CN107868147B

CN107868147B - Catalyst component for olefin polymerization, catalyst and application thereof

Info

Publication number: CN107868147B
Application number: CN201610846996.7A
Authority: CN
Inventors: 王军; 高明智; 马晶; 刘海涛; 蔡晓霞; 陈建华; 马吉星; 李昌秀; 胡建军; 张志会
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2016-09-23
Filing date: 2016-09-23
Publication date: 2020-09-15
Anticipated expiration: 2036-09-23
Also published as: CN107868147A

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 recent years, in the components for olefin polymerization catalysts disclosed in U.S. Pat. No. 4,497,1937 and european patent No. 0728769, special 1, 3-diether compounds containing two ether groups are used as electron donors, such as 2-isopropyl-2-isopentyl-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 commercially at present are aromatic dicarboxylic acidsEsters, such as di-n-butyl phthalate (DNBP) or diisobutyl phthalate (DIBP) (see U.S. Pat. No. 4,4784983), have 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 polydentate ligands of the C ═ N type, as found for the first time by Brookhart et al that diimine post-transition metal complexes have high catalytic activity in catalyzing olefin polymerization (Johnson l.k., Killian c.m., Brookhart m., j.am.chem.soc.,1995,117,6414; Johnson l.k., Ecking s.m., Brookhart m., j.am.chem.soc.,1996,118,267). Since then, the research on non-metallocene organic complexes has attracted great interest. McConville et al, 1996, reported a class of Ti, Zr metal complexes (formula 1) that sequester β -diamines, which is the first example of an N-N polydentate ligand-containing early transition metal complex that catalyzes olefin polymerization with high activity (Scollard J.D., McConville D.H., Payne N.C., Vital J.J, Macromolecules,1996,29, 5241; Scollard J.D., McConville D.H., J.Am.Chem.Soc.,1996,118,10008).

The beta-diamine complex (shown as formula 2) is also an important non-metallocene olefin polymerization catalyst containing N-N ligands. Due to the structural characteristics, steric hindrance and electronic effects of the ligand can be easily controlled by changing substituents on arylamine, and different metals and ligand environments can be changed, the beta-diamine ligand can be compatible with different metals in different bonding modes to form corresponding metal complexes, and the ligand compound has the characteristics of simple synthesis, easy regulation and control in structure and the like, and is a complex for researching the relationship between the structure and the catalyst performance, so that the ligand compound with the structure attracts people's extensive attention (Bourget-Merle L., Lappert M.F., Severn J.R., Chem.Rev.,2002,102,3031; Kim W.K., Fevola M.J., Liable-SandS.M., Rheindola. L., Therpooid K.H., Organometellics, 17, 4541; Jin X., Novak B.M., Maculomes, 2000, 6205, 1998, 6205).

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 component for olefin polymerization and a catalyst and use thereof. In the preparation process of the catalyst, a composite internal electron donor (such as a ketimine compound shown in a formula I and an aromatic acid ester compound shown in a 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 and hydrogen regulation sensitivity in a long period, 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 in a formula I and an aromatic acid ester compound shown in a formula II,

in the formula I, R is hydroxyl, C with or without halogen atom substituent₁～C₂₀With or without halogenC of substituent of element atom₂～C₂₀Alkenyl or C with or without halogen atom substituents₆～C₃₀An aromatic group of (a); r₁And R₂May be the same or different and are each independently hydrogen, C₁～C₂₀Alkyl of (C)₂～C₂₀Alkenyl of, C₁～C₂₀Alkoxy group of (C)₆～C₃₀Aralkyl of (2), C₆～C₃₀Alkylaryl of, C₉～C₄₀A condensed ring aromatic group of (3), a halogen atom or a hydroxyl group; a is (CR)₃R₄)_nOr a heteroatom wherein R₃And R₄May be the same or different and are each independently hydrogen, C₁～C₂₀Alkyl of (C)₂～C₂₀Alkenyl of, C₆～C₃₀Aralkyl of (2), C₆～C₃₀Alkylaryl or C of₉～C₄₀N is an integer of 0 to 6;

in the formula II, R^IIs 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); r^IIIs C₁～C₂₀Alkyl of (C)₂～C₂₀Alkenyl of, C₂～C₂₀Alkynyl or C₆～C₃₀An alkylaryl or ester or amide group; r^III、R^IV、R^VAnd R^VISame 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.

According to some embodiments, the amount of magnesium is 5 wt% to 50 wt%, the amount of titanium is 1.0 wt% to 8.0 wt%, the amount of halogen is 10 wt% to 70 wt%, and the total amount of internal electron donors is 0.1 wt% to 20 wt%, based on the weight of the catalyst component.

According to some 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 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 embodiments, R₁And R₂Respectively methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and pentyl.

According to some embodiments, A is (CR)₃R₄)_nAnd n is 1, 2,3 or 4. According to some further embodiments, a is a heteroatom, preferably a halogen, nitrogen, oxygen, phosphorus or silicon atom.

In the present invention, the ketimine compound represented by formula I is preferably: 4-butylimino-2-pentanone, 4-pentylimino-2-pentanone, 4-hexylimino-2-pentanone, 4-octylimino-2-pentanone, 4- [ (1-hydroxymethyl) propylimino ] -2-pentanone, 4-hydroxypropylimino-2-pentanone, 4-hydroxyethylimino-2-pentanone, 4-hydroxybutyimino-2-pentanone, 4-isopropylimino-2-pentanone, 4- (4-chlorophenylimino) -2-pentanone, 4- (2, 4-dichlorophenylimino) -2-pentanone, 4- (4-trifluoromethylphenylimino) -2-pentanone, and mixtures thereof, 4-phenylimino-2-pentanone, 4- (1-naphthylimino) -2-pentanone, 4- (2, 6-dimethylphenylimino) -2-pentanone, 4- (2, 6-diisopropylphenylimino) -2-pentanone, 4- (2,4, 6-trimethylphenylimino) -2-pentanone, 4- (8-quinolinylimino) -2-pentanone, 4- (4-quinolinylimino) -2-pentanone, 4- (3-quinolinylimino) -2-pentanone, 4- (2-chloro-6-hydroxyphenylimino) -2-pentanone, and mixtures thereof, 1,1, 1-trifluoro-4- (2, 6-diisopropylphenylimino) -2-pentanone, 1,1, 1-trifluoro-4- (2, 6-dimethylphenylimino) -2-pentanone, 3-methyl-4- (2, 6-dimethylphenylimino) -2-pentanone, 3-ethyl-4- (2, 6-dimethylphenylimino) -2-pentanone, 3-isopropyl-4- (2, 6-dimethylphenylimino) -2-pentanone, 3-butyl-4- (2, 6-dimethylphenylimino) -2-pentanone, 3-methyl-4- (2, 6-diisopropylphenylimino) -2-pentanone, 3-ethyl-4- (2, 6-diisopropylphenylimino) -2-pentanone, 3-isopropyl-4- (2, 6-diisopropylphenylimino) -2-pentanone, 3-butyl-4- (2, 6-diisopropylphenylimino) -2-pentanone, 1- (2-furyl) -3- (2, 6-diisopropylphenylimino) -4,4, 4-trifluoro-1-butanone, 1- (2-furyl) -3- (8-quinolinylimino) -4,4, 4-trifluoro-1-butanone, 1- (2-furyl) -3- (2, 6-dimethylbenzenylimino) -4,4, 4-trifluoro-1-butanone, 2-hexylimino-4-heptanone, 2-isopropylimino-4-heptanone, 4-hexylimino-2-heptanone, 4-isopropylimino-2-heptanone, 4- (2-trimethylsilyl) ethylimino-2-pentanone, 5-phenylimino-3-heptanone, 5- (1-naphthylimino) -3-heptanone, 5- (2-naphthylimino) -3-heptanone, 5- (8-quinolinimino) -3-heptanone, 5- (4-quinolinimino) -3-heptanone, 5- (3-quinolinimino) -3-heptanone, methyl ethyl ketone, ethyl methyl ketone, ethyl, 5- (2, 6-diisopropylimino) -3-heptanone, 5- (2, 6-dimethylbenzimido) -3-heptanone, 5-butylimino-3-heptanone, 5-isopropylimino-3-heptanone, 5-hydroxyethylimino-3-heptanone, 5-hydroxybutyimino-3-heptanone, 4-ethyl-5- (8-quinolinimino) -3-heptanone, 4-methyl-5- (8-quinolinimino) -3-heptanone, 4-ethyl-5- (1-naphthylimino) -3-heptanone, 4-ethyl-5- (2-naphthylimino) -3-heptanone, and mixtures thereof, 4-ethyl-5-phenylimino-3-heptanone, 4-butyl-5-phenylimino-3-heptanone, 4-methyl-5- (2, 6-diisopropylphenylimino) -3-heptanone, 4-ethyl-5- (2, 6-diisopropylphenylimino) -3-heptanone, 4-isopropyl-5- (2, 6-diisopropylphenylimino) -3-heptanone, 4-butyl-5- (2, 6-diisopropylphenylimino) -3-heptanone, 4-methyl-5- (2, 6-dimethylbenzenylimino) -3-heptanone, 4-ethyl-5- (2, 6-Dimethylbenzimidyl) -3-heptanone, 3-isopropylimino-5-octanone, 3- (2, 6-diisopropylphenylimino) -5-octanone, 5-isopropylimino-3-octanone, 6-isopropylimino-4-octanone, 5- (2, 6-diisopropylphenylimino) -2-heptanone, 5- (2,4, 6-trimethylphenylimino) -2-heptanone, 4-methyl-5- (2, 6-dimethylbenzimidyl) -2-heptanone, 4-ethyl-6- (2, 6-diisopropylphenylimino) -2-heptanone, 4-isopropyl-6- (2, 6-diisopropylphenylimino) -2-heptanone, 6- (2, 6-dimethylbenzenylimino) -3-octanone, 3- (2, 6-diisopropylphenylimino) -1, 3-diphenyl-1-propanone, 4- (2, 6-diisopropylphenylimino) -4-phenyl-2-butanone, 3- (2, 6-dimethylbenzenylimino) -1, 3-diphenyl-1-propanone, 3- (2, 6-diisopropylphenylimino) -1-phenyl-1-butanone, 3- (2, 6-dimethylbenzenylimino) -1-phenyl-1-butanone, 3- (8-quinolinylimino) -1, 3-diphenyl-1-acetone and 3- (3-quinolinylimino) -1, 3-diphenyl-1-acetone.

According to some embodiments, R^IIs 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 embodiments, R^IIIs 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.

In the present invention, the aromatic acid ester compound represented by formula II is preferably: 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. The homogeneous solution is mixed with titanium tetrahalide or its derivative, and when a precipitation assistant is present in the reaction system, a solid is precipitated. The compounds of formula I and formula II are carried on a solid and then treated with 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～C₁₅Oxygen of aliphatic alkane, olefin, diolefin, halogenated aliphatic olefin, diolefinAt least one of an amide, a glycidyl ether and an internal ether. 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 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 carrier or adding the 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 compounds of the formula I and the formula II, treating with titanium tetrahalide or an inert diluent, and finally filtering, washing and drying to obtain the solid catalyst component containing titanium, magnesium, halogen, electron donors 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: 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 to the compound of formula I and formula II. Mixing the solution with titanium tetrahalide or its derivatives, maintaining at low temperature for a period of time, heating, treating with titanium tetrahalide or inert diluent, filtering, washing, and drying to obtain the solid catalyst containing titanium, magnesium, halogen, electron donor, etc.

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. The homogeneous solution is mixed with titanium tetrahalide or its derivative, and when a precipitation assistant is present in the reaction system, a solid is precipitated. The compound of the formula II is carried on a solid, treated by titanium tetrahalide and then treated by the compound of the formula I, then treated by inert diluent, and finally filtered, washed and dried to obtain the solid catalyst containing components such as titanium, magnesium, halogen, electron donor and the like.

The present invention also provides a catalyst for the polymerization of olefins, in particular propylene, comprising: A) the catalyst component; B) an organoaluminum compound; and C) an organosilicon compound.

Wherein A) and B) are essential components of the catalyst, and C) is an optional component of the catalyst.

In the present invention, the organoaluminum compound is selected from the group consisting of trialkylaluminums, dialkylaluminum chlorides, alkylaluminum chlorides, alkylaluminoxanes, preferably C₁-C₆Of trialkylaluminum and dialkylaluminum chlorides, e.g. trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydride, and monoaluminum hydrideAt least one of diisobutylaluminum hydride, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloride. More preferably triethylaluminium and/or triisobutylaluminium.

In the present invention, the component B) may be used in an amount conventionally used in the art. Generally, the molar ratio of the organoaluminum compound B) to the catalyst component A) is from 5 to 2000:1, calculated as aluminum/titanium.

The organosilicon compounds according to the invention are preferably of the formula R⁵ _mSi(OR⁶)_4-mA compound shown in the formula, wherein m is more than or equal to 0 and less than or equal to 3, R⁵And R⁶Are identical or different alkyl, cycloalkyl, aryl, haloalkyl, amino, R⁵And 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, dipentydimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, dimethyldiethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyldimethylmethoxysilane, hexyldiethylmethoxysilane, dicyclopentyldimethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, 4-methylcyclohexylmethyldimethoxysilane, 4-methylcyclohexylethyldimethoxysilane, 4-methylcyclohexylpropyldimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane, 4-methylcyclohexylpentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like, and may preferably be selected from cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane and/or diisopropyldimethyldimethoxysilaneAn oxysilane. These organosilicon compounds may be used alone or in combination of two or more.

In the present invention, the amount of the component C) is not particularly limited. In a preferred case, the molar ratio of organosilicon compound C) to catalyst component A) is (0-500):1, calculated as silicon/titanium.

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, particularly propylene polymerization, the hydrogen regulation sensitivity of the catalyst is obviously improved, the catalyst has high activity and long-period activity, and the molecular weight distribution of the obtained polymer is wide.

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): measured at 150 ℃ using PL-GPC220 and trichlorobenzene as a solvent (standard: polystyrene, flow rate: 1.0mL/min, column: 3X Plgel 10um MlxED-B300 x7.5 nm).

4. And (3) activity calculation: the catalyst activity (mass of polyolefin prepared)/(mass of catalyst solid component) g/g.

Example 1

Synthesis of 4- (2, 6-diisopropylphenylimino) -2-pentanone: in a three-necked flask, after nitrogen purging, 2.00 g of acetylacetone, 80 ml of isopropyl alcohol, and 0.3 ml of glacial acetic acid were added, and the mixture was stirred at room temperature. At room temperature, 50ml of isopropanol solution containing 3.54 g of 2, 6-diisopropylaniline is slowly added dropwise, and after the addition is finished, the reaction is stirred for 4 hours, and then the temperature is increased for reflux reaction for 16 hours. The reaction solution was concentrated under reduced pressure and separated by column chromatography to give 3.52 g of 4- (2, 6-diisopropylphenylimino) -2-pentanone (yield 68%).¹H-NMR(,ppm,TMS,CDCl₃):7.63～7.60(1H,m,ArH),7.02～6.98(2H,m,ArH),3.35～3.31(2H,m,CH),3.24～3.20(2H,s,CH₂),2.10～2.07(3H,s,CH₃),1.38～1.32(6H,m,CH₃),1.25～1.21(6H,m,CH₃),1.03～0.98(3H,m,CH₃) (ii) a Mass Spectrometry, FD-MS: 259.

Example 2

Synthesizing 4-phenylimino-2-pentanone: in a 250 ml three-necked flask, after nitrogen gas was purged, 2.00 g of acetylacetone, 60ml of anhydrous ethanol, and 15 ml of toluene were added and stirred at room temperature. 1.92 g of aniline dissolved in 40 ml of ethanol solution is slowly added dropwise at room temperature, stirred for 2 hours and then heated for reflux reaction for 12 hours. The reaction solution was concentrated under reduced pressure and separated by column chromatography to give 2.03 g of 4-phenylimino-2-pentanone (58% yield).¹H-NMR(,ppm,TMS,CDCl₃):7.96～7.90(3H,m,ArH),7.53～7.47(2H,m,ArH),3.22～3.18(2H,s,CH₂),2.10～2.06(3H,s,CH₃),1.02～0.97(3H,s,CH₃) (ii) a Mass Spectrometry, FD-MS: 175.

Example 3

Synthesis of 4- (2, 6-dimethylbenzimido) -2-pentanone: in a three-necked flask, after nitrogen purging, 2.00 g of acetylacetone, 80 ml of isopropyl alcohol, and 0.2 ml of glacial acetic acid were added, and the mixture was stirred at room temperature. At room temperature, 30 ml of isopropanol solution containing 2.42 g of 2, 6-dimethylaniline is slowly added dropwise, after the addition, the reaction is stirred for 2 hours, and then the temperature is increased for reflux reaction for 18 hours. The reaction solution was concentrated, and subjected to column chromatography to obtain 1.42 g of 4- (2, 6-dimethylbenzimido) -2-pentanone as a pale yellow liquid (yield: 70%).¹H-NMR(,ppm,TMS,CDCl₃):7.62～7.59(1H,m,ArH),7.02～6.98(2H,m,ArH),3.31～3.28(2H,m,CH₂),2.54～2.51(6H,m,CH₃),2.10～2.07(3H,s,CH₃),1.04～0.99(3H,s,CH₃) (ii) a Mass Spectrometry, FD-MS: 203.

Example 4

Synthesis of 4- (2-hydroxypropylphenylimino) -2-pentanone: in a 250 ml three-necked flask, after nitrogen gas was purged, 2.00 g of acetylacetone, 80 ml of anhydrous ethanol, and 30 ml of toluene were added and stirred uniformly. Slowly dripping 40 ml of absolute ethanol solution containing 3.04 g of 2-hydroxypropyl aniline at room temperature, stirring at room temperature for reaction for 4 hours, and heating and refluxing for reaction for 24 hours. The reaction solution was concentrated under reduced pressure, and subjected to column chromatography to give 3.05 g of 4- (2-hydroxypropylphenylimino) -2-pentanone (yield 58%).¹H-NMR(,ppm,TMS,CDCl₃):7.66～7.64(1H,m,ArH),7.38～7.36(2H,m,ArH),7.08～7.06(1H,m,ArH),3.67～3.63(1H,s,OH),3.45～3.43(2H,s,CH₂),3.15～3.13(2H,s,CH₂),2.65～2.63(2H,s,CH₂),2.14～2.12(3H,s,CH₃),1.96～1.94(3H,s,CH₃),1.45～1.42(2H,m,CH₃) (ii) a Mass Spectrometry, FD-MS: 233.

Example 5

Synthesis of compound 4- (2,4, 6-trimethylphenylimino) -2-pentanone: in a three-necked flask, after nitrogen gas was purged, 2.00 g of acetylacetone, 80 ml of anhydrous ethanol, and 0.5 ml of glacial acetic acid were added, and the mixture was stirred at room temperature. Slowly dripping 50ml ethanol solution containing 2.70 g 2,4, 6-trimethylaniline at room temperature, stirring for 2 hours after the addition, and heating and refluxing for 36 hours. The reaction solution was concentrated under reduced pressure, and subjected to column chromatography to give 2.70 g of 4- (2,4, 6-trimethylphenylimino) -2-pentanone (yield 62%).¹H-NMR(,ppm,TMS,CDCl₃):7.86～7.84(2H,m,ArH),3.28～3.24(2H,m,CH₂),2.54～2.51(9H,m,CH₃),2.12～2.08(3H,s,CH₃),1.18～1.14(3H,s,CH₃) (ii) a Mass Spectrometry, FD-MS: 217. Example 6

Synthesizing 4- (2, 6-diisopropylphenylimino) -4-phenyl-2-butanone: into a 250 ml three-necked flask purged with nitrogen, 1.62 g was chargedIs added to the mixture of benzoylacetone (b), 60ml of isopropanol and 0.5 ml of formic acid, and stirred at room temperature. Slowly dropping 1.77 g of 2, 6-diisopropylaniline dissolved in 40 ml of isopropanol solution at room temperature, stirring for reaction for 4 hours after the addition is finished, and heating and refluxing for reaction for 36 hours. The reaction solution was concentrated under reduced pressure to give a pale yellow solid, which was recrystallized from ethanol to give 2.02 g of white crystals (yield 63%).¹H-NMR(,ppm,TMS,CDCl₃):7.72～7.68(3H,m,ArH),7.46～7.40(3H,m,ArH),7.02～6.98(2H,m,ArH),3.35～3.31(2H,m,CH),3.24～3.20(2H,s,CH₂),2.10～2.07(3H,s,CH₃),1.38～1.32(6H,m,CH₃),1.25～1.21(6H,m,CH₃) (ii) a Mass Spectrometry, FD-MS: 321.

Example 7

Synthesis of 3- (2, 6-diisopropylphenylimino) -1, 3-diphenyl-1-propanone: in a 250 ml three-necked flask after purging with nitrogen, 2.24 g of dibenzoylmethane, 80 ml of isopropanol and 0.5 ml of acetic acid were added and stirred at room temperature. Slowly dripping 1.80 g of 2, 6-diisopropylaniline dissolved in 20 ml of isopropanol solution at room temperature, stirring for reacting for 2 hours after the dripping is finished, heating for reflux reaction for 8 hours, and cooling to room temperature. The reaction solution was concentrated under reduced pressure to give a yellow solid, which was recrystallized from ethanol to give 2.65 g (yield: 69%) of pale yellow crystals.¹H-NMR(,ppm,TMS,CDCl₃):7.86～7.84(2H,m,ArH),7.68～7.63(3H,m,ArH),7.46～7.40(3H,m,ArH),7.32～7.28(3H,m,ArH),7.02～6.98(2H,m,ArH),3.35～3.31(2H,m,CH),3.24～3.20(2H,s,CH₂),1.28～1.25(6H,m,CH₃),1.18～1.14(6H,m,CH₃) (ii) a Mass Spectrometry, FD-MS: 383.

Example 8

Synthesizing 3- (2, 6-diisopropylphenylimino) -1-phenyl-1-butanone: in a 250 ml three-necked flask after purging with nitrogen, 1.62 g of benzoylacetone, 60ml of isopropyl alcohol and 0.4 ml of formic acid were added and stirred at room temperature. Slowly dropping 1.77 g of 2, 6-diisopropylaniline dissolved in 40 ml of isopropanol solution at room temperature, stirring and reacting for 12 hours after the dropping, and heating and refluxing for reacting for 12 hours. Concentrating the reaction solution under reduced pressure to obtain light yellow solid, and adding ethylRecrystallization of the alcohol gave 1.28 g of white crystals (40% yield).¹H-NMR(,ppm,TMS,CDCl₃):7.86～7.82(3H,m,ArH),7.46～7.42(2H,m,ArH),7.26～7.14(2H,m,ArH),3.35～3.31(2H,m,CH),3.24～3.21(2H,m,CH₂),1.36～1.32(6H,m,CH₃)，1.24～1.21(6H,m,CH₃) (ii) a Mass Spectrometry, FD-MS: 321.

Example 9

Synthesis of 5- (2, 6-diisopropylphenylimino) -3-heptanone: in a 250 ml three-necked flask after purging with nitrogen, 1.28 g of 3, 5-heptanedione, 80 ml of isopropanol and 0.2 ml of acetic acid were added, and 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 dripping is finished, heating for reflux reaction for 24 hours, and cooling to room temperature. The reaction solution was concentrated under reduced pressure to give a yellow liquid, which was separated by column chromatography to give 1.55 g (yield: 54%) of a pale yellow liquid.¹H-NMR(,ppm,TMS,CDCl₃):7.66～7.64(1H,m,ArH)，7.11～7.08(2H,m,ArH),3.31～3.28(2H,m,CH),3.22～3.18(2H,s,CH₂),2.50～2.47(2H,m,CH₂),1.68～1.66(2H,m,CH₂),1.28～1.25(6H,m,CH₃),1.18～1.14(6H,m,CH₃),1.12～1.07(3H,t,CH₃),0.98～0.94(3H,t,CH₃) (ii) a Mass Spectrometry, FD-MS: 287.

Example 10

Synthesis of 4- (1-naphthylimino) -2-pentanone: in a three-necked flask purged with nitrogen, 2.00 g of acetylacetone, 100ml of toluene, and 0.5 g of p-toluenesulfonic acid were added, and the mixture was stirred at room temperature. A toluene solution containing 2.84 g of 1-naphthylamine was slowly added dropwise at room temperature, and the mixture was refluxed for 24 hours. The reaction solution was subjected to solvent removal under reduced pressure, and 100ml of a saturated sodium bicarbonate solution was added thereto and stirred for 2 hours. Extraction is carried out three times with 50ml of anhydrous ether, the organic phases are combined, dried over anhydrous sodium sulfate, the solvent is removed and the initial product is recrystallized from ethanol to give 2.70 g of 4- (1-naphthylimino) -2-pentanone (yield 60%).¹H-NMR(,ppm,TMS,CDCl₃):8.14～8.10(3H,m,ArH),7.86～7.82(2H,m,ArH),7.34～7.30(2H,m,ArH),3.22～3.18(2H,s,CH₂),2.10～2.07(3H,s,CH₃)，1.08～1.05(3H,s,CH₃) (ii) a Mass Spectrometry, FD-MS: 225.

Example 11

Synthesis of 4- (2, 6-diisopropylphenylimino) -1,1, 1-trifluoro-2-pentanone: in a three-necked flask purged with nitrogen, 1.54 g of 1,1, 1-trifluoro-2, 4-pentanedione, 100ml of toluene and 0.35 g of p-toluenesulfonic acid were added and stirred at room temperature. 1.78 g of 2, 6-diisopropylaniline was slowly added dropwise at room temperature, and the mixture was refluxed and dehydrated for 24 hours. After cooling to room temperature, the reaction solution was freed of the solvent under reduced pressure, and 100ml of saturated sodium bicarbonate solution were added and stirred for 2 hours. Extraction is carried out three times with 60ml of anhydrous ether, the organic phases are combined, dried over anhydrous sodium sulfate, the solvent is removed, and the crude product is isolated by column chromatography to give 1.86 g of a pale yellow liquid (yield 60%).¹H-NMR(,ppm,TMS,CDCl₃):7.63～7.60(1H,m,ArH),7.06～7.03(2H,m,ArH),3.36～3.32(2H,m,CH),3.22～3.18(2H,s,CH₂),1.25～1.22(6H,m,CH₃),1.16～1.13(6H,m,CH₃),0.98～0.95(3H,t,CH₃) (ii) a Mass Spectrometry FD-MS 313.

Example 12

Synthesis of 4-ethyl-5- (2, 6-diisopropylphenylimino) -3-heptanone: in a 250 ml three-necked flask after purging with nitrogen, 2.56 g of 3, 5-heptanedione, 80 ml of isopropanol and 0.3 ml of acetic acid were added, and stirred at room temperature. Slowly dripping 3.56 g of 2, 6-diisopropylaniline dissolved in 40 ml of isopropanol solution at room temperature, stirring for reacting for 2 hours after the dripping is finished, heating for reflux reaction for 36 hours, and cooling to room temperature. The reaction solution was concentrated under reduced pressure to give a yellow liquid, which was separated by column chromatography to give 3.30 g (yield: 54%) of a pale yellow liquid.¹H-NMR(,ppm,TMS,CDCl₃):7.65～7.62(1H,m,ArH)，7.16～7.12(2H,m,ArH),3.32～3.30(1H,m,CH),3.24～3.21(2H,m,CH),2.53～2.50(2H,m,CH₂),1.86～1.82(4H,m,CH₂),1.26～1.22(6H,m,CH₃),1.18～1.14(6H,m,CH₃),1.10～1.08(3H,t,CH₃),0.90～0.86(6H,m,CH₃) (ii) a Mass Spectrometry, FD-MS: 315.

Example 13

Preparation of the catalyst component: at the warpIn a reactor fully replaced by high-purity nitrogen, 4.8g of magnesium chloride, 95mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate (TBP) are sequentially added, and the temperature is raised to 50 ℃ with 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 below-25 ℃, and TiCl is dropwise added within 1 hour₄Slowly raising the temperature to 80 ℃, and gradually separating out solids. DNBP (di-n-butyl phthalate, 0.003 mol) and 4- (2, 6-diisopropylphenylimino) -2-pentanone (0.006 mol) were added and the temperature was maintained for 1 hour. After hot filtration, 150mL of toluene was added and the mixture was washed twice to obtain a solid, and 100mL of toluene was added and stirred for 30 minutes, and the temperature was raised to 110 ℃ to carry out three times of washing for 10 minutes each. Additional hexane 60mL was added and washed twice to give 7.2g of a catalyst component containing Ti: 3.7%, Mg: 22.8%, Cl: 52.6 percent.

Example 14

Preparation of the catalyst component: in the same manner as in example 13, only 4- (2, 6-diisopropylphenylimino) -2-pentanone was replaced with 4- (2, 6-dimethylbenzenylimino) -2-pentanone.

Example 15

Preparation of the catalyst component: in the same manner as in example 13, only 4- (2, 6-diisopropylphenylimino) -2-pentanone was replaced by 4- (2,4, 6-trimethylphenylimino) -2-pentanone.

Example 16

Preparation of the catalyst component: as in example 13, only 4- (2, 6-diisopropylphenylimino) -2-pentanone was replaced by 5- (2, 6-diisopropylphenylimino) -3-heptanone.

Example 17

Preparation of the catalyst component: as in example 13, only 4- (2, 6-diisopropylphenylimino) -2-pentanone was replaced by 4- (1-naphthylimino) -2-pentanone.

Example 18

Preparation of the catalyst component: as in example 13, only 4- (2, 6-diisopropylphenylimino) -2-pentanone was replaced by 4- (2-hydroxypropylphenylimino) -2-pentanone.

Example 19

Preparation of the catalyst component: just DNBP was replaced with DIBP (diisobutylphthalate) as in example 13.

Example 20

Preparation of the catalyst component: 4.8g of magnesium chloride, 95mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate (TBP) were sequentially added to a reactor fully replaced with high-purity nitrogen, and the mixture was heated to 50 ℃ with 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 below-25 ℃, and TiCl is dropwise added within 1 hour₄Slowly raising the temperature to 80 ℃. The solid was gradually precipitated, DNBP (0.006 mol) was added and the temperature was maintained for 1 hour. After hot filtration, 150mL of toluene was added and the mixture was washed twice to obtain a solid, and 100mL of toluene was added and stirred for 30 minutes, and the temperature was raised to 110 ℃ to carry out three times of washing for 10 minutes each. Then, 60mL of hexane and 4- (2, 6-diisopropylphenylimino) -2-pentanone (0.003 mol) were added thereto, and the mixture was stirred for 30 minutes. And washed twice with 60mL of hexane to obtain 7.4g of a catalyst component containing Ti: 3.8%, Mg: 23.8%, Cl: 53.6 percent.

Example 21

Preparation of the catalyst component: 300ml of LTiCl is added into a reactor which is fully replaced by high-purity nitrogen₄Then, the temperature was reduced to-20 ℃ and 7.0g of a magnesium chloride alcoholate carrier was added (see patent CN 1330086A). While stirring, the temperature was raised to 40 ℃ in stages, DNBP (0.003 mol) and 4- (2, 6-diisopropylphenylimino) -2-pentanone (0.003 mol) were added, and the temperature was maintained for 2 hours. After filtration, TiCl is added₄100mL of the solution was heated to 110 ℃ and treated three times. An additional 60mL of hexane was added and the mixture was washed three times. 7.2g of a catalyst component containing Ti: 3.4%, Mg: 21.2%, Cl: 50.1 percent.

Example 22

Preparation of the catalyst component: 300ml of LTiCl is added into a reactor which is fully replaced by high-purity nitrogen₄Then, the temperature was reduced to-20 ℃ and 7.0g of magnesium ethoxide was added. While stirring, the temperature was raised to 40 ℃ in stages, DNBP (0.003 mol) and 4- (2, 6-diisopropylphenylimino) -2-pentanone (0.003 mol) were added, and the temperature was maintained for 3 hours. After filtration, TiCl is added₄100mL of the solution was heated to 110 ℃ and treated three times. An additional 60mL of hexane was added and the mixture was washed three times. To obtain a catalystComponent 6.7g, comprising Ti: 3.2%, Mg: 24.6%, Cl: 54.3 percent.

Example 23

Propylene polymerization reaction: after the 5L stainless steel reaction kettle is fully replaced by the gaseous propylene, adding AlEt₃2.5mL and 5mL of methylcyclohexyldimethoxysilane (CHMMS) were added to make Al/Si (mol) ═ 25. Then, 10mg of the solid component prepared in example 13 and 1.2NL of hydrogen were added thereto, and 2.5L of liquid propylene was introduced thereinto, and the temperature was raised to 70 ℃ and maintained at this temperature for 1 hour. The PP resin is obtained after cooling, pressure releasing and discharging, and the results are shown in Table 1.

Example 24

Propylene polymerization reaction: in the same manner as in example 23, only the catalyst component obtained in example 14 was used in place of the catalyst component, and the results are shown in Table 1.

Example 25

Propylene polymerization reaction: in the same manner as in example 23, the catalyst component was replaced with only the catalyst component obtained in example 15, and the results are shown in Table 1.

Example 26

Propylene polymerization reaction: in the same manner as in example 23, only the catalyst component obtained in example 16 was used in place of the catalyst component, and the results are shown in Table 1.

Example 27

Propylene polymerization reaction: in the same manner as in example 23, only the catalyst component obtained in example 17 was used in place of the catalyst component, and the results are shown in Table 1.

Example 28

Propylene polymerization reaction: in the same manner as in example 23, only the catalyst component obtained in example 18 was used in place of the catalyst component, and the results are shown in Table 1.

Example 29

Propylene polymerization reaction: in the same manner as in example 23, only the catalyst component obtained in example 19 was used in place of the catalyst component, and the results are shown in Table 1.

Example 30

Propylene polymerization reaction: in the same manner as in example 23, only the catalyst component obtained in example 20 was used in place of the catalyst component, and the results are shown in Table 1.

Example 31

Propylene polymerization reaction: in the same manner as in example 23, only the catalyst component obtained in example 21 was used in place of the catalyst component, and the results are shown in Table 1.

Example 32

Propylene polymerization reaction: in the same manner as in example 23, only the catalyst component obtained in example 22 was used in place of the catalyst component, and the results are shown in Table 1.

Example 33

Propylene polymerization reaction: as in example 23, the polymerization time was prolonged to 2 hours, and the results are shown in Table 1.

Example 34

Propylene polymerization reaction: as in example 23, the polymerization time was extended to only 3 hours, and the results are shown in Table 1.

Example 35

Propylene polymerization reaction: as in example 30, the polymerization time was prolonged to 2 hours, and the results are shown in Table 1.

Example 36

Propylene polymerization reaction: as in example 30, the polymerization time was extended to only 3 hours, and the results are shown in Table 1.

Example 37

Propylene polymerization reaction: as in example 23, the amount of hydrogenation was changed to 7.2NL only, and the results are shown in Table 1.

Comparative example 1

Preparation of the catalyst component: 4.8g of magnesium chloride, 95mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate (TBP) were sequentially added to a reactor fully replaced with high-purity nitrogen, and the mixture was heated to 50 ℃ with 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 below-25 ℃, and TiCl is dropwise added within 1 hour₄Slowly raising the temperature to 80 ℃, and gradually separating out solids. DNBP (0.006 mol) was added and the temperature was maintained for 1 hour. After hot filtration, 150mL of toluene was added and the mixture was washed twice to obtain a solid, and 100mL of toluene was added and the temperature was raised to 110 ℃ to carry out three times of washing for 10 minutes each. 60mL of hexane was added, the mixture was stirred for 30 minutes, and then 60mL of hexane was added thereto, and the mixture was washed three times.7.4g of a catalyst component containing Ti: 2.4%, Mg: 22.0%, Cl: 50.6 percent.

Propylene polymerization reaction: after the 5L stainless steel reaction kettle is fully replaced by the gaseous propylene, adding AlEt₃2.5mL of methylcyclohexyldimethoxysilane (CHMMS)5mL of Al/Si (mol) (25), 10mg of the solid fraction prepared above 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.

Comparative example 2

Propylene polymerization reaction: after the 5L stainless steel reaction kettle is fully replaced by the gaseous propylene, adding AlEt₃2.5mL and 5mL of methylcyclohexyldimethoxysilane (CHMMS) were added to make Al/Si (mol) () 25, 10mg of the solid component prepared in comparative example 1 and 7.2NL of hydrogen 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 then the temperature was lowered and the pressure was released to obtain a PP resin, and the results are shown in Table 1.

TABLE 1

As can be seen from the above examples and comparative examples, when the catalyst of the present invention is used in propylene polymerization, the hydrogen response of the catalyst is significantly improved, the catalyst has high activity and 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

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,

in the formula I, R is 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～C₂₀An aromatic group of (a);

R₁and R₂Identical or different, R₁Is hydrogen, C₁～C₂₀Alkyl of (C)₂～C₂₀Alkenyl of, C₁～C₂₀Alkoxy group of (C)₆～C₃₀Aralkyl of (2), C₆～C₃₀Alkylaryl of, C₉～C₄₀A condensed ring aromatic group of (3), a halogen atom or a hydroxyl group;

R₂is C₁～C₂₀Alkyl of (C)₂～C₂₀Alkenyl of, C₁～C₂₀Alkoxy group of (C)₆～C₃₀Aralkyl of (2), C₆～C₃₀Alkylaryl of, C₉～C₄₀A condensed ring aromatic group of (3), a halogen atom or a hydroxyl group;

a is (CR)₃R₄)_nOr a heteroatom wherein R₃And R₄The same or different are respectively and independently hydrogen and C₁～C₂₀Alkyl of (C)₂～C₂₀Alkenyl of, C₆～C₃₀Aralkyl of (2), C₆～C₃₀Alkylaryl or C of₉～C₄₀N is an integer of 0 to 6;

in the formula II, R^IIs 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); r^IIIs C₁～C₂₀Alkyl of (C)₂～C₂₀Alkenyl of, C₂～C₂₀Alkynyl or C₆～C₃₀An alkylaryl or ester or amide group; r^III、R^IV、R^VAnd R^VISame 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 internal electron donor 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 wherein 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; r₁And R₂Respectively methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl.

4. The catalyst component according to claim 3 in which the group containing a heterocyclic compound is an azole-containing group, a pyridine-containing group, a pyrimidine-containing group or a quinoline-containing group.

5. The catalyst component according to any of claims 1 to 4 characterized in that A is (CR)₃R₄)_nAnd n is 1, 2,3 or 4.

6. The catalyst component according to any of claims 1 to 4 in which R is^IIs 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.

7. The catalyst component according to any of claims 1 to 4 in which R is^IIIs 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.

8. The catalyst component according to claim 1, wherein the imine compound of formula I is: 4-butylimino-2-pentanone, 4-pentylimino-2-pentanone, 4-hexylimino-2-pentanone, 4-octylimino-2-pentanone, 4- [ (1-hydroxymethyl) propylimino ] -2-pentanone, 4-hydroxypropylimino-2-pentanone, 4-hydroxyethylimino-2-pentanone, 4-hydroxybutyimino-2-pentanone, 4-isopropylimino-2-pentanone, 4- (4-chlorophenylimino) -2-pentanone, 4- (2, 4-dichlorophenylimino) -2-pentanone, 4- (4-trifluoromethylphenylimino) -2-pentanone, and mixtures thereof, 4-phenylimino-2-pentanone, 4- (1-naphthylimino) -2-pentanone, 4- (2, 6-dimethylphenylimino) -2-pentanone, 4- (2, 6-diisopropylphenylimino) -2-pentanone, 4- (2,4, 6-trimethylphenylimino) -2-pentanone, 4- (8-quinolinylimino) -2-pentanone, 4- (4-quinolinylimino) -2-pentanone, 4- (3-quinolinylimino) -2-pentanone, 4- (2-chloro-6-hydroxyphenylimino) -2-pentanone, and mixtures thereof, 1,1, 1-trifluoro-4- (2, 6-diisopropylphenylimino) -2-pentanone, 1,1, 1-trifluoro-4- (2, 6-dimethylphenylimino) -2-pentanone, 3-methyl-4- (2, 6-dimethylphenylimino) -2-pentanone, 3-ethyl-4- (2, 6-dimethylphenylimino) -2-pentanone, 3-isopropyl-4- (2, 6-dimethylphenylimino) -2-pentanone, 3-butyl-4- (2, 6-dimethylphenylimino) -2-pentanone, 3-methyl-4- (2, 6-diisopropylphenylimino) -2-pentanone, 3-ethyl-4- (2, 6-diisopropylphenylimino) -2-pentanone, 3-isopropyl-4- (2, 6-diisopropylphenylimino) -2-pentanone, 3-butyl-4- (2, 6-diisopropylphenylimino) -2-pentanone, 1- (2-furyl) -3- (2, 6-diisopropylphenylimino) -4,4, 4-trifluoro-1-butanone, 1- (2-furyl) -3- (8-quinolinylimino) -4,4, 4-trifluoro-1-butanone, 1- (2-furyl) -3- (2, 6-dimethylbenzenylimino) -4,4, 4-trifluoro-1-butanone, 2-hexylimino-4-heptanone, 2-isopropylimino-4-heptanone, 4-hexylimino-2-heptanone, 4-isopropylimino-2-heptanone, 4- (2-trimethylsilyl) ethylimino-2-pentanone, 5-phenylimino-3-heptanone, 5- (1-naphthylimino) -3-heptanone, 5- (2-naphthylimino) -3-heptanone, 5- (8-quinolinimino) -3-heptanone, 5- (4-quinolinimino) -3-heptanone, 5- (3-quinolinimino) -3-heptanone, methyl ethyl ketone, ethyl methyl ketone, ethyl, 5- (2, 6-diisopropylimino) -3-heptanone, 5- (2, 6-dimethylbenzimido) -3-heptanone, 5-butylimino-3-heptanone, 5-isopropylimino-3-heptanone, 5-hydroxyethylimino-3-heptanone, 5-hydroxybutyimino-3-heptanone, 4-ethyl-5- (8-quinolinimino) -3-heptanone, 4-methyl-5- (8-quinolinimino) -3-heptanone, 4-ethyl-5- (1-naphthylimino) -3-heptanone, 4-ethyl-5- (2-naphthylimino) -3-heptanone, and mixtures thereof, 4-ethyl-5-phenylimino-3-heptanone, 4-butyl-5-phenylimino-3-heptanone, 4-methyl-5- (2, 6-diisopropylphenylimino) -3-heptanone, 4-ethyl-5- (2, 6-diisopropylphenylimino) -3-heptanone, 4-isopropyl-5- (2, 6-diisopropylphenylimino) -3-heptanone, 4-butyl-5- (2, 6-diisopropylphenylimino) -3-heptanone, 4-methyl-5- (2, 6-dimethylbenzenylimino) -3-heptanone, 4-ethyl-5- (2, 6-Dimethylbenzimidyl) -3-heptanone, 3-isopropylimino-5-octanone, 3- (2, 6-diisopropylphenylimino) -5-octanone, 5-isopropylimino-3-octanone, 6-isopropylimino-4-octanone, 5- (2, 6-diisopropylphenylimino) -2-heptanone, 5- (2,4, 6-trimethylphenylimino) -2-heptanone, 4-methyl-5- (2, 6-dimethylbenzimidyl) -2-heptanone, 4-ethyl-6- (2, 6-diisopropylphenylimino) -2-heptanone, 4-isopropyl-6- (2, 6-diisopropylphenylimino) -2-heptanone, 6- (2, 6-dimethylbenzenylimino) -3-octanone, 3- (2, 6-diisopropylphenylimino) -1, 3-diphenyl-1-propanone, 4- (2, 6-diisopropylphenylimino) -4-phenyl-2-butanone, 3- (2, 6-dimethylbenzenylimino) -1, 3-diphenyl-1-propanone, 3- (2, 6-diisopropylphenylimino) -1-phenyl-1-butanone, 3- (2, 6-dimethylbenzenylimino) -1-phenyl-1-butanone, 3- (8-quinolinylimino) -1, 3-diphenyl-1-propanone and 3- (3-quinolinylimino) -1, 3-diphenyl-1-propanone.

9. The catalyst component according to any of claims 1 to 4, wherein 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 any one of claims 1 to 4, wherein the molar ratio of the ketimine compound of formula I to the aromatic acid ester compound of formula II is 1 (0.05 to 20).

11. The catalyst component according to any one of claims 1 to 4, wherein the molar ratio of the ketimine compound of formula I to the aromatic acid ester compound of formula II is 1 (0.1 to 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 of the catalyst component according to any one of claims 1 to 11 or the catalyst according to claim 12 in the field of propylene polymerization.