CN112759676A - Solid catalyst component for preparing polyolefin, catalyst and application thereof - Google Patents

Solid catalyst component for preparing polyolefin, catalyst and application thereof Download PDF

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CN112759676A
CN112759676A CN201911002707.5A CN201911002707A CN112759676A CN 112759676 A CN112759676 A CN 112759676A CN 201911002707 A CN201911002707 A CN 201911002707A CN 112759676 A CN112759676 A CN 112759676A
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ester
acid
phenylimino
alkyl
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CN112759676B (en
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王军
马吉星
蔡晓霞
马晶
刘文蕊
何世雄
高明智
刘海涛
李昌秀
胡建军
许景琦
段瑞林
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a solid catalyst component for preparing polyolefin, a catalyst and application thereof. The solid catalyst component for preparing the polyolefin comprises magnesium, titanium, halogen and an internal electron donor, wherein the internal electron donor comprises an imine ester compound shown as a formula I and a glycol ester compound shown as a formula II. The compound internal electron donor compound can be used for obtaining a catalyst with excellent comprehensive performance, the hydrogen regulation sensitivity of the catalyst is good when the compound internal electron donor compound is used for propylene polymerization reaction, and the molecular weight distribution of the obtained polypropylene resin is wide.

Description

Solid catalyst component for preparing polyolefin, catalyst and application thereof
Technical Field
The invention relates to a solid catalyst component for preparing polyolefin, a catalyst and application thereof.
Background
For the conventional Ziegler-Natta catalyst, the polyolefin catalyst is continuously updated with the development of electron donor compounds in the catalyst, and the process technology of polypropylene is improved. Catalyst development from first/second generation of TiCl3The magnesium chloride from the alkyl aluminum system to the third generation is used as a carrier, TiCl4Adding TiCl taking monoester or aromatic dibasic acid ester as internal electron donor and silane as external electron donor as active center4·ED·MgCl2/AlR3The ED system, the catalytic activity of the catalyst for olefin polymerization and the high isotacticity of the obtained polypropylene are greatly improved. In the prior art, the catalyst system for propylene polymerization is mostly prepared from magnesium, titanium, halogen andan electron donor is taken as an essential component, wherein the electron donor compound is one of the indispensable components in the catalyst component. Currently, various electron donor compounds have been disclosed, such as mono-or polycarboxylic acid esters, anhydrides, ketones, mono-or polyethers, alcohols, amines, etc. and derivatives thereof, among which aromatic dicarboxylic acid esters (such as di-n-butyl phthalate or diisobutyl phthalate, etc., see US4784983) are more commonly used.
Recently, many novel internal electron donor compounds containing nitrogen atom structure have appeared, such as maleic amide internal electron donor compound (CN102268109) and hydrazide structure electron donor compounds (CN103539874 and CN103694385), diamide structure internal electron donor compound (US2017/0240667), diamine internal electron donor compound (CN1087918), imine internal electron donor compounds (CN105085733 and CN105085746), amino ester compounds (CN 101581049, CN 101891256 and CN101172965) and amide ester internal electron donor compound (US2012322962), but the obtained catalyst effect is not outstanding.
CN1436766A discloses a polyester compound which can be used as an internal electron donor component of an olefin polymerization catalyst, but the polyester compound has the defects of low hydrogen regulation sensitivity of the catalyst and narrow molecular weight distribution of the obtained polymer.
Disclosure of Invention
The inventor finds that a novel imine ester compound and a glycol ester compound are compounded to be used as an internal electron donor of an olefin polymerization catalytic system, so that a catalyst with excellent comprehensive performance can be obtained.
In a first aspect, the present invention provides a catalyst component for olefin polymerization, comprising magnesium, titanium, halogen and an internal electron donor, wherein the internal electron donor comprises an imido ester compound represented by formula I and a diol ester compound represented by formula II,
Figure BDA0002241820240000021
in the formula I, R1And R2The same or different, each independently selected from hydrogen, C with or without substituent1-C30Alkyl, C with or without substituents2-C30Alkenyl, C with or without substituents2-C30Alkynyl, C with or without substituents6-C30Aryl, C with or without substituents6-C30Heteroaryl, C with or without substituents4-C30A heterocyclic group of (A), a halogen atom, a hydroxyl group and C with or without a substituent1-C30Alkoxy, and R1And R2Not hydrogen at the same time; or R1And R2Linking to form a ring;
r is selected from C containing or not containing substituent1-C30Alkyl, C with or without substituents2-C30Alkenyl, C with or without substituents6-C30Aryl, C with or without substituents6-C30Heteroaryl, C with or without substituents4-C30A heterocyclic group of (A), a halogen atom, a hydroxyl group, C with or without a substituent1-C30Alkoxy, C with or without substituents1-C30Acyloxy groups and amino groups with or without substituents; r is selected from C containing or not containing substituent1-C30Alkyl, C with or without substituents2-C30Alkenyl, C with or without substituents2-C30Alkynyl, C with or without substituents6-C30Aryl, C with or without substituents6-C30Heteroaryl, C with or without substituents4-C30Heterocyclic group, halogen atom, hydroxyl group, C with or without substituent1-C30Alkoxy and amino with or without substituents;
a is C with or without substituents1-C30Alkylene or hetero atoms, preferably C with or without substituents1-C30Alkylene, C with or without substituents6-C30Arylene, C with or without substituents4-C30A heteroarylene group, or a combination thereof.
In the formula II, the reaction mixture is shown in the specification,x is C with or without substituents1-C30Alkylene or hetero atoms, preferably C with or without substituents1-C30Alkylene, C with or without substituents1-C30Alkenylene, C with or without substituents1-C30Alkynylene, C with or without substituents6-C30Arylene, C with or without substituents4-C30Heteroarylene, or a fused ring arylene with or without substituents; r1And R2Identical or different, each independently selected from C with or without substituents1-C30A hydrocarbon radical, preferably selected from C with or without substituents1-C30Alkyl, C with or without substituents2-C30Alkenyl, C with or without substituents6-C30Aryl, C with or without substituents6-C30Heteroaryl, C with or without substituents4-C30Or a condensed ring aromatic group with or without substituents.
The second aspect of the present invention also provides a catalyst for olefin polymerization, comprising:
1) the catalyst component according to the first aspect of the present invention,
2) an organoaluminum compound, preferably an alkylaluminum compound,
3) optionally, an external electron donor compound, preferably an organosilicon compound.
In a third aspect, the present invention also provides the use of the above solid catalyst component and/or the above catalyst in the polymerization of olefins.
In a fourth aspect, the present invention provides a process for the polymerization of olefins comprising polymerizing olefins in the presence of the solid catalyst component according to the above and/or the catalyst according to the above.
Detailed Description
In a first aspect, the present invention provides a catalyst component for olefin polymerization, comprising magnesium, titanium, halogen and an internal electron donor, wherein the internal electron donor comprises an imine ester compound represented by formula I and a glycol ester compound represented by formula II,
Figure BDA0002241820240000031
in the formula I, R1And R2The same or different, each independently selected from hydrogen, C with or without substituent1-C30Alkyl, C with or without substituents2-C30Alkenyl, C with or without substituents2-C30Alkynyl, C with or without substituents6-C30Aryl, C with or without substituents6-C30Heteroaryl, C with or without substituents4-C30A heterocyclic group of (A), a halogen atom, a hydroxyl group and C with or without a substituent1-C30Alkoxy, and R1And R2Not hydrogen at the same time; or R1And R2Linking to form a ring;
r is selected from C containing or not containing substituent1-C30Alkyl, C with or without substituents2-C30Alkenyl, C with or without substituents6-C30Aryl, C with or without substituents6-C30Heteroaryl, C with or without substituents4-C30A heterocyclic group of (A), a halogen atom, a hydroxyl group, C with or without a substituent1-C30Alkoxy, C with or without substituents1-C30Acyloxy groups and amino groups with or without substituents; r is selected from C containing or not containing substituent1-C30Alkyl, C with or without substituents2-C30Alkenyl, C with or without substituents2-C30Alkynyl, C with or without substituents6-C30Aryl, C with or without substituents6-C30Heteroaryl, C with or without substituents4-C30Heterocyclic group, halogen atom, hydroxyl group, C with or without substituent1-C30Alkoxy and amino with or without substituents;
a is C with or without substituents1-C30Alkylene or hetero atomsPreferably C with or without substituents1-C30Alkylene, C with or without substituents6-C30Arylene, C with or without substituents4-C30A heteroarylene group, or a combination thereof.
In the formula II, X is C with or without substituent1-C30Alkylene or hetero atoms, preferably C with or without substituents1-C30Alkylene, C with or without substituents1-C30Alkenylene, C with or without substituents1-C30Alkynylene, C with or without substituents6-C30Arylene, C with or without substituents4-C30Heteroarylene, or a fused ring arylene with or without substituents; r1And R2Identical or different, each independently selected from C with or without substituents1-C30A hydrocarbon radical, preferably selected from C with or without substituents1-C30Alkyl, C with or without substituents2-C30Alkenyl, C with or without substituents6-C30Aryl, C with or without substituents6-C30Heteroaryl, C with or without substituents4-C30Or a condensed ring aromatic group with or without substituents.
In the context of the present application, the term "substituent" refers to substituents common in the art, which may be selected from halogen, hydroxy, amino, C6-C20Aryl (including but not limited to phenyl, naphthyl, etc.), C7-C20Aralkyl (e.g., benzyl, phenethyl, etc.), C7-C20Alkylaryl (C)1-C6Alkyl-substituted phenyl), C1-C10Alkyl (including C)1-C6Alkyl, such as methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, etc.), C1-C20Alkoxy (including C)1-C6Alkoxy, e.g. methoxy, ethoxy, isopropoxy, n-propoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxyN-hexyloxy, etc.), etc. In the context of this application, halogen means fluorine, chlorine, bromine or iodine. In the context of the present application, the term "alkyl" includes straight chain alkyl, branched chain alkyl and cycloalkyl. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.
According to some embodiments of the invention, the substituent is selected from halogen, hydroxy, amino, C6-C20Aryl radical, C7-C20Aralkyl radical, C7-C20Alkylaryl group, C1-C10Alkyl and C1-C20Alkoxy, preferably selected from halogen, hydroxy, amino, phenyl, naphthyl, benzyl, phenethyl, C1-C6Alkyl-substituted phenyl, C1-C10Alkyl and C1-C20Alkoxy, more preferably selected from fluorine, chlorine, bromine, iodine, hydroxyl, amino, phenyl, naphthyl, benzyl, phenethyl, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, methoxy, ethoxy, isopropoxy, n-propoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, and n-hexoxy.
According to some embodiments of the invention, R1And R2Each independently selected from hydrogen, C with or without substituents1-C20Alkyl, C with or without substituents2-C20Alkenyl, C with or without substituents2-C30Alkynyl, C with or without substituents6-C20Aryl, C with or without substituents4-C20Heterocyclic group, halogen atom, hydroxyl group and C with or without substituent1-C20An alkoxy group.
According to some embodiments of the invention, R1And R2Each independently selected from hydrogen, C with or without substituents1-C10Alkyl, C with or without substituents2-C10Alkenyl, C with or without substituents6-C15Aryl, C with or without substituents4-C50A heterocyclic group of (A), a halogen atom, a hydroxyl group and C with or without a substituent1-C10An alkoxy group.
According to some embodiments, R1And R2Each independently selected from hydrogen, C with or without substituents1-C10Alkyl and C with or without substituents6-C15An aromatic group. According to some embodiments, R1And R2Is C with or without substituents1-C10Straight-chain alkyl, C with or without substituents3-C10Branched alkyl, C with or without substituents3-C10Cycloalkyl or substituted phenyl or unsubstituted phenyl. Preferably, said substituted phenyl, said substituted C1-C10Alkyl, substituted C3-C10Branched alkyl and substituted C3-C10The substituents on the cycloalkyl being selected from C1-C10Alkyl radical, C1-C10Alkoxy, halogen, hydroxy and amino.
According to some embodiments, R1And R2Each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, hydroxyalkyl, benzyl, phenyl, halophenyl, naphthyl, biphenyl, or a heterocyclic compound-containing group, etc.; the heterocyclic compound-containing group is preferably an azole-containing group, a pyridine-containing group, a pyrimidine-containing group, and a quinoline-containing group.
In some embodiments, R1Is hydrogen, R2Is C1-C10Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, etc.), phenyl, C1-C6Alkyl-substituted phenyl, hydroxy-substituted phenyl, halogen-substituted phenyl or C1-C6Phenyl substituted by at least two of alkyl, halogen and hydroxyl.
According to some embodiments, R is selected from C with or without substituents1-C10Alkyl and C with or without substituents6-C15Aromatic radical. According to some embodiments, R is C with or without substituents1-C10Straight-chain alkyl, C with or without substituents3-C10Branched alkyl, C with or without substituents3-C10Cycloalkyl or phenyl with or without substituents. Preferably, the substituents are selected from C1-C10Alkyl radical, C1-C10Alkoxy, halogen, hydroxy and amino.
According to some embodiments of the invention, A is C with or without substituents1-C20Alkylene, C with or without substituents6-C20Arylene, C with or without substituents4-C20A heteroarylene group, or a combination thereof.
According to some embodiments of the invention, A is C with or without substituents1-C10Alkylene, C with or without substituents6-C10Arylene, C with or without substituents4-C10A heteroarylene group, or a combination thereof.
According to some embodiments of the invention, A is C with or without substituents1-C8An alkylene group. According to some embodiments, a is unsubstituted C1-C8Alkylene (e.g. methylene, ethylene, propylene, butylene, pentylene, hexylene) or C1-C6Alkyl or C1-C6Alkoxy-substituted C1-C8An alkylene group.
According to some embodiments of the invention, A is- (CR)IRII)n-, wherein RI、RIIMay be the same or different and is selected from hydrogen, C with or without substituents1-C30Alkyl, C with or without substituents2-C30Alkenyl, C with or without substituents3-C30And C with or without substituents6-C30An aromatic group; n is 1-6; or said R isIAnd RIIThe links form a ring.
According to some embodiments, A is- (CR)IRII)n-, wherein RI、RIISame or different and selected from hydrogen, C with or without substituents1-C20Alkyl, C with or without substituents2-C20Alkenyl, C with or without substituents3-C10And C with or without substituents6-C20An aromatic group; n is 1,2,3,4,5 or 6.
According to some embodiments, A is- (CR)IRII)n-, wherein RI、RIISame or different and selected from hydrogen, C with or without substituents1-C10Alkyl, C with or without substituents2-C10Alkenyl, C with or without substituents3-C10Cycloalkane of (2) and C with or without substituents6-C10An aromatic group; n is 1,2,3,4,5 or 6.
According to some embodiments, A is- (CR)IRII)n-, wherein RI、RIISame or different and selected from hydrogen, C with or without substituents1-C10Alkyl, C with or without substituents2-C10Alkenyl, C with or without substituents3-C10Cycloalkane of (2) and C with or without substituents6-C10An aromatic group; n is 1,2,3,4,5 or 6.
According to some embodiments, A is- (CR)IRII)n-, wherein RI、RIISame or different and selected from hydrogen, C with or without substituents1-C8Alkyl, C with or without substituents2-C8Alkenyl, C with or without substituents3-C8Cycloalkane of (2) and C with or without substituents6-C10An aromatic group; n is 1,2,3,4,5 or 6.
According to some embodiments of the invention, a is a heteroatom selected from the group consisting of nitrogen, phosphorus and silicon atoms.
The imidate compound of formula I according to the present invention can be selected from, but is not limited to, the following compounds:
(2-phenyliminoethyl) benzoate, [2- (2-methyl) phenyliminoethyl ] benzoate, [2- (3-methyl) phenyliminoethyl ] benzoate, [2- (4-methyl) phenyliminoethyl ] benzoate, [2- (2-ethyl) phenyliminoethyl ] benzoate, [2- (3-ethyl) phenyliminoethyl ] benzoate, [2- (4-ethyl) phenyliminoethyl ] benzoate, [2- (2-propyl) phenyliminoethyl ] benzoate, [2- (3-propyl) phenyliminoethyl ] benzoate, [2- (2-butyl) phenyliminoethyl ] benzoate, [2- (3-butyl) phenyliminoethyl ] benzoate, and [2- (3-methoxy) phenyliminoethyl ] benzoate, Benzoic acid [2- (4-methoxy) phenyliminoethyl ester ], benzoic acid [2- (3-ethoxy) phenyliminoethyl ester ], benzoic acid [2- (4-ethoxy) phenyliminoethyl ester ], benzoic acid [2- (2-hydroxy) phenyliminoethyl ester ], benzoic acid [2- (2, 4-dimethyl) phenyliminoethyl ester ], [2- (2, 6-dimethyl) phenyliminoethyl ester ], benzoic acid [2- (2,4, 6-trimethyl) phenyliminoethyl ester ], benzoic acid [2- (2, 6-diisopropyl) phenyliminoethyl ester ], benzoic acid [2- (3, 5-di-tert-butyl) phenyliminoethyl ester ], benzoic acid [ 2-ethyliminoethyl ester ], benzoic acid [ 2-propyliminoethyl ester ], [ 2-butyliminoethyl benzoate ], [ 2-pentyliminoethyl benzoate ], [ 2-hexyliminoethyl benzoate ], 3-phenyliminopropyl benzoate, 3- (2-methyl) phenyliminopropyl benzoate, 3- (3-methyl) phenyliminopropyl benzoate, 3- (4-methyl) phenyliminopropyl benzoate, 3- (2-ethyl) phenyliminopropyl benzoate, 3- (3-ethyl) phenyliminopropyl benzoate, 3- (4-ethyl) phenyliminopropyl benzoate, 3- (2-propyl) phenyliminopropyl benzoate, 3- (3-propyl) phenyliminopropyl benzoate, 3- (2-butyl) phenyliminopropyl benzoate, Benzoic acid [3- (3-butyl) phenyliminopropyl ester ], benzoic acid [3- (4-butyl) phenyliminopropyl ester ], benzoic acid [3- (3-methoxy) phenyliminopropyl ester ], benzoic acid [3- (4-methoxy) phenyliminopropyl ester ], benzoic acid [3- (3-ethoxy) phenyliminopropyl ester ], benzoic acid [3- (4-ethoxy) phenyliminopropyl ester ], benzoic acid [3- (2-hydroxy) phenyliminopropyl ester ], benzoic acid [3- (3-hydroxy) phenyliminopropyl ester ], benzoic acid [3- (4-hydroxy) phenyliminopropyl ester ], benzoic acid [3- (2, 4-dimethyl) phenyliminopropyl ester ], benzoic acid [3- (2,4, 6-trimethyl) phenylimidopropyl ester, 3- (3, 5-di-tert-butyl) phenylimidopropyl benzoate, 3- (2, 6-dimethyl) phenylimidopropyl benzoate, 3- (2, 6-diisopropyl) phenylimidopropyl benzoate, 3-ethyliminopropyl benzoate, 3-propylimidopropyl benzoate, 3-butyliminopropyl benzoate, 3-pentyliminopropyl benzoate, 3-hexyliminopropyl benzoate, 4-phenylimido-2-pentyl benzoate, 4- (2-methyl) phenylimido-2-pentyl benzoate, 4- (3-methyl) phenylimido-2-pentyl benzoate, Benzoic acid [4- (4-methyl) phenylimino-2-pentyl ester ], benzoic acid [4- (2-ethyl) phenylimino-2-pentyl ester ], benzoic acid [4- (3-ethyl) phenylimino-2-pentyl ester ], benzoic acid [4- (4-ethyl) phenylimino-2-pentyl ester ], benzoic acid [4- (2-propyl) phenylimino-2-pentyl ester ], benzoic acid [4- (3-propyl) phenylimino-2-pentyl ester ], benzoic acid [4- (2-butyl) phenylimino-2-pentyl ester ], benzoic acid [4- (4-butyl) phenylimino-2-pentyl ester ], benzoic acid [4- (3-methoxy) phenylimino-2-pentyl ester ], (benzoic acid [4- (3-methoxy) phenylimino-2-pentyl ester ], Benzoic acid [4- (4-methoxy) phenylimino-2-pentyl ester ], benzoic acid [4- (3-ethoxy) phenylimino-2-pentyl ester ], benzoic acid [4- (4-ethoxy) phenylimino-2-pentyl ester ], benzoic acid [4- (2, 4-dimethyl) phenylimino-2-pentyl ester ], benzoic acid [4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], benzoic acid [4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], benzoic acid [4- (2, 6-dimethyl) phenylimino-2-pentyl ester ], benzoic acid [4- (2, 6-diisopropyl) phenylimino-2-pentyl ester ], [4- (2, 6-diisopropyl) phenylimino-2-pentyl ester ], Benzoic acid [ 4-ethylimino-2-propyl ester ], benzoic acid [ 4-propylimino-2-pentyl ester ], benzoic acid [ 4-butylimino-2-pentyl ester ], benzoic acid [ 4-pentylimino-2-pentyl ester ], benzoic acid [ 4-hexylimino-2-pentyl ester ], benzoic acid [ 4-heptylimino-2-pentyl ester ], benzoic acid [ 4-octylimino-2-pentyl ester ], benzoic acid (3-methyl-4-phenylimino-2-pentyl ester), benzoic acid [ 3-ethyl-4- (2-methyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (3-methyl) phenylimino-2-pentyl ester ], [ 3-methyl-4- (3-methyl) phenylimino-2-pentyl ester ], Benzoic acid [ 3-ethyl-4- (4-methyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (2-ethyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (3-ethyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (4-ethyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-propyl-4- (2-propyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-butyl-4- (3-propyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-ethyl-4- (2-butyl) phenylimino-2-pentyl ester ], [ 3-ethyl-4- (2-butyl) phenylimino-2-pentyl ester ], Benzoic acid [ 3-ethyl-4- (4-butyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (3-methoxy) phenylimino-2-pentyl ester ], benzoic acid [ 3-ethyl-4- (4-methoxy) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (3-ethoxy) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (4-ethoxy) phenylimino-2-pentyl ester ], benzoic acid [4- (2, 4-dimethyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester, benzoic acid [ 3-ethyl-4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (2, 6-dimethyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4- (2, 6-diisopropyl) phenylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4-ethylimino-2-propyl ester ], benzoic acid [ 3-methyl-4-propylimino-2-pentyl ester ], benzoic acid [ 3-ethyl-4-butylimino-2-pentyl ester ], benzoic acid [ 3-ethyl-4-pentylimino-2-pentyl ester ], [ 3-ethyl-4-pentylimino-2-pentyl ester ], Benzoic acid [ 3-ethyl-4-hexylimino-2-pentyl ester ], benzoic acid [ 3-ethyl-4-heptylimino-2-pentyl ester ], benzoic acid [ 3-methyl-4-octylimino-2-pentyl ester ], 4-methylbenzoic acid (4-phenylimino-2-pentyl ester), 4-methylbenzoic acid [4- (2-methyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (3-methyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (4-methyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (2-ethyl) phenylimino-2-pentyl ester ], and mixtures thereof, 4-methylbenzoic acid [4- (3-ethyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (4-ethyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (2-propyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (3-propyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (4-propyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (2-butyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (4-butyl) phenylimino-2-pentyl ester ], (methyl-benzoic acid-4- (4-butyl) phenylimino-2-pentyl ester), 4-methylbenzoic acid [4- (3-methoxy) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (4-methoxy) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (3-ethoxy) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (4-ethoxy) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (2, 4-dimethyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], and, 4-methylbenzoic acid [ 3-methyl-4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-ethyl-4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-methyl-4- (2, 6-dimethyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-methyl-4- (2, 6-diisopropyl) phenylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-methyl-4-ethylimino-2-propyl ester ], 4-methylbenzoic acid [ 3-methyl-4-propylimino-2-pentyl ester ], (methyl-4-propylimino-2-pentyl ester), 4-methylbenzoic acid [ 3-ethyl-4-butylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-ethyl-4-pentylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-ethyl-4-hexylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-ethyl-4-heptylimino-2-pentyl ester ], 4-methylbenzoic acid [ 3-methyl-4-octylimino-2-pentyl ester ], 4-butylbenzoic acid (4-phenylimino-2-pentyl ester), 4-butylbenzoic acid [4- (2-methyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (3-methyl) phenylimino-2-pentyl ester ] Pentyl ester ], 4-butylbenzoic acid [4- (4-methyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (2-ethyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (3-ethyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (4-ethyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (2-propyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (3-propyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (4-propyl) phenylimino-2-pentyl ester ], (4-propyl) phenylimino-2-pentyl ester), 4-butylbenzoic acid [4- (2-butyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (4-butyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (3-methoxy) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (4-methoxy) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (3-ethoxy) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (4-ethoxy) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (2, 4-dimethyl) phenylimino-2-pentyl ester ], (methyl-ethyl-4-phenyl) imino-2-pentyl ester), 4-butylbenzoic acid [4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], 4-butylbenzoic acid [ 3-methyl-4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], 4-ethylbenzoic acid [ 3-ethyl-4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], 4-ethylbenzoic acid [ 3-methyl-4- (2, 6-dimethyl) phenylimino-2-pentyl ester ], 4-ethylbenzoic acid [ 3-methyl-4- (2, 6-diisopropyl) phenylimino-2-pentyl ester, 4-butylbenzoic acid [ 3-methyl-4-ethylimino-2-propyl ester ], 4-butylbenzoic acid [ 3-methyl-4-propylimino-2-pentyl ester ], 4-butylbenzoic acid [ 3-ethyl-4-butylimino-2-pentyl ester ], 4-butylbenzoic acid [ 3-ethyl-4-pentylimino-2-pentyl ester ], 4-butylbenzoic acid [ 3-ethyl-4-hexylimino-2-pentyl ester ], 4-butylbenzoic acid [ 3-ethyl-4-heptylimino-2-pentyl ester ], 4-butylbenzoic acid [ 3-methyl-4-octylimino-2-pentyl ester ] 4-propylbenzoic acid (4-phenylimino-2-pentyl ester), 4-propylbenzoic acid [4- (2-methyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (3-methyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (4-methyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (2-ethyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (3-ethyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (4-ethyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (2-propyl) phenylimino-2-pentyl ester ], (methyl-ethyl) phenylimino-2-pentyl ester), 4-propylbenzoic acid [4- (3-propyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (4-propyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (2-butyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (4-butyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (3-methoxy) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (4-methoxy) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (3-ethoxy) phenylimino-2-pentyl ester ], (methyl-4-propylbenzoic acid, methyl-4-phenylimino-2-pentyl ester), 4-propylbenzoic acid [4- (4-ethoxy) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (2, 4-dimethyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-methyl-4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-ethyl-4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], (methyl-ethyl-4-phenylimino-2-pentyl ester), 4-propylbenzoic acid [ 3-methyl-4- (2, 6-dimethyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-methyl-4- (2, 6-diisopropyl) phenylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-methyl-4-ethylimino-2-propyl ester ], 4-propylbenzoic acid [ 3-methyl-4-propylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-ethyl-4-butylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-ethyl-4-pentylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-ethyl-4-hexylimino-2-pentyl ester ], (N-methyl-4-hexylimino-2-pentyl ester), 4-propylbenzoic acid [ 3-ethyl-4-heptylimino-2-pentyl ester ], 4-propylbenzoic acid [ 3-methyl-4-octylimino-2-pentyl ester ], propionic acid (4-phenylimino-2-pentyl ester), propionic acid [4- (2-methyl) phenylimino-2-pentyl ester ], propionic acid [4- (3-methyl) phenylimino-2-pentyl ester ], propionic acid [4- (4-methyl) phenylimino-2-pentyl ester ], propionic acid [4- (2-ethyl) phenylimino-2-pentyl ester ], propionic acid [4- (3-ethyl) phenylimino-2-pentyl ester ], propionic acid [4- (4-ethyl) phenylimino-2-pentyl ester ], (4-ethyl) phenylimino-2-pentyl ester), [4- (2-propyl) phenylimino-2-pentyl propionate ], [4- (3-propyl) phenylimino-2-pentyl propionate ], [4- (4-propyl) phenylimino-2-pentyl propionate ], [4- (2-butyl) phenylimino-2-pentyl propionate ], [4- (4-butyl) phenylimino-2-pentyl propionate ], [4- (3-methoxy) phenylimino-2-pentyl propionate ], [4- (4-methoxy) phenylimino-2-pentyl propionate ], [4- (3-ethoxy) phenylimino-2-pentyl propionate ], and [4- (4-ethoxy) phenylimino-2-pentyl propionate ], Propionic acid [4- (2, 4-dimethyl) phenylimino-2-pentyl ester ], propionic acid [4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], propionic acid [4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], propionic acid [ 3-methyl-4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], propionic acid [ 3-ethyl-4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], propionic acid [ 3-methyl-4- (2, 6-dimethyl) phenylimino-2-pentyl ester ], propionic acid [ 3-methyl-4- (2, 6-diisopropyl) phenylimino-2-pentyl ester ], [ 3-methyl-4- (2, 6-diisopropyl) phenylimino-2-pentyl ester ], 3-methyl-4-ethylimino-2-propyl propionate, [ 3-methyl-4-propylimino-2-pentyl propionate ], [ 3-ethyl-4-butylimino-2-pentyl propionate ], [ 3-ethyl-4-pentylimino-2-pentyl propionate ], [ 3-ethyl-4-hexylimino-2-pentyl propionate ], [ 3-ethyl-4-heptylimino-2-pentyl propionate ], [ 3-methyl-4-octylimino-2-pentyl propionate ], [ 4-phenylimino-2-pentyl valerate ], [4- (2-methyl) phenylimino-2-pentyl valerate ], [ 3-methyl) phenylimino-2-pentyl valerate ], and mixtures thereof, Valeric acid [4- (3-methyl) phenylimino-2-pentyl ester ], valeric acid [4- (4-methyl) phenylimino-2-pentyl ester ], valeric acid [4- (2-ethyl) phenylimino-2-pentyl ester ], valeric acid [4- (3-ethyl) phenylimino-2-pentyl ester ], valeric acid [4- (4-ethyl) phenylimino-2-pentyl ester ], valeric acid [4- (2-propyl) phenylimino-2-pentyl ester ], valeric acid [4- (3-propyl) phenylimino-2-pentyl ester ], valeric acid [4- (4-propyl) phenylimino-2-pentyl ester ], valeric acid [4- (2-butyl) phenylimino-2-pentyl ester ], "valeric acid [4- (2-butyl) phenylimino-2-pentyl ester ], Valeric acid [4- (4-butyl) phenylimino-2-pentyl ester ], valeric acid [4- (3-methoxy) phenylimino-2-pentyl ester ], valeric acid [4- (4-methoxy) phenylimino-2-pentyl ester ], valeric acid [4- (3-ethoxy) phenylimino-2-pentyl ester ], valeric acid [4- (4-ethoxy) phenylimino-2-pentyl ester ], valeric acid [4- (2, 4-dimethyl) phenylimino-2-pentyl ester ], valeric acid [4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester ], valeric acid [4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], valeric acid [ 3-methyl-4- (2,4, 6-trimethyl) phenylimino-2-pentyl ester, valeric acid [ 3-ethyl-4- (3, 5-di-tert-butyl) phenylimino-2-pentyl ester ], valeric acid [ 3-methyl-4- (2, 6-dimethyl) phenylimino-2-pentyl ester ], valeric acid [ 3-methyl-4- (2, 6-diisopropyl) phenylimino-2-pentyl ester ], valeric acid [ 3-methyl-4-ethylimino-2-propyl ester ], valeric acid [ 3-methyl-4-propylimino-2-pentyl ester ], valeric acid [ 3-ethyl-4-butylimino-2-pentyl ester ], valeric acid [ 3-ethyl-4-pentylimino-2-pentyl ester ], [ 3-ethyl-4-pentylimino-2-pentyl ester ], Valeric acid [ 3-ethyl-4-hexylimino-2-pentyl ester ], valeric acid [ 3-ethyl-4-heptylimino-2-pentyl ester ], valeric acid [ 3-methyl-4-octylimino-2-pentyl ester ], 4-methylbenzoic acid (3-phenylimino-pentyl ester), 4-methylbenzoic acid [ 3-phenylimino-pentyl ester ], 4-methylbenzoic acid [3- (3-methyl) phenylimino-pentyl ester ], 4-methylbenzoic acid [3- (4-methyl) phenylimino-pentyl ester ], 4-methylbenzoic acid [3- (2-ethyl) phenylimino-pentyl ester ], 4-methylbenzoic acid [3- (3-ethyl) phenylimino-pentyl ester ], (methyl-o-pentyl ester), 4-methylbenzoic acid [3- (4-ethyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (2-propyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (3-propyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (4-propyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (2-butyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (3-butyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (4-butyl) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (3-methoxy) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (4-methoxy) phenyliminopentyl ester ], (4-methylbenzoic acid [3- (4-methoxy) phenyliminopentyl ester ], 4-methylbenzoic acid [3- (3-ethoxy) phenylimidopentyl ester ], 4-methylbenzoic acid [3- (4-ethoxy) phenylimidopentyl ester ], 4-methylbenzoic acid [3- (2, 4-dimethyl) phenylimidopentyl ester ], 4-methylbenzoic acid [3- (2,4, 6-trimethyl) phenylimidopentyl ester ], 4-methylbenzoic acid [3- (3, 5-di-tert-butyl) phenylimidopentyl ester ], benzoic acid (4-phenylimidobutyl ester), benzoic acid [4- (2-methyl) phenylimidobutyl ester ], benzoic acid [4- (3-methyl) phenylimidobutyl ester ], benzoic acid [4- (4-methyl) phenylimidobutyl ester ], benzoic acid [4- (2-ethyl) phenylimidobutyl ester ], (a) a-methyl ester, a-ethyl, Benzoic acid [4- (3-ethyl) phenyliminobutyl ester ], benzoic acid [4- (4-ethyl) phenyliminobutyl ester ], benzoic acid [4- (2-propyl) phenyliminobutyl ester ], benzoic acid [4- (3-propyl) phenyliminobutyl ester ], benzoic acid [4- (4-propyl) phenyliminobutyl ester ], benzoic acid [4- (2-butyl) phenyliminobutyl ester ], benzoic acid [4- (3-methoxy) phenyliminobutyl ester ], benzoic acid [4- (4-methoxy) phenyliminobutyl ester ], benzoic acid [4- (3-ethoxy) phenyliminobutyl ester ], benzoic acid [4- (4-ethoxy) phenyliminobutyl ester ], [4- (4-ethoxy) phenyliminobutyl ester ] (B-methyl ester, Benzoic acid [4- (2-hydroxy) iminobutyl ester ], benzoic acid [4- (3-hydroxy) phenyliminobutyl ester ], benzoic acid [4- (4-hydroxy) phenyliminobutyl ester ], benzoic acid [4- (2, 6-dimethyl) phenyliminobutyl ester ], benzoic acid [4- (2, 6-diisopropyl) phenyliminobutyl ester, ] benzoic acid [4- (2,4, 6-trimethyl) phenyliminobutyl ester ], benzoic acid [4- (3, 5-di-tert-butyl) phenyliminobutyl ester ], benzoic acid [4- (2, 6-dimethyl) phenyliminobutyl ester ], benzoic acid [4- (2, 6-diisopropyl) phenyliminobutyl ester ], benzoic acid [ 4-ethyliminobutyl ester ], benzoic acid [ 4-propyliminobutyl ester ] (I), Benzoic acid [ 4-butyliminobutyl ] acid, benzoic acid [ 4-pentyliminobutyl ] acid, benzoic acid [ 4-hexyliminobutyl ] acid, benzoic acid [ 4-heptiminobutyl ] acid, benzoic acid [ 4-octyliminobutyl ] acid, benzoic acid (3-phenyliminobutyl) acid, benzoic acid [3- (2-methyl) phenyliminobutyl ] acid, benzoic acid [3- (3-methyl) phenyliminobutyl ] acid, benzoic acid [3- (4-methyl) phenyliminobutyl ] acid, benzoic acid [3- (2-ethyl) phenyliminobutyl ] acid, benzoic acid [3- (3-ethyl) phenyliminobutyl ] acid, benzoic acid [3- (4-ethyl) phenyliminobutyl ] acid, benzoic acid [3- (2-propyl) phenyliminobutyl ] acid, Benzoic acid [3- (3-propyl) phenyliminobutyl ester ], benzoic acid [3- (4-propyl) phenyliminobutyl ester ], benzoic acid [3- (2-butyl) phenyliminobutyl ester ], benzoic acid [3- (3-methoxy) phenyliminobutyl ester ], benzoic acid [3- (4-ethoxy) phenyliminobutyl ester ], benzoic acid [3- (2-hydroxy) phenyliminobutyl ester ], benzoic acid [3- (2, 4-dimethyl) phenyliminobutyl ester ], benzoic acid [3- (2,4, 6-trimethyl) phenyliminobutyl ester ], benzoic acid [3- (3, 5-di-tert-butyl) phenyliminobutyl ester ], benzoic acid [3- (2, 6-dimethyl) phenyliminobutyl ester ], benzoic acid [3- (2, 6-diisopropyl) phenyliminobutyl ester ], benzoic acid [ 3-ethyliminobutyl ester ], benzoic acid [ 3-propyliminobutyl ester ], benzoic acid [ 3-butyliminobutyl ester ], benzoic acid [ 3-pentyliminobutyl ester ], benzoic acid [ 3-hexyliminobutyl ester ], benzoic acid [ 3-heptiminobutyl ester ], benzoic acid [ 4-noniminobutyl ester ], 4-methylbenzoic acid (3-phenyliminobutyl ester), 4-methylbenzoic acid [3- (2-methyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (3-methyl) phenyliminobutyl ester ], (methyl) phenylobuty, 4-methylbenzoic acid [3- (4-methyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (2-ethyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (3-ethyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (4-ethyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (2-propyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (3-propyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (4-propyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (2-butyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (3-butyl) phenyliminobutyl ester ], (methyl-4-methylbenzoic acid [3- (3-, 4-methylbenzoic acid [3- (4-butyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (3-methoxy) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (4-methoxy) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (3-ethoxy) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (4-ethoxy) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (2, 4-dimethyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (2,4, 6-trimethyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (3, 5-di-tert-butyl) phenyliminobutyl ester ], 4-methylbenzoic acid [3- (2, 6-dimethyl) phenyliminobutyl 4-methylbenzoic acid [3- (2, 6-diisopropyl) phenyliminobutyl ] 4-methylbenzoic acid [ 3-ethyliminobutyl ] 4-methylbenzoic acid [ 3-propyliminobutyl ] 4-methylbenzoic acid, 3-butyliminobutyl ] benzoic acid [ 3-pentyliminobutyl ] 4-methylbenzoic acid [ 3-hexyliminobutyl ] 4-methylbenzoic acid [ 4-nonyiiminobutyl ] 4-methylbenzoic acid [ 3-marinobutyl ] 4-methylbenzoic acid [ 3-phenyliminopropyl ] 4-propylbenzoic acid [3- (2-methyl) phenyliminopropyl ] 4-propylbenzoic acid [3- (3-methyl) phenyliminopropyl ] 4-propylbenzoic acid, 4-propylbenzoic acid [3- (4-methyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (2-ethyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (3-ethyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (4-ethyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (2-propyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (3-propyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (4-propyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (2-butyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (3-butyl) phenyliminopropyl ester ], (methyl) phenylthiopropionic acid, 4-propylbenzoic acid [3- (4-butyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (3-methoxy) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (4-methoxy) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (3-ethoxy) phenyliminopropyl ester ], 4-butylbenzoic acid [3- (4-ethoxy) phenyliminopropyl ester ], 4-butylbenzoic acid [3- (2, 4-dimethyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (2,4, 6-trimethyl) phenyliminopropyl ester ], 4-butylbenzoic acid [3- (3, 5-di-tert-butyl) phenyliminopropyl ester ], 4-propylbenzoic acid [3- (2, 6-dimethyl) phenyliminobutyl, 4-propylbenzoic acid [3- (2, 6-diisopropyl) phenyliminobutyl ], 4-propylbenzoic acid [ 3-ethyliminobutyl ], 4-propylbenzoic acid [ 3-propyliminobutyl ], 4-butylbenzoic acid [ 3-butyliminobutyl ], 4-propylbenzoic acid [ 3-pentyliminobutyl ], 4-butylbenzoic acid [ 3-hexyliminobutyl ], 4-butylbenzoic acid [ 4-nonyliminobutyl ], 4-butylbenzoic acid [ 3-sunflower iminobutyl ], 4-methoxybenzoic acid (3-phenyliminopropyl), 4-methoxybenzoic acid [3- (2-methyl) phenyliminopropyl ], (methyl) phenyliminobutyl) and (methyl) phenylimino-butyl) ether, 4-methoxybenzoic acid [3- (3-methyl) phenylimidopropyl ester ], 4-methoxybenzoic acid [3- (4-methyl) phenylimidopropyl ester ], 4-methoxybenzoic acid [3- (2-ethyl) phenylimidopropyl ester ], 4-methoxybenzoic acid [3- (3-ethyl) phenylimidopropyl ester ], 4-methoxybenzoic acid [3- (2-propyl) phenylimidopropyl ester ], 4-methoxybenzoic acid [3- (3-propyl) phenylimidopropyl ester ], 4-methoxybenzoic acid [3- (4-propyl) phenylimidopropyl ester ], 4-methoxybenzoic acid [3- (2-butyl) phenylimidopropyl ester ], 4-methoxybenzoic acid [3- (3-butyl) phenylimidopropyl ester ], (methyl-ethyl) phenylimidopropyl ester), 4-methoxybenzoic acid [3- (4-butyl) phenyliminopropyl ester ], 4-methoxybenzoic acid [3- (3-methoxy) phenyliminopropyl ester ], 4-methoxybenzoic acid [3- (4-methoxy) phenyliminopropyl ester ], 4-methoxybenzoic acid [3- (3-ethoxy) phenyliminopropyl ester ], 4-methoxybenzoic acid [3- (4-ethoxy) phenyliminopropyl ester ], 4-ethoxybenzoic acid [3- (2, 4-dimethyl) phenyliminopropyl ester ], 4-ethoxybenzoic acid [3- (2,4, 6-trimethyl) phenyliminopropyl ester ], 4-ethoxybenzoic acid [3- (3, 5-di-tert-butyl) phenyliminopropyl ester ], 4-methoxybenzoic acid [3- (2, 6-dimethyl) phenyliminopropyl ester ], 4-methoxybenzoic acid [3- (2, 6-diisopropyl) phenyliminopropyl ester ], 4-methoxybenzoic acid [ 3-ethyliminobutyl ester ], 4-methoxybenzoic acid [ 3-propyliminobutyl ester ], 4-methoxybenzoic acid [ 3-butyliminobutyl ester ], 4-methoxybenzoic acid [ 3-pentyliminobutyl ester ], 4-methoxybenzoic acid [ 3-hexyliminobutyl ester ], 4-methoxybenzoic acid [ 4-nonyiiminobutyl ester ], 4-methoxybenzoic acid [ 3-sunflower iminobutyl ester ], acetic acid (3-phenyliminopropyl ester), acetic acid [3- (2-methyl) phenyliminopropyl ester ] (methyl) phenyliminopropyl ester, Acetic acid [3- (3-methyl) phenyliminopropyl ester ], acetic acid [3- (4-methyl) phenyliminopropyl ester ], acetic acid [3- (2-ethyl) phenyliminopropyl ester ], acetic acid [3- (3-ethyl) phenyliminopropyl ester ], acetic acid [3- (4-ethyl) phenyliminopropyl ester ], acetic acid [3- (2-propyl) phenyliminopropyl ester ], acetic acid [3- (3-propyl) phenyliminopropyl ester ], acetic acid [3- (4-propyl) phenyliminopropyl ester ], acetic acid [3- (2-butyl) phenyliminopropyl ester ], acetic acid [3- (4-methoxy) phenyliminopropyl ester ], acetic acid [3- (3-ethoxy) phenyliminopropyl ester ], acetic acid [3- (4-ethoxy) phenyliminopropyl ester ], acetic acid [3- (2, 4-dimethyl) phenyliminopropyl ester ], acetic acid [3- (2,4, 6-trimethyl) phenyliminopropyl ester ], acetic acid [3- (3, 5-di-tert-butyl) phenyliminopropyl ester ], acetic acid [3- (2, 6-dimethyl) phenyliminopropyl ester ], acetic acid [3- (2, 6-diisopropyl) phenyliminopropyl ester ], acetic acid [ 3-propyliminopropyl ester ], acetic acid [ 3-butyliminopropyl ester ], acetic acid [ 3-pentyliminopropyl ester ], acetic acid [ 3-hexyliminopropyl ester ], acetic acid [ 3-heptiminopropyl ester ], acetic acid [ 4-noniminopropyl ester ], propionic acid (3-phenyliminopropyl ester), Propionic acid [3- (2-methyl) phenyliminopropyl ester ], butyric acid [3- (4-methyl) phenyliminopropyl ester, valeric acid [3- (2-methyl) phenyliminopropyl ester ], valeric acid [3- (4-methyl) phenyliminopropyl ester ], caproic acid [3- (4-methyl) phenyliminopropyl ester, heptanoic acid [3- (2-methyl) phenyliminopropyl ester ], caprylic acid [3- (4-methyl) phenyliminopropyl ester ], propionic acid [3- (2-ethyl) phenyliminopropyl ester ], propionic acid [3- (3-ethyl) phenyliminopropyl ester ], propionic acid [3- (4-ethyl) phenyliminopropyl ester ], (a salt thereof, Propionic acid [3- (2-propyl) phenylimino-propyl ester ], propionic acid [3- (3-propyl) phenylimino-propyl ester ], propionic acid [3- (4-propyl) phenylimino-propyl ester ], propionic acid [3- (2-butyl) phenylimino-propyl ester ], propionic acid [3- (3-butyl) phenylimino-propyl ester ], propionic acid [3- (4-butyl) phenylimino-propyl ester ], propionic acid [3- (3-methoxy) phenylimino-propyl ester ], propionic acid [3- (4-methoxy) phenylimino-propyl ester ], propionic acid [3- (3-ethoxy) phenylimino-propyl ester ], propionic acid [3- (4-ethoxy) phenylimino-propyl ester ], [3- (2, 4-dimethyl) phenyliminopropyl propionate ], [3- (2,4, 6-trimethyl) phenyliminopropyl propionate ], [3- (3, 5-di-tert-butyl) phenyliminopropyl cyclohexanoate ], [3- (3, 5-di-tert-butyl) phenyliminopropyl 2-naphthoate ], [3- (2, 6-dimethyl) phenyliminopropyl propionate ], [3- (2, 6-diisopropyl) phenyliminopropyl propionate ], [ 3-ethyliminopropyl propionate ], [ 3-propyliminopropyl propionate ], [ 3-butyliminopropyl acetate ], [ 3-pentyliminopropyl propionate ], [ 3-hexyliminopropyl propionate ], (a mixture of, Propionic acid [ 3-heptimidopropyl ester ], propionic acid [ 4-nonimidopropyl ester ], and the like.
According to some embodiments of the invention, R in formula II1-R4May be the same or different and is halogen, hydroxy, C with or without substituents1-C8Alkyl, C with or without substituents1-C8Alkoxy, C with or without substituents2-C8Alkenyl, C with or without substituents2-C8Alkenyloxy, C with or without substituents2-C8Alkynyl, C with or without substituents2-C8Alkynyloxy, C with or without substituents6-C10Aryl, C with or without substituents6-C10Aryloxy group of (2), C with or without substituents7-C15Or C with or without substituents7-C15Or a fused ring aromatic group.
According to some embodiments of the inventionIn the formula II, R1-R4May be the same or different and is halogen, hydroxy, C with or without substituents1-C8Alkyl, C with or without substituents1-C8Alkoxy, C with or without substituents2-C8Alkenyl, C with or without substituents2-C8Alkenyloxy, C with or without substituents2-C8Alkynyl, C with or without substituents2-C8Alkynyloxy, C with or without substituents6-C10Aryl, C with or without substituents6-C10Aryloxy group of (2), C with or without substituents7-C15Or C with or without substituents7-C15Or a fused ring aromatic group.
According to some embodiments of the invention, in formula II, X is C with or without substituents1-C20Alkylene, C with or without substituents1-C20Alkenylene, C with or without substituents1-C20Alkynylene, C with or without substituents6-C20Arylene, C with or without substituents4-C20Heteroarylene, or a fused ring arylene with or without substituents.
According to some embodiments of the invention, in formula II, X is C with or without substituents1-C10Alkylene, C with or without substituents6-C20Arylene, C with or without substituents4-C20Heteroarylene, or a fused ring arylene with or without substituents.
According to some embodiments of the invention, R in formula II1And R2Identical or different, each independently selected from C with or without substituents1-C20Alkyl, C with or without substituents2-C20Alkenyl, C with or without substituents6-C20Aryl, C with or without substituents6-C20Heteroaryl, C with or without substituents4-C20Or a condensed ring aromatic group with or without substituents.
According to some embodiments of the invention, R in formula II1And R2Identical or different, each independently selected from C with or without substituents1-C10Alkyl, C with or without substituents2-C10Alkenyl, C with or without substituents6-C15Aryl, C with or without substituents6-C15Heteroaryl, C with or without substituents4-C15Or a condensed ring aromatic group with or without substituents.
In the present invention, the diol ester compounds represented by formula II cover the polycarboxylic acid ester compounds disclosed in CN1436766A, and the related contents are introduced into the present invention.
The diol ester compounds represented by formula II may be selected from, but not limited to, the following compounds: 2-methyl-1, 3-dibenzylcarboxypropane, 2-ethyl-1, 3-dibenzylcarboxypropane, 2-isopropyl-1, 3-dibenzylcarboxypropane, 2-butyl-1, 3-dibenzylcarboxypropane, 2-cyclohexyl-1, 3-dibenzylcarboxypropane, 2-benzyl-1, 3-dibenzylcarboxypropane, 2-phenyl-1, 3-dibenzylcarboxypropane, 2- (1-naphthyl) -1, 3-dibenzylcarboxypropane, 2-isopropyl-1, 3-diethylcarboxypropane, 2-isopropyl-2-isopentyl-1, 3-dibenzylcarboxypropane, 2-isopropyl-2-isobutyl-1, 3-dibenzylcarboxypropane, 2-isopropyl-2-isoamyl-1, 3-dipropylcarboxypropane, 2-isopropyl-2-butyl-1, 3-dibenzylcarboxypropane, 2-isopropyl-2-isoamyl-1-benzylcarboxy-3-butylcarboxypropane, 2-isopropyl-2-isoamyl-1-benzylcarboxy-3-cinnamocarboxypropane, 2-isopropyl-2-isoamyl-1-benzylcarboxy-3-ethylcarboxypropane, 2-dicyclopentyl-1, 3-dibenzylcarboxypropane, 2-dicyclohexyl-1, 3-dibenzylcarboxypropane, 2, 2-dibutyl-1, 3-dibenzylcarboxypropane, 2-diisobutyl-1, 3-dibenzylcarboxypropane, 2-diisopropyl-1, 3-diphenylcarboxypropane, 2-diethyl-1, 3-diphenylcarboxypropane, 2-ethyl-2-butyl-1, 3-diphenylcarboxypropane, 2, 4-diphenylcarboxypentane, 3-ethyl-2, 4-diphenylcarboxypentane, 3-methyl-2, 4-diphenylcarboxypentane, 3-propyl-2, 4-diphenylcarboxypentane, 3-isopropyl-2, 4-diphenylcarboxypentane, 2, 4-bis (2-propylbenzylcarboxy) pentane, 2, 4-bis (4-propylbenzacarboxy) pentane, 2, 4-bis (2, 4-dimethylbenzylcarboxy) pentane, 2, 4-bis (2, 4-dichlorobenzacarboxy) pentane, 2, 4-bis (4-chlorobenzylcarboxy) pentane, 2, 4-bis (4-isopropylbenzacarboxy) pentane, 2, 4-bis (4-butylbenzocarboxy) pentane, 2, 4-bis (4-isobutylbenzacarboxy) pentane, 3, 5-diphenylocarboxoheptane, 4-ethyl-3, 5-diphenylocarboxoheptane, 4-propyl-3, 5-diphenylocarboxoheptane, 4-isopropyl-3, 5-diphenylocarboxoheptane, 3, 5-bis (4-propylbenzacarboxy) heptane, 3, 5-bis (4-isopropylbenzoylcarboxy) heptane, 3, 5-bis (4-isobutylbenzoylcarboxy) heptane, 3, 5-bis (4-butylbenzocarboxy) heptane, 2-benzoylcarboxy-4- (4-isobutylbenzoylcarboxy) pentane, 2-benzoylcarboxy-4- (4-butylbenzocarboxy) pentane, 2-benzoylcarboxy-4- (4-propylbenzoylcarboxy) pentane, 3-benzoylcarboxy-5- (4-isobutylbenzoylcarboxy) heptane, 3-benzoylcarboxy-5- (4-butylbenzocarboxy) heptane, 3-benzoylcarboxy-5- (4-propylbenzoylcarboxy) heptane, 9-diphenylcarboxymethylfluorene, 9, 9-dipropylcarboxymethylfluorene, 9-diisobutylcarboxylymethylfluorene, 9-dibutylcarboxymethylfluorene, 9-dibenzylcarboxymethyl-4-tert-butylfluorene, 9-dibenzylcarboxymethyl-4-propylfluorene, 9-dibenzylcarboxymethyl-1, 2,3, 4-tetrahydrofluorene, 9-dibenzylcarboxymethyl-1, 2,3,4,5,6,7, 8-octahydrofluorene, 9-dibenzylcarboxymethyl-2, 3, 6, 7-diphenylindene, 9-dibenzylcarboxymethyl-1, 8-dichlorofluorene, 7-dibenzylcarboxymethyl-2, 5-didenadiene, 1, 4-dibenzylcarboxybutane, 2, 3-diisopropyl-1, 4-diphenylcarboxybutane, 2, 3-dibutyl-1, 4-diphenylcarboxybutane, 1, 2-diphenylcarboxybenzene, 3-ethyl-1, 2-diphenylcarboxybenzene, 4-butyl-1, 2-diphenylcarboxybenzene, 1, 8-diphenylcarboxynaphthalene, 2-ethyl-1, 8-diphenylcarboxynaphthalene, 2-propyl-1, 8-diphenylcarboxynaphthalene, 2-butyl-1, 8-diphenylcarboxynaphthalene, 4-isobutyl-1, 8-diphenylcarboxynaphthalene, 4-isopropyl-1, 8-diphenylcarboxynaphthalene, One or more of 4-propyl-1, 8-dibenzyl carboxyl naphthalene.
According to some embodiments of the invention, the magnesium is present in an amount of 5 wt% to 50 wt%, the titanium is present in an amount of 1.0 wt% to 8.0 wt%, the halogen is present in an amount of 10 wt% to 70 wt%, and the internal electron donor is present in an amount of 0.1 wt% to 20 wt%, based on the weight of the catalyst component.
According to some embodiments of the present invention, the molar ratio of the imine ester compound represented by formula I to the glycol ester compound represented by formula II is (1-50): (50-1), and more preferably (1-20): (20-1).
The preparation method of the solid catalyst component can be that a magnesium compound, a titanium compound and an internal electron donor are contacted and reacted under certain conditions. The amounts of the titanium compound, the magnesium compound and the internal electron donor used for preparing the solid catalyst component are not particularly limited and may be those conventionally used in the art, respectively.
The magnesium compound may be selected from one of magnesium dihalides, hydrates or alcoholates of magnesium dihalides, and derivatives of magnesium dihalides in which one of the halogen atoms is replaced by a hydrocarbyloxy or halohydrocarbyloxy group, or mixtures thereof. Preference is given to magnesium dihalides or alcoholates of magnesium dihalides, such as magnesium dichloride, magnesium dibromide, magnesium diiodide and alcoholates thereof.
The titanium compound can be selected from the general formula of TiXm(OR1)4-mA compound of (1), wherein R1Is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and m is 1 to 4. For example: titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium, preferably titanium tetrachloride.
The magnesium compound may be dissolved in a solvent system containing an organic epoxy compound and an organic phosphorus compound, or may be dissolved in a 1, 3-diol ester compound. Wherein the organic epoxy compound comprises at least one of an oxide, a glycidyl ether and an internal ether of aliphatic olefin with 2-8 carbon atoms, diene or halogenated aliphatic olefin or diene. Specific compounds are as follows: ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran.
The organophosphorus compounds include hydrocarbyl or halohydrocarbyl esters of orthophosphoric acid or phosphorous acid, such as: trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and trityl phosphite.
Different methods can be selected for preparing the solid catalyst component of the present invention, and only a few methods for preparing the catalyst are listed below, but not limited thereto.
The above catalyst component can be prepared by the following method.
The method comprises the following steps: the magnesium halide is dissolved in a homogeneous solution of an organic epoxy compound and an organic phosphorus compound, and an inert diluent may also be added. The above homogeneous solution is mixed with titanium tetrahalide or its derivative, and when a precipitation assisting agent is present in the reaction system, a solid is precipitated. Adding an electron donor such as the compound with the structural general formula (I) for treatment, enabling the electron donor to be supported on a solid, and sequentially treating with titanium tetrahalide or an inert diluent to obtain the solid catalyst containing titanium, magnesium, halogen, the electron donor and the like.
Wherein the precipitation aid is one of organic acid anhydride, organic acid, ether, ketone and ester, or a mixture thereof. The method specifically comprises the following steps: 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, methyl ether, ethyl ether, propyl ether, butyl ether, pentyl ether, succinate, malonate, glutarate, 2, 4-pentanediol ester, 3, 5-heptanediol ester, and the like.
The components are calculated by each mole of magnesium halide, 0.1-10 moles of organic epoxy compound, 0.1-5 moles of organic phosphorus compound, 0-1.0 mole of precipitation assistant, 0.5-150 moles of titanium compound and 0.01-0.5 mole of compound in the general formula (I).
The method 2 comprises the following steps: suspending alkoxy magnesium or alkoxy magnesium chloride in inert solvent to form suspension, and mixing and contacting the suspension solution with titanium tetrahalide or its derivative to obtain solid. And then contacting the compound with the structure I with a solid to obtain the solid catalyst containing titanium, magnesium, halogen, electron donor and other components.
The method 3 comprises the following steps: fully mixing and stirring magnesium halide or an organic magnesium compound, an alcohol compound and a titanate or titanium halide compound in an inert solvent, heating and cooling to obtain a spherical carrier or adding the spherical carrier into the inert solvent to obtain a uniform alcohol compound solution. Mixing the carrier or the uniform solution with titanium tetrahalide or derivatives thereof, maintaining at a low temperature for a period of time, heating, adding the compound with the structure I, sequentially treating with the titanium tetrahalide and an inert diluent, and finally filtering, washing and drying to obtain the solid catalyst containing titanium, magnesium, halogen, electron donor and other components.
The method 4 comprises the following steps: according to the method disclosed by patent CN1091748 and the like, firstly preparing a spherical magnesium chloride alcoholate carrier, then processing the spherical carrier at low temperature by using excessive titanium tetrachloride, gradually heating, adding an electron donor compound with the structure in the processing process, washing for many times by using an inert solvent after processing, and drying to obtain a solid powdery spherical catalyst.
The molar ratio of the alcohol to the magnesium chloride in the carrier magnesium chloride alcoholate is 2-3, preferably 2-2.5. The particle size of the carrier is 10 to 300 microns, preferably 20 to 100 microns. The spherical catalyst obtained has the following characteristics: 1.5-3.0% of titanium (weight), 6.0-20.0% of ester, 40-60% of chlorine, 10-20% of magnesium, 1-6% of inert solvent and more than 250m of specific surface area of catalyst2/g。
The preparation method of the catalyst also comprises the steps of forming an emulsion by a magnesium compound, an electron donor compound with the structure and the like in a diluent, adding a titanium compound to fix the titanium compound to obtain a spherical solid, and then treating the spherical solid to obtain the solid catalyst. The compound of the general structural formula (I) may also be added at any step in the above preparation process.
The preparation method of the catalyst also comprises the steps of forming an emulsion by a magnesium compound, an electron donor compound with the structure and the like in a diluent, adding a titanium compound to fix the emulsion to obtain a spherical solid, and then treating the spherical solid to obtain the solid catalyst.
The compounds of the structure may also be added at any step during the preparation of the catalyst described above.
The catalyst for olefin polymerization comprises essential components (A), (B) and an optional component (C).
(A) the above catalyst component for olefin polymerization;
(B) an organoaluminum compound, preferably an alkylaluminum compound;
(C) an external electron donor, preferably an organosilicon compound.
The organoaluminum compound may be used in an amount conventionally used in the art according to the catalyst of the present invention. Preferably, the alkyl aluminium compound is calculated as aluminium, the catalyst component is calculated as titanium, and the molar ratio of the alkyl aluminium compound to the catalyst component is 5-5000: 1, preferably 20 to 1000: 1, more preferably 50 to 500: 1.
in the present invention, the aluminum alkyl compound may be any of various aluminum alkyl compounds commonly used in the field of olefin polymerization, which can be used as a cocatalyst of a Ziegler-Natta type catalyst. Preferably, the alkyl aluminum compound may be a compound represented by formula (V),
AlR'n'X'3-n'(V)，
in the formula (V), R' is selected from hydrogen and C1-C20Alkyl or C6-C20X 'is halogen and n' is an integer of 1 to 3. Preferably, specific examples of the alkyl aluminum compound may be at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloride.
According to the catalyst of the present invention, the kind and content of the external electron donor compound are not particularly limited. Preferably, the molar ratio of the alkylaluminum compound to the external electron donor compound, calculated as aluminum, is from 0.1 to 500:1, preferably from 1 to 300:1, more preferably from 3 to 100: 1.
According to the catalyst of the present invention, the external electron donor compound may be various external electron donor compounds commonly used in the field of olefin polymerization, which can be used as a cocatalyst of a ziegler-natta type catalyst. Preferably, the external electron donor compound may be an organosilicon compound represented by formula (VI),
R1” m”R2” n”Si(OR3”)4-m”-n”(VI)，
in the formula (VI), R1”And R2”Can be the same or different and are respectively selected from halogen, hydrogen atom and C1-C20Alkyl of (C)3-C20Cycloalkyl of, C6-C20Aryl and C1-C20One of the haloalkyl groups of (a); r3”Is selected from C1-C20Alkyl of (C)3-C20Cycloalkyl of, C6-C20Aryl and C1-C20One of the haloalkyl groups of (a); m 'and n' are each an integer of 0 to 3, and m "+ n"<4。
Specific examples of the external electron donor compound according to the preferred embodiment of the present invention may be trimethyl methoxysilane, trimethyl ethoxysilane, trimethyl phenoxy triethyl methoxysilane, triethyl ethoxysilane, dimethyl dimethoxysilane, dimethyl diethoxysilane, ethyl isopropyl dimethoxysilane, propyl isopropyl dimethoxysilane, diisopropyl dimethoxysilane, diisobutyl dimethoxysilane, isopropyl isobutyl dimethoxysilane, di-t-butyl dimethoxysilane, t-butyl methyl dimethoxysilane, t-butyl ethyl dimethoxysilane, t-butyl propyl dimethoxysilane, t-butyl isopropyl dimethoxysilane, t-butyl isobutyl dimethoxysilane, t-butyl (sec-butyl) dimethoxysilane, t-butyl amyl dimethoxysilane, tert-butyl dimethoxysilane, ethyl dimethoxysilane, propyl dimethoxysilane, butyl dimethoxy, T-butylnonyldimethoxysilane, t-butylhexyldimethoxysilane, t-butylheptyldimethoxysilane, t-butyloctyldimethoxysilane, t-butyldecyldimethoxysilane, methyl-t-butyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylt-butyldimethoxysilane, cyclopentylmethyl-dimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylpropyldimethoxysilane, cyclopentt-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, t-butyltrimethoxysilane, sec-butyltrimethoxysilane, pentyltrimethoxysilane, isopentyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane and at least one of (1,1, 1-trifluoro-2-propyl) -methyldimethoxysilane. More preferably, the external electron donor compound may be at least one of dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, cyclohexylmethyldimethoxysilane, methyl-t-butyldimethoxysilane, and tetramethoxysilane.
In a third aspect, the present invention provides the use of a solid catalyst component according to the first aspect and/or a catalyst system according to the second aspect in the polymerisation of olefins.
According to some embodiments of the present invention, the solid catalyst component and/or the catalyst system of the present invention may be used for homopolymerization of olefins, or for copolymerization of a plurality of olefins. At least one of the olefins is represented by the general formula CH2Olefins represented by ═ CHR, where R is hydrogen or C1-C6Alkyl of (2). Specific examples of the olefin may include: at least one of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene, and 4-methyl-1-pentene. Preferably, the olefin may be at least one of ethylene, propylene, 1-n-butene, 4-methyl-1-pentene, and 1-n-hexene. More preferably, the olefin is propylene.
In a fourth aspect, the present invention provides a process for the polymerisation of olefins, the process comprising: the olefin is polymerized in the presence of the catalyst component provided according to the first aspect or/and the catalyst provided according to the second aspect. Preferably, at least one of the olefins is of the formula CH2Olefins represented by ═ CHR, where R is hydrogen or C1-C6Alkyl group of (1).
The method for polymerizing the olefin can be used for homopolymerization of the olefin and copolymerization of a plurality of olefins. Specific examples of the olefin may include: at least one of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene, and 4-methyl-1-pentene. Preferably, the olefin may be at least one of ethylene, propylene, 1-n-butene, 4-methyl-1-pentene, and 1-n-hexene. More preferably, the olefin is propylene.
The invention has the following characteristics:
1. the compound used in the invention and the application thereof in the preparation of olefin polymerization catalysts and olefin polymerization reactions are not reported in documents.
2. The novel internal electron donor compound can be used for obtaining a catalyst with excellent comprehensive performance, the hydrogen regulation sensitivity of the catalyst is good when the catalyst is used for propylene polymerization reaction, and the molecular weight distribution of the obtained polypropylene resin is wide.
The test method comprises the following steps:
1. polymer Melt Index (MI): measured according to GB/T3682-2000;
2. propylene polymer Isotacticity Index (II): determination by heptane extraction: 2g of dried polymer sample is put in an extractor and extracted by boiling heptane for 6 hours, and the ratio of the weight (g) of the polymer to 2(g) of the residue is dried to constant weight, namely the isotacticity;
3. polymer molecular weight distribution MWD (MWD ═ Mw/Mn): measured at 150 ℃ using PL-GPC220 in trichlorobenzene (standard: polystyrene, flow rate: 1.0mL/min, column: 3X Plgel 10um MlxED-B300X 7.5 nm).
4. And (3) activity calculation: the catalyst activity (mass of polyolefin prepared)/(mass of catalyst solid component) g/g.
Examples
The following examples are given for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Synthesis of Compound (I)
Synthesis of benzoic acid (4-phenylimino-2-pentyl ester) (N-1)
Figure BDA0002241820240000201
In a 250 ml three-necked flask, after nitrogen purging, 3.26 g of 4-phenylimino-2-pentanol, 100 ml of THF and 2.15 ml of triethylamine were added, and 2.80 g of benzoyl chloride was added dropwise at room temperature and stirred well. After stirring for 4 hours, the reaction was refluxed for 8 hours at elevated temperature. After concentration under reduced pressure, the mixture was recrystallized from a mixed solution of ether/petroleum ether (1:50) to give pale yellow crystals, which were dried under vacuum to give 3.37 g of a product (yield 60%).1H-NMR(δ,ppm,TMS,CDCl3):8.01～7.99(2H,m,ArH),7.78～7.75(2H,m,ArH),7.46～7.44(2H,m,ArH),7.36～7.34(2H,m,ArH),7.35～7.32(3H,m,ArH),7.26～7.24(2H,m,ArH),4.15～4.13(1H,t,OCH),1.95～1.93(1H,m,CH2),1.58～1.56(1H,m,CH2),1.38～1.35(3H,d,CH3),0.99～0.95(3H,s,CH3)。
The following compounds were synthesized using a similar method:
benzoic acid [3- (3, 5-di-tert-butylphenylimino) propyl ester ] (N-2):
Figure BDA0002241820240000211
pale yellow crystals, 3.65 g (yield)Rate 50%).1H-NMR(δ,ppm,TMS,CDCl3):7.98～7.95(2H,m,ArH),7.63～7.61(2H,m,ArH),7.50～7.48(1H,m,ArH),7.43～7.41(1H,m,ArH),7.32～7.30(1H,m,ArH),7.26～7.23(2H,m,ArH),4.25～4.23(2H,t,OCH2),2.05～2.03(2H,t,CH2),1.35～1.33(3H,s,CH3),1.28～1.26(3H,s,CH3)。
Benzoic acid [4- (3, 5-di-tert-butyl-2-hydroxyphenylimino) -2-pentyl ester ] (N-3):
Figure BDA0002241820240000212
pale yellow crystals, 4.49 g (55% yield).1H-NMR(δ,ppm,TMS,CDCl3):8.03～8.01(2H,m,ArH),7.46～7.44(1H,m,ArH),7.38～7.36(2H,m,ArH),7.12～7.10(1H,m,ArH),6.96～6.95(1H,m,ArH),4.50～4.46(1H,m,OH),4.13～4.10(1H,m,OCH),2.05～2.03(2H,t,CH2),1.36～1.33(12H,m,CH3),1.30～1.27(9H,m,CH3),0.97～0.95(3H,s,CH3)。
4-N-propylbenzoic acid [4- (2-hydroxyphenylimino) -2-pentyl ester ] (N-4):
Figure BDA0002241820240000213
pale yellow crystals, 4.20 g product (62% yield).1H-NMR(δ,ppm,TMS,CDCl3):7.96～7.94(2H,m,ArH),7.26～7.23(2H,m,ArH),7.16～7.13(2H,m,ArH),6.96～6.94(2H,m,ArH),4.56～4.52(1H,m,OH),4.12～4.10(1H,m,OCH),2.56～2.54(2H,t,CH2),2.05～2.03(2H,m,CH2),1.68～1.66(2H,m,CH2),1.28～1.26(3H,s,CH3),1.04～1.02(3H,t,CH3),0.97～0.95(3H,s,CH3)。
Benzoic acid (4-butylimino-2-pentyl ester ] (N-5):
Figure BDA0002241820240000214
a light yellow viscous liquid, 2.50 g (48% yield).1H-NMR(δ,ppm,TMS,CDCl3):7.98～7.96(2H,m,ArH),7.46～7.44(1H,m,ArH),7.39～7.37(2H,m,ArH),4.20～4.19(1H,m,OCH),2.85～2.83(2H,dt,CH2),2.56～2.54(2H,t,CH2),1.56～1.54(2H,m,CH2),1.42～1.40(2H,m,CH2),1.35～1.33(3H,m,CH3),1.23～1.20(2H,m,CH2),1.04～1.02(3H,t,CH3),0.97～0.95(3H,s,CH3)。
4-N-propylbenzoic acid (4-butylimino-2-pentyl ester ] (N-6):
Figure BDA0002241820240000221
a light yellow viscous liquid, 2.73 g (45% yield).1H-NMR(δ,ppm,TMS,CDCl3):7.94～7.92(2H,m,ArH),7.25～7.23(2H,m,ArH),4.22～4.20(1H,m,OCH),2.86～2.84(2H,dt,CH2),2.57～2.55(2H,t,CH2),1.67～1.65(2H,m,CH2),1.56～1.54(2H,m,CH2),1.42～1.40(2H,m,CH2),1.35～1.33(3H,m,CH3),1.23～1.20(2H,m,CH2),1.04～1.02(3H,t,CH3),0.98～0.95(6H,m,CH3)。
Butyric acid [4- (3, 5-di-tert-butyl-2-hydroxyphenylimino) -2-pentyl ester ] (N-7):
Figure BDA0002241820240000222
a light yellow viscous liquid, 3.20 g (42% yield).1H-NMR(δ,ppm,TMS,CDCl3):7.40～7.38(1H,m,ArH),6.98～6.96(1H,m,ArH),4.52～4.49(1H,m,OH),4.10～4.09(1H,m,OCH),2.26～2.24(2H,t,CH2),1.74～1.72(2H,t,CH2),1.43～1.41(1H,m,CH2),1.36～1.32(12H,m,CH3),1.30～1.27(9H,m,CH3),1.18～1.17(1H,m,CH2),0.98～0.96(6H,m,CH3)。
3-methylbutyric acid [4- (3, 5-di-tert-butyl-2-hydroxyphenylimino) -2-pentyl ester ] (N-8):
Figure BDA0002241820240000223
a pale yellow viscous liquid, 3.11 g (40% yield).1H-NMR(δ,ppm,TMS,CDCl3):7.40～7.38(1H,m,ArH),6.98～6.96(1H,m,ArH),4.54～4.51(1H,m,OH),4.12～4.10(1H,m,OCH),2.47～2.46(1H,m,CH),2.22～2.20(2H,d,CH2),1.76～1.75(1H,t,CH2),1.43～1.42(1H,m,CH2),1.36～1.32(12H,m,CH3),1.30～1.27(9H,m,CH3),1.18～1.17(1H,m,CH2),1.04～1.02(6H,m,CH3),0.98～0.96(3H,s,CH3)。
4-propylbenzoic acid [4- (3-tert-butylbenzimidyl) -2-pentyl ester ] (N-9):
Figure BDA0002241820240000231
pale yellow crystals, 3.93 g (50% yield).1H-NMR(δ,ppm,TMS,CDCl3):7.96～7.94(2H,m,ArH),7.26～7.23(2H,m,ArH),7.20～7.18(2H,m,ArH),6.97～6.95(2H,m,ArH),4.12～4.10(1H,m,OCH),2.56～2.54(2H,t,CH2),2.23～2.21(2H,m,CH2),1.68～1.66(2H,m,CH2),1.34～1.31(12H,m,CH3),1.04～1.02(3H,t,CH3),0.98～0.95(6H,m,CH3)。
4-chlorobenzoic acid [4- (3-tert-butylphenylimino) -2-pentyl ester ] (N-10):
Figure BDA0002241820240000232
pale yellow crystals, 3.41 g (46% yield).1H-NMR(δ,ppm,TMS,CDCl3):7.95～7.93(2H,m,ArH),7.35～7.33(2H,m,ArH),7.22～7.20(2H,m,ArH),6.96～6.94(2H,m,ArH),4.12～4.10(1H,m,OCH),2.04～2.02(1H,m,CH2),1.48～1.47(1H,m,CH2),1.34～1.31(12H,m,CH3),0.97～0.95(3H,m,CH3)。
Benzoic acid [4- (8-quinolinimino) -2-pentyl ester ] (N-11):
Figure BDA0002241820240000233
pale yellow crystals, 3.32 g (50% yield).1H-NMR(δ,ppm,TMS,CDCl3):8.14～8.12(2H,m,ArH),7.97～7.95(2H,m,ArH),7.69～7.67(2H,m,ArH),7.48～7.46(2H,m,ArH),7.35～7.33(3H,m,ArH),4.12～4.10(1H,m,OCH),1.98～1.97(1H,m,CH2),1.43～1.41(1H,m,CH2),0.98～0.96(3H,m,CH3)。
Benzoic acid (4-cyclohexylimino-2-pentyl ester) (N-12):
Figure BDA0002241820240000241
pale yellow crystals, 2.42 g (42% yield).1H-NMR(δ,ppm,TMS,CDCl3):8.01～7.99(2H,m,ArH),7.47～7.46(1H,m,ArH),7.38～7.36(2H,m,ArH),4.08～4.07(1H,m,OCH),2.85～2.84(1H,m,CH2),2.63～2.62(1H,m,CH2),1.70～1.68(2H,m,CH2),1.52～1.50(4H,m,CH2),1.46～1.43(4H,m,CH2),1.38～1.36(4H,m,CH2),1.32～1.30(3H,m,CH3),0.98～0.96(3H,m,CH3)。
4-propylbenzoic acid [3- (3-tert-butylbenzimido) -5-heptyl ester ] (N-13):
Figure BDA0002241820240000242
yellow crystals, 3.82 g (47% yield).1H-NMR(δ,ppm,TMS,CDCl3):7.95～7.93(2H,m,ArH),7.37～7.36(2H,m,ArH),7.23～7.21(2H,m,ArH),6.97～6.95(2H,m,ArH),4.16～4.15(1H,m,OCH),2.55～2.53(2H,m,CH2),2.03～2.02(1H,m,CH2),1.78～1.76(2H,m,CH2),1.66～1.64(2H,m,CH2),1.58～1.56(1H,m,CH2),1.46～1.43(2H,m,CH2),1.35～1.33(9H,m,CH3),1.04～1.02(3H,m,CH3),0.98～0.95(6H,m,CH3)。
(II) preparation of solid component in catalyst and examples of propylene polymerization are as follows:
(1) preparation of solid catalyst component
4.8g of magnesium chloride, 95mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate are sequentially added into a reactor fully replaced by high-purity nitrogen, and the temperature is raised to 50 ℃ under stirring and maintained for 2.5 hours. After the solid is completely dissolved, 1.4g of phthalic anhydride is added, the solution is continuously maintained for 1 hour, the solution is cooled to the temperature below minus 25 ℃, and TiCl is dropwise added within 1 hour456mL of the reaction solution was gradually heated to 80 ℃ to gradually precipitate a solid, and 3mmol of the compound of the general structural formula (I) and 3mmol of the diol ester compound of the general structural formula (II) were added thereto and the temperature was maintained for 1 hour. After hot filtration, 150mL of toluene was added and washed twice to obtain a solid. Then 60mL of toluene and TiCl were added440mL of the mixture was heated to 110 ℃ and maintained for 2 hours, the same operation was repeated once, and the mixture was washed with 70mL of toluene for 3 times each of 10min at 110 ℃ and then with 60mL of hexane for 2 times. Vacuum drying to obtain solid catalyst component.
(2) Polymerization of propylene
The stainless steel reaction kettle with the volume of 5L is fully replaced by gaseous propylene, and then AlEt is added32.5mL of methylcyclohexyldimethoxysilane (CHMMS)5mL of Al/Si (mol) () 25, 10mg of the solid fraction prepared in the above example and 1.2NL of hydrogen gas were added thereto, 2.5L of liquid propylene was introduced, the temperature was raised to 70 ℃ and maintained at this temperature for 1 hour, and the temperature was lowered and the pressure was released to obtain a PP resin, and the results are shown in Table 1.
TABLE 1
Figure BDA0002241820240000251
PDDB: 2, 4-dibenzylcarboxypentane;
MPDDB: 3-methyl-2, 4-dibenzylcarboxypentane;
PDDPB: 2, 4-bis (4-propyl) benzenedicarboxylpentane;
*H2(hydrogen addition amount): 7.2 NL.
It can be seen from the examples and comparative examples that the use of the built internal electron donor compound of the present invention can provide a catalyst with excellent overall performance, the catalyst has good hydrogen sensitivity when used in propylene polymerization, and the obtained polypropylene resin has a wide molecular weight distribution.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. A solid catalyst component for preparing polyolefin comprises magnesium, titanium, halogen and an internal electron donor, wherein the internal electron donor comprises an imine ester compound shown as a formula I and a glycol ester compound shown as a formula II,
Figure FDA0002241820230000011
in the formula I, R1And R2The same or different, each independently selected from hydrogen, C with or without substituent1-C30Alkyl, C with or without substituents2-C30Alkenyl, C with or without substituents2-C30Alkynyl, C with or without substituents6-C30Aryl of (2)C with or without substituents6-C30Heteroaryl, C with or without substituents4-C30A heterocyclic group of (A), a halogen atom, a hydroxyl group and C with or without a substituent1-C30Alkoxy, and R1And R2Not hydrogen at the same time; or R1And R2Linking to form a ring; r is selected from C containing or not containing substituent1-C30Alkyl, C with or without substituents2-C30Alkenyl, C with or without substituents6-C30Aryl, C with or without substituents6-C30Heteroaryl, C with or without substituents4-C30A heterocyclic group of (A), a halogen atom, a hydroxyl group, C with or without a substituent1-C30Alkoxy, C with or without substituents1-C30Acyloxy groups and amino groups with or without substituents; r is selected from C containing or not containing substituent1-C30Alkyl, C with or without substituents2-C30Alkenyl, C with or without substituents2-C30Alkynyl, C with or without substituents6-C30Aryl, C with or without substituents6-C30Heteroaryl, C with or without substituents4-C30Heterocyclic group, halogen atom, hydroxyl group, C with or without substituent1-C30Alkoxy and amino with or without substituents; a is C with or without substituents1-C30Alkylene or hetero atoms, preferably C with or without substituents1-C30Alkylene, C with or without substituents6-C30Arylene, C with or without substituents4-C30A heteroarylene group or a combination thereof;
in the formula II, X is C with or without substituent1-C30Alkylene or hetero atoms, preferably C with or without substituents1-C30Alkylene, C with or without substituents1-C30Alkenylene, C with or without substituents1-C30Alkynylene, C with or without substituents6-C30Arylene, with or without substituentsC of (A)4-C30Heteroarylene, or a fused ring arylene with or without substituents; r1And R2Identical or different, each independently selected from C with or without substituents1-C30A hydrocarbon radical, preferably selected from C with or without substituents1-C30Alkyl, C with or without substituents2-C30Alkenyl, C with or without substituents6-C30Aryl, C with or without substituents6-C30Heteroaryl, C with or without substituents4-C30Or a condensed ring aromatic group with or without substituents.
2. The solid catalyst component according to claim 1 in which the substituents are selected from halogen, hydroxy, amino, C6-C20Aryl radical, C7-C20Aralkyl radical, C7-C20Alkylaryl group, C1-C10Alkyl and C1-C20Alkoxy, preferably selected from halogen, hydroxy, amino, phenyl, naphthyl, benzyl, phenethyl, C1-C6Alkyl-substituted phenyl, C1-C10Alkyl and C1-C20Alkoxy, more preferably selected from fluorine, chlorine, bromine, iodine, hydroxyl, amino, phenyl, naphthyl, benzyl, phenethyl, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, methoxy, ethoxy, isopropoxy, n-propoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, and n-hexoxy.
3. The solid catalyst component according to claim 1 or 2, characterized in that R1And R2Each independently selected from hydrogen, C with or without substituents1-C20Alkyl, C with or without substituents2-C20Alkenyl, C with or without substituents2-C30Alkynyl, C with or without substituents6-C20Aryl radicals containing or containingC without substituents4-C20A heterocyclic group of (A), a halogen atom, a hydroxyl group and C with or without a substituent1-C20An alkoxy group;
preferably, R1And R2Each independently selected from hydrogen, C with or without substituents1-C10Alkyl, C with or without substituents2-C10Alkenyl, C with or without substituents6-C15Aryl, C with or without substituents4-C50A heterocyclic group of (A), a halogen atom, a hydroxyl group and C with or without a substituent1-C10An alkoxy group;
more preferably, R1And R2Each independently selected from hydrogen, C with or without substituents1-C10Alkyl and C with or without substituents6-C15An aryl group;
further preferably, R1And R2Each independently is C with or without substituent1-C10Straight-chain alkyl, C with or without substituents3-C10Branched alkyl, C with or without substituents3-C10Cycloalkyl or phenyl with or without substituents.
4. The catalyst component according to any of claims 1 to 3, wherein R is selected from C with or without substituents1-C10Alkyl and C with or without substituents6-C15An aryl group; preferably, R is C with or without substituents1-C10Straight-chain alkyl, C with or without substituents3-C10Branched alkyl, C with or without substituents3-C10Cycloalkyl or phenyl with or without substituents.
5. The solid catalyst component according to any one of claims 1 to 4, characterized in that A is C with or without substituents1-C20Alkylene radical, C6-C20Arylene radical, C4-C20A heteroarylene group, a heteroatom, or a combination thereof;
preferably, A is C with or without substituents1-C10Alkylene radical, C6-C10Arylene radical, C4-C10A heteroarylene group or a combination thereof; more preferably, A is C with or without substituents1-C8Alkylene, further preferably A is C1-C8Alkylene (e.g. methylene, ethylene, propylene, butylene, pentylene or hexylene), C1-C6Alkyl substituted C1-C8Alkylene or C1-C6Alkoxy-substituted C1-C8An alkylene group.
6. The solid catalyst component according to any one of claims 1 to 5 in which in formula II X is C with or without substituents1-C20Alkylene, C with or without substituents1-C20Alkenylene, C with or without substituents1-C20Alkynylene, C with or without substituents6-C20Arylene, C with or without substituents4-C20Heteroarylene, or a fused ring arylene with or without substituents; r1And R2Identical or different, each independently selected from C with or without substituents1-C20Alkyl, C with or without substituents2-C20Alkenyl, C with or without substituents6-C20Aryl, C with or without substituents6-C20Heteroaryl, C with or without substituents4-C20A heterocyclic group of (a) or a condensed ring aromatic group with or without a substituent;
preferably, in formula II, X is C with or without substituents1-C10Alkylene, C with or without substituents6-C20Arylene, C with or without substituents4-C20Heteroarylene, or a fused ring arylene with or without substituents; r1And R2Identical or different, each independently selected from C with or without substituents1-C10Alkyl, C with or without substituents2-C10Alkenyl, C with or without substituents6-C15Aryl, C with or without substituents6-C15Heteroaryl, C with or without substituents4-C15Or a condensed ring aromatic group with or without substituents.
7. The solid catalyst component according to any of claims 1 to 6, characterized in that the content of magnesium is 5 wt% to 50 wt%, the content of titanium is 1.0 wt% to 8.0 wt%, the content of halogen is 10 wt% to 70 wt%, the content of internal electron donor is 0.1 wt% to 20 wt%, based on the weight of the catalyst component; and/or the molar ratio of the imine ester compound shown in the formula I to the aromatic carboxylic acid compound shown in the formula II is (1-50): (50-1), and more preferably (1-20): (20-1).
8. A catalyst for the polymerization of olefins comprising the reaction product of:
1) the solid catalyst component of any of claims 1 to 7,
2) an organoaluminum compound, preferably an alkylaluminum compound,
3) optionally, an external electron donor compound, preferably an organosilicon compound.
9. Use of the solid catalyst component according to any one of claims 1 to 7 and/or the catalyst according to claim 8 in olefin polymerization reactions.
10. Process for the polymerization of olefins comprising the polymerization of olefins, preferably of the general formula CH, in the presence of a solid catalyst component according to any of claims 1 to 7 and/or of a catalyst according to claim 82Wherein R is hydrogen or C1-C6An alkyl group; the olefin is preferably at least one selected from the group consisting of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene.
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