[go: up one dir, main page]

CN109280103B - Catalyst system for olefin polymerization and application thereof - Google Patents

Catalyst system for olefin polymerization and application thereof Download PDF

Info

Publication number
CN109280103B
CN109280103B CN201710591181.3A CN201710591181A CN109280103B CN 109280103 B CN109280103 B CN 109280103B CN 201710591181 A CN201710591181 A CN 201710591181A CN 109280103 B CN109280103 B CN 109280103B
Authority
CN
China
Prior art keywords
compound
och
catalyst system
electron donor
titanium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710591181.3A
Other languages
Chinese (zh)
Other versions
CN109280103A (en
Inventor
黄庭
孙竹芳
周俊领
郭子芳
谢伦嘉
李秉毅
寇鹏
马永华
黄廷杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to CN201710591181.3A priority Critical patent/CN109280103B/en
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to KR1020207002897A priority patent/KR102336976B1/en
Priority to US16/631,482 priority patent/US11401356B2/en
Priority to BR112020001201-7A priority patent/BR112020001201B1/en
Priority to JP2020502696A priority patent/JP7038797B2/en
Priority to ES18835679T priority patent/ES2980848T3/en
Priority to MYPI2020000297A priority patent/MY201121A/en
Priority to FIEP18835679.4T priority patent/FI3656754T3/en
Priority to RU2020103744A priority patent/RU2740916C1/en
Priority to EP18835679.4A priority patent/EP3656754B1/en
Priority to PCT/CN2018/096248 priority patent/WO2019015638A1/en
Priority to CN201880002860.5A priority patent/CN109526217B/en
Publication of CN109280103A publication Critical patent/CN109280103A/en
Application granted granted Critical
Publication of CN109280103B publication Critical patent/CN109280103B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The invention belongs to the field of olefin polymerization catalysts, and particularly discloses a catalyst system for olefin polymerization and application thereof. The catalyst system comprises the reaction product of: 1) the solid catalyst component comprises the reaction product of: an alkoxy magnesium compound, a titanium compound and an optional internal electron donor compound; 2) and (3) a cocatalyst: selected from organoaluminum compounds; 3) external electron donor compound: at least one selected from cyclotri-veratrole hydrocarbons represented by formula (I) and derivatives thereof, wherein M is represented by formula (I)1、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～C10The substituent is selected from hydroxyl, amino, aldehyde group, carboxyl, acyl, halogen atom, alkoxy or hetero atom.

Description

Catalyst system for olefin polymerization and application thereof
Technical Field
The invention belongs to the field of olefin polymerization catalysts, and particularly relates to a catalyst system for olefin polymerization and application thereof.
Background
In the last 60 years, with the continuous development of olefin polymerization catalyst technology, the activity, hydrogen regulation sensitivity and copolymerization performance of Ziegler-Natta type polyolefin catalysts, and the parameters of bulk density, melt index, molecular weight distribution, fine powder content, copolymerization unit distribution and the like of the polymerization powder are remarkably optimized. 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, the hydrogen response of the catalyst can be improved by introducing an internal electron donor into the catalyst, for example: CN1958620A introduces siloxane electron donor; CN1743347A introduces ortho alkoxy substituted benzoate/carboxylic ester (or diether) compound electron donor; the CN102295717A and the CN103772536A introduce a benzoate compound as an electron donor, thereby improving the hydrogen regulation sensitivity of the catalyst. The copolymerization performance of the catalyst can also be improved by introducing internal/external electron donors into the catalyst, such as: CN1726230A introduces ether, ester, amine, ketone or nitrile electron donor compounds; CN1798774A takes alcohol, glycol, ester, ketone, amine, amide, nitrile, alkoxy silane and aliphatic ether as electron donor compounds; CN101050248A introduces alcohol, ketone, amine, amide, nitrile, alkoxysilane, aliphatic ether and aliphatic carboxylic acid ester electron donors.
According to the description of the prior art, the introduction of an external electron donor to modify the polymer properties during the polymerization of a Ziegler-Natta type polypropylene catalyst is a well-known technique in this field; however, there have been few reports of the introduction of external electron donors in the polymerization process of Ziegler-Natta type polyethylene catalysts. Research shows that if an external electron donor is introduced in the polymerization process of the Ziegler-Natta type polyethylene catalyst, the parameters of the catalyst, such as activity, hydrogen regulation sensitivity, copolymerization performance and the like, cannot be completely optimized, and partial performance is reduced. For the above reasons, the external electron donor technology of Ziegler-Natta type polyethylene catalyst has not been industrialized yet and has been reported less in the prior art.
Therefore, it is highly desirable to provide an external electron donor which can simultaneously improve the parameters of the Ziegler-Natta type polyolefin catalyst, such as activity, hydrogen response and copolymerization performance.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention provides a catalyst system for olefin polymerization and applications thereof, wherein an external electron donor having special properties, cyclotri veratryl hydrocarbon and derivatives thereof, is introduced into a Ziegler-Natta type polyolefin catalyst, so that the activity, hydrogen sensitivity and copolymerization performance of the catalyst can be simultaneously improved.
According to a first aspect of the present invention there is provided a catalyst system for the polymerisation of olefins, the catalyst system comprising the reaction product of:
1) solid catalyst component:
a reaction product comprising: an alkoxy magnesium compound, a titanium compound and an optional internal electron donor compound;
2) and (3) a cocatalyst:
selected from organoaluminum compounds having the general formula AlR1 dX1 3-dIn the formula, R1Is hydrogen or Cl～C20Hydrocarbyl radical, X1Is halogen atom, d is more than 0 and less than or equal to 3;
3) external electron donor compound:
at least one selected from cyclotri veratrole hydrocarbon and derivatives thereof represented by formula (I),
Figure BDA0001354784780000021
m in formula (I)1、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 the group consisting of-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 the use of a catalyst system as described above in the polymerisation of olefins.
According to the catalyst system for olefin polymerization, the ring-III veratrum hydrocarbon and the derivative thereof are used as external electron donors, so that the activity, hydrogen regulation sensitivity and copolymerization performance of the catalyst can be improved, and in addition, the bulk density and the content of copolymerization units of polymerization powder prepared by using the catalyst system are improved.
Detailed Description
In order that the invention may be more readily understood, the following detailed description of the invention is given in conjunction with the specific embodiments which are given by way of illustration only and are not intended to limit the invention.
According to a first aspect of the present invention there is provided a catalyst system for the polymerisation of olefins, the catalyst system comprising the reaction product of:
1) solid catalyst component:
a reaction product comprising: an alkoxy magnesium compound, a titanium compound and an optional internal electron donor compound;
2) and (3) a cocatalyst:
selected from organoaluminum compounds having the general formula AlR1 dX1 3-dIn the formula, R1Is hydrogen or Cl～C20Hydrocarbyl radical, X1Is halogen atom, d is more than 0 and less than or equal to 3;
3) external electron donor compound:
at least one selected from cyclotri veratrole hydrocarbon and derivatives thereof represented by formula (I),
Figure BDA0001354784780000041
m in formula (I)1、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 the group consisting of-R1OR-OR2When used, two adjacent groups may optionally form a ring with each other.
In the present invention, the hydrocarbon group may be an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group or an aralkyl group. Wherein, 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, dimethylhexyl and n-decyl.
C3～C10Examples of cycloalkyl groups may include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.
C6～C10Examples of aryl groups may include, but are not limited to: phenyl, 4-methylphenyl and 4-ethylphenyl.
C2～C10Examples of alkenyl groups may include, but are not limited to: vinyl and allyl.
C2～C10Examples of alkynyl groups may include, but are not limited to: ethynyl and propargyl.
C7～C10Examples of aralkyl groups 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 "hydrocarbon group" of (A) means "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.
According to the present invention, the internal electron donor compound may be selected from an internal electron donor a and/or an internal electron donor b.
Wherein the internal electron donor a is selected from at least one of cyclotri veratrole hydrocarbon shown in formula (I) and derivatives thereof; the internal electron donor a and the external electron donor compound may be the same or different.
The internal electron donor b may be other internal electron donors conventionally used in the art, other than the internal electron donor a, and 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, ethylene oxide, propylene oxide, epichlorohydrin, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triphenyl phosphate, trihexyl phosphate, polymethyl methacrylate, triethyl phosphate, and mixtures thereof, At least one of polystyrene, polyepichlorohydrin and polyethylene oxide.
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.
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 P: m1＝M3＝M5＝OCH3；M2＝M4＝M6＝OCH2CH2CH2Br；
Compound Q: m1＝M2＝M3＝M4＝M5＝M6＝OCH2CH2Cl。
In addition, when 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. However, such isomers are also 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 method 2 comprises the following steps: in the presence of an acidic substance, catalyzing a benzene ring derivative B shown in a formula (III) to perform condensation reaction, thereby obtaining the cyclotri-veratryl hydrocarbon and the derivative thereof;
the method 3 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 BDA0001354784780000071
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 according to conventional techniques, and will not be described herein.
According to the invention, the magnesium alkoxide compound may be represented by the general formula Mg (OR)3)a(OR4)2-a，R3And R4Each being substituted or unsubstituted C1～C10The substituent group of the alkyl is hydroxyl, amino, aldehyde group, carboxyl, acyl, halogen atom, alkoxy or hetero atom, and a is more than or equal to 0 and less than or equal to 2.
Preferably, the magnesium alkoxide compound is selected from Mg (OEt)a(OEHA)2-a1.5. ltoreq. a.ltoreq.2, or Mg (OEt)a(OBu)2-aA is more than or equal to 1.3 and less than or equal to 2; wherein Et is ethyl, EHA is 2-ethylhexyl, and Bu is butyl.
The alkoxy magnesium compound carrier can be obtained by the preparation method in the prior art, and the invention is not particularly limited in this regard.
According to the invention, the titanium compound may be chosen as is conventional in the art and may have the general formula Ti (OR)2)nX2 4－nWherein R is2Is C1～C8A hydrocarbon group, preferably C1～C8An alkyl group; x2Is Cl, Br or I, and n is more than or equal to 0 and less than or equal to 4.
In particular, the titanium compound may be selected from TiCl4、TiBr4、TiI4、Ti(OC2H5)Cl3、Ti(OCH3)Cl3、Ti(OC4H9)Cl3、Ti(OC2H5)Br3、Ti(OC2H5)2Cl2、Ti(OCH3)2Cl2、Ti(OCH3)2I2、Ti(OC2H5)3Cl、Ti(OCH3)3Cl、Ti(OC2H5)3I、Ti(OC2H5)4、Ti(OC3H7)4And Ti (OC)4H9)4At least one of (1).
Preferably, the titanium compound is selected from TiCl4、Ti(OC2H5)Cl3、Ti(OCH3)Cl3、Ti(OC4H9)Cl3And Ti (OC)4H9)4At least one of (1). More preferably, the titanium compound is TiCl4。
According to the invention, in the solid catalyst component, the amount of the titanium compound is 0.1-15 mol per mol of magnesium; the dosage of the internal electron donor compound is 0-0.1 mol, preferably 0-0.08 mol.
In the invention, the solid catalyst component is prepared by firstly dispersing the alkoxy magnesium compound in an inert solvent to prepare a suspension, and then adding other reactant components for contact reaction.
Preferably, the solid catalyst component can be prepared by the following method:
method 1
1) Dispersing an alkoxy magnesium compound in an inert solvent to obtain a suspension;
2) the suspension is contacted with a titanium compound for reaction, and then unreacted substances are removed and washed by an inert solvent;
3) contacting the precipitate obtained in the step 2) with the titanium compound and an optional internal electron donor a 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 2
1) Dispersing an alkoxy magnesium compound in an inert solvent to obtain a suspension;
2) the suspension is contacted with a titanium compound and an optional internal electron donor b for reaction, and then unreacted substances are removed and washed by an inert solvent;
3) contacting the precipitate obtained in the step 2) with the titanium compound and an optional internal electron donor a 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.
The method 1 may specifically include:
s1: dispersing the alkoxy magnesium compound in an inert solvent to obtain a suspension;
s2: adding the titanium compound to the suspension at a temperature of-20 to 20 ℃;
s3: heating to 50-95 ℃, reacting for 0.5-5 hours under the condition of stirring, standing for layering, pumping out supernatant, and washing precipitates with an inert solvent;
s4: adding a titanium compound and an optional internal electron donor a, stirring and reacting for 0.5-5 hours at 50-95 ℃, removing unreacted substances and a solvent, standing and layering, pumping out a supernatant, and washing a precipitate with an inert solvent to obtain the solid catalyst component.
The method 2 may specifically include:
s1: dispersing the alkoxy magnesium compound in an inert solvent to obtain a suspension;
s2: adding the titanium compound and optionally an internal electron donor b to the suspension at a temperature of-20 to 20 ℃;
s3: heating to 50-95 ℃, reacting for 0.5-5 hours under the condition of stirring, standing for layering, pumping out supernatant, and washing precipitates with an inert solvent;
s4: adding a titanium compound and an optional internal electron donor a, stirring and reacting for 0.5-5 hours at 50-95 ℃, removing unreacted substances and a solvent, standing and layering, pumping out a supernatant, and washing a precipitate with an inert solvent to obtain the solid catalyst component.
S4 in method 1 and S2 in method 2 can be carried out in stages, and different reaction components are added in each stage for reaction.
The inert solvent used in the above steps may be the same or different and may be selected with reference to the prior art, and the present invention is not particularly limited thereto. For example, the inert solvent is 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 the invention, the organoaluminium compound may be chosen 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)2And AlCl2(CH2CH3) At least one of (1).
Preferably, the organoaluminium compound is selected from Al (CH)2CH3)3、Al(n-C6H13)3And Al (i-Bu)3At least one of (1). More preferably, the organoaluminum compound is Al (CH)2CH3)3And/or Al (i-Bu)3。
According to the present invention, the molar ratio of aluminum in the organoaluminum compound to titanium in the solid catalyst component may be 5: 1 to 500: 1, preferably 20: 1 to 200: 1.
According to the present invention, the molar ratio of the external electron donor compound to titanium in the solid catalyst component is 0.5: 1 to 50: 1.
According to a second aspect of the present invention, there is provided the use of a catalyst system as described above in the polymerisation of olefins.
In the present invention, the olefin polymerization reaction includes homopolymerization and copolymerization of olefins.
In particular, the catalyst system of the present invention can be used for the homopolymerization of ethylene; the copolymerization of ethylene with butene, pentene, hexene, octene or 4-methyl-1-pentene is preferably a copolymerization of ethylene with butene.
In addition, the catalyst system is suitable for polymerization under various conditions, for example, the olefin polymerization can be carried out in liquid phase or in gas phase, or else in an operation combining liquid phase and gas phase polymerization stages. The polymerization temperature may be 0 to 150 ℃, preferably 60 to 90 ℃.
The medium used for the liquid phase polymerization may be selected from inert solvents such as saturated aliphatic hydrocarbons or aromatic hydrocarbons, such as isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, xylene, etc., and toluene, n-hexane, or cyclohexane is preferable.
In addition, hydrogen is used as a molecular weight regulator in order to regulate the molecular weight of the final polymer.
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 solid catalyst component is as follows: spectrophotometry is adopted.
2. Composition of the solid catalyst component: using liquid nuclear magnetism1H-NMR。
3. Polymer Melt Index (MI): measured according to ASTM D1238-99, load 2.16kg, 190 ℃.
4. Content of copolymerized units in the polymer powder: using liquid nuclear magnetism13C-NMR determination.
5. Weight percent of hexane extractables in polymer powder: transferring the whole powder slurry obtained by polymerization to a standard cylindrical container with nitrogen, thoroughly drying under ventilation conditions to obtain block powder, vertically cutting 20g of the obtained block powder, pulverizing, placing in the container, extracting with 300mL of hexane at 50 deg.C for 2 hours, subsequently extracting 20mL of the extract,placing it in an accurately weighed petri dish, weighing the dish completely dried, the weight gain of the dish being m1g, and the weight percentage of hexane extractables is thus calculated to be 75m1％。
6. In the polymerization reaction, the pressure in the reactor is absolute pressure.
Preparation examples 1 to 4 are provided to illustrate the preparation methods of the cyclotri veratryl hydrocarbon and the derivative thereof.
Preparation example 1
1, 2-o-dimethyl ether (1.0g) was added dropwise to a mixture of aqueous formaldehyde (4 mL/38%)/0.1 mL of chloroform/concentrated hydrochloric acid (6mL) under ice-bath conditions to effect a reaction, and after 30 minutes, the solution became a paste and was stirred at room temperature for 4 hours. The solid was collected by filtration, washed with ice water and thoroughly dried to obtain 0.5g of compound A represented by the formula (IV).
Figure BDA0001354784780000111
Preparation example 2
3-methoxy-4-ethoxy-benzyl alcohol (3g) was dissolved in 30mL of methanol under ice-bath conditions, and 15mL of 65% perchloric acid was added dropwise with stirring in an ice-bath. Stirring in ice bath for 18h under nitrogen protection. To the reaction product, 30mL of water was slowly added, followed by extraction of the organic phase with dichloromethane. The organic phase was washed carefully with aqueous sodium hydroxide, then with deionized water and dried. The organic phase was thoroughly drained and purified by column chromatography to obtain 1g of compound F represented by the formula (V).
Figure BDA0001354784780000121
Preparation example 3
Dissolving 1, 2-o-diethyl ether (3.3g) and trioxymethylene (0.63g) in dry dichloromethane (30mL), stirring in an ice bath, slowly dropping boron trifluoride diethyl etherate (4.25g), removing the ice bath after dropping, stirring at normal temperature for 3h, tracking the reaction by TLC until the reaction is complete, stopping the reaction, washing the mixture with water for 3 times, separating an organic layer, spin-drying the organic solvent to obtain an oily substance, adding a small amount of acetone to dissolve the oily substance, adding a large amount of methanol, standing in a refrigerator to separate out a white solid. After suction filtration and thorough drying, 1.5g of the compound B represented by the formula (VI) was obtained.
Figure BDA0001354784780000122
Preparation example 4
3-methoxy-4-bromo-benzyl alcohol (3.6g) was dissolved in 30mL of methanol under ice-bath conditions, and 15mL of 65% perchloric acid was added dropwise with stirring in an ice-bath. Stirring in ice bath for 18h under nitrogen protection. To the reaction product, 30mL of water was slowly added, followed by extraction of the organic phase with dichloromethane. The organic phase was washed carefully with aqueous sodium hydroxide, then with deionized water and dried. After thorough draining, purification was performed by column chromatography to obtain 0.8g of the compound M represented by the formula (VII).
Figure BDA0001354784780000131
Examples 1-3 illustrate the catalyst system of the present invention and the use of the catalyst system in olefin polymerization reactions.
Example 1
(1) Preparation of solid catalyst component
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 is slowly added, the temperature is slowly increased to 90 ℃ after the dropwise addition, 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. The solid catalyst component a with good fluidity is obtained by washing the solid catalyst component a for a plurality of times by an inert diluent toluene and an organic solvent hexane and then drying the washed solid catalyst component a, and the composition is shown in table 1.
(2) Homopolymerization reaction
Polymerization with low hydrogen/ethylene ratio
A stainless steel reaction vessel having a capacity of 2L was sufficiently purged with high-purity nitrogen, and then 1L of hexane, 1.0mL of triethylaluminum having a concentration of 1M and 0.01mmol of the compound A obtained in production example 1 were added, and the solid catalyst component a (containing 0.6mg of titanium) prepared by the above method was added, and the temperature was raised to 70 ℃ to introduce hydrogen gas so that the pressure in the vessel became 0.28MPa, and ethylene was introduced so that the total pressure in the vessel became 0.73MPa, and the polymerization was carried out at 80 ℃ for 2 hours, and the polymerization results were shown in Table 2.
② polymerization with high hydrogen/ethylene ratio
A stainless steel reaction vessel having a capacity of 2L was sufficiently purged with high-purity nitrogen, and then 1L of hexane, 1.0mL of triethylaluminum having a concentration of 1M and 0.01mmol of the compound A obtained in production example 1 were added, and the solid catalyst component a (containing 0.6mg of titanium) prepared by the above method was added, and the temperature was raised to 70 ℃ to introduce hydrogen so that the pressure in the reaction vessel became 0.58MPa, and ethylene was introduced so that the total pressure in the reaction vessel became 0.73MPa, and polymerization was carried out at 80 ℃ for 2 hours, the polymerization results were shown in Table 2.
(3) Copolymerization reaction
Firstly, an ethylene/butylene mixed gas is prepared in a gas preparation tank, and the molar ratio of the ethylene/butylene is 0.90/0.10.
A stainless steel reaction vessel having a volume of 2L was sufficiently purged with high-purity nitrogen, and then 1L of hexane, 1.0mL of triethylaluminum having a concentration of 1M and 0.01mmol of the compound A obtained in production example 1 were added, and the solid catalyst component a (containing 0.6mg of titanium) prepared by the above method was added, and the temperature was raised to 70 ℃ to introduce hydrogen gas so that the pressure in the reaction vessel became 0.28MPa, and then ethylene/butene mixed gas was introduced so that the total pressure in the reaction vessel became 0.73MPa, and polymerization was carried out at 80 ℃ for 2 hours, the polymerization results were shown in Table 3.
Example 2
(1) Preparation of solid catalyst component
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 ℃, 40mL of titanium tetrachloride is slowly added, the temperature is slowly increased to 90 ℃ after the dropwise addition, and the constant temperature is kept for 1 hour. Stopping stirring, standing still,the suspension was quickly separated and the supernatant was aspirated. Then, 60mL of toluene, 30mL of titanium tetrachloride and 0.2g of Compound F prepared in preparation example 2 were added, and the temperature was raised to 90 ℃ and maintained for 1 hour. Stopping stirring, standing, and removing supernatant. The solid catalyst component b with good fluidity was obtained by washing with toluene as an inert diluent and hexane as an organic solvent for several times and then drying, and the composition thereof is shown in Table 1.
(2) Homopolymerization reaction
Polymerization with low hydrogen/ethylene ratio
As in example 1, but changing the kind and addition amount of the external electron donor to 0.01mmol of the compound B prepared in preparation example 3, and further adding solid catalyst component B, the polymerization results are shown in Table 2.
② polymerization with high hydrogen/ethylene ratio
As in example 1, but changing the kind and addition amount of the external electron donor to 0.01mmol of the compound B prepared in preparation example 3, and further adding solid catalyst component B, the polymerization results are shown in Table 2.
(3) Copolymerization reaction
As in example 1, but changing the kind and addition amount of the external electron donor to 0.01mmol of the compound B prepared in preparation example 3, and further adding solid catalyst component B, the polymerization results are shown in Table 3.
Example 3
(1) Preparation of solid catalyst component
Mixing 10g Mg (OEt)1.7(OEHA)0.360mL of toluene were 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 ℃, 60mL of titanium tetrachloride and 0.5mL of ethyl acetate are slowly added in sequence, after the dropwise addition is finished, the temperature is slowly increased to 90 ℃, and the constant temperature is kept for 2 hours. Stopping stirring, standing, quickly demixing the suspension, and removing the supernatant. Then, 60mL of toluene and 50mL of titanium tetrachloride were added, and the temperature was raised to 90 ℃ and maintained for 2 hours. Stopping stirring, standing, and removing supernatant. The solid catalyst component c with good fluidity was obtained by washing with toluene as an inert diluent and hexane as an organic solvent for several times and then drying, and the composition thereof is shown in Table 1.
(2) Homopolymerization reaction
Polymerization with low hydrogen/ethylene ratio
As in example 1, but changing the kind and addition amount of the external electron donor to 0.02mmol of the compound M prepared in preparation example 4, and further adding solid catalyst component c, the polymerization results are shown in Table 2.
② polymerization with high hydrogen/ethylene ratio
As in example 1, but changing the kind and addition amount of the external electron donor to 0.02mmol of the compound M prepared in preparation example 4, and further adding solid catalyst component c, the polymerization results are shown in Table 2.
(3) Copolymerization reaction
As in example 1, but changing the kind and addition amount of the external electron donor to 0.02mmol of the compound M prepared in preparation example 4, and further adding solid catalyst component c, the polymerization results are shown in Table 3.
Comparative example 1
(1) Preparation of solid catalyst component
As in example 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 a (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 a (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
Firstly, an ethylene/butylene mixed gas is prepared in a gas preparation tank, and the molar ratio of the ethylene/butylene is 0.90/0.10.
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 a (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 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.
Comparative example 2
(1) Preparation of solid catalyst component
As in example 1.
(2) Homopolymerization reaction
Polymerization with low hydrogen/ethylene ratio
The same as example 1, except that the kind and the addition amount of the external electron donor were changed to 0.01mmol of ethyl benzoate, the polymerization results are shown in Table 2.
② polymerization with high hydrogen/ethylene ratio
The same as example 1, except that the kind and the addition amount of the external electron donor were changed to 0.01mmol of ethyl benzoate, the polymerization results are shown in Table 2.
(3) Copolymerization reaction
The same as example 1, except that the kind and the addition amount of the external electron donor were changed to 0.01mmol of ethyl benzoate, the polymerization results are shown in Table 3.
Comparative example 3
(1) Preparation of solid catalyst component
As in example 2.
(2) Homopolymerization reaction
Polymerization with low hydrogen/ethylene ratio
The polymerization results are shown in Table 2, as in comparative example 1, but with the addition of solid catalyst component b.
② polymerization with high hydrogen/ethylene ratio
The polymerization results are shown in Table 2, as in comparative example 1, but with the addition of solid catalyst component b.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in comparative example 1, but with the addition of solid catalyst component b.
Comparative example 4
(1) Preparation of solid catalyst component
As in example 2.
(2) Homopolymerization reaction
Polymerization with low hydrogen/ethylene ratio
As in example 1, but changing the kind and addition amount of the external electron donor to 0.01mmol of 1, 2-o-dimethylether and further adding solid catalyst component b, the polymerization results are shown in Table 2.
② polymerization with high hydrogen/ethylene ratio
As in example 1, but changing the kind and addition amount of the external electron donor to 0.01mmol of 1, 2-o-dimethylether and further adding solid catalyst component b, the polymerization results are shown in Table 2.
(3) Copolymerization reaction
As in example 1, but changing the kind and addition amount of the external electron donor to 0.01mmol of 1, 2-o-dimethylether and further adding solid catalyst component b, the polymerization results are shown in Table 3.
Comparative example 5
(1) Preparation of solid catalyst component
As shown in example 3.
(2) Homopolymerization reaction
Polymerization with low hydrogen/ethylene ratio
The polymerization results are shown in Table 2, as in comparative example 1, but with the addition of solid catalyst component c.
② polymerization with high hydrogen/ethylene ratio
The polymerization results are shown in Table 2, as in comparative example 1, but with the addition of solid catalyst component c.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in comparative example 1, but with the addition of solid catalyst component c.
Comparative example 6
(1) Preparation of solid catalyst component
As shown in example 3.
(2) Homopolymerization reaction
Polymerization with low hydrogen/ethylene ratio
As in example 1, but changing the kind and addition amount of the external electron donor to 0.02mmol of propyl acetate and adding solid catalyst component c, the polymerization results are shown in Table 2.
② polymerization with high hydrogen/ethylene ratio
As in example 1, but changing the kind and addition amount of the external electron donor to 0.02mmol of propyl acetate and adding solid catalyst component c, the polymerization results are shown in Table 2.
(3) Copolymerization reaction
As in example 1, but changing the kind and addition amount of the external electron donor to 0.02mmol of propyl acetate and adding solid catalyst component c, the polymerization results are shown in Table 3.
TABLE 1
Figure BDA0001354784780000191
*: does not contain ethoxy groups in the cyclotri-veratrum hydrocarbon and derivatives thereof.
TABLE 2
Figure BDA0001354784780000201
From the data in table 2, it can be seen that:
1. according to the catalyst system, the cyclo-tri-veratrum hydrocarbon and the derivative thereof are added as the external electron donor, so that compared with a catalyst system without the external electron donor, the activity and the hydrogen regulation sensitivity of a polyethylene catalyst system and the stacking density of polymerization powder can be simultaneously improved in the polymerization reaction of low hydrogen-to-ethylene ratio and high hydrogen-to-ethylene ratio;
2. when other compounds (such as ethyl benzoate, propyl acetate and 1, 2-o-dimethyl ether) are added to the catalyst system as external electron donors, the activity, hydrogen sensitivity and bulk density of the polymerized powder are reduced.
TABLE 3
Numbering External electron donor compound Content of copolymerized Unit (mol%) Hexane extractables (wt%)
Example 1 Compound A 2.4 4.2
Comparative example 1 - 2.2 5.3
Comparative example 2 Benzoic acid ethyl ester 1.8 4.3
Example 2 Compound B 2.6 3.6
Comparative example 3 - 2.5 3.9
Comparative example 4 1, 2-o-dimethyl ether 1.6 3.6
Example 3 Compound M 2.3 3.7
Comparative example 5 - 2.1 5.2
Comparative example 6 Propyl acetate 1.7 3.9
From the data in table 3, it can be seen that:
1. according to the invention, the tri-veratrum hydrocarbon and the derivative thereof are introduced into the catalyst system as external electron donors, so that the content of copolymerization units of the polymerized powder is increased, and the hexane extractables are reduced. This shows that as the content of copolymerized units in the polymer powder increases, the content of copolymerized units in the low-molecular weight component decreases, while the content of copolymerized units in the medium/high-molecular weight component increases. Therefore, the cyclotri-veratrum hydrocarbon and the derivative thereof improve the copolymerization performance of the catalyst system, thereby being beneficial to improving the comprehensive performance of the product.
2. Other compounds (listed as ethyl benzoate, propyl acetate and 1, 2-o-dimethyl ether, for example) were introduced into the catalyst system as external electron donors, and the content of copolymerized units and hexane extractables of the polymerized powder decreased. This indicates that the external electron donor reduces the comonomer addition probability and hexane extractables, but this is not an improvement in the copolymerization performance of the catalyst system.
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 (12)

1. A catalyst system for the polymerization of olefins, the catalyst system comprising the reaction product of:
1) solid catalyst component:
a reaction product comprising: an alkoxy magnesium compound, a titanium compound and an optional internal electron donor compound;
2) and (3) a cocatalyst:
selected from organoaluminum compounds having the general formula AlR1 dX1 3-dIn the formula, R1Is hydrogen or Cl～C20Hydrocarbyl radical, X1Is halogen atom, d is more than 0 and less than or equal to 3;
3) external electron donor compound:
at least one selected from cyclotri veratrole hydrocarbon and derivatives thereof represented by formula (I),
Figure FDA0002649620070000011
m in formula (I)1、M2、M3、M4、M5And M6Same OR different, each selected from halogen atoms OR-OR2Which isIn, R2Each being unsubstituted C1～C10A hydrocarbyl group.
2. The catalyst system according to claim 1, wherein said 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 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。
3. The catalyst system of claim 1, wherein the magnesium alkoxide compound has the formula Mg (OR)3)a(OR4)2-a，R3And R4Each being substituted or unsubstituted C1～C10The substituent group of the alkyl is hydroxyl, amino, aldehyde group, carboxyl, acyl, halogen atom, alkoxy or hetero atom, and a is more than or equal to 0 and less than or equal to 2.
4. The catalyst system according to claim 1, wherein the titanium compound has the general formula Ti (OR)2)nX2 4－nWherein R is2Is C1～C8A hydrocarbyl group; x2Is Cl, Br or I, and n is more than or equal to 0 and less than or equal to 4.
5. The catalyst system of claim 4, wherein R2Is C1～C8An alkyl group.
6. The catalyst system according to claim 4, wherein the titanium compound is selected from TiCl4、Ti(OC2H5)Cl3、Ti(OCH3)Cl3、Ti(OC4H9)Cl3And Ti (OC)4H9)4At least one of (1).
7. The catalyst system according to claim 1, wherein the titanium compound is used in an amount of 0.1 to 15mol per mol of magnesium in the solid catalyst component; the dosage of the internal electron donor compound is 0-0.1 mol.
8. According to claim 1The catalyst system according to (1), wherein the organoaluminum compound is selected from Al (CH)2CH3)3、Al(i-Bu)3And Al (n-C)6H13)3At least one of (1).
9. The catalyst system according to claim 1, 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 catalyst system 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. The catalyst system of claim 1, wherein the molar ratio of the external electron donor compound to titanium in the solid catalyst component is 0.5: 1 to 50: 1.
12. Use of a catalyst system according to any one of claims 1 to 11 in the polymerisation of olefins.
CN201710591181.3A 2017-07-19 2017-07-19 Catalyst system for olefin polymerization and application thereof Active CN109280103B (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
CN201710591181.3A CN109280103B (en) 2017-07-19 2017-07-19 Catalyst system for olefin polymerization and application thereof
RU2020103744A RU2740916C1 (en) 2017-07-19 2018-07-19 Olefin polymerisation catalyst comprising cyclotriveratrilene 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
JP2020502696A JP7038797B2 (en) 2017-07-19 2018-07-19 Olefin polymerization catalyst containing cyclotribellatrilen and its derivatives
ES18835679T ES2980848T3 (en) 2017-07-19 2018-07-19 Olefin polymerization catalyst comprising cyclotriveratrilene and derivatives thereof
MYPI2020000297A MY201121A (en) 2017-07-19 2018-07-19 Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof
KR1020207002897A KR102336976B1 (en) 2017-07-19 2018-07-19 Olefin polymerization catalyst comprising cyclotiberatrylene and derivatives thereof
US16/631,482 US11401356B2 (en) 2017-07-19 2018-07-19 Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof
EP18835679.4A EP3656754B1 (en) 2017-07-19 2018-07-19 Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof
PCT/CN2018/096248 WO2019015638A1 (en) 2017-07-19 2018-07-19 Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof
CN201880002860.5A CN109526217B (en) 2017-07-19 2018-07-19 Olefin polymerization catalyst containing cyclotri veratrum hydrocarbon and derivatives thereof
FIEP18835679.4T FI3656754T3 (en) 2017-07-19 2018-07-19 Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710591181.3A CN109280103B (en) 2017-07-19 2017-07-19 Catalyst system for olefin polymerization and application thereof

Publications (2)

Publication Number Publication Date
CN109280103A CN109280103A (en) 2019-01-29
CN109280103B true CN109280103B (en) 2021-02-05

Family

ID=65185026

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710591181.3A Active CN109280103B (en) 2017-07-19 2017-07-19 Catalyst system for olefin polymerization and application thereof

Country Status (1)

Country Link
CN (1) CN109280103B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN113004452B (en) * 2021-04-27 2022-12-06 东莞市学诚塑胶制品有限公司 Impact-resistant polypropylene and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1272851A (en) * 1998-06-16 2000-11-08 三井化学株式会社 Catalyst for olefin polymerization and method of polymerizing olefin
US6255419B1 (en) * 1997-02-07 2001-07-03 Mitsui Chemicals, Inc. Olefin polymerization catalyst and process for producing olefin polymers
CN103509218A (en) * 2012-06-18 2014-01-15 中国石油化工股份有限公司 Components of catalyst used for olefin polymerization and preparation method thereof
WO2015091984A1 (en) * 2013-12-20 2015-06-25 Saudi Basic Industries Corporation Procatalyst for polymerization of olefins

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6255419B1 (en) * 1997-02-07 2001-07-03 Mitsui Chemicals, Inc. Olefin polymerization catalyst and process for producing olefin polymers
CN1272851A (en) * 1998-06-16 2000-11-08 三井化学株式会社 Catalyst for olefin polymerization and method of polymerizing olefin
CN103509218A (en) * 2012-06-18 2014-01-15 中国石油化工股份有限公司 Components of catalyst used for olefin polymerization and preparation method thereof
WO2015091984A1 (en) * 2013-12-20 2015-06-25 Saudi Basic Industries Corporation Procatalyst for polymerization of olefins

Also Published As

Publication number Publication date
CN109280103A (en) 2019-01-29

Similar Documents

Publication Publication Date Title
CN110016094B (en) Solid catalyst component and catalyst system for olefin polymerization and olefin polymerization process
CN109280102B (en) Solid catalyst component and catalyst system for olefin polymerization and olefin polymerization process
CN109280101B (en) Solid catalyst component and catalyst system for olefin polymerization and olefin polymerization process
CN110016093B (en) Solid catalyst component and catalyst system for olefin polymerization and olefin polymerization process
CN107629153B (en) Catalyst component for olefin polymerization, preparation method thereof, catalyst for olefin polymerization and application thereof
CN109280110B (en) Solid catalyst component for olefin polymerization, olefin polymerization catalyst, application thereof and ethylene copolymer
CN109280104B (en) Application of cyclotri-veratrum hydrocarbon and derivative thereof in olefin polymerization catalyst
KR102336976B1 (en) Olefin polymerization catalyst comprising cyclotiberatrylene and derivatives thereof
EP3868794A1 (en) Carrier for alkene polymerization catalyst, and preparation method therefor and application thereof
CN109280106B (en) Solid catalyst component and catalyst system for olefin polymerization and olefin polymerization process
CN109280107B (en) Catalyst system for olefin polymerization and application thereof
CN109280103B (en) Catalyst system for olefin polymerization and application thereof
EP4053174A1 (en) Method for preparing olefin-polar monomer copolymer
CN110734510B (en) Olefin polymerization catalyst containing cyclotri veratrum hydrocarbon and its derivatives
CN109280111B (en) Catalyst system for olefin polymerization and application thereof
CN109280105B (en) Catalyst system for olefin polymerization and application thereof
CN113754799A (en) Solid catalyst component and solid catalyst system containing same
CN109280109B (en) Catalyst system for olefin polymerization and application thereof
CN110016096B (en) Catalyst carrier for olefin polymerization and preparation method thereof, solid catalyst component, catalyst system and olefin polymerization method
CN109280108B (en) Solid catalyst component and catalyst system for olefin polymerization and olefin polymerization process
CN102453152A (en) Olefin polymerization catalyst system and olefin polymerization method using the same
CN116769089B (en) Preparation process and device of polybutene-1 resin
CN111057168B (en) Catalyst for olefin polymerization and preparation method and application thereof
CN116769095A (en) A kind of 1-butene solution polymerization method and device
CN106478844B (en) Catalyst carrier, catalyst component and catalyst for olefin polymerization

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant