups. 10 Branched alkyl, C5-C 10 Cyclic hydrocarbon group, C6-C 15 Aryl, C7-C 15 Hydrocarbon aryl and C7-C 15 At least one of the aromatic groups;

[0061] R 10 -R 13 Each element is independently selected from hydrogen, halogens, C1-C6 straight-chain alkyl groups, and C3-C4 alkyl groups. 10 Branched alkyl, C5-C 10 Cyclic hydrocarbon group, C6-C 20 Aryl, C7-C 20 Hydrocarbon aryl and C7-C 20 At least one of the aromatic groups; for R 10 -R 13 The C1-C6 straight-chain alkyl group, C3-C 10 Branched alkyl, C5-C 10 Cyclic hydrocarbon group, C6-C 20 Aryl, C7-C 20 Hydrocarbon aryl and C7-C 20 The hydrogen atom on the aromatic group can be optionally substituted with a substituent;

[0062] R1-R4, R5-R6, R7-R8 and R 10 -R 13 In this context, each substituent is independently selected from at least one of -OH, -NH2, C1-C6 alkyl-substituted amino, -CHO, -COOH, halogen, C1-C6 alkyl, and C1-C6 alkoxy.

[0063] In a preferred embodiment of the present invention, the amino groups substituted with C1-C6 alkyl groups include -NHCH3 and / or -N(CH3)2; and / or, the halogens include at least one of fluorine, chlorine, bromine, and iodine; and / or, the C1-C6 alkyl groups include at least one of methyl, ethyl n-propyl, and isopropyl; and / or, the C1-C6 alkoxy groups include at least one of methoxy, ethoxy, n-propoxy, and isopropoxy.

[0064] In a preferred embodiment of the present invention, R1 is selected from hydrogen, C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C5-C 10 Cyclic hydrocarbon group, C2-C 10 alkenyl, C2-C 10 alkynyl group, C6-C 18 Aryl, C7-C 18 Hydrocarbon aryl, C7-C 18 Aromatic group, C6-C 18 heteroaryl, C4-C 18At least one of heterocyclic groups and halogens; preferably, R1 is selected from at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloheptyl, cyclooctyl, phenyl, naphthyl, 4-methylphenyl, 4-ethylphenyl, benzyl, phenethyl, phenyl n-propyl, phenyl n-butyl, phenyl tert-butyl, phenyl isopropyl, phenyl n-pentyl, and phenyl n-butyl.

[0065] In a preferred embodiment of the present invention, R1 is selected from at least one of hydrogen, C1-C4 straight-chain alkyl, C3-C4 branched-chain alkyl, C5-C8 cyclic hydrocarbon, C2-C5 alkenyl, C6-C9 aryl, C7-C9 hydrocarbon aryl, C7-C9 aromatic hydrocarbon, C6-C9 heteroaryl and halogen.

[0066] In a preferred embodiment of the present invention, R2 is selected from hydrogen, C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C5-C 10 Cyclic hydrocarbon group, C2-C 10 alkenyl, C2-C 10 alkynyl group, C6-C 18 Aryl, C7-C 18 Hydrocarbon aryl, C7-C 18 Aromatic group, C6-C 18 heteroaryl, C4-C 18 At least one of heterocyclic groups and halogens; preferably, R2 is selected from at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloheptyl, cyclooctyl, phenyl, naphthyl, 4-methylphenyl, 4-ethylphenyl, benzyl, phenethyl, phenyl n-propyl, phenyl n-butyl, phenyl tert-butyl, phenyl isopropyl, phenyl n-pentyl, and phenyl n-butyl.

[0067] In a preferred embodiment of the present invention, R2 is selected from at least one of hydrogen, C1-C4 straight-chain alkyl, C3-C4 branched-chain alkyl, C5-C8 cyclic hydrocarbon, C2-C5 alkenyl, C6-C9 aryl, C7-C9 hydrocarbon aryl, C7-C9 aromatic hydrocarbon, C6-C9 heteroaryl, and halogen.

[0068] In a preferred embodiment of the present invention, R3 is selected from hydrogen, C1-C 10 Straight-chain alkyl, C3-C10 Branched alkyl, C5-C 10 Cyclic hydrocarbon group, C2-C 10 alkenyl, C2-C 10 alkynyl group, C6-C 18 Aryl, C7-C 18 Hydrocarbon aryl, C7-C 18 Aromatic group, C6-C 18 heteroaryl, C4-C 18 At least one of heterocyclic groups and halogens; preferably, R3 is selected from at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloheptyl, cyclooctyl, phenyl, naphthyl, 4-methylphenyl, 4-ethylphenyl, benzyl, phenethyl, phenyl n-propyl, phenyl n-butyl, phenyl tert-butyl, phenyl isopropyl, phenyl n-pentyl, and phenyl n-butyl.

[0069] In a preferred embodiment of the present invention, R3 is selected from at least one of hydrogen, C1-C4 straight-chain alkyl, C3-C4 branched-chain alkyl, C5-C8 cyclic hydrocarbon, C2-C5 alkenyl, C6-C9 aryl, C7-C9 hydrocarbon aryl, C7-C9 aromatic hydrocarbon, C6-C9 heteroaryl, and halogen.

[0070] In a preferred embodiment of the present invention, R4 is selected from hydrogen, C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C5-C 10 Cyclic hydrocarbon group, C2-C 10 alkenyl, C2-C 10 alkynyl group, C6-C 18 Aryl, C7-C 18 Hydrocarbon aryl, C7-C 18 Aromatic group, C6-C 18 heteroaryl, C4-C 18 At least one of heterocyclic groups and halogens; preferably, R4 is selected from at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloheptyl, cyclooctyl, phenyl, naphthyl, 4-methylphenyl, 4-ethylphenyl, benzyl, phenethyl, phenyl n-propyl, phenyl n-butyl, phenyl tert-butyl, phenyl isopropyl, phenyl n-pentyl, and phenyl n-butyl.

[0071] In a preferred embodiment of the present invention, R4 is selected from at least one of hydrogen, C1-C4 straight-chain alkyl, C3-C4 branched alkyl, C5-C8 cyclic hydrocarbon, C2-C5 alkenyl, C6-C9 aryl, C7-C9 hydrocarbon aryl, C7-C9 aromatic hydrocarbon, C6-C9 heteroaryl and halogen.

[0072] In a preferred embodiment of the present invention, R5 is selected from hydrogen, C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C5-C 10 Cyclic hydrocarbon group, C2-C 10 alkenyl, C2-C 10 alkynyl group, C6-C 18 Aryl, C7-C 18 Hydrocarbon aryl, C7-C 18 Aromatic group, C6-C 18 heteroaryl, C4-C 18 R5 is selected from at least one of heterocyclic groups and halogens; R5 is selected from at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloheptyl, cyclooctyl, phenyl, naphthyl, 4-methylphenyl, 4-ethylphenyl, benzyl, phenethyl, phenyl n-propyl, phenyl n-butyl, phenyl tert-butyl, phenyl isopropyl, phenyl n-pentyl, and phenyl n-butyl.

[0073] In a preferred embodiment of the present invention, R5 is selected from at least one of hydrogen, C1-C4 straight-chain alkyl, C3-C4 branched-chain alkyl, C5-C8 cyclic hydrocarbon, C2-C5 alkenyl, C6-C9 aryl, C7-C9 hydrocarbon aryl, C7-C9 aromatic hydrocarbon, C6-C9 heteroaryl, and halogen.

[0074] In a preferred embodiment of the present invention, R6 is selected from hydrogen, C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C5-C 10 Cyclic hydrocarbon group, C2-C 10 alkenyl, C2-C 10 alkynyl group, C6-C 18 Aryl, C7-C 18 Hydrocarbon aryl, C7-C 18 Aromatic group, C6-C 18 heteroaryl, C4-C 18At least one of heterocyclic groups and halogens; R6 is selected from at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloheptyl, cyclooctyl, phenyl, naphthyl, 4-methylphenyl, 4-ethylphenyl, benzyl, phenethyl, phenyl n-propyl, phenyl n-butyl, phenyl tert-butyl, phenyl isopropyl, phenyl n-pentyl, and phenyl n-butyl.

[0075] In a preferred embodiment of the present invention, R6 is selected from at least one of hydrogen, C1-C4 straight-chain alkyl, C3-C4 branched-chain alkyl, C5-C8 cyclic hydrocarbon, C2-C5 alkenyl, C6-C9 aryl, C7-C9 hydrocarbon aryl, C7-C9 aromatic hydrocarbon, C6-C9 heteroaryl, and halogen.

[0076] In a preferred embodiment of the present invention, R7 is selected from C1-C8 straight-chain alkyl, C3-C8 branched alkyl, and C4-C6 branched alkyl. 10 Cyclic hydrocarbon group, C2-C8 alkenyl group, C2-C8 alkynyl group, C6-C 15 Aryl, C7-C 15 Hydrocarbon aryl, C7-C 15 Aromatic group, C6-C 15 heteroaryl and C4-C 12 At least one of the heterocyclic groups; preferably, R7 is selected from at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloheptyl, cyclooctyl, phenyl, naphthyl, 4-methylphenyl, 4-ethylphenyl, benzyl, phenethyl, phenyl n-propyl, phenyl n-butyl, phenyl tert-butyl, phenyl isopropyl, phenyl n-pentyl, and phenyl n-butyl.

[0077] In a preferred embodiment of the present invention, R7 is selected from C1-C4 straight-chain alkyl, C3-C4 branched-chain alkyl, C5-C8 cyclic hydrocarbon, C2-C5 alkenyl, C6-C9 aryl, C7-C9 hydrocarbon aryl, C7-C9 aromatic hydrocarbon, C6-C9 heteroaryl, and C4-C 10 At least one of the heterocyclic groups.

[0078] In a preferred embodiment of the present invention, R8 is selected from C1-C8 straight-chain alkyl, C3-C8 branched alkyl, C4-C8 branched alkyl, and C5-C8 branched alkyl. 10 Cyclic hydrocarbon group, C2-C8 alkenyl group, C2-C8 alkynyl group, C6-C 15Aryl, C7-C 15 Hydrocarbon aryl, C7-C 15 Aromatic group, C6-C 15 heteroaryl and C4-C 12 At least one of the heterocyclic groups; preferably, R8 is selected from at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloheptyl, cyclooctyl, phenyl, naphthyl, 4-methylphenyl, 4-ethylphenyl, benzyl, phenethyl, phenyl n-propyl, phenyl n-butyl, phenyl tert-butyl, phenyl isopropyl, phenyl n-pentyl, and phenyl n-butyl.

[0079] In a preferred embodiment of the present invention, R8 is selected from C1-C4 straight-chain alkyl, C3-C4 branched-chain alkyl, C5-C8 cycloalkyl, C2-C5 alkenyl, C6-C9 aryl, C7-C9 aryl, C7-C9 aromaticyl, C6-C9 heteroaryl, and C4-C 10 At least one of the heterocyclic groups.

[0080] In a preferred embodiment of the present invention, R 10 It is selected from at least one of hydrogen, halogen, C1-C6 straight-chain alkyl and C3-C8 branched alkyl.

[0081] In a preferred embodiment of the present invention, R 11 It is selected from at least one of hydrogen, halogen, C1-C6 straight-chain alkyl and C3-C8 branched alkyl.

[0082] In a preferred embodiment of the present invention, R 12 It is selected from at least one of hydrogen, halogen, C1-C6 straight-chain alkyl and C3-C8 branched alkyl.

[0083] In a preferred embodiment of the present invention, R 13 It is selected from at least one of hydrogen, halogen, C1-C6 straight-chain alkyl and C3-C8 branched alkyl.

[0084] In this invention, the term "cycloalkyl" refers to cycloalkyl, cycloalkenyl, or cycloynyl, "alkylaryl" refers to alkylaryl, alkenylaryl, or ynylaryl, and "aromatic" refers to aralkyl, arkenyl, or arynyl.

[0085] In a preferred embodiment of the present invention, the first internal electron-donating compound is selected from dimethyl 2,2'-(1,3-dioxolane-2,2-diyl)diacetate, dimethyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate, dimethyl 2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate, diethyl 2,2'-(1,3-dioxolane-2,2-diyl)diacetate, diethyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate, diethyl 2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate, di-n-propyl 2,2'-(1,3-dioxolane-2,2-diyl)diacetate, and diethyl 2,2'-(1,3-dioxolane-2,2-diyl)diacetate. Di(1,3-dioxolane-2,2-diyl)dipropionate, di(2,2'-dioxolane-2,2-diyl)dibutyrate, diisopropyl 2,2'-(1,3-dioxolane-2,2-diyl)diacetic acid, diisopropyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate, diisopropyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate, diisopropyl 2,2'-(1,3-dioxolane-2,2-diyl)di... Diisopropyl butyrate, di-n-butyl 2,2'-(1,3-dioxolane-2,2-diyl)diacetate, di-n-butyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate, di-n-butyl 2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate, di-n-butyl 2,2'-(1,3-dioxolane-2,2-diyl)diacetate Ester, 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate diisobutyl ester, 2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate diisobutyl ester, 2,2'-(1,3-dioxolane-2,2-diyl)diacetic acid ditert-butyl ester, 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate ditert-butyl ester, 2, Di-tert-butyl 2'-(1,3-dioxolane-2,2-diyl)dibutyrate, diphenyl 2,2'-(1,3-dioxolane-2,2-diyl)diacetate, diphenyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate, diphenyl 2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate, diphenyl 2,2'-(1,3- Di(1,3-dioxolane-2,2-diyl)diacetic acid di-p-methylphenyl ester, 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate di-p-methylphenyl ester, 2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate di-p-methylphenyl ester, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetic acid dimethyl ester, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate dimethyl ester, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate dimethyl ester, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetic acid diethyl ester, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetic acid diethyl ester, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetic acid diethyl ester, 2,2'-(4,5-dimethyl-1,Diethyl 3-dioxolane-2,2-diyl)dipropionate, diethyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, di-n-propyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetic acid, di-n-propyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate, di-n-propyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, diisopropyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetic acid, diisopropyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate, Diisopropyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, di-n-butyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetate, di-n-butyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate, di-n-butyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, di-n-butyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, diisobutyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate ... Diisobutyl diisobutyl dibutyrate (2,2-diyl)diisobutyl dibutyrate, di-tert-butyl diacetate (4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetate, di-tert-butyl dipropionate (4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate, di-tert-butyl dibutyrate (4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, diphenyl diacetate (4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetate, diphenyl dipropionate (4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate, diphenyl dibutyrate (4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, diphenyl dibutyrate (4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, diphenyl dibutyrate (4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, diphenyl dibutyrate (4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, diphenyl dibutyrate (4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, diphenyl dibutyrate (4,2 ... Di(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetic acid di-p-methylphenyl ester, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate di-p-methylphenyl ester, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate di-p-methylphenyl ester, 2,2'-(1,3-dioxane-2,2-diyl)diacetic acid dimethyl ester, 2,2'-(1,3-dioxane-2,2-diyl)dipropionate dimethyl ester, 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate dimethyl ester, 2,2'-(1,3-dioxane-2,2-diyl)diacetic acid diethyl ester, 2,2'-(1,3-dioxane-2,2-diyl)diacetic acid diethyl ester, 2,2'-(1,3-dioxane-2,2-diyl)diacetic acid diethyl ester, 2,2'-(1,3-dioxane-2,2-diyl)diacetic acid diethyl ester, 2,2'-(1,3-dioxane-2,2-diyl)diacetic acid diethyl ester,Diethyl 2,2'-(1,3-dioxane-2,2-diyl)dipropionate, diethyl 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate, di-n-propyl 2,2'-(1,3-dioxane-2,2-diyl)diacetic acid, di-n-propyl 2,2'-(1,3-dioxane-2,2-diyl)dipropionate, di-n-propyl 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate, diisopropyl 2,2'-(1,3-dioxane-2,2-diyl)diacetic acid, diisopropyl 2,2'-(1,3-dioxane-2,2-diyl)dipropionate, diisopropyl 2,2'-(1,3-dioxane-2,2-diyl)dipropionate, diisopropyl 2,2'-(1,3-dioxane-2,2-diyl)dipropionate, di-n- ... Diisopropyl 2,2'-(1,3-dioxane-2,2-diyl)diacetic acid di-n-butyl ester, diisopropyl 2,2'-(1,3-dioxane-2,2-diyl)dipropionate ... Di-tert-butyl diacetate, 2,2'-(1,3-dioxane-2,2-diyl)dipropionate, di-tert-butyl dibutyrate, 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate, diphenyl diacetate, diphenyl dipropionate, diphenyl dipropionate, diphenyl dibutyrate, diphenyl dibutyrate, diphenyl di-2,2'-(1,3-dioxane-2,2-diyl)diacetate, di-p-methylphenyl diacetate, di-2,2'-(1,3-dioxane-2,2-diyl)di ... At least one of di-p-methylphenyl 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate and di-p-methylphenyl 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate, preferably selected from at least one of 2,2'-(1,3-dioxane-2,2-diyl)diacetic acid dimethyl ester, 2,2'-(1,3-dioxane-2,2-diyl)diacetic acid diethyl ester, 2,2'-(1,3-dioxane-2,2-diyl)diacetic acid diethyl ester, 2,2'-(1,3-dioxane-2,2-diyl)dipropionate dimethyl ester and 2,2'-(1,3-dioxane-2,2-diyl)dipropionate diethyl ester.

[0086] In a preferred embodiment of the present invention, the second internal electron-donating compound is selected from dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, di-n-hexyl phthalate, diisohexyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, dibenzyl phthalate, tetramethyl dimethyl phthalate, tetramethyl diethyl phthalate, tetramethyl di-n-propyl phthalate, tetramethyl diisopropyl phthalate, tetramethyl di-n-butyl phthalate, tetramethyl diisobutyl phthalate, tetramethyl di-n-pentyl phthalate, and tetramethyl phthalic acid. At least one of diisoamyl phthalate, tetramethyl di-n-hexyl phthalate, tetramethyl diisohexyl phthalate, tetramethyl di-n-octyl phthalate, tetramethyl diisooctyl phthalate, tetramethyl dibenzyl phthalate, tetrabromodimethyl phthalate, tetrabromodiethyl phthalate, tetrabromodi-n-propyl phthalate, tetrabromodiisopropyl phthalate, tetrabromodi-n-butyl phthalate, tetrabromodiisobutyl phthalate, tetrabromodi-n-pentyl phthalate, tetrabromodiisoamyl phthalate, tetrabromodi-n-hexyl phthalate, tetrabromodiisohexyl phthalate, tetrabromodi-n-octyl phthalate, tetrabromodiisooctyl phthalate, and tetrabromodibenzyl phthalate; preferably di-n-butyl phthalate or diisobutyl phthalate.

[0087] In a preferred embodiment of the present invention, the molar ratio of the first internal electron donor compound to the second internal electron donor compound is 1:0.02-50, preferably 1:0.05-20, and more preferably 1:0.2-6.

[0088] In a preferred embodiment of the present invention, the magnesium in the catalyst component is derived from a magnesium compound; preferably, the magnesium compound includes at least one of magnesium dihalide, magnesium alkoxy, alkyl magnesium, magnesium dihalide hydrate, magnesium dihalide ethanolate, derivatives of magnesium dihalide in which the halogen atom is substituted with an alkoxy group, and derivatives of magnesium dihalide in which the halogen atom is substituted with a haloalkoxy group; preferably, the alkoxy group in the derivative of magnesium dihalide in which the halogen atom is substituted with an alkoxy group is C1-C. 10 alkoxy groups.

[0089] In a preferred embodiment of the present invention, the magnesium compound is magnesium dihalide and / or an alcoholysis of magnesium dihalide; preferably, the magnesium compound includes at least one of magnesium dichloride, magnesium dibromide, magnesium diiodide, an alcoholysis of magnesium dichloride, an alcoholysis of magnesium dibromide, and an alcoholysis of magnesium diiodide.

[0090] In a preferred embodiment of the present invention, the titanium in the catalyst component is derived from a titanium compound; preferably, the titanium compound includes compounds with the general formula TiX.m (OR 1 ) 4-m The compound, the TiX m (OR 1 ) 4-m R in 1 For C1-C 20 The hydrocarbon group, where X is a halogen, 1≤m≤4; preferably, R 1 For C1-C 20 Alkyl groups, preferably C1-C 10 Alkyl, more preferably C1-C6 alkyl; and / or, the X is selected from at least one of fluorine, chlorine, bromine and iodine.

[0091] In a preferred embodiment of the present invention, 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, preferably titanium tetrachloride.

[0092] In a preferred embodiment of the present invention, the molar ratio of magnesium, titanium, halogen, and the internal electron-donating compound is 1:0.5-150:0.1-800:0.02-0.4, more preferably 1:0.5-50:1-200:0.05-0.2. In this invention, the halogen is sourced from titanium compounds and magnesium compounds.

[0093] In this invention, the catalyst component can be prepared using conventional methods in the art. During the preparation of the catalyst component, the magnesium compound can be dissolved in a solvent system containing an organic epoxy compound and an organophosphorus compound, or it can be dissolved in a 1,3-diol ester compound.

[0094] According to some embodiments of the present invention, the organic epoxy compound includes at least one or more of C2-C8 aliphatic olefins, C2-C8 dienes, C2-C8 haloaliphatic olefins, oxides of C2-C8 dienes, glycidyl ethers, and C2-C8 internal ethers. Specific examples include, but are not limited to, at least one or more of ethylene oxide, propylene oxide, butane oxide, butadiene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, and tetrahydrofuran.

[0095] According to some embodiments of the present invention, the organophosphorus compound is a hydrocarbon ester or haloalkyl ester of orthophosphoric acid or phosphorous acid, specifically selected from trimethyl orthophosphoric acid, triethyl orthophosphoric acid, tributyl orthophosphoric acid, triphenyl orthophosphoric acid, trimethyl orthophosphoric acid, triethyl orthophosphoric acid, tributyl orthophosphoric acid, triphenyl phosphoric acid, etc.

[0096] Specifically, the catalyst component for olefin polymerization of the present invention can be prepared by the following method.

[0097] Preparation Method 1: The catalyst component was prepared according to the method disclosed in CN1506384A. First, a magnesium compound and an organic alcohol compound were mixed with an inert solvent at a molar ratio of 2–5, and the mixture was heated to 120–150°C and reacted for 1–5 hours at a magnesium / anhydride molar ratio of 5–10 and a magnesium / silicon molar ratio of 20–50. Then, the alcohol compound cooled to room temperature was added to a titanium compound solution pre-cooled to -15 to -40°C at a titanium / magnesium molar ratio of 20–50, and the mixture was heated to 90–110°C. An electron donor compound was added at a magnesium / ester molar ratio of 2–10, and the mixture was reacted at 100–130°C for 1–3 hours. The solid particles were then separated by filtration. Next, the solid particles were added to the titanium compound solution at a titanium / magnesium molar ratio of 20–50, stirred, and reacted at 100–130°C for 1.5–3 hours. The solid particles were then separated by filtration. Finally, the solid particles were washed with an inert solvent at 50–80°C and dried to obtain the catalyst component.

[0098] Preparation Method 2: The catalyst component is prepared according to the method disclosed in CN1006071B. First, a magnesium compound is dissolved in a solvent system composed of an organic epoxy compound, an organophosphorus compound, and an inert diluent to form a homogeneous solution. This solution is then mixed with a titanium compound, and a solid is precipitated in the presence of a precipitation aid. The solid is then treated with the electron donor compound of this invention to attach it to the solid. If necessary, the solid is further treated with titanium tetrahalide and an inert diluent.

[0099] The precipitant used is at least one or more of organic anhydrides, organic acids, ethers, ketones, and esters. Examples include: acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, dimethyl ether, diethyl ether, propyl ether, butyl ether, pentyl ether, succinate, malonic ester, glutaric ester, 2,4-pentanediol ester, and 3,5-heptanediol ester.

[0100] Relative to 1 mol of magnesium halide, the amounts of organic epoxy compounds are 0.2–10 mol, organic phosphorus compounds are 0.1–3 mol, precipitation aids are 0–1.0 mol, titanium compounds are 0.5–150 mol, and electron donor compounds are 0.02–0.5 mol.

[0101] Preparation Method 3: The catalyst component was prepared according to the method disclosed in CN1091748A. The magnesium chloride alcohol melt was dispersed in a dispersant system of white oil and silicone oil by high-speed stirring to form an emulsion. This emulsion was then discharged into a cooling liquid for rapid cooling and solidification, forming magnesium chloride alcohol microspheres. The cooling liquid was an inert hydrocarbon solvent with a low boiling point, such as petroleum ether, pentane, hexane, or heptane. The obtained magnesium chloride alcohol microspheres were washed and dried to form a spherical carrier. The molar ratio of alcohol to magnesium chloride was 2–3, preferably 2–2.5. The carrier particle size was 10–300 micrometers, with 30–150 micrometers being optimal.

[0102] The spherical support was treated with an excess of titanium tetrachloride at low temperature, with the temperature gradually increased. An electron donor was added during the treatment process. After treatment, the catalyst was repeatedly thawed with an inert solvent and dried to obtain a solid powdered spherical catalyst. The molar ratio of titanium tetrachloride to magnesium chloride was 20–200, preferably 30–60; the initial treatment temperature was -30–0°C, preferably -25–-20°C; and the final treatment temperature was 80–136°C, preferably 100–130°C.

[0103] The obtained spherical catalyst has the following characteristics: titanium content 1.5-3.0 wt%; ester content 6.0-20.0 wt%; chlorine content 52-60 wt%; magnesium content 10-20 wt%; inert solvent content 1-6 wt%; and catalyst specific surface area greater than 250 m² / g.

[0104] Preparation Method 4: Dialkoxymagnesium is added to an aromatic hydrocarbon compound and stirred to form a suspension. The suspension is treated with tetravalent titanium chloride at -20 to 100°C and reacted at 0 to 130°C. During this process, an electron donor is added at -20 to 130°C to carry out the reaction. The resulting solid is washed with the aromatic hydrocarbon compound. Then, at 0 to 130°C, it is treated again with tetravalent titanium chloride in an aromatic hydrocarbon solvent. Finally, it is washed with an inert solvent and dried to obtain a solid catalyst. The amount of tetravalent titanium chloride used per mole of dialkylmagnesium is 0.5 to 100 mol, and the amount of electron donor is 0.01 to 10 mol.

[0105] Preparation method 5: Halogenate dialkoxymagnesium compounds such as magnesium dialkoxy or magnesium diaryloxy with TiCl4 or its aromatic solution at 80-130°C. The treatment with TiCl4 or its aromatic solution can be repeated once or multiple times, and an electron donor compound is added during one or more such treatments.

[0106] Preparation Method Six: The catalyst components are prepared according to the method disclosed in US4540679A. A transition metal compound (preferably a tetravalent titanium compound) and an alkoxy magnesium compound react with an electron donor in a certain ratio in an inert solvent, wherein the molar ratio of the transition metal element to magnesium element is at least 0.5:1, and the amount of the electron donor compound is at most 1.0 mol / g titanium atom. The inert solvent needs to be easily removable and needs to be dehydrated, deoxygenated, and free of gases that can poison the catalyst. The reaction is carried out at -10 to 170°C for a period of several minutes to several hours.

[0107] In this invention, the preparation method of the catalyst component further includes forming an emulsion of magnesium compound, electron donor, etc. in a diluent, adding titanium compound to fix it to obtain a spherical solid, and then processing it to obtain a solid catalyst.

[0108] In any of the above preparation methods, the required internal electron donor compound can be added either in the form of a compound or in other ways, such as by obtaining it in situ using an internal electron donor compound precursor. The internal electron donor compound can also be added in any step of the above catalyst preparation method.

[0109] In a second aspect, the present invention provides a catalyst for olefin polymerization, the catalyst raw materials comprising the catalyst components described in the first aspect, an organoaluminum compound, and optionally an external electron donor compound;

[0110] In a preferred embodiment of the present invention, the external electron donor compound comprises an organosilicon compound, wherein the general formula of the organosilicon compound is R. 3 kSi(OR 4 ) 4-k , 0≤k≤3; R 3 Selected from halogens, hydrogen, C1-C 20 Alkyl, C3-C 20 Cyclic hydrocarbon group, C6-C 20 Aryl, C1-C 20 At least one of alkyl halogroups and amino groups; R 4 Selected from C1-C 20 Alkyl, C3-C 20 Cyclic hydrocarbon group, C6-C 20 Aryl, C1-C 20 At least one of halogenated alkyl and amino groups; preferably, 1 ≤ k ≤ 3. Using this preferred external electron donor compound in combination with the internal electron donor compound can further improve the melt index and isotactic index of the olefin polymer.

[0111] In a preferred embodiment of the present invention, the organosilicon compound is selected from at least one of trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, n-propyltriethoxysilane, isopropyltriethoxysilane, n-butyltriethoxysilane, isobutyltriethoxysilane, phenyltriethoxysilane, cyclohexylmethyldimethoxysilane, and methyltert-butyldimethoxysilane.

[0112] Preferably, it is selected from at least one of n-propyltrimethoxysilane, n-butyltrimethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, and dicyclopentyldimethoxysilane; more preferably, it is selected from at least one of cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, and dicyclopentyldimethoxysilane.

[0113] In a preferred embodiment of the present invention, the organoaluminum compound is an alkylaluminum compound; preferably, the alkylaluminum compound has the general formula AlR. 2 j X 3-j R 2 It is hydrogen or C1-C 20 Hydrocarbon group, X is halogen, 1≤j≤3; more preferably, R 2 It is a C1-C8 alkyl group.

[0114] In a preferred embodiment of the present invention, the alkyl aluminum compound 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, preferably triethylaluminum and / or triisobutylaluminum.

[0115] In a preferred embodiment of the present invention, the molar ratio of aluminum in the alkylaluminum compound to titanium in the catalyst component is 5-5000:1, preferably 5-1000:1, and more preferably 25-100:1;

[0116] In a preferred embodiment of the present invention, the molar ratio of silicon in the external electron donor compound to titanium in the catalyst component is 0.1-500:1, preferably 25-100:1.

[0117] Thirdly, the present invention provides the application of the catalyst component described in the first aspect or the catalyst described in the second aspect in olefin polymerization reactions.

[0118] In this invention, the olefin polymerization reaction includes homopolymerization or copolymerization.

[0119] Fourthly, the present invention provides a method for olefin polymerization, the method comprising: contacting an olefin with the catalyst component described in the first aspect or the catalyst described in the second aspect under olefin polymerization conditions to carry out a polymerization reaction.

[0120] In a preferred embodiment of the present invention, the olefin comprises an olefin as shown in the general formula CH2=CHR, wherein R is hydrogen, C1-C 12 Alkyl or C1-C 12 The aryl group, preferably C1-C 12 Alkyl, more preferably C1-C6 alkyl.

[0121] In a preferred embodiment of the present invention, the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene, preferably at least one of ethylene, propylene and 1-butene.

[0122] In this invention, the polymerization reaction employs conventional polymerization methods, such as slurry polymerization or gas-phase fluidized bed polymerization. Specifically, the polymerization reaction is carried out under the protection of an inert gas, in a liquid monomer or an inert solvent containing the monomer, or in the gas phase, or through a combined gas-liquid phase polymerization process.

[0123] In this invention, the polymerization reaction temperature is 0–150°C, preferably 60–90°C. The polymerization reaction pressure is atmospheric pressure or higher, preferably 0.01–10 MPa, more preferably 0.01–6 MPa, and even more preferably 0.1–4 MPa. All pressures in this invention refer to gauge pressure. During the polymerization process, hydrogen can be added to the reaction system as a polymer molecular weight regulator to adjust the polymer's molecular weight and melt index. Furthermore, in the polymerization reaction of olefins, the types and amounts of inert gases and solvents are well known to those skilled in the art and will not be described further here.

[0124] The olefin polymerization method of the present invention can be a homopolymerization of a single olefin or a copolymerization of multiple olefins.

[0125] In a preferred embodiment of the present invention, the method further includes: prepolymerizing the olefin by contacting the catalyst component or catalyst prior to the polymerization reaction. In this invention, the term "prepolymerization" refers to polymerization with a lower degree of conversion.

[0126] In a preferred embodiment of the present invention, the prepolymerization ratio is: relative to 1g of catalyst component, 0.1-1000g of olefin polymer is obtained, preferably 0.5-20g of olefin polymer is obtained.

[0127] In this invention, the olefin used for prepolymerization may be the same as or different from the olefin used for polymerization. Preferably, the olefin used for prepolymerization is selected from ethylene or propylene.

[0128] In a preferred embodiment of the present invention, ethylene or propylene is prepolymerized with an α-olefin; preferably, the amount of the α-olefin is 0.1-20 mol% of the amount of ethylene or propylene.

[0129] Preferably, the conversion degree of the catalyst component participating in the prepolymerization is 0.2-800 g polymer / gram catalyst component.

[0130] In a preferred embodiment of the present invention, the prepolymerization is carried out in a liquid or gas phase at a temperature of -40 to 80°C, preferably -20 to 50°C, and at a pressure of 0.01 to 10 MPa, preferably 0.01 to 6 MPa.

[0131] In this invention, the prepolymerization can be performed online as a step in the olefin polymerization method, or it can be performed independently in a batch operation, preferably independently in a batch operation.

[0132] In a preferred embodiment of the present invention, the prepolymerization is carried out independently in a batch operation, and is a polymer prepared in an amount of 0.5–20 g / g of solid catalyst component.

[0133] The following detailed description of preferred embodiments of the present invention illustrates the principles of the invention and is not intended to limit the scope of the invention.

[0134] Test methods

[0135] 1) Polymer isotactic index: The isotactic index is determined by heptane extraction. 2g of dried 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 2 (g) is the isotactic index.

[0136] 2) Melt index (MI) of the polymer: determined according to GB / T 3682-2000; measurement temperature 230℃, load 2.16kg pressure.

[0137] Preparation Example 1

[0138] Preparation of dimethyl 2,2'-(1,3-dioxolane-2,2-diyl)diacetate (ID-1)

[0139] (1) Take 30g of dimethyl 3-carbonyl-glutarate, 29mL of ethylene glycol and 1.6g of p-toluenesulfonic acid and disperse them in 200mL of toluene to carry out the cyclization reaction. After connecting the Dean-Stark apparatus, heat and reflux for 12h to obtain the reaction mixture.

[0140] (2) Cool the reaction mixture obtained from the cyclization reaction to room temperature, add 100 mL of saturated sodium bicarbonate solution to wash and collect the aqueous phase. Repeat the washing and collection of the aqueous phase until the washed organic phase is neutral. Add 50 mL of ethyl acetate to the obtained aqueous phase for extraction, and combine the extracted organic phase with the organic phase obtained from the previous washing. Then add 100 mL of saturated brine to wash the organic phase, and dry the organic phase with anhydrous sodium sulfate. Then filter the organic phase and remove the solvent by rotary evaporation to obtain the product 2,2'-(1,3-dioxolane-2,2-diyl)diacetic acid dimethyl ester (ID-1).

[0141]

[0142] Preparation Example 2

[0143] Preparation of diethyl 2,2'-(1,3-dioxolane-2,2-diyl)diacetate (ID-2)

[0144] The preparation method is the same as ID-1, except that 30g of dimethyl 3-carbonyl-glutarate is replaced with 35g of diethyl 3-carbonyl-glutarate.

[0145]

[0146] Preparation Example 3

[0147] Preparation of diethyl 2,2'-(1,3-dioxane-2,2-diyl)diacetate (ID-3)

[0148] The preparation method is the same as ID-1, except that 30g of dimethyl 3-carbonyl-glutarate is replaced with 35g of diethyl 3-carbonyl-glutarate, and 29mL of ethylene glycol is replaced with 38mL of 1,3-propanediol.

[0149]

[0150] Preparation Example 4

[0151] Preparation of dimethyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate (ID-4)

[0152] (1) Dissolve 60g of 3-carbonyl-3-carbonyl-glutarate in 600mL of tetrahydrofuran, add 120g of potassium carbonate, heat the resulting mixture to 45°C, and then slowly add 98.2g of iodomethane under stirring to carry out the reaction (the reaction temperature is about 55°C). Keep the reaction temperature below 60°C throughout the process. After reacting for 1 hour, cool the reaction solution to room temperature, filter and collect the filtrate. Wash the filter cake with 200mL of tetrahydrofuran and filter. Combine the two collected filtrates and remove the solvent by vacuum evaporation to obtain the product 2,4-dimethyl-3-carbonyl-3-glutarate.

[0153] (2) Take 30g of 2,4-dimethyl-3-carbonyl-glutaric acid dimethyl ester, 29mL of ethylene glycol and 1.6g of p-toluenesulfonic acid and disperse them in 200mL of toluene. After connecting the Dean-Stark apparatus, heat and reflux for 12h to obtain the reaction mixture.

[0154] (3) Cool the reaction mixture obtained from the cyclization reaction to room temperature, add 100 mL of saturated sodium bicarbonate solution to wash and collect the aqueous phase, repeat the washing and collection of the aqueous phase until the organic phase is neutral. Add 50 mL of ethyl acetate to the obtained aqueous phase for extraction, and combine the extracted organic phase with the organic phase obtained from the previous washing; then add 100 mL of saturated brine to wash the organic phase, and dry the organic phase with anhydrous sodium sulfate. Then filter the organic phase, remove the solvent by rotary evaporation, and obtain the product 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate dimethyl ester (ID-4).

[0155]

[0156] Preparation Example 5

[0157] Preparation of diethyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate (ID-5)

[0158] (1) Dissolve 70g of 3-carbonyl-3-carbonyl-glutarate in 600mL of tetrahydrofuran, add 120g of potassium carbonate, heat the resulting mixture to 45℃, and then slowly add 98.2g of iodomethane under stirring to carry out the reaction (the reaction temperature is about 55℃). Keep the reaction temperature below 60℃ throughout the process. After reacting for 1h, cool the reaction solution to room temperature, filter and collect the filtrate. Wash the filter cake with 200mL of tetrahydrofuran and filter. Combine the two collected filtrates and remove the solvent under vacuum to obtain the product 2,4-dimethyl-3-carbonyl-3-glutarate diethyl ester.

[0159] (2) Take 30g of diethyl 2,4-dimethyl-3-carbonyl-glutarate, 29mL of ethylene glycol, and 1.6g of p-toluenesulfonic acid and disperse them in 200mL of toluene. After connecting the Dean-Stark apparatus, heat and reflux for 12h to obtain the reaction mixture.

[0160] (3) Cool the reaction mixture obtained from the cyclization reaction to room temperature, add 100 mL of saturated sodium bicarbonate solution to wash and collect the aqueous phase, repeat the washing and collection of the aqueous phase until the organic phase is neutral. Add 50 mL of ethyl acetate to the obtained aqueous phase for extraction, and combine the extracted organic phase with the organic phase obtained from the previous washing; then add 100 mL of saturated brine to wash the organic phase, and dry the organic phase with anhydrous sodium sulfate. Then filter the organic phase, remove the solvent by rotary evaporation, and obtain the product 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate diethyl ester (ID-5).

[0161]

[0162] Examples 1-6

[0163] Step (1) Preparation of catalyst components

[0164] Nitrogen gas was introduced into the reactor to create a nitrogen atmosphere. Magnesium chloride 4.8 g, toluene 95 mL, epichlorohydrin 4 mL, and tributyl phosphate (TBP) 12.5 mL were added sequentially. The mixture was heated to 50 °C with stirring and maintained for 2.5 h.

[0165] After the solid has completely dissolved, add 1.4 g of phthalic anhydride, cool the solution to -25°C, add 56 mL of TiCl4 dropwise over 1 hour, maintain this temperature for 1 hour, and then slowly raise the temperature to 80°C. During the heating process, the solid gradually precipitates out.

[0166] Then, 6 mmol of the internal electron donor compound from Table 1 was added, and the mixture was kept at 80 °C for 1 h. After hot filtration, the resulting solid precipitate was washed twice with 150 mL of toluene. Then, 60 mL of toluene and 40 mL of TiCl4 were added to the washed solid precipitate, the temperature was raised to 110 °C, and the mixture was kept at 2 h before filtration. Then, 60 mL of toluene and 40 mL of TiCl4 were added to the resulting solid precipitate, the temperature was raised to 110 °C, and the mixture was kept at 2 h before filtration. Then, 70 mL of toluene was added to the resulting solid precipitate, and the mixture was washed at 110 °C. The washing was repeated three times, with each washing time being 10 min. Then, 60 mL of hexane was added to the washed solid precipitate, and the mixture was washed at room temperature. The washing was repeated twice, and then the mixture was dried under vacuum to obtain the solid catalyst component.

[0167] Step (2) Propylene polymerization experiment

[0168] In a 5L stainless steel reactor, after sufficient replacement with gaseous propylene, 2.5 mmol of AlEt3 (triethylaluminum) and 0.1 mmol of methylcyclohexyldimethoxysilane (CHMDMS) were added to make Al:Si (mol) = 25:1. Then, 9 mg of the solid catalyst component prepared in step (1) and 1.2L of hydrogen were added, and 2.3L of liquid propylene was introduced. The temperature was raised to 70℃ for polymerization reaction and maintained at this temperature for 1h to obtain PP resin.

[0169] The melt index, isotactic index, and catalytic activity data of the prepared PP resin are shown in Table 1.

[0170] Example 7

[0171] The catalyst components were prepared and olefin polymerization was carried out in the same manner as in Example 1, except that in step (2) propylene polymerization experiment, 0.05 mmol methylcyclohexyldimethoxysilane was replaced with tetramethoxysilane.

[0172] Example 8

[0173] The catalyst components were prepared and olefin polymerization was carried out in the same manner as in Example 2. The difference was that in step (2) propylene polymerization experiment, after the gaseous propylene was fully replaced in a 5L stainless steel reactor, 32.5 mmol of AlEt and 0.012 mmol of methylcyclohexyldimethoxysilane (CHMDMS) were added to make Al:Si (mol) = 200:1. Then, 9 mg of the solid catalyst component prepared in step (1) and 1.2L of hydrogen were added, and 2.3L of liquid propylene was introduced. The temperature was raised to 70°C to carry out the polymerization reaction. This temperature was maintained for 1h to obtain PP resin.

[0174] The melt index, isotactic index, and catalytic activity data of the prepared PP resin are shown in Table 1.

[0175] Comparative Example 1

[0176] The catalyst component was prepared and propylene polymerization was carried out in the same manner as in Example 1, except that in step (1) of preparing the catalyst component, ID-1 was replaced with an equal amount of di-n-butyl phthalate (DNBP); thus, the catalyst component was obtained.

[0177] The melt index, isotactic index, and catalytic activity data of the prepared PP resin are shown in Table 1.

[0178] Comparative Example 2

[0179] The catalyst component was prepared and propylene polymerization was carried out in the same manner as in Example 1, except that in step (1) of preparing the catalyst component, DNBP was replaced with an equal amount of ID-1; thus, the catalyst component was obtained.

[0180] The melt index, isotactic index, and catalytic activity data of the prepared PP resin are shown in Table 1.

[0181] Comparative Example 3

[0182] The catalyst component was prepared and propylene polymerization was carried out in the same manner as in Example 5, except that in step (1) of preparing the catalyst component, DNBP was replaced with an equal amount of ID-4; thus, the catalyst component was obtained.

[0183] The melt index, isotactic index, and catalytic activity data of the prepared PP resin are shown in Table 1.

[0184] Comparative Example 4

[0185] The catalyst component was prepared and propylene polymerization was carried out in the same manner as in Example 1, except that in step (1) of preparing the catalyst component, the molar ratio of ID-1 to DNBP in 6 mmol of internal electron-donating compound was 1:110; thus, the catalyst component was obtained.

[0186] The melt index, isotactic index, and catalytic activity data of the prepared PP resin are shown in Table 1.

[0187] Comparative Example 5

[0188] The catalyst component was prepared and olefin polymerization was carried out in the same manner as in Example 1, except that ID-1 was replaced with ethyl benzoate (EB) in step (1) of the preparation of the catalyst component; thus, the catalyst component was obtained.

[0189] The melt index, isotactic index, and catalytic activity data of the prepared PP resin are shown in Table 1.

[0190] Comparative Example 6

[0191] The catalyst component was prepared according to the method of Example 1 and an olefin polymerization reaction was carried out. The difference was that in step (1) of the preparation of the catalyst component, DNBP was replaced with an equal amount of ethyl benzoate.

[0192] The melt index, isotactic index, and catalytic activity data of the prepared PP resin are shown in Table 1.

[0193] Table 1

[0194]

[0195] As shown in Table 1, the catalyst components prepared using the technical solution of the present invention not only have high hydrogen sensitivity for olefin polymerization and the resulting olefin polymer has a high melt index, reaching more than 5.3 g / 10 min, which is beneficial for subsequent processing and product development; moreover, the catalyst components and catalyst of the present invention have high catalytic activity (reaching more than 25 kg PP / gcat), and the obtained polymerization product also has a high isotactic index (reaching more than 96.6%).

[0196] Compared to Example 7, which uses a combination of methylcyclohexyldimethoxysilane and tetramethoxysilane as external electron donors, Example 1 of this invention uses methylcyclohexyldimethoxysilane as an external electron donor. The catalyst prepared for olefin polymerization has higher polymerization activity (up to 30.5 kg PP / gcat), and the resulting olefin polymer has a higher isotactic index (up to 97.6%).

[0197] Compared to Example 7, where the catalyst has an Al:Si (mol) ratio of 200:1, the catalyst prepared in Example 2 of this invention has an Al:Si (mol) ratio of 25:1. The olefin polymer obtained by this catalyst in olefin polymerization has a higher isotactic index (up to 97.1%).

[0198] Compared to Comparative Example 1, which uses DNBP alone as an internal electron donor, the catalyst component prepared by combining ID-1 and DNBP as an internal electron donor in Example 1 exhibits higher hydrogen regulation sensitivity and can effectively improve the melt index of olefin polymers.

[0199] Compared to Comparative Example 2, which uses ID-1 alone as an internal electron donor, Example 1 uses a combination of ID-1 and DNBP as internal electron donors to prepare a catalyst component for olefin polymerization, which not only has higher polymerization activity but also improves the isotactic index of the olefin polymer.

[0200] Compared to Comparative Example 3, which used ID-4 alone as an internal electron donor, Example 5 used a combination of ID-4 and DNBP as internal electron donors to prepare a catalyst component for olefin polymerization, which had higher polymerization activity and isotactic index.

[0201] Compared to Comparative Example 4, where the molar ratio of ID-1 to DNBP is 1:110, the catalyst component prepared in Example 1 with a molar ratio of ID-1 to DNBP of 1:3 exhibits higher hydrogen sensitivity in olefin polymerization and can effectively improve the melt index of olefin polymers.

[0202] Compared to Comparative Example 5, which uses a combination of EB and DNBP as internal electron donors, Example 1, which uses a combination of ID-1 and DNBP as internal electron donors to prepare a catalyst component for olefin polymerization, has higher hydrogen regulation sensitivity and can effectively improve the melt index of olefin polymers.

[0203] Compared to Comparative Example 6, which uses a combination of ID-1 and EB as internal electron donors, Example 1 uses a combination of ID-1 and DNBP as internal electron donors to prepare a catalyst component for olefin polymerization, which not only has higher polymerization activity but also improves the isotactic index of the olefin polymer.

[0204] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A catalyst component for olefin polymerization, characterized in that, The catalyst components include magnesium, titanium, halogens and internal electron donor compounds, wherein the internal electron donor compounds include a first internal electron donor compound represented by general formula (I) and a second internal electron donor compound represented by general formula (II); The molar ratio of the first internal electron donor compound to the second internal electron donor compound is 1:0.01-100; In general formula (I), R1-R4 are each independently selected from hydrogen, C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl, C3-C 12 Cyclic hydrocarbon group, C2-C 12 alkenyl, C2-C 12 alkynyl group, C6-C 20 Aryl, C7-C 20 Hydrocarbon aryl, C7-C 20 Aromatic group, C6-C 20 heteroaryl, C4-C 20 At least one of heterocyclic groups and halogens; for R1-R4, the C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl, C3-C 12 Cyclic hydrocarbon group, C2-C 12 alkenyl, C2-C 12 alkynyl group, C6-C 20 Hydrocarbon aryl, C6-C 20 Aromatic group, C6-C 20 heteroaryl and C4-C 20 The hydrogen atom on the heterocyclic group may optionally be substituted with a substituent; R5 and R6 are each independently selected from hydrogen, C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl, C3-C 12 Cyclic hydrocarbon group, C2-C 12 alkenyl, C2-C 12 alkynyl group, C6-C 20 Aryl, C7-C 20 Hydrocarbon aryl, C7-C 20 Aromatic group, C6-C 20 heteroaryl, C4-C 20 At least one of heterocyclic groups and halogens; for R5 and R6, the C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl, C3-C 12 Cyclic hydrocarbon group, C2-C 12 alkenyl, C2-C 12 alkynyl group, C6-C 20 Hydrocarbon aryl, C6-C 20 Aromatic group, C6-C 20 heteroaryl and C4-C 20 The hydrogen atom on the heterocyclic group may optionally be substituted with a substituent; R7 and R8 are each independently selected from C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C3-C 12 Cyclic hydrocarbon group, C2-C 10 alkenyl, C2-C 10 alkynyl group, C6-C 20 Aryl, C7-C 20 Hydrocarbon aryl, C7-C 20 Aromatic group, C6-C 20 heteroaryl and C4-C 15 At least one of the heterocyclic groups; for R7 and R8, the C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C3-C 12 Cyclic hydrocarbon group, C2-C 10 alkenyl, C2-C 10 alkynyl group, C6-C 20 Hydrocarbon aryl, C6-C 20 Aromatic group, C6-C 20 heteroaryl and C4-C 15 The hydrogen atom on the heterocyclic group may optionally be substituted with a substituent; n is an integer between 0 and 4; In general formula (II), R9 is selected from C2-C8 straight-chain alkyl groups, C3-C6 alkyl groups, and C4-C6 alkyl groups. 10 Branched alkyl, C5-C 10 Cyclic hydrocarbon group, C6-C 15 Aryl, C7-C 15 Hydrocarbon aryl and C7-C 15 At least one of the aromatic groups; R 10 -R 13 Each element is independently selected from hydrogen, halogens, C1-C6 straight-chain alkyl groups, and C3-C4 alkyl groups. 10 Branched alkyl, C5-C 10 Cyclic hydrocarbon group, C6-C 20 Aryl, C7-C 20 Hydrocarbon aryl and C7-C 20 At least one of the aromatic groups; for R 10 -R 13 The C1-C6 straight-chain alkyl group, C3-C 10 Branched alkyl, C5-C 10 Cyclic hydrocarbon group, C6-C 20 Aryl, C7-C 20 Hydrocarbon aryl and C7-C 20 The hydrogen atom on the aromatic group can be optionally substituted with a substituent; R1-R4, R5-R6, R7-R8 and R 10 -R 13 In this context, each substituent is independently selected from at least one of -OH, -NH2, C1-C6 alkyl-substituted amino, -CHO, -COOH, halogen, C1-C6 alkyl, and C1-C6 alkoxy.

2. The catalyst component according to claim 1, characterized in that, R1-R4 are each independently selected from C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C5-C 10 Cyclic hydrocarbon group, C2-C 10 alkenyl, C2-C 10 alkynyl group, C6-C 18 Aryl, C7-C 18 Hydrocarbon aryl, C7-C 18 Aromatic group, C6-C 18 heteroaryl and C4-C 18 At least one of the heterocyclic groups; preferably, R1-R4 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloheptyl, cyclooctyl, phenyl, naphthyl, 4-methyl The alkyl phenyl, 4-ethylphenyl, benzyl, phenethyl, phenyl n-propyl, phenyl n-butyl, phenyl tert-butyl, phenyl isopropyl, phenyl n-pentyl, and phenyl n-butyl; more preferably, R1-R4 are each independently selected from at least one of C1-C4 straight-chain alkyl, C3-C4 branched-chain alkyl, C5-C8 cyclic hydrocarbon, C2-C5 alkenyl, C6-C9 aryl, C7-C9 aryl, C7-C9 aromatic hydrocarbon, and C6-C9 heteroaryl. And / or, R5 and R6 are each independently selected from C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl, C5-C 10 Cyclic hydrocarbon group, C2-C 10 alkenyl, C2-C 10 alkynyl group, C6-C 18 Aryl, C7-C 18 Hydrocarbon aryl, C7-C 18 Aromatic group, C6-C 18 heteroaryl and C4-C 18 At least one of the heterocyclic groups; R5 and R6 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloheptyl, cyclooctyl, phenyl, naphthyl, 4-methylbenzene R5 is selected from at least one of the following: 4-ethylphenyl, benzyl, phenethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-tert-butyl, phenyl isopropyl, phenyl-n-pentyl, and phenyl-n-butyl; more preferably, R5 and R6 are each independently selected from at least one of the following: C1-C4 straight-chain alkyl, C3-C4 branched-chain alkyl, C5-C8 cycloalkyl, C2-C5 alkenyl, C6-C9 aryl, C7-C9 alkylaryl, C7-C9 aryl, and C6-C9 heteroaryl. And / or, R7 and R8 are each independently selected from C1-C8 straight-chain alkyl, C3-C8 branched alkyl, C4-C8 branched alkyl, and C5-C8 branched alkyl. 10 Cyclic hydrocarbon group, C2-C8 alkenyl group, C2-C8 alkynyl group, C6-C 15 Aryl, C7-C 15 Hydrocarbon aryl, C7-C 15 Aromatic group, C6-C 15 heteroaryl and C4-C 12 At least one of the heterocyclic groups; preferably, R7 and R8 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloheptyl, cyclooctyl, phenyl, naphthyl, 4- At least one of methylphenyl, 4-ethylphenyl, benzyl, phenethyl, phenyl n-propyl, phenyl n-butyl, phenyl tert-butyl, phenyl isopropyl, phenyl n-pentyl, and phenyl n-butyl; more preferably, R7 and R8 are each independently selected from C1-C4 straight-chain alkyl, C3-C4 branched-chain alkyl, C5-C8 cycloalkyl, C2-C5 alkenyl, C6-C9 aryl, C7-C9 aryl, C7-C9 aromatic, C6-C9 heteroaryl, and C4-C 10 At least one of the heterocyclic groups; And / or, R 10 -R 13 Each is independently selected from C1-C6 straight-chain alkyl or C3-C8 branched alkyl.

3. The catalyst component according to claim 1 or 2, characterized in that, The first internal electron-donating compound is selected from dimethyl 2,2'-(1,3-dioxolane-2,2-diyl)diacetate, dimethyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate, dimethyl 2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate, diethyl 2,2'-(1,3-dioxolane-2,2-diyl)diacetate, diethyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate, diethyl 2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate, di-n-propyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate, and di-n-propyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate. 2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate di-n-propyl ester, 2,2'-(1,3-dioxolane-2,2-diyl)diacetic acid diisopropyl ester, 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate diisopropyl ester, 2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate diisopropyl ester, 2,2' Di-(1,3-dioxolane-2,2-diyl)diacetic acid dibutyl ester, 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate dibutyl ester, 2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate dibutyl ester, 2,2'-(1,3-dioxolane-2,2-diyl)diacetic acid diisobutyl ester, 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate diisobutyl ester, 2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate diisobutyl ester, 2,2'-(1,3-dioxolane-2,2-diyl)diacetic acid ditert-butyl ester, 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate ... Di-tert-butyl dibutyl dibutyrate (2,2-diyl)dibutyrate, diphenyl diacetate (2,2'-(1,3-dioxolane-2,2-diyl)diacetic acid, diphenyl dipropionate (2,2'-(1,3-dioxolane-2,2-diyl)dipropionate, diphenyl dibutyl dibutyrate (2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate, diphenyl dibutyl dibutyrate (2,2'-(1,3-dioxolane-2,2-diyl)diacetic acid ...), diphenyl dipropionate (2,2'-(1,3-dioxolane-2,2-diyl)diacetic acid), diphenyl dibutyl dibutyrate (2,2'-(1,3-di Dimethyl 2,2'-(1,3-dioxolane-2,2-diyl)dipropionate, dimethyl 2,2'-(1,3-dioxolane-2,2-diyl)dibutyrate, dimethyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetate, dimethyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate, dimethyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, diethyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetate, dimethyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetate ...Diethyl 2,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate, diethyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, di-n-propyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetate, di-n-propyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate, di-n-propyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, diisopropyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetate, diisopropyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropion ... Diisopropyl dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetic acid di-n-butyl ester, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate di-n-butyl ester, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate di-n-butyl ester, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetic acid diisobutyl ester, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate ... Diisobutyl butyrate, di-tert-butyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetate, di-tert-butyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate, di-tert-butyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate, diphenyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetate, diphenyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate, diphenyl 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate ... Di(4,5-dimethyl-1,3-dioxolane-2,2-diyl)diacetate di-p-methylphenyl ester, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dipropionate di-p-methylphenyl ester, 2,2'-(4,5-dimethyl-1,3-dioxolane-2,2-diyl)dibutyrate di-p-methyl ester, 2,2'-(1,3-dioxane-2,2-diyl)diacetate dimethyl ester, 2,2'-(1,3-dioxane-2,2-diyl)dipropionate dimethyl ester, 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate dimethyl ester, 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate dimethyl ester, 2,2'-(1,3-dioxane-2,2-diyl)diacetate diethyl ester, 2,2'-(1,3-dioxane-2,2-diyl)dipropionate diethyl ester, 2,Diethyl 2'-(1,3-dioxane-2,2-diyl)dibutyrate, di-n-propyl 2,2'-(1,3-dioxane-2,2-diyl)diacetate, di-n-propyl 2,2'-(1,3-dioxane-2,2-diyl)dipropionate, di-n-propyl 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate, di-n-propyl 2,2'-(1,3-dioxane-2,2-diyl)diacetate, diisopropyl 2,2'-(1,3-dioxane-2,2-diyl)diacetate, di-n- ... Diisopropyl dipropionate, 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate, di-n-butyl diacetate, 2,2'-(1,3-dioxane-2,2-diyl)dipropionate, di-n-butyl dibutyrate, 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate, di-n-butyl dibutyrate, 2,2'-(1,3-dioxane-2,2-diyl)diacetate, diisobutyl diacetate, 2,2'-( Diisobutyl 1,3-dioxane-2,2-diyl)dipropionate, diisobutyl 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate, di-tert-butyl 2,2'-(1,3-dioxane-2,2-diyl)diacetate, di-tert-butyl 2,2'-(1,3-dioxane-2,2-diyl)dipropionate, di-tert-butyl 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate, di-tert-butyl 2,2'-(1,3-dioxane-2,2-diyl)dipropionate ... At least one of the following: diphenyl acetate, diphenyl 2,2'-(1,3-dioxane-2,2-diyl)dipropionate, diphenyl 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate, di-p-methylphenyl 2,2'-(1,3-dioxane-2,2-diyl)diacetate, di-p-methylphenyl 2,2'-(1,3-dioxane-2,2-diyl)dipropionate, and di-p-methylphenyl 2,2'-(1,3-dioxane-2,2-diyl)dibutyrate; And / or, the second internal electron-donating compound is selected from dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, di-n-hexyl phthalate, diisohexyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, dibenzyl phthalate, tetramethyl dimethyl phthalate, tetramethyl diethyl phthalate, tetramethyl di-n-propyl phthalate, tetramethyl diisopropyl phthalate, tetramethyl di-n-butyl phthalate, tetramethyl diisobutyl phthalate, tetramethyl di-n-pentyl phthalate, tetramethyl di-n-butyl ... At least one of the following: diisoamyl methyl phthalate, di-n-hexyl tetramethyl phthalate, diisohexyl tetramethyl phthalate, di-n-octyl tetramethyl phthalate, diisooctyl tetramethyl phthalate, dibenzyl tetramethyl phthalate, dimethyl tetrabromophthalate, diethyl tetrabromophthalate, di-n-propyl tetrabromophthalate, diisopropyl tetrabromophthalate, di-n-butyl tetrabromophthalate, diisobutyl tetrabromophthalate, di-n-pentyl tetrabromophthalate, diisoamyl tetrabromophthalate, di-n-hexyl tetrabromophthalate, di-n-octyl tetrabromophthalate, diisooctyl tetrabromophthalate, and dibenzyl tetrabromophthalate.

4. The catalyst component according to any one of claims 1-3, characterized in that, The molar ratio of the first internal electron donor compound to the second internal electron donor compound is 1:0.02-50, preferably 1:0.05-20, and more preferably 1:0.2-6.

5. The catalyst component according to any one of claims 1-4, characterized in that, The magnesium in the catalyst component is derived from magnesium compounds; Preferably, the magnesium compound includes at least one of magnesium dihalide, magnesium alkoxy, alkyl magnesium, magnesium dihalide hydrate, magnesium dihalide alcohol, derivatives of magnesium dihalide in which the halogen atom is replaced by an alkoxy group, and derivatives of magnesium dihalide in which the halogen atom is replaced by a haloalkoxy group. More preferably, the alkoxy group in the magnesium dihalide derivative in which the halogen atom is replaced by an alkoxy group is C1-C. 10 alkoxy groups; Preferably, the magnesium compound includes at least one of magnesium dichloride, magnesium dibromide, magnesium diiodide, an alcoholysis of magnesium dichloride, an alcoholysis of magnesium dibromide, and an alcoholysis of magnesium diiodide; And / or, the titanium in the catalyst component is derived from titanium compounds; Preferably, the titanium compound comprises the general formula TiX. m (OR 1 ) 4-m The compound, the TiX m (OR 1 ) 4-m R in 1 For C1-C 20 The hydrocarbon group, where X is a halogen, 1≤m≤4; More preferably, R 1 For C1-C 20 Alkyl groups, preferably C1-C 10 Alkyl groups, more preferably C1-C6 alkyl groups; 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 trichloroethoxy.

6. The catalyst component according to any one of claims 1-5, characterized in that, The molar ratio of the magnesium, titanium, halogen and the internal electron donor compound is 1:0.5-150:0.1-800:0.02-0.4, more preferably 1:0.5-50:1-200:0.05-0.

2.

7. A catalyst for olefin polymerization, characterized in that, The catalyst comprises the catalyst component according to any one of claims 1-6, an organoaluminum compound, and optionally an external electron donor compound; The external electron donor compound includes an organosilicon compound.

8. The catalyst according to claim 7, characterized in that, The general formula of the organosilicon compound is R 3 k Si(OR 4 ) 4-k 0≤k≤3, preferably 1≤k≤3; R 3 Selected from halogens, hydrogen, C1-C 20 Alkyl, C3-C 20 Cyclic hydrocarbon group, C6-C 20 Aryl, C1-C 20 At least one of alkyl halogens and amino groups; R 4 Selected from C1-C 20 Alkyl, C3-C 20 Cyclic hydrocarbon group, C6-C 20 Aryl, C1-C 20 At least one of alkyl halogens and amino groups; Preferably, the organosilicon compound is selected from at least one of the following: trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, n-propyltriethoxysilane, isopropyltriethoxysilane, n-butyltriethoxysilane, isobutyltriethoxysilane, phenyltriethoxysilane, cyclohexylmethyldimethoxysilane, and methyltert-butyldimethoxysilane. And / or, the organoaluminum compound is an alkylaluminum compound; Preferably, the alkylaluminum compound has the general formula AlR 2 j X 3-j R 2 It is hydrogen or C1-C 20 Hydrocarbon group, where X is a halogen, 1≤j≤3; More preferably, R 2 It is a C1-C8 alkyl group; Preferably, the alkylaluminum compound is selected from at least one of triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, triisooctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloro, diisobutylaluminum monochloro, sesquiethylaluminum chloride, and diethylaluminum dichloro. And / or, the molar ratio of aluminum to titanium in the alkylaluminum compound is 5-5000:1, preferably 5-1000:1, more preferably 25-100:1; And / or, the molar ratio of silicon to titanium in the external electron donor compound is 0.1-500:1, preferably 25-100:

1.

9. The use of the catalyst component according to any one of claims 1-6 or the catalyst according to claim 7 or 8 in olefin polymerization reactions.

10. A method for olefin polymerization, characterized in that, The method includes: contacting an olefin with a catalyst component according to any one of claims 1-6 or a catalyst according to claim 7 or 8 under olefin polymerization conditions to carry out a polymerization reaction; Preferably, the method further includes: prepolymerizing the olefin by contacting the catalyst component or catalyst prior to the polymerization reaction; Preferably, the olefin comprises an olefin as shown in the general formula CH2=CHR, wherein R is hydrogen, C1-C2, C2 ... 12 Alkyl or C1-C 12 aryl; More preferably, R is a C1-C6 alkyl group; More preferably, the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 1-hexene; And / or, the conditions for the polymerization reaction include: a temperature of 0–150°C, preferably 60–90°C; and a pressure of 0.01–10 MPa, preferably 0.01–6 MPa. And / or, the conditions for the prepolymerization reaction include: a temperature of -40 to 80°C, preferably -20 to 50°C; and a pressure of 0.01 to 10 MPa, preferably 0.01 to 6 MPa.

Images