CN109280110B - Solid catalyst component for olefin polymerization, olefin polymerization catalyst, application thereof and ethylene copolymer - Google Patents

Solid catalyst component for olefin polymerization, olefin polymerization catalyst, application thereof and ethylene copolymer Download PDF

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CN109280110B
CN109280110B CN201710592386.3A CN201710592386A CN109280110B CN 109280110 B CN109280110 B CN 109280110B CN 201710592386 A CN201710592386 A CN 201710592386A CN 109280110 B CN109280110 B CN 109280110B
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catalyst component
solid catalyst
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titanium
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CN109280110A (en
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黄庭
孙竹芳
郭子芳
周俊领
谢伦嘉
苟清强
杨红旭
朱孝恒
李秉毅
黄廷杰
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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 PCT/CN2018/096248 priority patent/WO2019015638A1/en
Priority to EP18835679.4A priority patent/EP3656754B1/en
Priority to RU2020103744A priority patent/RU2740916C1/en
Priority to CN201880002860.5A priority patent/CN109526217B/en
Priority to BR112020001201-7A priority patent/BR112020001201B1/en
Priority to US16/631,482 priority patent/US11401356B2/en
Priority to JP2020502696A priority patent/JP7038797B2/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
    • 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
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    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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    • 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
    • C08F4/647—Catalysts containing a specific non-metal or metal-free compound
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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
    • 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
    • C08F4/6494—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen

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Abstract

The invention belongs to the field of olefin polymerization catalysts, and particularly relates to a solid catalyst component for olefin polymerization, an olefin polymerization catalyst, application thereof and an ethylene copolymer. The solid catalyst component comprises magnesium, titanium, halogen and an internal electron donor compound, wherein the internal electron donor compound comprises at least one of cyclotri-veratrolene shown in formula (I) and derivatives thereof, and in the formula (I), M is1、M2、M3、M4、M5And M6Each selected from hydrogen, hydroxyl, amino, aldehyde, carboxyl, acyl, etc. The invention provides the use of the cyclotri veratrum hydrocarbon and the derivative thereof as an internal electron donor of the olefin polymerization catalyst, and compared with a solid catalyst component which does not contain the cyclotri veratrum hydrocarbon and the derivative thereof, the cyclotri veratrum hydrocarbon and the derivative thereof are introduced into the olefin polymerization catalyst, so that the activity, the hydrogen regulation sensitivity and the copolymerization performance of the catalyst can be simultaneously improved.

Description

Solid catalyst component for olefin polymerization, olefin polymerization catalyst, application thereof and ethylene copolymer
Technical Field
The invention belongs to the field of olefin polymerization catalysts, and particularly relates to a solid catalyst component for olefin polymerization, an olefin polymerization catalyst and application thereof, and an ethylene copolymer.
Background
In the last 60 years, the activity, hydrogen response, copolymerization performance and bulk density of the polymerized powder, melt index, molecular weight distribution, fines content, copolymerization unit distribution and other parameters of Ziegler-Natta type olefin polymerization catalysts have been significantly optimized due to the continuous development of technology. However, in order to better meet the requirements of industrial production and produce products with better performance, the above parameters of the catalyst and the polymerization powder thereof need to be further improved.
In the prior art, some electron donors can be introduced into olefin polymerization catalysts to improve the hydrogen regulation sensitivity of the olefin polymerization catalysts, for example, CN1958620A, CN1743347A, CN102295717A and CN103772536A respectively introduce siloxane electron donors, ortho alkoxy substituted benzoate/carboxylic ester (or diether) compound electron donors and benzoate electron donors. The introduction of other electron donors into the catalyst can improve the copolymerization performance of the catalyst, for example, the electron donors such as alcohol, ketone, amine, amide, nitrile, alkoxy silane, aliphatic ether and aliphatic carboxylic ester are respectively introduced into CN1726230A, CN1798774A and CN 101050248A. In addition, a compound long-carbon-chain monoester/short-carbon-chain monoester electron donor can be introduced into the catalyst to improve the activity of the catalyst (as shown in CN 102807638A).
The electron donor can improve the performance of the olefin polymerization catalyst in a certain aspect, but in the field of Ziegler-Natta type olefin polymerization catalysts, the electron donor capable of simultaneously improving the activity, hydrogen sensitivity and copolymerization performance of the catalyst is rarely reported, and the universality is poor; for example, ethyl benzoate, which is used in slurry polyethylene catalysts, cannot be used in gas phase polyethylene catalysts.
If a special electron donor capable of simultaneously improving the activity, the hydrogen regulation sensitivity and the copolymerization performance of a Ziegler-Natta type polyolefin catalyst is found, the performance of the electron donor is obviously superior to that of the electron donor known in the field, and the electron donor can be applied to various catalysts, so that the electron donor has great value.
Disclosure of Invention
The inventor of the present invention surprisingly found in the research process that: the cyclotri-veratrum hydrocarbon and the derivative thereof are introduced into the solid catalyst component as internal electron donors of the olefin polymerization catalyst, and the activity, the hydrogen regulation sensitivity and the copolymerization performance of the catalyst can be improved. The present invention has been made based on this finding.
According to a first aspect of the present invention, there is provided a solid catalyst component for olefin polymerization, comprising magnesium, titanium, halogen and an internal electron donor compound comprising at least one of cyclotri veratryl hydrocarbon of formula (i) and derivatives thereof:
Figure BDA0001355059300000021
in formula (I), M1、M2、M3、M4、M5And M6The same or different, each being selected from hydrogen, hydroxyl, amino, aldehyde, carboxyl, acyl, halogen atom, -R1OR-OR2Wherein R is1And R2Each being substituted or unsubstituted C1-C10A hydrocarbyl group, the substituent being selected from a hydroxyl group, an amino group, an aldehyde group, a carboxyl group, an acyl group, a halogen atom, an alkoxy group or a heteroatom;
when two radicals M are adjacent on the benzene ring1And M2Or M3And M4Or M5And M6Are each selected from R1OR-OR2When used, two adjacent groups may optionally form a ring with each other.
According to a second aspect of the present invention there is provided an olefin polymerisation catalyst comprising the reaction product of:
1) the solid catalyst component;
2) an organoaluminum compound.
According to a third aspect of the present invention, there is provided the use of the olefin polymerisation catalyst in an olefin polymerisation reaction.
According to a fourth aspect of the present invention, there is provided an ethylene copolymer obtained by copolymerizing ethylene with an α -olefin in the presence of the olefin polymerization catalyst.
The invention provides the use of the cyclo-tri-veratrum hydrocarbon and the derivative thereof as an internal electron donor of a Ziegler-Natta type olefin polymerization catalyst, and compared with a solid catalyst component which does not contain the cyclo-tri-veratrum hydrocarbon and the derivative thereof, the cyclo-tri-veratrum hydrocarbon and the derivative thereof introduced into the olefin polymerization catalyst can simultaneously improve the activity, the hydrogen regulation sensitivity and the copolymerization performance of the catalyst.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
According to a first aspect of the present invention, there is provided a solid catalyst component for olefin polymerization, comprising magnesium, titanium, halogen and an internal electron donor compound comprising at least one of cyclotri veratryl hydrocarbon of formula (i) and derivatives thereof:
Figure BDA0001355059300000031
in formula (I), M1、M2、M3、M4、M5And M6The same or different, each being selected from hydrogen, hydroxyl, amino, aldehyde, carboxyl, acyl, halogen atom, -R1OR-OR2Wherein R is1And R2Each being substituted or unsubstituted C1-C10A hydrocarbyl group, the substituent being selected from a hydroxyl group, an amino group, an aldehyde group, a carboxyl group, an acyl group, a halogen atom, an alkoxy group or a heteroatom;
when two radicals M are adjacent on the benzene ring1And M2Or M3And M4Or M5And M6Are each selected from R1OR-OR2When used, two adjacent groups may optionally form a ring with each other.
In the present invention, C1-C10The hydrocarbyl group may be selected from C1-C10Alkyl radical, C3-C10Cycloalkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C6-C10Aryl and C7-C10Arylalkyl, and the like.
C1-C10Alkyl is C1-C10Straight chain alkyl or C3-C10Non-limiting examples of branched alkyl groups of (a) include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and n-decyl.
C3-C10Examples of cycloalkyl groups of (a) may include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.
C6-C10Examples of aryl groups of (a) may include, but are not limited to: phenyl, naphthyl, 4-methylphenyl and 4-ethylphenyl.
C2-C10Examples of alkenyl groups of (a) may include, but are not limited to: vinyl and allyl.
C2-C10Examples of alkynyl groups of (a) may include, but are not limited to: ethynyl and propargyl.
C7-C10Examples of arylalkyl groups of (a) may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-t-butyl and phenyl-isopropyl.
In the present invention, "substituted C1-C10The hydrocarbyl radical of (A) is generally referred to as "C1-C10The hydrogen atom (preferably one hydrogen atom) or the carbon atom on the "hydrocarbon group" of (1) is substituted with the substituent(s).
The heteroatom refers to atoms which are usually contained in the molecular structure of other cyclotri-veratrum hydrocarbon and derivatives thereof except halogen atoms, carbon atoms and hydrogen atoms, such as O, N, S, P, Si, B and the like.
Preferably, in formula (I), M1、M2、M3、M4、M5And M6Identical or different, each being selected from the group consisting of a hydroxyl group, an amino group, an aldehyde group, a halogen atom, -R1OR-OR2And R is1And R2Each selected from C substituted or unsubstituted by halogen atoms1-C10A hydrocarbyl group.
Preferably, M1、M3And M5Same, M2、M4And M6The same, and the two groups are the same or different.
More preferably, the cyclotri veratrum hydrocarbon and its derivatives are selected from at least one of the following compounds:
a compound A: m1＝M2＝M3＝M4＝M5＝M6＝OCH3；
Compound B: m1＝M2＝M3＝M4＝M5＝M6＝OCH2CH3；
Compound C: m1＝M2＝M3＝M4＝M5＝M6＝OCH2CH2CH3；
Compound D: m1＝M2＝M3＝M4＝M5＝M6＝OCH(CH3)2；
Compound E: m1＝M2＝M3＝M4＝M5＝M6＝OCH2CH2CH2CH3；
Compound F: m1＝M3＝M5＝OCH3；M2＝M4＝M6＝OCH2CH3；
Compound G: m1＝M3＝M5＝OCH3；M2＝M4＝M6＝OCH2CH2CH3；
Compound H: m1＝M3＝M5＝OCH3；M2＝M4＝M6＝OCH2CH2CH2CH3；
A compound I: m1＝M2＝M3＝M4＝M5＝M6＝OH；
Compound J: m1＝M3＝M5＝OCH3；M2＝M4＝M6＝OH；
Compound K: m1＝M3＝M5＝OCH3；M2＝M4＝M6＝NH2；
A compound L: m1＝M3＝M5＝OCH3；M2＝M4＝M6＝Cl；
Compound M: m1＝M3＝M5＝OCH3；M2＝M4＝M6＝Br；
Compound N: m1＝M3＝M5＝OCH3；M2＝M4＝M6＝I；
Compound O: m1＝M3＝M5＝OCH3；M2＝M4＝M6＝CHO；
Compound (I)P：M1＝M3＝M5＝OCH3；M2＝M4＝M6＝OCH2CH2CH2Br；
Compound Q: m1＝M3＝M5＝OH，M2＝M4＝M6＝OCH2CH3。
According to the invention, M1＝M3＝M5＝X，M2＝M4＝M6Y (X, Y represents M in the present invention1、M3、M5And M2、M4、M6Optional groups, and X is different from Y), the cyclotri-veratryl hydrocarbons and derivatives thereof may exist in the following isomers: m1＝M4＝M5＝X， M2＝M3＝M6Y. Said isomers are also intended to be within the scope of the present invention.
In the invention, the cyclotri-veratrum hydrocarbon and the derivative thereof can be prepared according to one of the following methods:
the method comprises the following steps: reacting a benzene ring derivative A shown in a formula (II) with formaldehyde or a derivative thereof in the presence of an acidic substance and an optional halogenated hydrocarbon to obtain the cyclotri-veratryl hydrocarbon and the derivative thereof;
the second method comprises the following steps: catalyzing a benzene ring derivative B shown in a formula (III) to condense in the presence of an acidic substance to obtain the cyclotri-veratryl hydrocarbon and a derivative thereof;
the third method comprises the following steps: in the presence of Lewis acid, catalyzing a benzene ring derivative A shown in a formula (II) to react with formaldehyde or a derivative thereof in halogenated hydrocarbon to obtain the cyclotri-veratryl hydrocarbon and the derivative thereof;
Figure BDA0001355059300000061
wherein, for M7、M8、M9、M10Definition of (A) and M1～M6The same will not be described herein.
The acidic substance may be at least one selected from the group consisting of hydrochloric acid, perchloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, pyrosulfuric acid, sulfurous acid, phosphoric acid, pyrophosphoric acid, phosphorous acid, boric acid, formic acid, acetic acid, benzoic acid, trifluoroacetic acid, sulfonic acid, and benzenesulfonic acid.
The halogenated hydrocarbon may be at least one selected from the group consisting of carbon tetrachloride, chloroform, dichloromethane, methyl bromide, ethyl monochloride, propyl monochloride, butyl monochloride, pentane monochloride, hexane monochloride, ethyl bromide, 1, 2-dichloroethane, 1, 3-dichloropropane, 1, 4-dichlorobutane, 1, 5-dichloropentane, 1, 6-dichlorohexane, chlorocyclopentane, chlorocyclohexane, chlorobenzene, dichlorobenzene, and benzene bromobenzene.
The lewis acid may be selected from at least one of boron trifluoride diethyl etherate, ferric trichloride, aluminum trichloride, and titanium tetrachloride.
The derivative of formaldehyde may be selected from paraformaldehyde, for example trioxane.
In the above methods, the amount of each raw material may be selected by referring to conventional techniques, and will not be described herein.
In the present invention, the solid catalyst component comprises a reaction product of a magnesium compound, a titanium compound and an internal electron donor compound.
The magnesium compound and the titanium compound are conventional choices in Ziegler-Natta type olefin polymerization catalysts.
Generally, the magnesium compound may be selected from at least one of magnesium halide, hydrate or alcoholate of magnesium halide, alkyl magnesium, and derivatives in which (at least one) halogen atom in the formula of magnesium halide is replaced with alkoxy group or haloalkoxy group.
The titanium compound may be represented by the general formula Ti (OR)nX’4-nWherein R is C1-C8A hydrocarbon group, preferably C1-C8Alkyl, X' is a halogen atom such as fluorine, chlorine or bromine, 0. ltoreq. n.ltoreq.4.
Preferably, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, tetraethoxy titanium, chlorotriethoxy titanium, dichlorodiethoxy titanium, tetrabutyl titanate and trichloromonoethoxy titanium.
More preferably, the titanium compound is titanium tetrachloride and/or tetrabutyl titanate.
According to a preferred embodiment, said solid catalyst component comprises said titanium compound and said cyclotri-veratrolene and its derivatives supported on a magnesium halide.
In the invention, the molar ratio of the cyclotri-veratrole hydrocarbon and the derivative thereof to magnesium (or the magnesium compound) is 0.001-0.1: 1, preferably 0.002-0.05: 1.
In the present invention, the titanium compound may be used in an amount of 0.1 to 100mol per mol of magnesium.
Such an internal electron donor compound of the present invention may further comprise other internal electron donors (hereinafter, referred to as internal electron donor b) conventionally used in the art other than the internal electron donor a, in addition to the cyclotri-veratrum hydrocarbon and its derivatives (hereinafter, referred to as "internal electron donor a"), and the internal electron donor b may be selected from organic alcohols, organic acids, organic acid esters, organic acid halides, organic acid anhydrides, ethers, ketones, amines, phosphate esters, amides, carbonates, phenols, pyridines, high molecular compounds having polar groups, and the like. Specifically, the internal electron donor b may be selected from methyl acetate, ethyl acetate, propyl acetate, butyl acetate, n-octyl acetate, methyl benzoate, ethyl benzoate, butyl benzoate, hexyl benzoate, ethyl p-methylbenzoate, methyl naphthoate, ethyl naphthoate, methyl methacrylate, ethyl acrylate, butyl acrylate, diethyl ether, butyl ether, tetrahydrofuran, 2-dimethyl-1, 3-diethoxypropane, methanol, ethanol, propanol, isopropanol, butanol, isooctanol, octylamine, triethylamine, acetone, butanone, cyclopentanone, 2-methylcyclopentanone, cyclohexanone, phenol, hydroquinone, organic epoxy compounds (e.g., ethylene oxide, propylene oxide, epichlorohydrin, polyepichlorohydrin, polyethylene oxide), organic phosphorus compounds (e.g., trimethyl phosphate, dimethyl methacrylate, ethyl acrylate, butyl ether, tetrahydrofuran, 2-dimethyl-1, 3-diethoxypropane, methanol, ethanol, propanol, isopropanol, butanol, isooctanol, octylamine, triethylamine, acetone, butanone, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triphenyl phosphate, trihexyl phosphate), polymethyl methacrylate, and polystyrene.
In the solid catalyst component, when the internal electron donor b is contained, the molar ratio of the internal electron donor b to titanium may be 1000: 1 to 1: 1000.
In addition, the solid catalyst component can also comprise a reaction product of an ultrafine carrier, magnesium halide, titanium halide and an internal electron donor compound, wherein the particle size of the ultrafine carrier is 0.01-10 micrometers, and the ultrafine carrier can be at least one of alumina, activated carbon, clay, silica, titanium dioxide, polystyrene and calcium carbonate.
Specifically, the solid catalyst component can be prepared by the following method:
method 1
1) Under the condition that magnesium halide is activated, mixing and grinding the magnesium halide, the internal electron donor compound and an optional titanium compound;
2) treating the mixed and ground product one or more times by adopting excessive titanium compound;
3) washing the treated product with a hydrocarbon solvent to obtain the solid catalyst component.
Method 2
1) Reacting magnesium halide with an alcohol compound and an internal electron donor compound in the presence of an inert solvent;
2) then adding an organic silicon compound for contact reaction;
3) carrying out contact reaction on the system in the step 2) and a titanium compound;
4) removing unreacted substances and solvent, and washing precipitate to obtain the solid catalyst component;
alternatively, the internal electron donor compound may be added after step 3) but not in step 1).
Method 3
1) Dissolving magnesium halide, titanium halide and an internal electron donor compound, and reacting to obtain mother liquor;
2) mixing a superfine carrier with the mother liquor to prepare slurry liquid;
3) and carrying out spray drying on the slurry liquid to obtain the solid catalyst component.
Any of the organoaluminum compounds mentioned above can be used as an activator component of the solid catalyst component to reduce the titanium atom in the solid catalyst component to a state in which an olefin such as ethylene can be efficiently polymerized to obtain a prereduced solid catalyst component.
Method 4
1) Reacting magnesium halide with an organic epoxy compound, an organic phosphorus compound, organic alcohol and an internal electron donor a in the presence of an inert solvent;
2) contacting the reaction solution obtained in the step 1) with a titanium compound and an organic silicon compound for reaction, and carrying out high-temperature treatment;
3) removing unreacted substances and the solvent, and washing precipitates to obtain the solid catalyst component.
Method 5
1) In the presence of an inert solvent, reacting magnesium halide with an organic epoxy compound, an organic phosphorus compound and optional organic alcohol, and then adding an organic anhydride compound (a precipitation aid) to continuously react to obtain a solution;
2) contacting the solution with a titanium compound for reaction;
3) adding an internal electron donor a and optional organic alcohol into a reaction system to carry out reaction;
4) removing unreacted substances and the solvent, and washing precipitates to obtain the solid catalyst component.
Method 6
1) Reacting a magnesium halide with an organic epoxy compound, an organophosphorus compound and an organic alcohol in the presence of an inert solvent;
2) contacting the solution with a titanium compound and an organic silicon compound for reaction;
3) adding an internal electron donor compound into a reaction system to carry out contact reaction;
4) removing unreacted substances and the solvent, and washing precipitates to obtain the solid catalyst component.
Method 7
1) Dispersing a magnesium halide alcoholate in an inert solvent to obtain a suspension;
2) contacting the suspension with an optional organic aluminum compound and an internal electron donor compound for reaction, and then removing unreacted substances and washing the unreacted substances with an inert solvent;
3) contacting the precipitate obtained in the step 2) with the titanium compound in the presence of an inert solvent for reaction, then removing unreacted substances and the solvent, and washing the precipitate to obtain the solid catalyst component.
In step 2), the organoaluminum compound may be specifically selected from Al (CH)3)3、Al(CH2CH3)3、 Al(i-Bu)3、Al(n-C6H13)3、AlH(CH2CH3)2、AlH(i-Bu)2、AlCl(CH2CH3)2、 AlCl1.5(CH2CH3)1.5、AlCl(CH2CH3)2、AlCl2(CH2CH3) And the like alkyl aluminum compounds. In addition, the organoaluminum compound is preferably Al (CH)2CH3)3、Al(n-C6H13)3And Al (i-Bu)3More preferably Al (CH)2CH3)3。
Method 8
1) Dispersing a magnesium halide alcoholate in an inert solvent to obtain a suspension;
2) the suspension and a titanium compound are subjected to contact reaction at low temperature (such as below-5 ℃), and then are treated at high temperature (such as above 50 ℃), unreacted substances are removed, and the suspension is washed by an inert solvent;
3) in the presence of an inert solvent, the precipitate obtained in the step 2) is contacted with a titanium compound and an internal electron donor compound for reaction, then unreacted substances and the solvent are removed, and the precipitate is washed to obtain the solid catalyst component.
Method 9
1) Dispersing an alkyl magnesium/alkoxy magnesium halide compound in an inert solvent to obtain a solution or a suspension;
2) the solution or the suspension is contacted with a titanium compound and an internal electron donor compound for reaction, then unreacted substances are removed, and the solution or the suspension is washed by an inert solvent;
3) contacting the precipitate obtained in the step 2) with the titanium compound in the presence of an inert solvent for reaction, then removing unreacted substances and the solvent, and washing the precipitate to obtain the solid catalyst component.
Method 10
1) Reacting an alkoxy magnesium compound with a titanium compound and an internal electron donor compound to form a transparent solution, and adding an inert solvent for dilution;
2) adding an organic aluminum compound into the diluted solution, removing unreacted substances and a solvent after reaction, and washing precipitates to obtain the solid catalyst component.
The compounds used in the above preparation methods are all conventionally selected in the art, and for example, the organic epoxy compound, the organic phosphorus compound, the alcohol compound, and the silicone compound can be selected according to the prior art, and are not particularly limited herein. The inert solvent used in each process may be the same or different and may be selected with reference to the prior art, for example, toluene and/or hexane.
In addition, the above preparation methods are more detailed examples of the solid catalyst component of the present invention, but the present invention is not limited to these preparation methods.
According to a second aspect of the present invention there is provided an olefin polymerisation catalyst comprising the reaction product of:
1) the solid catalyst component;
2) an organoaluminum compound.
In the olefin polymerization catalyst, the organoaluminum compound is a well-known cocatalyst in olefin polymerization catalysts. The general formula of the organic aluminum compound is AlR'dX’3-dWherein R' is hydrogen or Cl-C20A hydrocarbon group, X' is a halogen atom, 0<d≤3。Cl-C20Hydrocarbyl radicals such as Cl-C20Alkyl, aralkyl or aryl of (a). The organo-aluminum compound is preferably selected from Al (CH)3)3、Al(CH2CH3)3、Al(i-Bu)3、AlH(CH2CH3)2、AlH(i-Bu)2、AlCl(CH2CH3)2、Al2Cl3(CH2CH3)3、AlCl(CH2CH3)2、 AlCl2(CH2CH3) More preferably from Al (CH)2CH3)3And/or Al (i-Bu)3。
The molar ratio of the aluminum in the component 2) to the titanium in the component 1) may be 5: 1 to 500: 1, preferably 20: 1 to 200: 1.
According to a third aspect of the present invention, there is provided the use of the olefin polymerisation catalyst in an olefin polymerisation reaction. The olefin polymerization catalyst system is suitable for homopolymerization of olefin or copolymerization of multiple olefins. Specific examples of the olefin include: ethylene, butene, pentene, hexene, octene, 4-methyl-1-pentene.
Preferably, the olefin is ethylene and/or butene.
In addition, the olefin polymerization catalyst is suitable for use in olefin polymerization reactions under various conditions, for example, the olefin polymerization reaction may be carried out in a liquid phase or a gas phase, or may be carried out in an operation in which a combination of liquid phase and gas phase polymerization stages is carried out. The polymerization temperature may be 0 to 150 ℃, preferably 60 to 90 ℃.
The liquid phase polymerization medium comprises: and inert solvents such as saturated aliphatic hydrocarbons and aromatic hydrocarbons, such as isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, and xylene.
In addition, hydrogen is used as a molecular weight regulator in order to regulate the molecular weight of the final polymer.
According to a fourth aspect of the present invention, there is provided an ethylene copolymer obtained by copolymerizing ethylene with an α -olefin in the presence of the olefin polymerization catalyst.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples,
1. the relative weight percentage of titanium element in the catalyst system is as follows: spectrophotometry is adopted.
2. Composition of the catalyst component: using liquid nuclear magnetism1H-NMR。
3. Determination of the melt index of the polymer (MI): load 2.16kg according to ASTM D1238-99.
4. Content of copolymerized units in polymer powder: using liquid nuclear magnetism13C-NMR，
5. Weight content of hexane extractables in polymer powder: 20g of the dried powder were taken, placed in a container, extracted with 300mL of hexane for 2 hours at 50 ℃ and subsequently 20mL of the extract was extracted, placed in an accurately weighed petri dish, the dish was weighed completely dry and the total mass of hexane extractables was calculated therefrom: the mass gain of the watch glass is m1(g) And from this the weight percentage of hexane extractables is calculated to be 75m1％。
The polymer powder was obtained by transferring the whole powder slurry obtained by the following copolymerization reaction into a standard cylindrical vessel with nitrogen and drying under ventilation. The pressure in the kettle is absolute pressure.
Example 1
(1) Preparation of solid catalyst component a
6.0g of MgCl on a spherical support are added in sequence to a reactor which is fully replaced by high-purity nitrogen2·2.6C2H5OH, 120mL of toluene, was cooled to-10 ℃ with stirring, 50mL of a hexane solution of triethylaluminum (triethylaluminum: 1.2M) and 0.3g of Compound A were added dropwise, and then the temperature was raised to 60 ℃ and the reaction was maintained for 3 hours. Stirring was stopped, the suspension was allowed to settle, the supernatant was removed quickly, and the precipitate was washed several times with toluene and hexane in succession. 120mL of toluene was added, the system was cooled to 0 ℃ and 8mL of titanium tetrachloride was slowly added dropwise, followed by heating to 60 ℃ and reacting for 2 hours. Stopping stirring, standing, quickly layering the suspension, pumping out supernatant, washing the precipitate twice with hexane, transferring the precipitate into a chromatography funnel through hexane, and drying the precipitate with high-purity nitrogen to obtain a solid spherical catalyst component a with good fluidity, wherein the composition of the solid spherical catalyst component a is shown in table 1.
(2) Homopolymerization reaction
Polymerization with low hydrogen/ethylene ratio
A stainless steel reaction kettle with the volume of 2L is fully replaced by high-purity nitrogen, 1L of hexane and 1.0mL of 1M triethyl aluminum are added, then the solid catalyst component (containing 0.6mg of titanium) prepared by the method is added, the temperature is raised to 75 ℃, hydrogen is introduced to ensure that the pressure in the kettle reaches 0.28MPa, ethylene is introduced to ensure that the total pressure in the kettle reaches 1.03MPa, and the polymerization is carried out for 2 hours at the temperature of 85 ℃, wherein the polymerization result is shown in Table 2.
② polymerization with high hydrogen/ethylene ratio
A stainless steel reaction kettle with the volume of 2L is fully replaced by high-purity nitrogen, 1L of hexane and 1.0mL of 1M triethyl aluminum are added, then the solid catalyst component (containing 0.6mg of titanium) prepared by the method is added, the temperature is raised to 75 ℃, hydrogen is introduced to ensure that the pressure in the kettle reaches 0.68MPa, ethylene is introduced to ensure that the total pressure in the kettle reaches 1.03MPa, and the polymerization is carried out for 2 hours at the temperature of 85 ℃, wherein the polymerization result is shown in Table 2.
(3) Copolymerization reaction
A stainless steel reaction kettle with the volume of 2L is fully replaced by high-purity nitrogen, 1L of hexane and 1.0ml of triethyl aluminum with the concentration of 1M are added, then the solid catalyst component (containing 0.6mg of titanium) prepared by the method is added, the temperature is raised to 70 ℃, hydrogen is introduced to ensure that the pressure in the kettle reaches 0.28MPa, then ethylene/butylene mixed gas (the molar ratio is 0.9: 0.1) is introduced to ensure that the total pressure in the kettle reaches 0.73MPa, and the polymerization is carried out for 2 hours at the temperature of 80 ℃, wherein the polymerization result is shown in Table 3.
Example 2
(1) Preparation of solid catalyst component b
6.0g of MgCl on a spherical support are added in sequence to a reactor which is fully replaced by high-purity nitrogen2·2.6C2H5120mL of OH and toluene were cooled to-10 ℃ with stirring, 50mL of a hexane solution of triethylaluminum (triethylaluminum: 1.2M) was added dropwise, 1mL of ethyl benzoate and 0.2g of Compound Q were added, and the reaction was then allowed to warm to 60 ℃ and was maintained for 3 hours. Stopping stirring, standing, quickly separating the suspension, removing supernatant, and collecting precipitate with toluene and hexaneWashing was carried out several times successively. 120mL of hexane was added, the system was cooled to 0 ℃ and 8mL of titanium tetrachloride was slowly added dropwise, after which the temperature was raised to 60 ℃ to react for 2 hours. Stirring was stopped, the suspension was allowed to stand still, the supernatant was quickly separated, the precipitate was washed twice with hexane, transferred to a chromatography funnel with hexane, and blown dry with high purity nitrogen to obtain a solid spherical catalyst component b with good fluidity, the composition of which is shown in table 1.
(2) Homopolymerization reaction
The polymerization results are shown in Table 2, as in example 1.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Comparative example 1
(1) Preparation of solid catalyst component D1
4.0g of MgCl on a spherical support are added in sequence to a reactor which is fully replaced by high-purity nitrogen2·3.0C2H5OH, hexane 150mL, was cooled to-10 ℃ with stirring, and 60mL of a hexane solution of triethylaluminum (triethylaluminum: 1.2M) and 1mL of n-octyl acetate, 1mL of ethyl benzoate were added dropwise, followed by heating to 50 ℃ and maintaining the reaction for 3 hours. Stirring was stopped, the suspension was allowed to settle, the supernatant was removed quickly, and the precipitate was washed several times with toluene and hexane in succession. 150mL of hexane was added, the system was cooled to 0 ℃ and 6mL of titanium tetrachloride was slowly added dropwise, after which the temperature was raised to 60 ℃ to react for 2 hours. Stirring was stopped, the suspension was allowed to stand still, the supernatant was quickly separated, the precipitate was washed twice with hexane, transferred to a chromatography funnel with hexane, and blown dry with high purity nitrogen to obtain a solid spherical catalyst component D1 having good fluidity and having a composition shown in Table 1.
(2) Homopolymerization reaction
The polymerization results are shown in Table 2, as in example 1.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Example 3
(1) Preparation of solid catalyst component c
4.0g of magnesium chloride, 50mL of toluene, 3.0mL of epichlorohydrin, 9mL of tri-n-butyl phosphate, 4.4mL of ethanol, and 0.3g of compound B were added to the reaction vessel, and the mixture was reacted at a constant temperature of 70 ℃ for 2 hours. The system is cooled to-10 ℃, 70mL of titanium tetrachloride is slowly dropped, 5mL of tetraethoxysilane is added, the temperature is gradually raised to 85 ℃, and the constant temperature is kept for 1 hour. Stopping stirring, standing, quickly layering the suspension, removing supernatant, washing with toluene and hexane for multiple times, and drying to obtain a solid catalyst component c with good fluidity, wherein the composition of the solid catalyst component c is shown in table 1.
(2) Homopolymerization reaction
Polymerization with low hydrogen/ethylene ratio
A stainless steel reaction kettle with the volume of 2L is fully replaced by high-purity nitrogen, 1L of hexane and 1.0mL of 1M triethyl aluminum are added, then the solid catalyst component (containing 0.6mg of titanium) prepared by the method is added, the temperature is raised to 70 ℃, hydrogen is introduced to ensure that the pressure in the kettle reaches 0.28MPa, then ethylene is introduced to ensure that the total pressure in the kettle reaches 0.73MPa, and the polymerization is carried out for 2 hours at the temperature of 80 ℃, wherein the polymerization result is shown in Table 2.
② polymerization with high hydrogen/ethylene ratio
A stainless steel reaction kettle with the volume of 2L is fully replaced by high-purity nitrogen, 1L of hexane and 1.0mL of 1M triethyl aluminum are added, then the solid catalyst component (containing 0.6mg of titanium) prepared by the method is added, the temperature is raised to 70 ℃, hydrogen is introduced to ensure that the pressure in the kettle reaches 0.58MPa, then ethylene is introduced to ensure that the total pressure in the kettle reaches 0.73MPa, and the polymerization is carried out for 2 hours at the temperature of 80 ℃, wherein the polymerization result is shown in Table 2.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Example 4
(1) Preparation of solid catalyst component d
4.0g of magnesium chloride, 50mL of toluene, 3.0mL of epichlorohydrin, 9mL of tri-n-butyl phosphate and 4.4mL of ethanol were put into a reaction vessel and reacted at 70 ℃ for 2 hours. The system is cooled to-10 ℃, 70mL of titanium tetrachloride is slowly dropped, 5mL of tetraethoxysilane is added, the temperature is gradually raised to 85 ℃, and the constant temperature is kept for 1 hour. 0.2g of Compound F is added and the incubation is continued for 1 hour. The stirring was stopped, the suspension was allowed to stand, the supernatant was quickly separated, and the supernatant was removed, washed with toluene and hexane several times and dried to obtain a solid catalyst component d having good fluidity, the composition of which is shown in table 1.
(2) Homopolymerization reaction
The polymerization results are shown in Table 2, as in example 3.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Comparative example 2
(1) Preparation of solid catalyst component D2
4.0g of magnesium chloride, 50mL of toluene, 3.0mL of epichlorohydrin, 9.0mL of tri-n-butyl ester and 4.4mL of ethanol are sequentially added into a reactor which is fully replaced by high-purity nitrogen, the temperature is raised to 70 ℃ under stirring, and the reaction is carried out for 2 hours at 70 ℃ after the solid is completely dissolved to form a uniform solution. The system was cooled to-10 ℃ and 4.0mL of ethyl benzoate was added dropwise slowly, and after keeping the temperature for 10 minutes, 60mL of titanium tetrachloride was added dropwise. The temperature was slowly raised to 85 ℃ and the reaction was carried out for 2 hours. Stirring was stopped, the suspension was allowed to settle, the suspension was quickly separated, the supernatant was removed and washed four times with hexane. High purity nitrogen was blown dry to obtain solid catalyst component D2 having good flowability and the composition shown in Table 1.
(2) Homopolymerization reaction
The polymerization results are shown in Table 2, as in example 3.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Example 5
(1) Preparation of solid catalyst component e
Adding 4.0g of magnesium chloride, 90mL of toluene, 8.0mL of epoxy chloropropane and 16.0mL of tri-n-butyl phosphate into a reaction kettle, reacting for 2 hours under the conditions of stirring speed of 450rpm and temperature of 60 ℃, adding 3g of phthalic anhydride, continuously keeping the temperature for 1 hour, cooling to-40 ℃, dropwise adding 70mL of titanium tetrachloride, gradually heating to 95 ℃, and keeping the temperature for 1 hour. 0.3g of Compound B is added and the incubation is continued for 1 hour. The mother liquor was filtered off, washed with toluene and hexane several times and dried to obtain a solid catalyst component e having good flowability, the composition of which is shown in table 1.
(2) Homopolymerization reaction
The polymerization results are shown in Table 2, as in example 1.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Comparative example 3
(1) Preparation of solid catalyst component D3
Adding 4.0g of magnesium chloride, 90mL of toluene, 8.0mL of epoxy chloropropane and 16.0mL of tri-n-butyl phosphate into a reaction kettle, reacting for 2 hours under the conditions of stirring speed of 450rpm and temperature of 60 ℃, adding 3g of phthalic anhydride, continuously keeping the temperature for 1 hour, cooling to-40 ℃, dropwise adding 70mL of titanium tetrachloride, gradually heating to 95 ℃, and keeping the temperature for 1 hour. The mother liquor was filtered off, washed with toluene and hexane several times and dried to obtain a solid catalyst component D3 having good flowability, the composition of which is shown in Table 1.
(2) Homopolymerization reaction
The polymerization results are shown in Table 2, as in example 1.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Example 6
(1) Preparation of solid catalyst component f
4.0g of magnesium chloride, 100mL of toluene, 6.0mL of epichlorohydrin and 12mL of triisobutyl phosphate are added into a reaction kettle, and the mixture is reacted for 2 hours under the conditions that the stirring speed is 450rpm and the temperature is 60 ℃. The temperature is reduced to-40 ℃, 75mL of titanium tetrachloride is dripped, the temperature is gradually increased to 85 ℃, and the constant temperature is kept for 1 hour. The temperature of the system is reduced to 60 ℃, 0.2g of the compound A and 1mL of ethanol are added, the temperature is gradually increased to 85 ℃, and the constant temperature is continuously maintained for 1 hour. The mother liquor was filtered off, washed several times with toluene, an inert diluent and hexane, and dried to obtain a solid catalyst component f with good flowability, the composition of which is shown in table 1.
(2) Homopolymerization reaction
The polymerization results are shown in Table 2, as in example 1.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Comparative example 4
(1) Preparation of solid catalyst component D4
4.0g of magnesium chloride, 100mL of toluene, 6.0mL of epichlorohydrin and 12mL of triisobutyl phosphate are added into a reaction kettle, and the mixture is reacted for 2 hours under the conditions that the stirring speed is 450rpm and the temperature is 60 ℃. The temperature is reduced to-40 ℃, 75mL of titanium tetrachloride is dripped, the temperature is gradually increased to 85 ℃, and the constant temperature is kept for 1 hour. The temperature of the system is reduced to 60 ℃, 1mL of ethanol is added, the temperature is gradually increased to 85 ℃, and the constant temperature is continuously maintained for 1 hour. The mother liquor was filtered off, washed with toluene and hexane several times and dried to obtain a solid catalyst component D4 having good flowability, the composition of which is shown in Table 1.
(2) Polymerisation reaction
The polymerization results are shown in Table 2, as in example 1.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Example 7
(1) Preparation of solid catalyst component g
Into a 250mL three-necked flask purged with nitrogen, 1.5g of TiCl were added44.4g of anhydrous MgCl20.1g of compound A and 100mL of tetrahydrofuran are heated to 65 ℃ under stirring, and react for 3 hours at the constant temperature, and then the temperature is reduced to 35 ℃ to obtain mother liquor.
Adding 6g of silica gel (Cabot Corporation TS-610, particle size of 0.02-0.1 micron) into another 250mL three-necked bottle which is blown off by nitrogen, adding the mother liquor after cooling, keeping the temperature at 35 ℃, stirring for 1h, and then carrying out spray drying on the mother liquor after mixing the silica gel by using a spray dryer, wherein the spray conditions are as follows: the inlet temperature was 180 ℃ and the outlet temperature was 110 ℃ to give g of solid catalyst component, the composition of which is shown in Table 1.
(2) Pre-reduction treatment
Adding 100mL of hexane, 5g of the solid catalyst component and 4mL of tri-n-hexylaluminum (1M) into a 250mL three-necked flask which is blown off by nitrogen, heating to 50 ℃ under stirring, and keeping the temperature constant for 1 h; 9mL of diethyl aluminum monochloride (1M) were added, and the temperature was kept constant for 1 hour. The mother liquor is filtered, washed by hexane for a plurality of times and then dried to obtain the pre-reduced solid catalyst component with good fluidity.
(2) Homopolymerization reaction
The polymerization results are shown in Table 2, as in example 1.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Example 8
(1) Preparation of solid catalyst component h
A solid catalyst component h was prepared according to the method of example 7, except that 0.2g of the compound F was used in place of the compound A of example 7, and its composition was shown in Table 1.
(2) Pre-reduction treatment
The same as in example 7.
(3) Homopolymerization reaction
The polymerization results are shown in Table 2, as in example 1.
(4) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Comparative example 5
(1) Preparation of solid catalyst component D5
Into a 250mL three-necked flask purged with nitrogen, 1.5g of TiCl were added44.4g of anhydrous MgCl2And 100mL of tetrahydrofuran, heating to 65 ℃ under stirring, reacting for 3 hours at the constant temperature, and cooling to 35 ℃ to obtain mother liquor.
Adding 6g of silica gel (Cabot Corporation TS-610, particle size of 0.02-0.1 micron) into another 250mL three-necked bottle which is blown off by nitrogen, adding the mother liquor after cooling, keeping the temperature at 35 ℃, stirring for 1h, and then carrying out spray drying on the mother liquor after mixing the silica gel by using a spray dryer, wherein the spray conditions are as follows: the inlet temperature was 195 ℃ and the outlet temperature was 110 ℃ to give a solid catalyst component D5, the composition of which is shown in Table 1.
(2) Pre-reduction treatment
The same as in example 7.
(3) Homopolymerization reaction
The polymerization results are shown in Table 2, as in example 1.
(4) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Example 9
(1) Preparation of solid catalyst component i
Adding 4.8 g of magnesium chloride, 30mL of decane, 20mL of isooctanol and 0.2g of compound B into a reaction kettle, reacting for 3 hours under the conditions of stirring speed of 300rpm and temperature of 130 ℃, cooling the system to 50 ℃, adding 3.5mL of tetraethoxysilane, and continuing stirring for 2 hours. The system is cooled to room temperature, slowly dropped into 200mL titanium tetrachloride at 0 ℃, and kept at the constant temperature for 1h after the dropping is finished. The system was gradually warmed to 110 ℃ and held at that temperature for 2 hours. Stopping stirring, standing, quickly layering the suspension, removing supernatant, washing with toluene and hexane for multiple times, and drying to obtain a solid catalyst component i with good fluidity, wherein the composition of the solid catalyst component i is shown in table 1.
(2) Homopolymerization reaction
The polymerization results are shown in Table 2, as in example 3.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Example 10
(1) Preparation of solid catalyst component j
4.8 g of magnesium chloride, 30mL of decane and 20mL of isooctanol were charged into the reaction vessel and reacted at a stirring rate of 300rpm and a temperature of 130 ℃ for 3 hours. Cooling the system to 50 ℃, adding 3.5mL of tetraethoxysilane, continuing to stir for 2 hours, cooling the system to room temperature, slowly dripping the system into 200mL of titanium tetrachloride which is cooled to 0 ℃, and keeping the temperature for 1 hour after dripping is finished. The system was gradually warmed to 110 ℃ and held at that temperature for 1 hour. 0.2g of Compound A is added and the incubation is continued for 1 hour. Stopping stirring, standing, quickly layering the suspension, removing supernatant, washing with toluene and hexane for multiple times, and drying to obtain a solid catalyst component j with good fluidity, wherein the composition of the solid catalyst component j is shown in table 1.
(2) Homopolymerization reaction
The polymerization results are shown in Table 2, as in example 3.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Comparative example 6
(1) Preparation of solid catalyst component D6
4.8 g of magnesium chloride, 30mL of decane and 20mL of isooctanol were charged into the reaction vessel and reacted at a stirring rate of 300rpm and a temperature of 130 ℃ for 3 hours. The system was cooled to 50 ℃ and 3.5mL of tetraethoxysilane was added and stirring was continued for 2 hours. The system is cooled to room temperature, slowly dropped into 200mL titanium tetrachloride which is cooled to 0 ℃, and kept at the constant temperature for 1h after dropping. The temperature of the system is gradually increased to 110 ℃, the temperature is kept constant for 1 hour, 0.2mL of 1, 2-o-dimethyl ether is added, and the temperature is kept constant for 1 hour. The stirring was stopped, the suspension was allowed to stand, the supernatant liquid was quickly separated, and the supernatant liquid was removed, washed with toluene and hexane several times and dried to obtain a solid catalyst component D6 having good fluidity, the composition of which is shown in table 1.
(2) Homopolymerization reaction
The polymerization results are shown in Table 2, as in example 3.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Example 11
(1) Preparation of solid catalyst component k
Mixing 10g Mg (OEt)255mL of toluene was added to the reaction vessel and the suspension was formed at a stirring rate of 300 rpm. The temperature of the system is reduced to 0 ℃, 30mL of titanium tetrachloride and 0.2g of compound M are slowly and successively added, after the dropwise addition is finished, the temperature is slowly increased to 90 ℃, and the constant temperature is kept for 1.5 hours. Stopping stirring and standing, quickly demixing the suspension, and pumping out the supernatant. Then, 60mL of toluene and 30mL of titanium tetrachloride were added, and the temperature was raised to 90 ℃ and maintained at the same temperature for 2 hours. Stopping stirring, standing, and removing supernatant. After washing with toluene and hexane several times, drying was carried out to obtain a solid catalyst component k having good fluidity, the composition of which is shown in Table 1.
(2) Homopolymerization reaction
The polymerization results are shown in Table 2, as in example 3.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Comparative example 7
(1) Preparation of solid catalyst component D7
Mixing 10g Mg (OEt)255mL of toluene was added to the reaction vessel and the suspension was formed at a stirring rate of 300 rpm. The temperature of the system is reduced to 0 ℃, 30mL of titanium tetrachloride and 1mL of ethyl benzoate are slowly and successively added, after the dropwise addition is finished, the temperature is slowly increased to 90 ℃, and the constant temperature is kept for 1.5 hours. Stopping stirring, standing, quickly demixing the suspension, and removing the supernatant. Then, 60mL of toluene and 30mL of titanium tetrachloride were added, and the temperature was raised to 90 ℃ and maintained at the same temperature for 2 hours. Stopping stirring, standing, and removing supernatant. After washing with toluene and hexane for a plurality of times, and drying, a solid catalyst component D7 having good flowability was obtained, the composition of which is shown in Table 1.
(2) Homopolymerization reaction
The polymerization results are shown in Table 2, as in example 3.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
TABLE 1 composition of the solid catalyst component
Figure BDA0001355059300000231
Injecting: does not contain ethoxy groups in the cyclotri-veratrum hydrocarbon and derivatives thereof.
TABLE 2 catalyst Activity and Hydrogen tuning sensitivity
Figure BDA0001355059300000241
As can be seen from Table 2, the catalyst activity and the powder melt index of the inventive example are slightly higher than those of the comparative example under the polymerization condition of low hydrogen/ethylene ratio, while the catalyst activity and the powder melt index of the inventive example are significantly higher than those of the comparative example under the polymerization condition of higher hydrogen/ethylene ratio, which is very beneficial to industrial production. In particular, it is particularly advantageous for the production of bimodal products in slurry polymerisation processes, and for the production of high melt index products in gas phase polymerisation processes. Therefore, the cyclotri veratrum hydrocarbon and the derivative thereof can improve the activity and the hydrogen regulation sensitivity of the catalyst.
TABLE 3 content of copolymerized units and hexane extractables in the powder
Figure BDA0001355059300000251
As can be seen from Table 3, when the copolymerized unit content of the examples is slightly higher than that of the comparative examples, the hexane extractables are significantly lower. It can be seen from this that the low molecular weight component of the powder of the examples of the invention contains fewer copolymerized units and the medium/high molecular weight component contains more copolymerized units than the comparative examples. Therefore, the cyclotri-veratrum hydrocarbon and the derivative thereof improve the copolymerization performance of the catalyst, which is beneficial to improving the comprehensive performance of the product.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the illustrated embodiments.

Claims (11)

1. A solid catalyst component for olefin polymerization, characterized in that the solid catalyst component comprises magnesium, titanium, halogen and an internal electron donor compound comprising at least one of cyclotri veratrole hydrocarbon of formula (i) and derivatives thereof:
Figure FDA0002649626190000011
in formula (I), M1、M2、M3、M4、M5And M6Identical OR different, each being selected from hydroxyl, halogen OR-OR2Wherein R is2Is unsubstituted C1-C10A hydrocarbyl group.
2. The solid catalyst component according to claim 1 in which the cyclotri veratryl hydrocarbon and its derivatives are selected from at least one of the following compounds:
a compound A: m1＝M2＝M3＝M4＝M5＝M6＝OCH3；
Compound B: m1＝M2＝M3＝M4＝M5＝M6＝OCH2CH3；
Compound C: m1＝M2＝M3＝M4＝M5＝M6＝OCH2CH2CH3；
Compound D: m1＝M2＝M3＝M4＝M5＝M6＝OCH(CH3)2；
Compound E: m1＝M2＝M3＝M4＝M5＝M6＝OCH2CH2CH2CH3；
Compound F: m1＝M3＝M5＝OCH3；M2＝M4＝M6＝OCH2CH3；
Compound G: m1＝M3＝M5＝OCH3；M2＝M4＝M6＝OCH2CH2CH3；
Compound H: m1＝M3＝M5＝OCH3；M2＝M4＝M6＝OCH2CH2CH2CH3；
A compound I: m1＝M2＝M3＝M4＝M5＝M6＝OH；
Compound J: m1＝M3＝M5＝OCH3；M2＝M4＝M6＝OH；
A compound L: m1＝M3＝M5＝OCH3；M2＝M4＝M6＝Cl；
Compound M: m1＝M3＝M5＝OCH3；M2＝M4＝M6＝Br；
Compound N: m1＝M3＝M5＝OCH3；M2＝M4＝M6＝I；
Compound Q: m1＝M3＝M5＝OH，M2＝M4＝M6＝OCH2CH3。
3. The solid catalyst component according to claim 1 in which the solid catalyst component comprises a titanium compound supported on a magnesium halide and the cyclotri veratrole hydrocarbon and its derivatives.
4. The solid catalyst component according to claim 1 or 3, wherein the molar ratio of cyclotri veratrole and its derivatives to magnesium is 0.001-0.1: 1.
5. The solid catalyst component according to claim 4, wherein the molar ratio of cyclotri veratrole hydrocarbon and its derivatives to magnesium is 0.002-0.05: 1.
6. The solid catalyst component according to claim 3 in which the titanium compound has the general formula Ti (OR)nX’4－nWherein R is C1-C8A hydrocarbon group, X' is a halogen atom, and n is 0 to 4.
7. The solid catalyst component according to claim 6 in which the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, tetraethoxy titanium, chlorotriethoxy titanium, dichlorodiethoxy titanium, tetrabutyl titanate and trichloromonoethoxy titanium.
8. An olefin polymerization catalyst, comprising the reaction product of:
1) the solid catalyst component of any one of claims 1 to 7;
2) an organoaluminum compound.
9. The olefin polymerization catalyst according to claim 8, wherein the molar ratio of aluminum in the organoaluminum compound to titanium in the solid catalyst component is 5: 1 to 500: 1.
10. The olefin polymerization catalyst according to claim 9, wherein the molar ratio of aluminum in the organoaluminum compound to titanium in the solid catalyst component is 20: 1 to 200: 1.
11. Use of an olefin polymerisation catalyst as claimed in any one of claims 8 to 10 in an olefin polymerisation reaction.
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EP18835679.4A EP3656754B1 (en) 2017-07-19 2018-07-19 Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof
RU2020103744A RU2740916C1 (en) 2017-07-19 2018-07-19 Olefin polymerisation catalyst comprising cyclotriveratrilene and derivatives thereof
CN201880002860.5A CN109526217B (en) 2017-07-19 2018-07-19 Olefin polymerization catalyst containing cyclotri veratrum hydrocarbon and derivatives thereof
PCT/CN2018/096248 WO2019015638A1 (en) 2017-07-19 2018-07-19 Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof
BR112020001201-7A BR112020001201B1 (en) 2017-07-19 2018-07-19 ZIEGLER-NATTA CATALYST SYSTEM FOR OLEFIN POLYMERIZATION, SOLID CATALYST COMPONENT FOR OLEFIN POLYMERIZATION AND OLEFIN POLYMERIZATION PROCESS
US16/631,482 US11401356B2 (en) 2017-07-19 2018-07-19 Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof
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CN110734510B (en) * 2018-07-19 2022-02-08 中国石油化工股份有限公司 Olefin polymerization catalyst containing cyclotri veratrum hydrocarbon and its derivatives
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