CN107868149B - Catalyst component for olefin polymerization, catalyst and application thereof - Google Patents

Catalyst component for olefin polymerization, catalyst and application thereof Download PDF

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CN107868149B
CN107868149B CN201610847664.0A CN201610847664A CN107868149B CN 107868149 B CN107868149 B CN 107868149B CN 201610847664 A CN201610847664 A CN 201610847664A CN 107868149 B CN107868149 B CN 107868149B
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ethyl
acetylpyridine
phthalate
butyl
benzoate
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CN107868149A (en
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王军
高明智
刘海涛
蔡晓霞
陈建华
马吉星
马晶
胡建军
李昌秀
张志会
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Priority to JP2019515798A priority patent/JP7178991B2/en
Priority to RU2019112055A priority patent/RU2757372C2/en
Priority to PCT/CN2017/103044 priority patent/WO2018054362A1/en
Priority to KR1020197011214A priority patent/KR102466260B1/en
Priority to US16/336,102 priority patent/US11325994B2/en
Priority to EP17852430.2A priority patent/EP3517555A4/en
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    • 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
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    • 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
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    • C08F10/06—Propene
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
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    • C08F4/647—Catalysts containing a specific non-metal or metal-free compound
    • C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
    • C08F4/6494—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/647—Catalysts containing a specific non-metal or metal-free compound
    • C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
    • C08F4/6495—Catalysts containing a specific non-metal or metal-free compound organic containing nitrogen

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Abstract

The invention provides a catalyst component for olefin polymerization, which comprises a magnesium element, a titanium element, halogen and an internal electron donor, wherein the internal electron donor comprises a ketimine compound shown as a formula I and an aromatic acid ester compound shown as a formula II,

Description

Catalyst component for olefin polymerization, catalyst and application thereof
Technical Field
The invention relates to the field of olefin polymerization, and in particular relates to a catalyst component for olefin polymerization, a catalyst and application thereof.
Background
Olefin polymerization catalysts can be divided into three broad categories, namely, traditional Ziegler-Natta catalysts, metallocene catalysts, and non-metallocene catalysts. For the conventional Ziegler-Natta catalysts for propylene polymerization, polyolefin catalysts are continuously updated with the development of electron donor compounds in the catalysts. Development of the catalyst from the first TiCl3/AlCl3/AlEt2Cl system and second generation of TiCl3/AlEt2Cl system, TiCl from the third generation taking magnesium chloride as carrier, monoester or aromatic dibasic acid ester as internal electron donor and silane as external electron donor4·ED·MgCl2/AlR3The catalytic polymerization activity of the ED system and the catalyst system which takes diethers and diesters as internal electron donors and is newly developed, and the isotacticity of the obtained polypropylene are greatly improved. In the prior art, a titanium catalyst system for propylene polymerization mostly uses magnesium, titanium, halogen and an electron donor as basic components, wherein the electron donor compound is one of the essential 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. In the components disclosed in US4971937 and EP0728769 for olefin polymerization catalysts, specific 1, 3-diether compounds containing two ether groups are used as electron donors, such as 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 9-bis (methoxymethyl) fluorene, etc. Thereafter, a special class of aliphatic dicarboxylic acid ester compounds such as succinate, malonate, glutarate and the like is disclosed (see WO98/56830, WO98/56834, WO01/57099, WO01/63231 and WO00/55215), and the use of the electron donor compound can not only improve the activity of the catalyst, but also obviously widen the molecular weight distribution of the obtained propylene polymer. The most widely used in industry are aromatic dicarboxylic acid esters such as di-n-butyl phthalate (DNBP) or diisobutyl phthalate (DIBP), etc. (see U.S.A.)Patent US4784983), but the catalyst has the disadvantages of poor hydrogen regulation sensitivity, rapid activity decay and the like.
The most common non-metallocene olefin polymerization catalysts are transition metal complexes containing multidentate ligands of the C ═ N type, as first found by Brookhart et al that post-diimine transition metal complexes have high catalytic activity in catalyzing olefin polymerization (Johnson L. k., kilian c.m., Brookhart m., j.am.chem.so., 1995,117,6414; Johnson L. k., Ecking s.m., Brookhart m., j.am.chem.so., 1996,118,267), since then, research on non-metallocene organic complexes has led to great interest McConville et al in 1996 report a class of chelating β -diamine Ti, Zr metal complexes (formula 1), which is the first example of N-N multidentate ligand containing pre-transition metal complexes (scalded j.d., McConville, h.5229, mcollen.g., mich.g., michelson, inc. 5229.
Figure BDA0001119793110000021
β -diamine complexes (as shown in formula 2) are also important non-metallocene olefin polymerization catalysts containing N-N ligands, β -diamine ligands can be combined with different metals to form corresponding metal complexes in different bonding modes due to the structural characteristics, steric hindrance and electronic effects of the ligands are easily controlled by changing substituents on aromatic amines, and different metals and ligand environments are changed, and the ligand compounds have the characteristics of simple synthesis, easy structural control and the like, and are ideal complexes for researching the relationship between the structure and the catalyst performance, so that the ligand compounds with the structure attract extensive attention (secret-Merle L, L ap M.F., Severn J.R., chem.Rev.,2002,102,3031; Kim W.K., Fevola M.J., Tttr Tttt translation L "=Lg g oi/T. &W.19, Yotlo K., Rgaol K., 25, York, Rgaol K., Rgaol, 23, 25, York, Rgaol, K., Rgaol, 23, Rgaol, 23, et al, No. 23, et al, No. 5, et al.
The well petrochemical Beijing chemical research institute polyethylene laboratory discloses a metal complex of a bidentate ligand in a class in patent CN00107258.7, which is used for ethylene and copolymerization reaction thereof. A similar transition metal complex catalyst was subsequently disclosed in patents CN02129548.4 (2002), 200410086388.8 (2004) and 200710176588.6 (2007), respectively, for ethylene and its copolymerization. Patents 201010554473.8 and 201010108695.7 of Shanghai institute of Chinese academy of sciences disclose a polydentate ligand metal catalyst of similar structure for use in the copolymerization of ethylene and ethylene to produce high molecular weight polyethylene having ultra-low branching.
In the above-mentioned related patent reports, catalysts for olefin polymerization are all corresponding ligand metal compounds. So far, no report about the direct application of the ligand compound in the preparation of propylene polymerization catalysts and the propylene polymerization reaction is found.
Disclosure of Invention
In view of the above deficiencies of the prior art, it is an object of the present invention to develop a catalyst and components thereof for the polymerization of olefins. In the preparation process of the catalyst, a compound electron donor (comprising compounds shown as formula I and formula II) is added to form a novel catalytic polymerization reaction system. When the catalyst is used for olefin polymerization, especially propylene polymerization, the catalyst has high activity with long period and good hydrogen regulation sensitivity, and the obtained polymer has the characteristics of high isotacticity and wide molecular weight distribution.
The invention provides a catalyst component for olefin polymerization, which comprises a magnesium element, a titanium element, halogen and an internal electron donor, wherein the internal electron donor comprises a ketimine compound shown as a formula I and an aromatic acid ester compound shown as a formula II,
Figure BDA0001119793110000031
in formula I, R is selected from hydroxyl, C with or without halogen atom substituent1～C20Alkyl group of (2), C with or without halogen atom substituents2～C20Alkenyl or C with or without halogen atom substituents1～C20Alkyl group C of6～C30An aromatic group of (a); r1～R5May be the same or different and are each independently hydrogen, C1～C20Alkyl of (C)2～C20Alkenyl of, C6～C30Aralkyl of (2), C6～C30Alkylaryl of, C9～C40A condensed ring aromatic group of (A), a halogen atom, a hydroxyl group or C1～C20Alkoxy group of (a); x is selected from the group consisting of halogen, nitrogen, oxygen, phosphorus or silicon heteroatoms, substituted or unsubstituted alkyl, C5～C20Cycloalkyl of, C6～C30Aryl or C of9～C40A condensed ring aryl group of (4);
in the formula II, RIIs C with or without halogen atom substituents1～C20Alkyl group of (2), C with or without halogen atom substituents2～C20Alkenyl, C with or without halogen atom substituents2～C20Alkynyl, or C with or without halogen atom substituents6～C30An alkylaryl group of (a); rIIIs C1～C20Alkyl of (C)2～C20Alkenyl radical, C2～C20Alkynyl, C6～C30An alkylaryl or ester or amide group; rIII、RIV、RVAnd RVISame or different is C1～C20Alkyl of (C)2～C20Alkenyl radical, C2～C20Alkynyl, C1～C20Alkoxy group of (C)6～C30Aralkyl of (2), C6～C30Alkylaryl of, C9～C40A fused ring aromatic group of (3) or a halogen.
In the invention, based on the weight of the catalyst component, the content of the magnesium element is preferably 5 wt% -50 wt%, the content of the titanium element is 1.0 wt% -8.0 wt%, the content of the halogen element is 10 wt% -70 wt%, and the total content of the internal electron donor is 0.1 wt% -20 wt%.
According to some preferred embodiments, the molar ratio of the ketimine compound of formula I to the aromatic acid ester compound of formula II is 1 (0.05-20), preferably 1 (0.1-10).
According to some preferred embodiments, R is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, hydroxyalkyl, phenyl, halophenyl, alkyl-substituted phenyl, naphthyl, biphenyl, or a group containing a heterocyclic compound; the group of the heterocyclic compound is preferably an azole-containing group, a pyridine-containing group, a pyrimidine-containing group or a quinoline-containing group.
According to some preferred embodiments, R3～R5Respectively hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl or isobutyl.
According to some preferred embodiments, X is a nitrogen atom or CH.
According to some preferred embodiments, the ketimine compound of formula I is: 6- (butylimino) ethyl-2-acetylpyridine, 6- (hexylimino) ethyl-2-acetylpyridine, 6- (pentylimino) ethyl-2-acetylpyridine, 6- (octylimino) ethyl-2-acetylpyridine, 6- (benzylimino) ethyl-2-acetylpyridine, 6- (4-hydroxybutylimino) ethyl-2-acetylpyridine, 6- (2-hydroxyphenylimino) ethyl-2-acetylpyridine, 6- (2, 6-dimethylbenzimido) ethyl-2-acetylpyridine, 6- (2, 6-diisopropylimido) ethyl-2-acetylpyridine, 6- (phenylimino) ethyl-2-acetylpyridine, 6- (2-naphthylimino) ethyl-2-acetylpyridine, 6- (1-naphthylimino) ethyl-2-acetylpyridine, 6- (4-chlorophenylimino) ethyl-2-acetylpyridine, 6- (4-trifluoromethylphenylimino) ethyl-2-acetylpyridine, 6- (2-hydroxy-4-chlorophenylimino) ethyl-2-acetylpyridine, 6- (8-quinolinimino) ethyl-2-acetylpyridine, 6- (4-quinolinimino) ethyl-2-acetylpyridine, 6- (3-quinolinimino) ethyl-2-acetylpyridine, a salt thereof, a hydrate thereof, 6- (2,4, 6-trimethylphenylimino) ethyl-2-acetylpyridine, 6- (2-ethylphenylimino) ethyl-2-acetylpyridine, 6- (4-ethylphenylimino) ethyl-2-acetylpyridine, 6- (2-propylphenylimino) ethyl-2-acetylpyridine, 6- (4-propylphenylimino) ethyl-2-acetylpyridine, 6- (3-propylphenylimino) ethyl-2-acetylpyridine, 6- (2-butylphenylimino) ethyl-2-acetylpyridine, 6- (4-butylphenylimino) ethyl-2-acetylpyridine, 3- (phenylimino) ethylacetophenone, methyl ethyl-2-acetylpyridine, methyl ethyl, 3- (2, 6-Dimethylbenzimido) ethyl acetophenone, 3- (2, 6-diisopropylphenylimino) ethyl acetophenone, 3- (2-naphthylimino) ethyl acetophenone, 3- (benzylimino) ethyl acetophenone, 3- (8-quinolinimino) ethyl acetophenone, 3- (2-quinolinimino) ethyl acetophenone, 6- (butylimino) ethyl-2-propionylpyridine, 6- (hexylimino) ethyl-2-propionylpyridine, 6- (2, 6-dimethylbenzimido) ethyl-2-propionylpyridine, 6- (2, 6-diisopropylphenylimino) ethyl-2-propionylpyridine, 6- (phenylimino) ethyl-2-propionylpyridine, and mixtures thereof, 6- (pentylimino) ethyl-2-butyrylpyridine, 6- (2-naphthylimino) ethyl-2-butyrylpyridine, 6- (butylimino) propyl-2-propionylpyridine, 6- (hexylimino) butyl-2-propionylpyridine, one or more of 6- (2, 6-dimethylbenzimido) propyl-2-propionylpyridine, 6- (2, 6-diisopropylphenylimino) propyl-2-propionylpyridine, 6- (phenylimino) propyl-2-propionylpyridine, 6- (pentylimino) propyl-2-butyrylpyridine and 6- (2-naphthylimino) propyl-2-butyrylpyridine.
According to some preferred embodiments, RIIs methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, vinyl, allyl, ethynyl, phenyl, halophenyl, alkyl-substituted phenyl, naphthyl or biphenyl.
According to some preferred embodiments, RIIIs methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, vinyl, allyl, ethynyl, phenyl, halophenyl, alkyl-substituted phenyl, naphthyl, biphenyl, ethoxyformyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, hexyloxycarbonyl, isohexoxycarbonyl, neoxyformyl, heptyloxyformyl, isoheptyloxyformyl, neoheptyloxyformyl, octyloxycarbonyl, isooctyloxyformyl or neooctyloxycarbonyl.
According to some preferred embodiments, the aromatic acid ester compound of formula II is: ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, hexyl benzoate, heptyl benzoate, octyl benzoate, nonyl benzoate, decyl benzoate, isobutyl benzoate, isopentyl benzoate, isohexyl benzoate, isoheptyl benzoate, isooctyl benzoate, isononyl benzoate, isodecyl benzoate, neopentyl benzoate, neohexyl benzoate, neoheptyl benzoate, neooctyl benzoate, octylnonyl benzoate, neodecyl benzoate, diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dinonyl phthalate, diisohexyl phthalate, Diisoheptyl phthalate, diisooctyl phthalate, diisononyl phthalate, diisobutyl 3-methylphthalate, di-n-butyl 3-methylphthalate, diisoamyl 3-methylphthalate, di-n-pentyl 3-methylphthalate, diisooctyl 3-methylphthalate, di-n-octyl 3-methylphthalate, diisobutyl 3-ethylphthalate, di-n-butyl 3-ethylphthalate, di-n-octyl 3-ethylphthalate, diisobutyl 3-ethylphthalate, di-n-pentyl 3-ethylphthalate, diisoamyl 3-ethylphthalate, diisobutyl 3-propylphthalate, di-n-butyl 3-propylphthalate, diisobutyl 3-chlorophthalate, diisononyl 3-methylphthalate, diisobutyl 3-ethylphthalate, di-n-butyl 3-ethylphthalate, diisobutyl 3-methylphthalate, diisobuty, 3-butyl phthalate diisobutyl ester, 3-butyl phthalate di-n-butyl ester, 4-propyl phthalate diisobutyl ester, 4-butyl phthalate di-isoamyl ester, 4-chloro phthalate di-n-butyl ester, 4-chloro phthalate di-isobutyl ester, 4-chloro phthalate di-n-octyl ester, 4-methoxy phthalate di-n-butyl ester and 4-methoxy phthalate di-isobutyl ester.
The catalyst component provided by the invention can be prepared by the following optional 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. Mixing the homogeneous solution with titanium tetrahalide or its derivative, and adding precipitation assistant to precipitate solid. The internal electron donor is carried on the solid and then treated by titanium tetrahalide or inert diluent to obtain the solid catalyst component containing titanium, magnesium, halogen, electron donor and other components.
The organic epoxy compound preferably comprises C2～C15At least one of aliphatic alkanes, alkenes, dienes, halogenated aliphatic alkenes, oxides of dienes, glycidyl ethers, and internal ethers. Specific compounds are, for example, butylene oxide, propylene oxide, ethylene oxide, butadiene double oxide, epichlorohydrin, chlorobutylene oxide, chloropentylene oxide, methylglycidyl ether, diglycidyl ether, tetrahydrofuran, tetrahydropyran, etc. More preferably, ethylene oxide, propylene oxide, epichlorohydrin, tetrahydrofuran, tetrahydropyran are included.
The organic phosphorus compound preferably includes a hydrocarbyl or halohydrocarbyl ester of orthophosphoric acid or phosphorous acid, and specific examples thereof are trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, tripentyl orthophosphate, trihexyl orthophosphate, triheptyl orthophosphate, trioctyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite or benzyl phosphite, etc., more preferably tributyl orthophosphate, triethyl orthophosphate.
The inert diluent is preferably selected from C5～C20And at least one of alkane, cycloalkane and aromatic hydrocarbon such as hexane, heptane, octane, decane, cyclohexane, benzene, toluene, xylene or derivatives thereof, etc., more preferably hexane, toluene.
The precipitation assistant preferably includes organic acid anhydride, organic acid, ether, ketone or ester, specifically, acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, methyl ethyl ketone, acetone, benzophenone, diethyl ether, propyl ether, butyl ether, malonate, succinate, maleate, glutarate, 2, 4-pentanediol ester, 3, 5-heptanediol ester, 9-diphenylcarboxyfluorene, etc., more preferably, phthalic anhydride, 2, 4-pentanediol ester, 3, 5-heptanediol ester.
The method 2 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 an internal electron donor, treating with titanium tetrahalide or an inert diluent, and finally filtering, washing and drying to obtain the solid catalyst component containing titanium, magnesium, halogen, the electron donor and other components.
The magnesium halide preferably includes at least one of magnesium dichloride, magnesium dibromide, magnesium diiodide, magnesium methoxychloride, magnesium ethoxychloride, magnesium propoxide, magnesium butoxychloride, and the like, more preferably magnesium dichloride and/or magnesium ethoxychloride.
The organomagnesium compound preferably includes at least one of dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, methylethylmagnesium, methylpropylmagnesium, methylbutylgagnesium, ethylpropylmagnesium, ethylbutylmagnesium, dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, ethoxyethylmagnesium, dibutoxymagnesium, diisobutyoxymagnesium, and the like, and more preferably dibutylmagnesium, diethylmagnesium, or diethoxymagnesium.
The method 3 comprises the following steps: magnesium halide is dissolved in a homogeneous solution of an organic epoxy compound and an organic phosphorus compound, and an inert diluent and an internal electron donor may also be added. Mixing the solution with titanium tetrahalide or derivatives thereof, maintaining the mixture at a low temperature for a period of time, heating the mixture, treating the mixture with titanium tetrahalide or an inert diluent, and finally filtering, washing and drying the treated mixture to obtain the solid catalyst component containing titanium, magnesium, halogen, electron donors and the like.
The method 4 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. Mixing the solution with titanium tetrahalide or its derivative, adding precipitation assistant to precipitate solid. The compound shown as the formula II is carried on a solid, treated by titanium tetrahalide, treated by the compound shown as the formula I, and then treated by a diluent. Finally, the solid catalyst component containing titanium, magnesium, halogen, electron donor and other components is obtained after filtration, washing and drying.
The present invention also provides a catalyst for propylene polymerization, comprising: A) the catalyst component; B) an organoaluminum compound; and optionally C) an organosilicon compound.
Wherein components A) and B) are essential components of the catalyst and component C) is an optional component of the catalyst.
In the present invention, the organoaluminum compound preferably includes trialkylaluminum, dialkylaluminum chloride, alkylaluminum chloride, alkylaluminoxane, preferably C1-C6Such as at least one of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydrochloride, diisobutylaluminum monohydrochloride, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichlorochloride. More preferably triethylaluminium and/or triisobutylaluminium.
The organosilicon compound is preferably of the formula RA mSi(ORB)4-mA compound shown in the formula, wherein m is more than or equal to 0 and less than or equal to 3, RAAnd RBAre identical or different alkyl, cycloalkyl, aryl, haloalkyl, amino, RAAnd may be a halogen or hydrogen atom. Preferably, the organosilicon compound is selected from at least one of the following compounds: trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, tri-n-propylmethoxysilane, dimethyldimethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, dipentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, dimethyldiethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyldimethylmethoxysilane, hexyldimethylmethoxysilaneOrganosilicon compounds such as diethylmethoxysilane, dicyclopentyldimethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, 4-methylcyclohexylmethyldimethoxysilane, 4-methylcyclohexylethyldimethoxysilane, 4-methylcyclohexylpropyldimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane, 4-methylcyclohexylpentyldimethoxysilane, 4-methylcyclohexyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, may preferably be selected from cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane and/or diisopropyldimethoxysilane. These organosilicon compounds may be used alone or in combination of two or more.
In the present invention, the molar ratio of the components A), B) and C) is preferably 1 (5-2000) to (0-500), more preferably 1 (10-800) to (0-300).
The invention also provides the application of the catalyst component and the catalyst in the field of olefin polymerization, in particular the field of propylene polymerization.
The invention has the beneficial effects that:
when the catalyst is used for olefin polymerization reaction, the catalyst activity and the isotactic index of the obtained polymer are higher, the hydrogen regulation sensitivity is better, the catalyst activity decay is slow, and the molecular weight distribution of the obtained polymer is wider.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
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) was measured at 150 ℃ using P L-GPC 220 and trichlorobenzene as solvent (standard: polystyrene, flow rate: 1.0m L/min, column: 3X Plgel 10um MlxED-B300 X7.5nm).
4. And (3) activity calculation: the catalyst activity (mass of polyolefin prepared)/(mass of catalyst solid component) g/g.
Example 1
Synthesis of 6- (phenylimino) ethyl-2-acetylpyridine: in a 250 ml three-necked flask, after nitrogen purging, 3.26 g of 2, 6-diacetylpyridine, 100 ml of isopropanol and 0.2 ml of glacial acetic acid were added and stirred at room temperature. 1.96 g of aniline dissolved in 20 ml of isopropanol solution is slowly added dropwise at room temperature, and after the addition is finished, the reaction is stirred for 2 hours, and then the temperature is increased for reflux reaction for 12 hours. The reaction solution was concentrated under reduced pressure and separated by column chromatography to give 2.83 g (62% yield) of the product.1H-NMR(,ppm,TMS,CDCl3):8.46～8.42(2H,m,ArH),7.96～7.93(2H,m,ArH),7.32～7.28(2H,m,ArH),7.10～7.06(2H,m,ArH),2.35～2.32(3H,s,CH3),1.15～1.12(3H,s,CH3) (ii) a Mass Spectrometry, FD-MS: 238.
Example 2
Synthesis of 6- (4-chlorophenylimino) ethyl-2-acetylpyridine: in a 250 ml three-necked flask, 1.63 g of 2, 6-diacetylpyridine, 80 ml of isopropanol and 0.2 ml of glacial acetic acid were added after nitrogen purging, and the mixture was stirred at room temperature. Slowly dropwise adding 1.27 g of parachloroaniline dissolved in 20 ml of isopropanol solution at room temperature, stirring for reacting for 2 hours after the addition, and then heating and refluxing for reacting for 18 hours. The reaction solution was concentrated under reduced pressure and separated by column chromatography to give 1.63 g (69% yield) of the product.1H-NMR(,ppm,TMS,CDCl3):8.44～8.40(2H,m,ArH),816～8.14(1H,m,ArH),7.46～7.41(2H,m,ArH),7.12～7.08(2H,m,ArH),2.38～2.34(3H,s,CH3),1.12～1.09(3H,s,CH3) (ii) a Mass Spectrometry, FD-MS: 272.
Example 3
Synthesis of 6- (2, 6-diisopropylphenylimino) ethyl-2-acetylpyridine: in a 250 ml three-necked flask, 1.63 g of 2, 6-diacetylpyridine, 80 ml of isopropanol and 0.1 ml of glacial acetic acid were added after nitrogen purging, and the mixture was stirred at room temperature. Slowly dripping 1.78 g of 2, 6-diisopropylaniline dissolved in 20 ml of isopropanol solution at room temperature, stirring for reacting for 2 hours after the addition, and heating for reflux reaction for 12 hours. The reaction solution was concentrated under reduced pressure and separated by column chromatography to give 2.32 g (72% yield) of the product.1H-NMR(,ppm,TMS,CDCl3):8.45～8.41(2H,m,ArH),7.96～7.92(2H,m,ArH),7.36～7.34(2H,m,ArH),3.22～3.18(2H,m,CH),2.27～2.24(3H,s,CH3),1.28～1.24(6H,m,CH3),1.14～1.10(6H,m,CH3),1.10～1.07(3H,s,CH3) (ii) a Mass Spectrometry, FD-MS: 322.
Example 4
Synthesis of 6- (2, 6-dimethylbenzimido) ethyl-2-acetylpyridine: in a 250 ml three-necked flask, 1.63 g of 2, 6-diacetylpyridine, 80 ml of isopropanol and 0.15 g of p-toluenesulfonic acid were added after nitrogen purging, and the mixture was stirred at room temperature. Slowly dripping 1.25 g of 2, 6-dimethylaniline dissolved in 20 ml of isopropanol solution at room temperature, stirring for reacting for 2 hours after the dripping is finished, and heating and refluxing for reacting for 10 hours. The reaction solution was concentrated under reduced pressure and separated by column chromatography to give 1.85 g (70% yield) of the product.1H-NMR(,ppm,TMS,CDCl3):8.22～8.18(2H,m,ArH),7.68～7.64(2H,m,ArH),7.12～7.08(2H,m,ArH),2.30～2.27(3H,s,CH3),2.24～2.21(3H,s,CH3),2.10～2.06(3H,s,CH3),1.02～0.98(3H,s,CH3) (ii) a Mass Spectrometry, FD-MS: 266.
Example 5
Synthesis of 6- (3-quinolineimine) -2-acetylpyridine: in a 250 ml three-necked flask, 1.63 g of 2, 6-diacetylpyridine, 80 ml of isopropanol and 0 are added after purging with nitrogen15 g of p-toluenesulfonic acid, stirred well at room temperature. Slowly dripping 1.38 g of 2,4, 6-trimethylaniline dissolved in 20 ml of isopropanol solution at room temperature, stirring for reaction for 2 hours after the addition, and heating for reflux reaction for 16 hours. The reaction solution was concentrated under reduced pressure and separated by column chromatography to give 1.82 g (65% yield) of the product.1H-NMR(,ppm,TMS,CDCl3):8.56～8.53(3H,m,ArH),7.95～7.91(2H,m,ArH),7.32～7.28(2H,m,ArH),7.12～7.08(2H,m,ArH),2.35～2.31(3H,s,CH3),1.02～0.98(3H,s,CH3) (ii) a Mass Spectrometry, FD-MS: 289.
Example 6
Synthesis of 6- (1-naphthylimino) ethyl-2-acetylpyridine: in a 250 ml three-necked flask, 1.63 g of 2, 6-diacetylpyridine, 80 ml of isopropanol and 0.2 ml of glacial acetic acid were added after nitrogen purging, and the mixture was stirred at room temperature. Slowly dripping 1.45 g of 1-naphthylamine dissolved in 20 ml of isopropanol solution at room temperature, stirring for reacting for 2 hours after the addition, and heating and refluxing for reacting for 14 hours. The reaction solution was concentrated under reduced pressure and separated by column chromatography to give 1.96 g (68% yield) of the product.1H-NMR(,ppm,TMS,CDCl3):8.50～8.46(1H,m,ArH),8.36～8.33(2H,m,ArH),7.78～7.75(2H,m,ArH),7.32～7.28(2H,m,ArH),7.12～7.08(3H,m,ArH),2.26～2.24(3H,s,CH3),1.08～1.06(3H,s,CH3) (ii) a Mass Spectrometry, FD-MS: 288.
Example 7
Synthesis of 6- (benzylimino) ethyl-2-acetylpyridine: in a 250 ml three-necked flask, after nitrogen purging, 3.26 g of 2, 6-diacetylpyridine, 120 ml of isopropanol and 0.3 ml of glacial acetic acid were added and stirred at room temperature. 2.20 g of benzylamine dissolved in 30 ml of isopropanol solution is slowly added dropwise at room temperature, and after the addition is finished, the mixture is stirred for reaction for 2 hours, and then the temperature is increased for reflux reaction for 18 hours. The reaction solution was concentrated under reduced pressure and separated by column chromatography to give 3.43 g (yield 70%) of the product.1H-NMR(,ppm,TMS,CDCl3):8.36～8.34(2H,m,ArH),7.96～7.93(1H,m,ArH),7.32～7.28(2H,m,ArH),7.12～7.08(3H,m,ArH),,2.62～2.58(2H,s,CH2),2.28～2.25(3H,s,CH3),1.10～1.07(3H,s,CH3) (ii) a Mass Spectrometry, FD-MS: 252.
Example 8
Synthesis of 6- (8-quinolineimine) ethyl-2-acetylpyridine: in a 250 ml three-necked flask, 1.63 g of 2, 6-diacetylpyridine, 70 ml of isopropanol and 0.15 g of p-toluenesulfonic acid were added after nitrogen purging, and the mixture was stirred at room temperature. Slowly dripping 1.48 g of 8-aminoquinoline dissolved in 35 ml of isopropanol solution at room temperature, stirring for reaction for 4 hours after the dripping is finished, and heating and refluxing for reaction for 12 hours. The reaction solution was concentrated under reduced pressure and separated by column chromatography to give 1.82 g (63% yield) of the product.1H-NMR(,ppm,TMS,CDCl3):8.58～8.53(3H,m,ArH),7.98～7.95(2H,m,ArH),7.32～7.28(2H,m,ArH),7.08～7.05(2H,m,ArH),2.28～2.24(3H,s,CH3),1.10～1.06(3H,s,CH3) (ii) a Mass Spectrometry, FD-MS: 289.
Example 9
The catalyst component is prepared by sequentially adding 4.8g of magnesium chloride, 95m of toluene L, 4ml of epichlorohydrin and 12.5m of tributyl phosphate (TBP) L into a reactor fully replaced by high-purity nitrogen, heating to 50 ℃ under stirring, maintaining for 2.5 hours, adding 1.4g of phthalic anhydride after the solid is completely dissolved, continuously maintaining for 1 hour, cooling the solution to below-25 ℃, and dropwise adding TiCl within 1 hour4Slowly heating to 80 ℃, gradually precipitating solids, adding DNBP (di-n-butyl phthalate 0.003 mol) and 6- (2, 6-diisopropylimido) ethyl-2-acetylpyridine (0.003 mol), maintaining the temperature for 1 hour, carrying out hot filtration, adding toluene 150m L, washing twice to obtain solids, adding toluene 100m L, stirring for 30 minutes, heating to 110 ℃, carrying out washing for three times, wherein the times are 10 minutes respectively, adding hexane 60m L, and washing twice to obtain a catalyst component 7.5g, which contains 3.6% of Ti, 22.8% of Mg and 52.6% of Cl.
Example 10
Preparation of the catalyst component: as in example 9, only 6- (2, 6-diisopropylphenylimino) ethyl-2-acetylpyridine was replaced by 6- (2, 6-dimethylbenzenylimino) ethyl-2-acetylpyridine.
Example 11
Preparation of the catalyst component: as in example 9, only 6- (2, 6-diisopropylphenylimino) ethyl-2-acetylpyridine was replaced by 6- (2,4, 6-trimethylphenylimino) ethyl-2-acetylpyridine.
Example 12
Preparation of the catalyst component: as in example 9, only 6- (2, 6-diisopropylphenylimino) ethyl-2-acetylpyridine was replaced by 6- (8-quinolinimino) ethyl-2-acetylpyridine.
Example 13
Preparation of the catalyst component: just DNBP was replaced with DIBP (diisobutylphthalate) as in example 9.
Example 14
The catalyst component is prepared by sequentially adding 4.8g of magnesium chloride, 95m of toluene L, 4ml of epichlorohydrin and 12.5m of tributyl phosphate (TBP) L into a reactor fully replaced by high-purity nitrogen, heating to 50 ℃ under stirring, maintaining for 2.5 hours, adding 1.4g of phthalic anhydride after the solid is completely dissolved, continuously maintaining for 1 hour, cooling the solution to below-25 ℃, and dropwise adding TiCl within 1 hour4The temperature was slowly raised to 80 ℃ to gradually precipitate a solid, DNBP (0.006 mol) was added and the temperature was maintained for 1 hour, after thermal filtration, toluene 150m L was added and washed twice to obtain a solid, toluene 100m L was added and stirred for 30 minutes, and then heated to 110 ℃ to carry out three times of washing for 10 minutes each, hexane 60m L and 6- (2, 6-diisopropylphenylimino) ethyl-2-acetylpyridine (0.006 mol) were added and stirred for 30 minutes, and hexane 60m L was added and washed twice to obtain 7.2g of a catalyst component containing 3.8% of Ti, 22.1% of Mg and 51.3% of Cl.
Example 15
The catalyst component is prepared by charging 300m L TiCl into a reactor fully replaced by high-purity nitrogen4The temperature was lowered to-20 ℃ and 7.0g of a magnesium chloride hydrate support (see patent CN1330086A) was added, and while the temperature was raised to 40 ℃ in stages with stirring, DNBP (0.003 mol) and 6- (2, 6-diisopropylimido) ethyl-2-acetylpyridine (0.003 mol) were added, and the temperature was maintained for 2 hours. Filtering, adding TiCl4100m L, heating to 110 ℃, processing for three times, adding hexane 60m L, and washing for three times to obtain the catalyst component 7.3g, which contains 3.5 percent of Ti, 23.2 percent of Mg and 54.2 percent of Cl.
Example 16
The catalyst component is prepared by charging 300m L TiCl into a reactor fully replaced by high-purity nitrogen4The temperature was lowered to-20 ℃ and 7.0g of magnesium ethoxide was added, and while stirring and the temperature was raised to 40 ℃ in stages, DNBP (0.003 mol) and 6- (2, 6-diisopropylimido) ethyl-2-acetylpyridine (0.003 mol) were added, and the temperature was maintained for 3 hours. Filtering, adding TiCl4100m L, heating to 110 ℃, processing for three times, adding hexane 60m L, and washing for three times to obtain 6.6g of catalyst component containing 3.0 percent of Ti, 22.6 percent of Mg and 52.0 percent of Cl.
Example 17
Propylene polymerization reaction, 5L stainless steel reaction kettle is fully replaced by gaseous propylene, and then AlEt is added32.5m L and 5ml methylcyclohexyldimethoxysilane (CHMMS) Al/Si (mol) () 25, 10mg of the solid component prepared in example 9 and 1.2N L hydrogen gas were added, and liquid propylene was added 2.5L, and the temperature was raised to 70 ℃ for 1 hour, and then the temperature was lowered, and the pressure was released to obtain a PP resin, and the results are shown in Table 1.
Example 18
Propylene polymerization reaction: the catalyst in example 17 was replaced with the catalyst component of example 10 alone, and the results are shown in Table 1.
Example 19
Propylene polymerization reaction: the catalyst in example 17 was replaced with the catalyst component of example 11 alone, and the results are shown in Table 1.
Example 20
Propylene polymerization reaction: the catalyst component of example 12 was used alone in place of the catalyst of example 17, and the results are shown in Table 1.
Example 21
Propylene polymerization reaction: the catalyst in example 17 was replaced with the catalyst component of example 13 alone, and the results are shown in Table 1.
Example 22
Propylene polymerization reaction: the catalyst in example 17 was replaced with the catalyst component of example 14 only, and the results are shown in Table 1.
Example 23
Propylene polymerization reaction: the catalyst component of example 15 was used alone in place of the catalyst of example 17, and the results are shown in Table 1.
Example 24
Propylene polymerization reaction: the catalyst in example 17 was replaced with the catalyst component of example 16 only, and the results are shown in Table 1.
Example 25
Propylene polymerization reaction: as in example 17, the polymerization time was prolonged to 2 hours, and the results are shown in Table 1.
Example 26
Propylene polymerization reaction: as in example 17, the polymerization time was extended to only 3 hours, and the results are shown in Table 1.
Example 27
Propylene polymerization reaction: as in example 21, the polymerization time was prolonged to 2 hours, and the results are shown in Table 1.
Example 28
Propylene polymerization reaction: as in example 21, the polymerization time was extended to only 3 hours, and the results are shown in Table 1.
Example 29
Propylene polymerization reaction in the same manner as in example 17, the amount of hydrogenation was changed to 7.2N L, and the results are shown in Table 1.
Comparative example 1
The catalyst component is prepared by sequentially adding 4.8g of magnesium chloride, 95m of toluene L, 4ml of epichlorohydrin and 12.5m of tributyl phosphate (TBP) L into a reactor fully replaced by high-purity nitrogen, heating to 50 ℃ under stirring, maintaining for 2.5 hours, adding 1.4g of phthalic anhydride after the solid is completely dissolved, continuously maintaining for 1 hour, cooling the solution to below-25 ℃, and dropwise adding TiCl within 1 hour4Slowly heating to 80 deg.C, gradually separating out solid, adding DNBP (0.006 mol), maintaining temperature for 1 hr, heat filtering, adding toluene 150m L, washing twice to obtain solid, adding toluene 100m L, heating to 110 deg.C, washing for three times (10 min each), adding hexane 60m L, stirring for 30 min, adding hexane 60m L, and washing for three times to obtain catalyst component7.4g, Ti: 2.4%, Mg: 22.0%, Cl: 50.6 percent.
Propylene polymerization reaction 5L after complete replacement by gaseous propylene, AlEt was added32.5m L and 5ml methylcyclohexyldimethoxysilane (CHMMS) Al/Si (mol): 25 were added, 10mg of the above prepared catalyst component and 1.2N L hydrogen were added, liquid propylene 2.5L was introduced, the temperature was raised to 70 ℃ and maintained at this temperature for 1 hour, the temperature was lowered, the pressure was released, and PP resin was obtained by discharging, and the results are shown in Table 1.
Comparative example 2
Propylene polymerization reaction 5L after complete replacement by gaseous propylene, AlEt was added32.5m L and 5ml methylcyclohexyldimethoxysilane (CHMMS) Al/Si (mol): 25 were added, 10mg of the above prepared catalyst component and 7.2N L hydrogen were added, liquid propylene 2.5L was introduced, the temperature was raised to 70 ℃ and maintained at this temperature for 1 hour, the temperature was lowered, the pressure was released, and PP resin was obtained by discharging, and the results are shown in Table 1.
TABLE 1
Figure BDA0001119793110000121
Figure BDA0001119793110000131
As can be seen from the above examples and comparative examples, when the catalyst of the present invention is used in propylene polymerization, the catalyst activity and the isotactic index of the obtained polymer are high, the hydrogen response is good, the catalyst has long-period activity, and the molecular weight distribution of the obtained polymer is wide.
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 (14)

1. A catalyst component for olefin polymerization comprises magnesium, titanium, halogen and an internal electron donor, wherein the internal electron donor comprises a ketimine compound shown as a formula I and an aromatic acid ester compound shown as a formula II,
Figure FDA0002345243080000011
in formula I, R is selected from hydroxyl, C with or without halogen atom substituent1～C20Alkyl group of (2), C with or without halogen atom substituents2～C20Alkenyl or C with or without halogen atom substituents6～C30An aromatic group of (a); r1～R5The same or different are respectively and independently hydrogen and C1～C20Alkyl of (C)2～C20Alkenyl of, C6～C30Aralkyl of (2), C6～C30Alkylaryl of, C9～C40A condensed ring aromatic group of (A), a halogen atom, a hydroxyl group or C1～C20An alkoxy group; x is selected from the group consisting of halogen, nitrogen, oxygen, phosphorus or silicon heteroatoms, substituted or unsubstituted alkyl, C5～C20Cycloalkyl of, C6～C30Aryl or C of9～C40A condensed ring aryl group of (4);
in the formula II, RIIs C with or without halogen atom substituents1～C20Alkyl group of (2), C with or without halogen atom substituents2～C20Alkenyl, C with or without halogen atom substituents2～C20Alkynyl or C with or without halogen atom substituents6～C30An alkylaryl group of (a); rIIIs C1～C20Alkyl of (C)2～C20Alkenyl of, C2～C20Alkynyl of (A), C6～C30Alkylaryl or ester ofA group or amide group; rIII、RIV、RVAnd RVISame or different is C1～C20Alkyl of (C)2～C20Alkenyl radical, C2～C20Alkynyl, C1～C20Alkoxy group of (C)6～C30Aralkyl of (2), C6～C30Alkylaryl of, C9～C40A fused ring aromatic group of (3) or a halogen.
2. The catalyst component of claim 1, wherein 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 total internal electron donor content is present in an amount of 0.1 wt% to 20 wt%, based on the weight of the catalyst component.
3. The catalyst component according to claim 1 or 2 in which R is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, hydroxyalkyl, phenyl, halophenyl, alkyl-substituted phenyl, naphthyl, biphenyl or a group containing heterocyclic compounds.
4. The catalyst component according to claim 3 in which the group containing a heterocyclic compound is a pyrrole-containing group, a pyridine-containing group, a pyrimidine-containing group or a quinoline-containing group.
5. The catalyst component according to claim 1 or 2, characterized in that R3～R5Respectively hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl or isobutyl.
6. The catalyst component according to claim 1 or 2 characterized in that X is a nitrogen atom or CH.
7. The catalyst component according to claim 1 or 2 in which the ketimine compound of formula I is: 6- (butylimino) ethyl-2-acetylpyridine, 6- (hexylimino) ethyl-2-acetylpyridine, 6- (pentylimino) ethyl-2-acetylpyridine, 6- (octylimino) ethyl-2-acetylpyridine, 6- (benzylimino) ethyl-2-acetylpyridine, 6- (4-hydroxybutylimino) ethyl-2-acetylpyridine, 6- (2-hydroxyphenylimino) ethyl-2-acetylpyridine, 6- (2, 6-dimethylbenzimido) ethyl-2-acetylpyridine, 6- (2, 6-diisopropylimido) ethyl-2-acetylpyridine, 6- (phenylimino) ethyl-2-acetylpyridine, 6- (2-naphthylimino) ethyl-2-acetylpyridine, 6- (1-naphthylimino) ethyl-2-acetylpyridine, 6- (4-chlorophenylimino) ethyl-2-acetylpyridine, 6- (4-trifluoromethylphenylimino) ethyl-2-acetylpyridine, 6- (2-hydroxy-4-chlorophenylimino) ethyl-2-acetylpyridine, 6- (8-quinolinimino) ethyl-2-acetylpyridine, 6- (4-quinolinimino) ethyl-2-acetylpyridine, 6- (3-quinolinimino) ethyl-2-acetylpyridine, a salt thereof, a hydrate thereof, 6- (2,4, 6-trimethylphenylimino) ethyl-2-acetylpyridine, 6- (2-ethylphenylimino) ethyl-2-acetylpyridine, 6- (4-ethylphenylimino) ethyl-2-acetylpyridine, 6- (2-propylphenylimino) ethyl-2-acetylpyridine, 6- (4-propylphenylimino) ethyl-2-acetylpyridine, 6- (3-propylphenylimino) ethyl-2-acetylpyridine, 6- (2-butylphenylimino) ethyl-2-acetylpyridine, 6- (4-butylphenylimino) ethyl-2-acetylpyridine, 3- (phenylimino) ethylacetophenone, methyl ethyl-2-acetylpyridine, methyl ethyl, 3- (2, 6-Dimethylbenzimido) ethyl acetophenone, 3- (2, 6-diisopropylphenylimino) ethyl acetophenone, 3- (2-naphthylimino) ethyl acetophenone, 3- (benzylimino) ethyl acetophenone, 3- (8-quinolinimino) ethyl acetophenone, 3- (2-quinolinimino) ethyl acetophenone, 6- (butylimino) ethyl-2-propionylpyridine, 6- (hexylimino) ethyl-2-propionylpyridine, 6- (2, 6-dimethylbenzimido) ethyl-2-propionylpyridine, 6- (2, 6-diisopropylphenylimino) ethyl-2-propionylpyridine, 6- (phenylimino) ethyl-2-propionylpyridine, and mixtures thereof, 6- (pentylimino) ethyl-2-butyrylpyridine, 6- (2-naphthylimino) ethyl-2-butyrylpyridine, 6- (butylimino) propyl-2-propionylpyridine, 6- (hexylimino) butyl-2-propionylpyridine, one or more of 6- (2, 6-dimethylbenzimido) propyl-2-propionylpyridine, 6- (2, 6-diisopropylphenylimino) propyl-2-propionylpyridine, 6- (phenylimino) propyl-2-propionylpyridine, 6- (pentylimino) propyl-2-butyrylpyridine and 6- (2-naphthylimino) propyl-2-butyrylpyridine.
8. The catalyst component according to claim 1 or 2, characterized in that RIIs methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, vinyl, allyl, ethynyl, phenyl, halophenyl, alkyl-substituted phenyl, naphthyl or biphenyl; and/or, RIIIs methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, vinyl, allyl, ethynyl, phenyl, halophenyl, alkyl-substituted phenyl, naphthyl, biphenyl, ethoxyformyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, hexyloxycarbonyl, isohexoxycarbonyl, neoxyformyl, heptyloxyformyl, isoheptyloxyformyl, neoheptyloxyformyl, octyloxycarbonyl, isooctyloxyformyl or neooctyloxycarbonyl.
9. The catalyst component according to claim 1 or 2, characterized in that the aromatic acid ester compound of formula II is: ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, hexyl benzoate, heptyl benzoate, octyl benzoate, nonyl benzoate, decyl benzoate, isobutyl benzoate, isopentyl benzoate, isohexyl benzoate, isoheptyl benzoate, isooctyl benzoate, isononyl benzoate, isodecyl benzoate, neopentyl benzoate, neohexyl benzoate, neoheptyl benzoate, neooctyl benzoate, octylnonyl benzoate, neodecyl benzoate, diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dinonyl phthalate, diisohexyl phthalate, Diisoheptyl phthalate, diisooctyl phthalate, diisononyl phthalate, diisobutyl 3-methylphthalate, di-n-butyl 3-methylphthalate, diisoamyl 3-methylphthalate, di-n-pentyl 3-methylphthalate, diisooctyl 3-methylphthalate, di-n-octyl 3-methylphthalate, diisobutyl 3-ethylphthalate, di-n-butyl 3-ethylphthalate, di-n-octyl 3-ethylphthalate, diisobutyl 3-ethylphthalate, di-n-pentyl 3-ethylphthalate, diisoamyl 3-ethylphthalate, diisobutyl 3-propylphthalate, di-n-butyl 3-propylphthalate, diisobutyl 3-chlorophthalate, diisononyl 3-methylphthalate, diisobutyl 3-ethylphthalate, di-n-butyl 3-ethylphthalate, diisobutyl 3-methylphthalate, diisobuty, 3-butyl phthalate diisobutyl ester, 3-butyl phthalate di-n-butyl ester, 4-propyl phthalate diisobutyl ester, 4-butyl phthalate di-isoamyl ester, 4-chloro phthalate di-n-butyl ester, 4-chloro phthalate di-isobutyl ester, 4-chloro phthalate di-n-octyl ester, 4-methoxy phthalate di-n-butyl ester and 4-methoxy phthalate di-isobutyl ester.
10. The catalyst component according to claim 1 or 2, wherein the molar ratio of the ketimine compound of formula I to the aromatic acid ester compound of formula II is 1 (0.05-20).
11. The catalyst component according to claim 10, wherein the molar ratio of the ketimine compound of formula I to the aromatic acid ester compound of formula II is 1 (0.1-10).
12. A catalyst for the polymerization of olefins comprising: A) the catalyst component according to any one of claims 1 to 11; B) an organoaluminum compound; and optionally C) an organosilicon compound.
13. Use of the catalyst component according to any one of claims 1 to 11 or the catalyst according to claim 12 in the field of olefin polymerization.
14. Use according to claim 13, characterized in that the olefin is propylene.
CN201610847664.0A 2016-09-23 2016-09-23 Catalyst component for olefin polymerization, catalyst and application thereof Active CN107868149B (en)

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RU2019112055A RU2757372C2 (en) 2016-09-23 2017-09-22 Catalyst component for olefin polymerization, catalyst and their application
PCT/CN2017/103044 WO2018054362A1 (en) 2016-09-23 2017-09-22 Catalyst component for use in olefin polymerization, catalyst, and applications thereof
KR1020197011214A KR102466260B1 (en) 2016-09-23 2017-09-22 Catalyst components for olefin polymerization, catalysts, and uses thereof
JP2019515798A JP7178991B2 (en) 2016-09-23 2017-09-22 Catalyst components for olefin polymerization, catalysts and their applications
US16/336,102 US11325994B2 (en) 2016-09-23 2017-09-22 Catalyst component for olefin polymerization, catalyst, and use thereof
EP17852430.2A EP3517555A4 (en) 2016-09-23 2017-09-22 Catalyst component for use in olefin polymerization, catalyst, and applications thereof
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