CN114426599B - Catalyst component for preparing polyolefin, preparation method thereof, olefin polymerization catalyst and application thereof - Google Patents

Catalyst component for preparing polyolefin, preparation method thereof, olefin polymerization catalyst and application thereof Download PDF

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CN114426599B
CN114426599B CN202011105038.7A CN202011105038A CN114426599B CN 114426599 B CN114426599 B CN 114426599B CN 202011105038 A CN202011105038 A CN 202011105038A CN 114426599 B CN114426599 B CN 114426599B
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dibenzoate
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electron donor
internal electron
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CN114426599A (en
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付梅艳
严立安
岑为
周俊领
张纪贵
张晓帆
林洁
张军辉
赵惠
齐琳
王宇
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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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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a catalyst component for preparing polyolefin, a preparation method thereof, an olefin polymerization catalyst and application thereof. The catalyst component comprises magnesium element, halogen element, titanium element, an internal electron donor a and an internal electron donor b, wherein the internal electron donor a is a diether compound shown in a formula I, and the internal electron donor b is a glycol ester compound shown in a formula II. The catalyst component can greatly improve the activity and hydrogen regulation sensitivity of the catalyst, can still keep higher isotacticity under the condition of high hydrogen concentration, can be used for propylene homopolymerization and propylene copolymerization, and has wider application range.

Description

Catalyst component for preparing polyolefin, preparation method thereof, olefin polymerization catalyst and application thereof
Technical Field
The invention belongs to the field of olefin polymerization, and particularly relates to a catalyst component for preparing polyolefin, a preparation method thereof, an olefin polymerization catalyst and application thereof.
Background
The solid titanium catalyst component with magnesium, titanium, halogen and electron donor compound as basic components is used in olefin polymerization reaction, and has high polymerization activity and stereospecificity especially in propylene polymerization. Among them, the electron donor compound is one of indispensable ingredients in the catalyst component, and plays a decisive role in important indexes such as polymerization activity, isotactic index of polymer, molecular weight and molecular weight distribution. With the development of internal electron donor compounds, polyolefin catalysts are continually updated.
In the industrial production of polyolefin, the requirements on the properties of materials are higher and higher, and generally, a single internal electron donor cannot meet the requirements of the polymer on various aspects such as melt index, molecular weight distribution, toughness balance of steel and the like. In order to obtain polymer materials with more comprehensive properties, researchers have made efforts on the one hand in the modification of resins and on the other hand in the compounding of electron donors in catalysts.
Several specific internal electron donors, which are dicarboxylic acid esters with high stereotacticity, medium activity and medium molecular weight distribution width, have been discovered to date by the development of Ziegler-Natta type polyolefin catalysts; 1, 3-diether compounds with higher activity, narrower molecular weight distribution and higher hydrogen regulation sensitivity; succinic acid ester compounds with a broader molecular weight distribution and a lower hydrogen regulation sensitivity; has better comprehensive performance, glycol ester compounds with relatively weak hydrogen regulation sensitivity, and the like. Due to the superior performance of diether compounds, reports of the compounding of different electron donors and 1, 3-diether electron donors are endless in recent years, and the hydrogen regulation sensitivity performance of the catalyst can be effectively improved. For example, the catalyst component and the catalyst disclosed in CN101724102A are compounded by glycol ester compounds and diether compounds as internal electron donors, and the catalyst containing the combined internal electron donors has ultrahigh polymerization activity and higher stereospecificity when used for olefin polymerization. Compared with the similar catalyst, the activity and stereospecificity of the catalyst are all at a higher level. However, the preparation method of the diether compound is complex, the preparation cost is high, and the production cost is high in industrial large-scale application.
The CN103044586B and CN101589068a patent use long-chain and short-chain α, ω -diethers with more than 5 carbons respectively, which are used in polyethylene catalysts to reduce the molecular weight distribution of ethylene polymers, but the catalyst components are used in polypropylene catalysts with lower isotacticity and poorer catalyst efficiency.
Disclosure of Invention
Aiming at the problems that the existing preparation method of the catalyst component for preparing polyolefin is complex, the preparation cost is high, the activity of the catalyst is low, or the catalyst can only be applied to ethylene polymerization reaction, but can not be applied to propylene homopolymerization and propylene copolymerization, the application has certain limitation, so that the novel catalyst component for preparing polyolefin is provided, the catalyst component adopts the internal electron donor a which has the advantages of simple structure, convenience, easiness in obtaining and low price, is compounded with the internal electron donor b for use, can greatly improve the hydrogen regulation sensitivity of the catalyst, and the obtained polymer has higher isotacticity, can be applied to propylene homopolymerization and propylene copolymerization, and has wider application range.
The first aspect of the invention provides a catalyst component for preparing polyolefin, which comprises magnesium element, halogen, titanium element, an internal electron donor a and an internal electron donor b, wherein the internal electron donor a is a diether compound shown in a formula I, the internal electron donor b is a glycol ester compound shown in a formula II,
In the formula I, R' 1 And R'. 2 Identical or different, each independently selected from C 1 -C 30 Alkyl, C of (2) 6 -C 30 Aryl, C with or without substituents 7 -C 30 Aralkyl groups with or without substituents and C 7 -C 30 An alkylaryl group with or without a substituent;
in the formula I, R' 3 、R’ 4 、R’ 5 And R'. 6 The same or different, each independently selected from hydrogen, halogen, C 1 -C 30 Alkyl, C of (2) 6 -C 30 Aryl, C with or without substituents 7 -C 30 Aralkyl groups with or without substituents and C 7 -C 30 An alkylaryl group with or without a substituent;
in the formula I, n' is an integer of 1-10;
in formula II, R 1 And R is 2 Identical or different, each independently selected from C 1 -C 20 Alkyl, C with or without substituents 2 -C 20 Alkenyl, C with or without substituents 6 -C 20 Aryl, C with or without substituents 7 -C 20 Alkylaryl, C with or without substituents 7 -C 20 Aralkyl groups with or without substituents and C 10 -C 20 A condensed ring aryl group with or without a substituent; m is a divalent linking group.
In the present invention, the term "alkyl" includes straight chain alkyl, branched alkyl and cycloalkyl. For example C 1 -C 30 The alkyl group of (C) includes C 1 -C 30 Straight chain alkyl, C 3 -C 30 Branched alkyl and C of (2) 3 -C 30 Cycloalkyl groups of (a).
According to some embodiments of the catalyst component of the invention, the halogen is selected from one or more of bromine, chlorine and iodine.
Some embodiments of the catalyst component according to the inventionOf the formula, R 'in the formula I' 1 And R'. 2 Wherein the substituents are each independently selected from halogen, C 1 -C 10 Alkyl and C of (C) 1 -C 10 One or more of the alkoxy groups of (a). Preferably, R 'in formula I' 1 And R'. 2 Wherein the substituents are each independently selected from one or more of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-octyl, n-nonyl, n-decyl, 12-alkyl, 18-alkyl, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl, benzyl and p-methylbenzyl.
In the context of the present invention, halogen refers to one or more selected from bromine, chlorine and iodine.
According to some embodiments of the catalyst component of the present invention, in R 'of formula I' 3 、R’ 4 、R’ 5 And R'. 6 Wherein the substituents are each independently selected from hydrogen, halogen, C 1 -C 10 Alkyl and C of (C) 1 -C 10 One or more of the alkoxy groups of (a). Preferably, R 'in formula I' 3 、R’ 4 、R’ 5 And R'. 6 In which the substituents are each independently selected from one or more of hydrogen, halogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-octyl, n-nonyl, n-decyl, 12-alkyl, 18-alkyl, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl, benzyl and p-methylbenzyl.
According to a preferred embodiment of the catalyst component of the present invention, the internal electron donor a is selected from one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, butylene glycol dimethyl ether, butylene glycol diethyl ether, 1, 4-diethoxybutane and butylene glycol dibutyl ether. More preferably, the internal electron donor a is selected from one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, butylene glycol dimethyl ether, butylene glycol diethyl ether and butylene glycol dibutyl ether. In the present invention, the internal electron donor a may be obtained synthetically or commercially.
According to some embodiments of the catalyst component of the invention, in formula II, R 1 And R is 2 Each independently selected from C 1 -C 10 Alkyl, C with or without substituents 2 -C 10 Alkenyl, C with or without substituents 6 -C 10 Aryl, C with or without substituents 7 -C 10 Alkylaryl, C with or without substituents 7 -C 10 Aralkyl groups with or without substituents and C 10 -C 15 With or without substituents.
According to some embodiments of the catalyst component of the invention, R in formula II 1 And R is 2 Wherein the substituents are selected from hydroxy, halogen, cyano, nitro, amino, mono- (C) 1 -C 6 Alkyl) amino, bis- (C 1 -C 6 Alkyl) amino, aldehyde, carboxyl and heteroatom.
According to some embodiments of the catalyst component of the present invention, in formula II, M is selected from C 1 -C 20 Alkylene, C, with or without substituents 3 -C 20 Cycloalkyl radicals and C, with or without substituents 6 -C 20 Or (a) arylene group with or without a substituent.
According to some embodiments of the catalyst component of the invention, in M of formula II, the substituent is C 1 -C 20 One or more of the alkyl groups, and the substituents are optionally bonded to form one or more rings.
According to some embodiments of the catalyst component of the invention, the carbon atoms or/and hydrogen atoms in M are optionally substituted by nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atoms.
According to a preferred embodiment of the catalyst component of the present invention, the internal electron donor b is a glycol ester compound represented by formula III,
in formula III, R 1 And R is 2 Identical or different, each independently selected from C 1 -C 10 Alkyl, C with or without substituents 2 -C 10 Alkenyl, C with or without substituents 2 -C 10 Alkynyl, C with or without substituents 6 -C 20 Aryl, C with or without substituents 7 -C 20 Aralkyl groups with or without substituents and C 7 -C 20 An alkylaryl group with or without a substituent. Preferably, in formula III, R 1 And R is 2 Each independently selected from C 1 -C 6 Alkyl, C with or without substituents 2 -C 6 Alkenyl, C with or without substituents 2 -C 6 Alkynyl, C with or without substituents 6 -C 10 Aryl, C with or without substituents 7 -C 10 Aralkyl groups with or without substituents and C 7 -C 10 An alkylaryl group with or without a substituent.
In the general formula IIIRepresents n carbon atoms bonded in turn and each carbon atom is also bonded to 2 substituents, i.e. n carbon atoms and R in brackets 1 、R 2 、R 3 …R 2n And 2n substituents. In particular, the method comprises the steps of,
when n=0, the middle bracket part is absent, i.e. the structure of formula III is
When n=1, the number of the groups,is->
When n=2, the number of the groups,is->
When n=3, the number of the groups,is->
When n=4, the number of the groups,is->
When n=5, the number of the groups,is->
When n=6, the number of the groups,is->
And so on,
when n=10, the number of the groups,is that
According to some embodiments of the catalyst component of the invention, R of formula III 1 And R is 2 Wherein the substituents are selected from halogen, C 1 -C 6 Alkyl and C of (C) 1 -C 6 One or more of the alkoxy groups of (a).
According to some embodiments of the catalyst component of the invention, in formula III, R 3 、R 4 、R 5 、R 6 And R is 1 -R 2n The same or different, each independently selected from hydrogen, halogen, C 1 -C 20 Alkyl, C with or without substituents 2 -C 10 Alkenyl, C with or without substituents 2 -C 10 Alkynyl, C with or without substituents 6 -C 20 Aryl, C with or without substituents 7 -C 20 Alkylaryl, C with or without substituents 7 -C 20 Aralkyl groups with or without substituents and C 10 -C 20 With or without substituents. Preferably, in formula III, R 3 、R 4 、R 5 、R 6 And R is 1 -R 2n Each independently selected from hydrogen, halogen, C 1 -C 10 Alkyl, C with or without substituents 2 -C 6 Alkenyl, C with or without substituents 2 -C 6 Alkynyl, C with or without substituents 6 -C 10 Aryl, C with or without substituents 7 -C 10 Alkylaryl, C with or without substituents 7 -C 10 With or without (C)Aralkyl of substituents and C 10 -C 15 With or without substituents.
According to some embodiments of the catalyst component of the invention, R of formula III 3 、R 4 、R 5 、R 6 And R is 1 -R 2n Wherein the substituents are selected from halogen, C 1 -C 6 Alkyl and C of (C) 1 -C 6 One or more of the alkoxy groups of (a).
According to some embodiments of the catalyst component of the invention, in formula III, R 3 、R 4 、R 5 、R 6 And R is 1 -R 2n Optionally containing heteroatoms which are one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus, or, in formula III, R 3 、R 4 、R 5 、R 6 And R is 1 -R 2n Single and/or multiple rings formed by two or more of (a) and (b); preferably, the single and/or multiple rings are each independently saturated or unsaturated.
According to some embodiments of the catalyst component of the invention, in formula III, n is an integer from 0 to 10, preferably an integer from 1 to 8, more preferably an integer from 2 to 6.
According to some embodiments of the catalyst component of the present invention, in formula III, when n is 0, the substituent is R 3 And R is 4 Is R as carbon atom and substituent 5 And R is 6 Is bonded to a carbon atom of (c).
According to a preferred embodiment of the catalyst component according to the invention, the internal electron donor b is selected from the group consisting of 2, 4-pentanediol dibenzoate, 3-methyl-2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 3, 5-heptanediol diphosven methyl benzoate, 3, 5-heptanediol dibenzoate, 3, 5-heptanediol diphosven chlorobenzoate, 3, 5-heptanediol dimethoxybenzoate, 2-methyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-heptanediol dibenzoate, 6-methyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 5-ethyl-3, 5-heptanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 4-butyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-heptanediol dibenzoate, 6-dimethyl-3, 6-heptanediol dibenzoate, 6-dimethyl-4-heptanediol dibenzoate, 6-dimethyl-heptanediol, 2-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-propyl-3, 5-heptanediol dibenzoate, 4-methyl-4-propyl-3, 5-heptanediol dibenzoate, 6-methyl-2, 4-heptanediol di (p-chlorobenzoic acid) ester, 6-methyl-2, 4-heptanediol di (p-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenzoic acid) ester, 2, 6-tetramethyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-octanediol dibenzoate 4-ethyl-3, 5-octanediol dibenzoate, 4-propyl-3, 5-octanediol dibenzoate, 4-butyl-3, 5-octanediol dibenzoate, 4-dimethyl-3, 5-octanediol dibenzoate, 4-methyl-4-ethyl-3, 5-octanediol dibenzoate, 2-methyl-6-ethyl-3, 5-octanediol dibenzoate, 5-methyl-4, 6-nonanediol dibenzoate, 5-ethyl-4, 6-nonanediol dibenzoate, 5-propyl-4, 6-nonanediol dibenzoate, 5-butyl-4, 6-nonanediol dibenzoate, 5, 5-dimethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-ethyl-4, 6-nonanediol dibenzoate, 5-phenyl-4, 6-nonanediol dibenzoate, 4, 6-nonanediol dibenzoate and 4-butyl-3, 5-heptanediol dibenzoate, 1, 2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1, 2-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-phenylene dibenzoate, 3, 6-dimethyl-1, 2-phenylene dibenzoate, 4-tert-butyl-1, 2-phenylene dibenzoate, 1, 2-naphthalene dibenzoate, 2, 3-naphthalene dibenzoate, dibenzoate-1, 8-naphthalene, di-4-methylbenzoic acid-1, 8-naphthalene, di-4-ethylbenzoic acid-1, 8-naphthalene, di-4-n-propyl-benzoic acid, 1, 8-naphthalene, 4-diphenyl-benzoic acid, 4-isopropyl-4-naphthalene, 4-isopropyl-benzoic acid, 4-isopropyl-4-naphthalene, 4-diphenyl-4-isopropyl-benzoic acid, 4-isopropyl-4-phenyl-4, 8-naphthalene, one or more of 1, 8-naphthalene di-3-fluorobenzoate and 1, 8-naphthalene di-2-fluorobenzoate. In the present invention, the internal electron donor b may be prepared by the method disclosed with reference to CN 1213080C.
According to some embodiments of the catalyst component of the present invention, the content of magnesium element is 5-30%, preferably 8-25%, more preferably 10-22% by total weight of the catalyst component; the halogen content is 30-80%, preferably 40-70%; the content of titanium element is 0.5-10%, preferably 1-6%; the content of the internal electron donor a is 0.5 to 25% by weight, preferably 1 to 20% by weight; the content of the internal electron donor b is 0.5 to 25% by weight, preferably 1 to 20% by weight. Within the preferred content range of the present invention, the olefin polymerization catalyst containing the catalyst component for producing polyolefin of the present invention has higher activity, better hydrogen tone sensitivity, better isotacticity of the obtained polymer and wider application reaction.
According to a preferred embodiment of the invention, the weight ratio of the content of the internal electron donor a to the content of the internal electron donor b is 1: (0.1-10), has better hydrogen sensitivity and isotacticity effect.
The internal electron donor a and the internal electron donor b in the invention are used together as the internal electron donor, and can play a role in synergy. Greatly improves the activity of the catalyst and the hydrogen regulation sensitivity of the catalyst.
The second aspect of the present invention provides a process for preparing the above-described catalyst component for preparing polyolefin, comprising the steps of:
Step A: carrying out first contact on a magnesium halide compound, an organic phosphorus compound, an organic epoxy compound and an optional internal electron donor a in a solvent to obtain a first mixture;
and (B) step (B): and (B) step (B): in the presence of a precipitation aid, carrying out second contact on the first mixture, a titanium compound and an optional internal electron donor a to obtain a second mixture;
step C: contacting the second mixture with an internal electron donor b and optionally an internal electron donor a for a third time, washing and drying;
wherein at least one of the steps A, B and C uses an internal electron donor a,
wherein the internal electron donor a is a diether compound shown in the formula I; the internal electron donor b is a glycol ester compound shown in a formula II,
in the formula I, R' 1 And R'. 2 Identical or different, each independently selected from C 1 -C 30 Alkyl, C of (2) 6 -C 30 Aryl, C with or without substituents 7 -C 30 Aralkyl groups with or without substituents and C 7 -C 30 An alkylaryl group with or without a substituent;
in the formula I, R' 3 、R’ 4 、R’ 5 And R'. 6 The same or different, each independently selected from hydrogen, halogen, C 1 -C 30 Alkyl, C of (2) 6 -C 30 Aryl, C with or without substituents 7 -C 30 Aralkyl groups with or without substituents and C 7 -C 30 An alkylaryl group with or without a substituent;
in the formula I, n' is an integer of 1-10;
in formula II, R 1 And R is 2 Identical or different, each independently selected from C 1 -C 20 Alkyl, C with or without substituents 2 -C 20 Alkenyl, C with or without substituents 6 -C 20 Aryl, C with or without substituents 7 -C 20 Alkylaryl, C with or without substituents 7 -C 20 Aralkyl groups with or without substituents and C 10 -C 20 A condensed ring aryl group with or without a substituent; m is a divalent linking group.
In the present invention, the term "alkyl" includes straight chain alkyl, branched alkyl and cycloalkyl. For example C 1 -C 30 The alkyl group of (C) includes C 1 -C 30 Straight chain alkyl, C 3 -C 30 Branched alkyl and C of (2) 3 -C 30 Cycloalkyl groups of (a).
According to some embodiments of the method of preparation of the present invention, the halogen is selected from one or more of bromine, chlorine and iodine.
According to some embodiments of the preparation method of the present invention, in R 'of formula I' 1 And R'. 2 Wherein the substituents are each independently selected from halogen, C 1 -C 10 Alkyl and C of (C) 1 -C 10 One or more of the alkoxy groups of (a). Preferably, R 'in formula I' 1 And R'. 2 Wherein the substituents are each independently selected from one or more of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-octyl, n-nonyl, n-decyl, 12-alkyl, 18-alkyl, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl, benzyl and p-methylbenzyl.
In the context of the present invention, halogen refers to one or more selected from bromine, chlorine and iodine.
According to some embodiments of the preparation method of the present invention, in R 'of formula I' 3 、R’ 4 、R’ 5 And R'. 6 Wherein the substituents are each independently selected from hydrogen, halogen, C 1 -C 10 Alkyl and C of (C) 1 -C 10 One or more of the alkoxy groups of (a). Preferably, R 'in formula I' 3 、R’ 4 、R’ 5 And R'. 6 Wherein the substituents are each independently selected from hydrogen, halogenOne or more of plain, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-octyl, n-nonyl, n-decyl, 12-alkyl, 18-alkyl, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl, benzyl and p-methylbenzyl.
According to a preferred embodiment of the preparation method of the present invention, the internal electron donor a is selected from one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, butanediol dimethyl ether, butanediol diethyl ether, 1, 4-diethoxybutane and butanediol dibutyl ether. More preferably, the internal electron donor a is selected from one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, butylene glycol dimethyl ether, butylene glycol diethyl ether and butylene glycol dibutyl ether. In the present invention, the internal electron donor a may be obtained synthetically or commercially.
According to some embodiments of the preparation method of the present invention, in formula II, R 1 And R is 2 Each independently selected from C 1 -C 10 Alkyl, C with or without substituents 2 -C 10 Alkenyl, C with or without substituents 6 -C 10 Aryl, C with or without substituents 7 -C 10 Alkylaryl, C with or without substituents 7 -C 10 Aralkyl groups with or without substituents and C 10 -C 15 With or without substituents.
According to some embodiments of the preparation methods of the present invention, R in formula II 1 And R is 2 Wherein the substituents are selected from hydroxy, halogen, cyano, nitro, amino, mono- (C) 1 -C 6 Alkyl) amino, bis- (C 1 -C 6 Alkyl) amino, aldehyde, carboxyl and heteroatom.
According to the inventionSome embodiments of the preparation method, formula II, M is selected from C 1 -C 20 Alkylene, C, with or without substituents 3 -C 20 Cycloalkyl radicals and C, with or without substituents 6 -C 20 Or (a) arylene group with or without a substituent.
According to some embodiments of the preparation method of the present invention, in M of formula II, the substituent is C 1 -C 20 One or more of the alkyl groups, and the substituents are optionally bonded to form one or more rings.
According to some embodiments of the preparation method of the invention, the carbon atoms or/and hydrogen atoms in M are optionally substituted by nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atoms.
According to a preferred embodiment of the preparation method of the present invention, the internal electron donor b is a glycol ester compound represented by formula III,
in formula III, R 1 And R is 2 Identical or different, each independently selected from C 1 -C 10 Alkyl, C with or without substituents 2 -C 10 Alkenyl, C with or without substituents 2 -C 10 Alkynyl, C with or without substituents 6 -C 20 Aryl, C with or without substituents 7 -C 20 Aralkyl groups with or without substituents and C 7 -C 20 An alkylaryl group with or without a substituent. Preferably, in formula III, R 1 And R is 2 Each independently selected from C 1 -C 6 Alkyl, C with or without substituents 2 -C 6 Alkenyl, C with or without substituents 2 -C 6 Alkynyl, C with or without substituents 6 -C 10 Aryl, C with or without substituents 7 -C 10 With or without substitution(s)Aralkyl of radicals and C 7 -C 10 An alkylaryl group with or without a substituent.
According to some embodiments of the preparation method of the present invention, R of formula III 1 And R is 2 Wherein the substituents are selected from halogen, C 1 -C 6 Alkyl and C of (C) 1 -C 6 One or more of the alkoxy groups of (a).
According to some embodiments of the preparation method of the present invention, in formula III, R 3 、R 4 、R 5 、R 6 And R is 1 -R 2n The same or different, each independently selected from hydrogen, halogen, C 1 -C 20 Alkyl, C with or without substituents 2 -C 10 Alkenyl, C with or without substituents 2 -C 10 Alkynyl, C with or without substituents 6 -C 20 Aryl, C with or without substituents 7 -C 20 Alkylaryl, C with or without substituents 7 -C 20 Aralkyl groups with or without substituents and C 10 -C 20 With or without substituents. Preferably, in formula III, R 3 、R 4 、R 5 、R 6 And R is 1 -R 2n Each independently selected from hydrogen, halogen, C 1 -C 10 Alkyl, C with or without substituents 2 -C 6 Alkenyl, C with or without substituents 2 -C 6 Alkynyl, C with or without substituents 6 -C 10 Aryl, C with or without substituents 7 -C 10 Alkylaryl, C with or without substituents 7 -C 10 Aralkyl groups with or without substituents and C 10 -C 15 With or without substituents.
According to some embodiments of the preparation method of the present invention, R of formula III 3 、R 4 、R 5 、R 6 And R is 1 -R 2n Wherein the substituents are selected from halogen, C 1 -C 6 Alkyl and C of (C) 1 -C 6 One or more of the alkoxy groups of (a).
According to some embodiments of the preparation method of the present invention, in formula III, R 3 、R 4 、R 5 、R 6 And R is 1 -R 2n Optionally containing heteroatoms which are one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus, or, in formula III, R 3 、R 4 、R 5 、R 6 And R is 1 -R 2n Single and/or multiple rings formed by two or more of (a) and (b); preferably, the single and/or multiple rings are each independently saturated or unsaturated.
According to some embodiments of the preparation process of the present invention, in formula III, n is an integer from 0 to 10, preferably an integer from 1 to 8, more preferably an integer from 2 to 6.
According to some embodiments of the preparation methods of the present invention, in formula III, when n is 0, the substituent is R 3 And R is 4 Is R as carbon atom and substituent 5 And R is 6 Is bonded to a carbon atom of (c).
According to a preferred embodiment of the preparation method according to the invention, the internal electron donor b is selected from the group consisting of 2, 4-pentanediol dibenzoate, 3-methyl-2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 3, 5-heptanediol diphosven methyl benzoate, 3, 5-heptanediol dibenzoate, 3, 5-heptanediol diphosven chlorobenzoate, 3, 5-heptanediol dimethoxybenzoate, 2-methyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-heptanediol dibenzoate, 6-methyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 5-ethyl-3, 5-heptanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 4-butyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-heptanediol dibenzoate, 6-dimethyl-3, 6-heptanediol dibenzoate, 6-dimethyl-4-heptanediol dibenzoate, 6-dimethyl-heptanediol, 2-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-propyl-3, 5-heptanediol dibenzoate, 4-methyl-4-propyl-3, 5-heptanediol dibenzoate, 6-methyl-2, 4-heptanediol di (p-chlorobenzoic acid) ester, 6-methyl-2, 4-heptanediol di (p-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenzoic acid) ester, 2, 6-tetramethyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-octanediol dibenzoate 4-ethyl-3, 5-octanediol dibenzoate, 4-propyl-3, 5-octanediol dibenzoate, 4-butyl-3, 5-octanediol dibenzoate, 4-dimethyl-3, 5-octanediol dibenzoate, 4-methyl-4-ethyl-3, 5-octanediol dibenzoate, 2-methyl-6-ethyl-3, 5-octanediol dibenzoate, 5-methyl-4, 6-nonanediol dibenzoate, 5-ethyl-4, 6-nonanediol dibenzoate, 5-propyl-4, 6-nonanediol dibenzoate, 5-butyl-4, 6-nonanediol dibenzoate, 5, 5-dimethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-ethyl-4, 6-nonanediol dibenzoate, 5-phenyl-4, 6-nonanediol dibenzoate, 4, 6-nonanediol dibenzoate and 4-butyl-3, 5-heptanediol dibenzoate, 1, 2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1, 2-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-phenylene dibenzoate, 3, 6-dimethyl-1, 2-phenylene dibenzoate, 4-tert-butyl-1, 2-phenylene dibenzoate, 1, 2-naphthalene dibenzoate, 2, 3-naphthalene dibenzoate, dibenzoate-1, 8-naphthalene, di-4-methylbenzoic acid-1, 8-naphthalene, di-4-ethylbenzoic acid-1, 8-naphthalene, di-4-n-propyl-benzoic acid, 1, 8-naphthalene, 4-diphenyl-benzoic acid, 4-isopropyl-4-naphthalene, 4-isopropyl-benzoic acid, 4-isopropyl-4-naphthalene, 4-diphenyl-4-isopropyl-benzoic acid, 4-isopropyl-4-phenyl-4, 8-naphthalene, one or more of 1, 8-naphthalene di-3-fluorobenzoate and 1, 8-naphthalene di-2-fluorobenzoate. In the present invention, the internal electron donor b may be prepared by the method disclosed with reference to CN 1213080C.
According to some embodiments of the preparation method of the present invention, the magnesium halide compound has the general formula MgX 2 Wherein X is bromine, chlorine or iodine; preferably, the magnesium halide compound is selected from one or more of magnesium dichloride, magnesium dibromide and magnesium diiodide, more preferably magnesium dichloride, and still more preferably anhydrous magnesium dichloride.
According to some embodiments of the preparation method of the present invention, the organophosphorus compound is selected from one or more of tripentyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite and benzyl phosphite; more preferably tributyl phosphate or tripentyl phosphate.
According to some embodiments of the preparation method of the present invention, the organic epoxy compound is C 2 -C 8 One or more of aliphatic olefins, oxidation products of halogenated aliphatic olefins; more preferably one or more of ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, methyl glycidyl ether and diglycidyl ether; more preferably epichlorohydrin.
According to some embodiments of the preparation method of the present invention, the solvent may be a mixture capable of dissolving a magnesium compound, an organic epoxy compound, an organic phosphorus compound, an internal electron donor a and an internal electron donor b, preferably, the solvent is selected from one or more of toluene, ethylbenzene, benzene, xylene, chlorobenzene, hexane, heptane, octane and decane; toluene is more preferred.
According to some embodiments of the preparation method of the present invention, the precipitation aid is selected from one or more of an organic acid, an organic anhydride, an organic ether and an organic ketone; more preferably one or more of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, diethyl ether, propyl ether, butyl ether and amyl ether; more preferably phthalic anhydride.
According to some embodiments of the preparation method of the present invention, the titanium compound has the general formula TiX m (ORn) 4-m Wherein X is halogen, preferably X is bromine, chlorine or iodine, rn is C 1 -C 20 M is an integer of 1 to 4; preferably, the titanium compound is selected from one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium monochlorotriethoxide, titanium dichlorodiethoxide and titanium trichloromonoethoxide; more preferably titanium tetrachloride.
According to some embodiments of the preparation method of the present invention, the amount of the organic phosphorus compound is 0.1 to 5 moles, the amount of the organic epoxy compound is 0.2 to 10 moles, the total amount of the internal electron donor a is 0.0001 to 5 moles, the amount of the precipitation aid is 0.025 to 1 mole, the amount of the titanium compound is 0.5 to 20 moles, and the amount of the internal electron donor b is 0.0001 to 5 moles, per mole of the magnesium halide compound; preferably, the amount of the organic phosphorus compound is 0.3 to 3 moles, the amount of the organic epoxy compound is 0.5 to 4 moles, the total amount of the internal electron donor a is 0.01 to 1 mole, the amount of the precipitation aid is 0.05 to 0.5 mole, the amount of the titanium compound is 1 to 15 moles, and the amount of the internal electron donor b is 0.01 to 1 mole, per mole of the magnesium halide compound. The total amount of the internal electron donor a refers to the total amount of the step A, the step B and the step C, and if the internal electron donor a is used once, the total amount is the use amount. For example, only 0.05 mole of the internal electron donor a is used in step C, and the total amount of the internal electron donor a is 0.05 mole.
According to some embodiments of the methods of preparation of the present invention, the conditions of the first contacting include: the temperature is 10-100deg.C, preferably 30-80deg.C, and the time is 0.05-6 hr, preferably 0.1-2 hr.
According to some embodiments of the methods of preparation of the present invention, the conditions of the second contacting include: -30 to 60 ℃, preferably-30 to 20 ℃, for a time of 0.1 to 5 hours, preferably 0.2 to 4 hours.
According to some embodiments of the methods of preparation of the present invention, the conditions of the third contacting include: the temperature is 30-200deg.C, preferably 60-120deg.C, and the time is 0.5-8 hr, preferably 1-6 hr.
According to some embodiments of the preparation method of the present invention, the drying condition may be conventional vacuum drying, and will not be described herein.
According to some embodiments of the method of the invention, the washing process may comprise: washing with toluene for 2-5 times, washing with a mixture of titanium tetrachloride and toluene for 2-5 times, and washing with hexane for 4-6 times. Among them, the amounts of titanium tetrachloride and toluene used in the mixture of titanium tetrachloride and toluene have a wide range, and the purpose of the present invention is to enable sufficient washing. For example, 0.4 mole of titanium tetrachloride and 60 milliliters of toluene. For example, 2 washes with toluene, 2 washes with a mixture of 0.4 mole titanium tetrachloride and 60 ml toluene, and finally 5 washes with hexane.
In a third aspect, the present invention provides an olefin polymerization catalyst comprising the following catalyst components:
(1) Catalyst component for the preparation of polyolefin according to any of claims 1 to 4 and/or obtained according to the preparation process of any of claims 5 to 8;
(2) An alkyl aluminum compound;
and (3) optionally an external electron donor compound.
According to some embodiments of the olefin polymerization catalyst of the present invention, the alkyl aluminum compound has the general formula AlR n X 3-n Compounds of the formula, wherein R is hydrogen or C 1 -C 20 Preferably R is alkyl, aralkyl or aryl, X is halogen, preferably X is bromine, chlorine or iodine, n is an integer from 1 to 3; further preferably, the alkyl aluminum compound is one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride and ethylaluminum dichloride, furtherPreferably, the step is triethylaluminum and/or triisobutylaluminum.
According to some embodiments of the olefin polymerization catalyst of the present invention, the molar ratio of the alkyl aluminum compound, calculated as aluminum, to the catalyst component, calculated as titanium, is from 5 to 5000:1, more preferably from 20 to 1000:1. For example 20:1, 50: 1. 100: 1. 200: 1. 300: 1. 400: 1. 500: 1. 600: 1. 700: 1. 800: 1. 900: 1. 1000:1, and any value therebetween.
According to some embodiments of the olefin polymerization catalyst of the present invention, the external electron donor compound is an organosilicon compound, preferably of the formula R1 n Si(ORy) 4-n Wherein n is an integer of 0 to 3, R1 is one or more selected from the group consisting of alkyl, cycloalkyl, aryl, halogenated alkyl, halogen and hydrogen atom, and Ry is one or more selected from the group consisting of alkyl, cycloalkyl, aryl and halogenated alkyl; preferably, the external electron donor compound is selected from one or more of trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl t-butyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dicyclohexyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, methylcyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane and (1, 1-trifluoro-2-propyl) -methyldimethoxysilane, more preferably methylcyclohexyldimethoxysilane.
According to some embodiments of the olefin polymerization catalyst of the present invention, the molar ratio of the alkyl aluminum compound to the external electron donor compound, calculated as aluminum, is from 0.1 to 500:1, preferably from 1 to 300:1, more preferably from 3 to 100:1. For example 3:1, 5: 1. 10: 1. 20: 1. 30: 1. 40: 1. 50: 1. 60: 1. 70: 1. 80: 1. 90: 1. 100:1, and any value therebetween.
In a fourth aspect, the present invention provides the use of an olefin polymerisation catalyst as described above in an olefin polymerisation reaction.
According to some embodiments of the inventive use, the reaction is a homopolymerization and/or a copolymerization.
According to some embodiments of the inventive use, the olefin comprises a compound represented by formula CH 2 Olefins represented by =chr, wherein R is hydrogen, C 1 -C 6 Alkyl of (a); more preferably, the olefin is selected from the group consisting of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene; further preferably, the olefin is selected from one or more of ethylene, propylene, 1-n-butene, 1-n-hexene and 4-methyl-1-pentene; still further preferably, the formula CH 2 The alkene represented by =chr is propylene. Such as propylene homo-polymerization, or copolymerization of propylene with other olefins, which may be, but are not limited to: ethylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene.
According to some embodiments of the application of the present invention, the polymerization of olefins may be carried out in the liquid phase of the monomer or a solution of the monomer in an inert solvent, or in the gas phase, or by a combined polymerization process in the gas-liquid phase. The polymerization temperature may be from 0 to 150℃and preferably from 60 to 100 ℃. The polymerization pressure is 0.01 to 10MPa, preferably 0.5 to 5MPa. The polymerization time is 0.1 to 5 hours, preferably 0.5 to 3 hours.
Detailed Description
The present invention will be further described in detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more easily understood. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the following examples, the test methods involved are as follows:
1. determination of titanium content in the catalyst: colorimetric assays were performed using an ultraviolet-visible spectrophotometer model 722.
2. The magnesium content was measured using magnesium ion and EDTA complexation titration.
3. The halogen content is AgNO 3 -NH 4 CNS regurgitation measurements.
4. Determination of the content of internal electron donor compounds in the catalyst: the method comprises decomposing catalyst dry powder with dilute acid, extracting internal electron donor compound with extractant, and measuring with liquid chromatograph.
5. The melt flow index (MFR) of the polymer was measured using a model 6932 melt flow index meter from CEAST, italy, reference GB/T3682.1-2018 standard.
6. The propylene polymer Isotacticity Index (II) was determined using the heptane extraction method: after 2 g of the dried polymer sample was extracted with boiling heptane in an extractor for 6 hours, the residue was dried to constant weight and the ratio of the weight (g) of the obtained polymer to 2 (g) was isotacticity.
7. AC calculation method and formula: the polymerization gives powder weight/(catalyst weight x polymerization time).
In the following examples of the present invention,
ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1, 4-diethoxybutane, tributyl phosphate, tripentyl phosphate, phthalic anhydride, methylcyclohexyldimethoxy silane, triethylaluminum were purchased from carbofuran corporation.
The preparation of 2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate and 4-methyl-3, 5-heptanediol dibenzoate was described with reference to CN1213080C.
[ example 1 ]
(1) In a glove box protected by high-purity nitrogen, sequentially adding 0.04 mol of anhydrous magnesium dichloride, 80 mL of toluene, 0.0325 mol of epichlorohydrin, 0.04 mol of tributyl phosphate and 0.0025 mol of ethylene glycol diethyl ether (internal electron donor a) into a 300mL reaction kettle, and reacting for 120 minutes at the temperature of 60 ℃ to obtain a uniform solution;
(2) Adding 0.0075 mole of phthalic anhydride (precipitation aid) into the uniform solution, continuing to react for one hour, then cooling to-28 ℃, and dropwise adding 0.4 mole of titanium tetrachloride;
(3) Heating to 85 ℃ at a heating rate of 0.5 ℃/min, wherein 0.004 mol of 2, 4-pentanediol dibenzoate (internal electron donor b) is added at a temperature of 80 ℃, the temperature is kept constant for one hour, filtration is carried out, the solid is washed twice with toluene, a mixture of 0.4 mol of titanium tetrachloride and 60 ml of toluene is added again, the temperature is kept constant for 0.5 hours at 110 ℃ and filtration is carried out for two times, and then the obtained solid is washed with hexane for 5 times and then vacuum-dried, so that the catalyst component for preparing polyolefin is obtained. The test data for the content of each substance are shown in table 1.
[ example 1A ]
This example is intended to illustrate the use of the catalyst component for preparing polyolefin of example 1 in propylene polymerization.
Application 1:
after the 5-liter stainless steel autoclave was sufficiently replaced with nitrogen, 5 ml of a hexane solution of triethylaluminum at a concentration of 0.5 mol/liter and 1 ml of a hexane solution of methylcyclohexyldimethoxy silane (CMMS, external electron donor) at a concentration of 1 mol/liter and 10 mg of the catalyst component prepared in example 1 were added, and then the feed line was flushed with 10 ml of hexane, and then 1 liter of hydrogen and 2 liters of purified propylene in a standard state were added, and the temperature was raised to 70℃and polymerization was carried out at this temperature for 1 hour. After the reaction, the reaction vessel was cooled and stirred to discharge the reaction product, thereby obtaining an olefin polymerization product, and the catalyst Activity (AC) 1 ) Testing melt index MFR 1 And isotacticity II 1 The specific results are shown in Table 2.
Application 2:
after the 5-liter stainless steel autoclave was sufficiently replaced with nitrogen, 5 ml of a hexane solution of triethylaluminum at a concentration of 0.5 mol/liter and 1 ml of a hexane solution of methylcyclohexyldimethoxy silane (CMMS, external electron donor) at a concentration of 1 mol/liter and 10 mg of the catalyst component prepared in example 1 were added, and then the feed line was flushed with 10 ml of hexane, and 4.5 liters of hydrogen and 2 liters of purified propylene were further added, and the temperature was raised to 70℃and polymerization was carried out at this temperature for 1 hour. After the reaction, the reaction vessel was cooled and stirred to discharge the reaction product, thereby obtaining an olefin polymerization product, and the catalyst Activity (AC) 2 ) Testing melt index MFR 2 And isotacticity II 2 The specific results are shown in Table 2.
[ example 2 ]
The procedure of example 1 was followed except that 0.0025 mol of ethylene glycol dibutyl ether was used instead of ethylene glycol diethyl ether. The test data for the content of each substance are shown in table 1.
[ example 2A ]
An olefin polymerization product was prepared as in example 1A, except that the catalyst component for preparing polyolefin prepared in example 2 was used. Catalyst Activity AC 1 And AC 2 Melt index MFR 1 And MFR (MFR) 2 Isotacticity II 1 And II 2 The specific results are shown in Table 2.
[ example 3 ]
(1) In a glove box protected by high-purity nitrogen, sequentially adding 0.04 mol of anhydrous magnesium dichloride, 80 mL of toluene, 0.0325 mol of epichlorohydrin and 0.04 mol of tributyl phosphate into a 300mL reaction kettle, and reacting for 120 minutes at the temperature of 60 ℃ to obtain a uniform solution;
(2) Adding 0.0075 mole of phthalic anhydride (precipitation aid) into the uniform solution, continuing to react for one hour, then cooling to-28 ℃, and dropwise adding 0.4 mole of titanium tetrachloride;
(3) Heating to 85 ℃ at a heating rate of 0.3 ℃/min, wherein 0.0025 mol of ethylene glycol diethyl ether (internal electron donor a) is added at a temperature of 40 ℃, then 0.004 mol of 2, 4-pentanediol dibenzoate (internal electron donor b) is added at a temperature of 80 ℃, the temperature is kept constant for one hour, filtration is performed, the solid is washed twice with toluene, a mixture of 0.4 mol of titanium tetrachloride and 60 ml of toluene is added again at a temperature of 110 ℃ for 0.5 hours and is washed twice by filtration, and then the obtained solid is washed 5 times with hexane and then dried in vacuum, thereby obtaining a catalyst component for preparing polyolefin. The test data for the content of each substance are shown in table 1.
[ example 3A ]
An olefin polymerization product was prepared as in example 1A, except that the catalyst component for preparing polyolefin prepared in example 3 was used. Catalyst Activity AC 1 And AC 2 Melt index MFR 1 And MFR (MFR) 2 Isotacticity II 1 And II 2 The specific results are shown in Table 2.
[ example 4 ]
(1) In a glove box protected by high-purity nitrogen, sequentially adding 0.04 mol of anhydrous magnesium dichloride, 80 mL of toluene, 0.0325 mol of epichlorohydrin and 0.04 mol of tributyl phosphate into a 300mL reaction kettle, and reacting for 120 minutes at the temperature of 60 ℃ to obtain a uniform solution;
(2) Adding 0.01 mole of phthalic anhydride (precipitation aid) into the uniform solution, continuing to react for one hour, then cooling to-28 ℃, and dropwise adding 0.4 mole of titanium tetrachloride;
(3) Heating to 85 ℃ at a heating rate of 0.3 ℃/min, wherein 0.0025 mol of ethylene glycol dibutyl ether (internal electron donor a) is added at a temperature of 40 ℃, then 0.004 mol of 2, 4-pentanediol dibenzoate (internal electron donor b) is added at a temperature of 80 ℃, the temperature is kept constant for one hour, filtration is carried out, the solid is washed twice with toluene, a mixture of 0.4 mol of titanium tetrachloride and 60 ml of toluene is added, the temperature is kept constant for 0.5 hours at 110 ℃ and the filtration and washing are carried out twice, and then the obtained solid is washed 5 times with hexane and then dried in vacuum, thereby obtaining the catalyst component for preparing polyolefin. The test data for the content of each substance are shown in table 1.
Example 4A
An olefin polymerization product was prepared as in example 1A, except that the catalyst component for preparing polyolefin prepared in example 4 was used. Catalyst Activity AC 1 And AC 2 Melt index MFR 1 And MFR (MFR) 2 Isotacticity II 1 And II 2 The specific results are shown in Table 2.
[ example 5 ]
The procedure of example 2 was followed except that ethylene glycol dibutyl ether was used in an amount of 0.004 mol. The test data for the content of each substance are shown in table 1.
[ example 5A ]
An olefin polymerization product was prepared as in example 1A, except that the catalyst component for preparing polyolefin prepared in example 5 was used. Catalyst Activity AC 1 And AC 2 Melt index MFR 1 And MFR (MFR) 2 Isotacticity II 1 And II 2 The specific results are shown in Table 2.
[ example 6 ]
The procedure of example 2 was followed except that 0.0025 mol of 1, 4-diethoxybutane was used instead of ethylene glycol dibutyl ether. The test data for the content of each substance are shown in table 1.
Example 6A
An olefin polymerization product was prepared as in example 1A, except that the catalyst component for preparing polyolefin prepared in example 6 was used. Catalyst Activity AC 1 And AC 2 Melt index MFR 1 And MFR (MFR) 2 Isotacticity II 1 And II 2 The specific results are shown in Table 2.
[ example 7 ]
The procedure of example 2 was followed except that 0.004 mol of 3, 5-heptanediol dibenzoate was used instead of 2, 4-pentanediol dibenzoate. The test data for the content of each substance are shown in table 1.
Example 7A
An olefin polymerization product was prepared as in example 1A, except that the catalyst component for preparing polyolefin prepared in example 7 was used. Catalyst Activity AC 1 And AC 2 Melt index MFR 1 And MFR (MFR) 2 Isotacticity II 1 And II 2 The specific results are shown in Table 2.
[ example 8 ]
(1) In a glove box protected by high-purity nitrogen, sequentially adding 0.04 mol of anhydrous magnesium chloride, 80 mL of toluene, 0.04 mol of epichlorohydrin and 0.06 mol of tripentyl phosphate into a 300mL reaction kettle, and reacting for 120 minutes at the temperature of 60 ℃ to obtain a uniform solution;
(2) To the homogeneous solution, 0.01 mol of phthalic anhydride (precipitation aid) was added, the reaction was continued for one hour, and then the temperature was lowered to-20℃and after 30mL of hexane and 0.01 mol of ethylene glycol dibutyl ether (internal electron donor a) were added, 0.5 mol of titanium tetrachloride was added dropwise.
(3) Heating to 85 ℃ at a heating rate of 0.5 ℃/min, then adding 0.002 mol of 4-methyl-3, 5-heptanediol dibenzoate (internal electron donor b) at a temperature of 80 ℃, keeping the temperature for one hour, filtering, washing the solid twice with toluene, adding a mixture of 0.4 mol of titanium tetrachloride and 60 ml of toluene at a temperature of 110 ℃ for 0.5 hours and filtering and washing twice, washing the obtained solid with hexane for 5 times, and then drying in vacuum to obtain the catalyst component for preparing polyolefin. The test data for the content of each substance are shown in table 1.
[ example 8A ]
An olefin polymerization product was prepared as in example 1A, except that the catalyst component for preparing polyolefin prepared in example 8 was used. Catalyst Activity AC 1 And AC 2 Melt index MFR 1 And MFR (MFR) 2 Isotacticity II 1 And II 2 The specific results are shown in Table 2.
Comparative example 1
The procedure of example 1 was followed except that ethylene glycol diethyl ether (internal electron donor compound a) was not used. The test data for the content of each substance are shown in table 1.
Comparative example 1B
An olefin polymerization product was prepared as in example 1A, except that the catalyst component for preparing polyolefin prepared in comparative example 1 was used. Catalyst Activity AC 1 And AC 2 Melt index MFR 1 And MFR (MFR) 2 Isotacticity II 1 And II 2 The specific results are shown in Table 2.
Comparative example 2
The procedure of example 7 was followed except that ethylene glycol dibutyl ether (internal electron donor compound a) was not used. The test data for the content of each substance are shown in table 1.
Comparative example 2B
An olefin polymerization product was prepared as in example 1A, except that the catalyst component for preparing polyolefin prepared in comparative example 2 was used. Catalyst Activity AC 1 And AC 2 Melt index MFR 1 And MFR (MFR) 2 Isotacticity II 1 And II 2 The specific results are shown in Table 2.
[ comparative example 3 ]
The procedure of example 1 was followed except that 2, 4-pentanediol dibenzoate (internal electron donor compound b) was not used. The test data for the content of each substance are shown in table 1.
Comparative example 3B
An olefin polymerization product was prepared as in example 1A, except that the catalyst component for preparing polyolefin prepared in comparative example 3 was used. Catalyst Activity AC 1 And AC 2 Melt index MFR 1 And MFR (MFR) 2 Isotacticity II 1 And II 2 The specific results are shown in Table 2.
TABLE 1
TABLE 2
As can be seen from Table 2, the catalyst component for preparing polyolefin, namely the diether compound shown in the formula I and the glycol ester compound shown in the formula II, are used together as internal electron donors, so that the synergistic effect can be achieved, the catalyst activity can be greatly improved, the hydrogen regulation sensitivity of the catalyst is greatly improved, and the higher isotacticity can be maintained under the condition of high hydrogen concentration.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent modifications and improvements will occur to those skilled in the art, and are intended to be within the scope of the present invention, as a matter of common general knowledge in the art, in light of the technical teaching provided by the present invention.

Claims (60)

1. The catalyst component for preparing polyolefin contains magnesium element, halogen element, titanium element, internal electron donor a and internal electron donor b, wherein the internal electron donor a is a diether compound shown in formula I, the internal electron donor b is a glycol ester compound shown in formula II,
in the formula I, R' 1 And R'. 2 Identical or different, each independently selected from C 1 -C 30 Alkyl, C of (2) 6 -C 30 Aryl, C with or without substituents 7 -C 30 Aralkyl groups with or without substituents and C 7 -C 30 An alkylaryl group with or without a substituent;
in the formula I, R' 3 、R’ 4 、R’ 5 And R'. 6 The same or different, each independently selected from hydrogen, halogen, C 1 -C 30 Alkyl, C of (2) 6 -C 30 Aryl, C with or without substituents 7 -C 30 Aralkyl groups with or without substituents and C 7 -C 30 An alkylaryl group with or without a substituent;
in the formula I, n' is 1 or an internal electron donor a is one or more of butanediol dimethyl ether, butanediol diethyl ether and butanediol dibutyl ether;
in formula II, R 1 And R is 2 Identical or different, each independently selected from C 1 -C 20 Alkyl, C with or without substituents 2 -C 20 Alkenyl, C with or without substituents 6 -C 20 Aryl, C with or without substituents 7 -C 20 Alkylaryl, C with or without substituents 7 -C 20 Aralkyl groups with or without substituents and C 10 -C 20 A condensed ring aryl group with or without a substituent; m is a divalent linking group;
the content of magnesium element is 5-30% based on the total weight of the catalyst component; the halogen content is 30-80%; the content of titanium element is 0.5-10%; the content of the internal electron donor a is 0.5 to 25 wt%; the content of the internal electron donor b is 0.5-25%;
the preparation method of the catalyst component for preparing polyolefin comprises the following steps:
step A: carrying out first contact on a magnesium halide compound, an organic phosphorus compound, an organic epoxy compound and an optional internal electron donor a in a solvent to obtain a first mixture;
and (B) step (B): in the presence of a precipitation aid, carrying out second contact on the first mixture, a titanium compound and an optional internal electron donor a to obtain a second mixture;
step C: contacting the second mixture with an internal electron donor b and optionally an internal electron donor a for a third time, washing and drying;
wherein at least one of the steps A, B and C uses an internal electron donor a.
2. The catalyst component according to claim 1 in which the halogen is selected from one or more of chlorine, bromine and iodine.
3. The catalyst component according to claim 1, characterized in that in formula I R' 1 And R'. 2 Wherein the substituents are each independently selected from halogen, C 1 -C 10 Alkyl and C of (C) 1 -C 10 One or more of the alkoxy groups of (a).
4. The catalyst component according to claim 1, characterized in that in formula I R' 1 And R'. 2 Wherein the substituents are each independently selected from methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, n-heptylOne or more of 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-octyl, n-nonyl, n-decyl, 12-alkyl, 18-alkyl, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl, benzyl and p-methylbenzyl.
5. The catalyst component according to claim 1, characterized in that in formula I R' 3 、R’ 4 、R’ 5 And R'. 6 Wherein the substituents are each independently selected from hydrogen, halogen, C 1 -C 10 Alkyl and C of (C) 1 -C 10 One or more of the alkoxy groups of (a).
6. The catalyst component according to claim 1, characterized in that in formula I R' 3 、R’ 4 、R’ 5 And R'. 6 Wherein the substituents are each independently selected from one or more of hydrogen, halogen, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-octyl, n-nonyl, n-decyl, 12-alkyl, 18-alkyl, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl, benzyl and p-methylbenzyl.
7. The catalyst component according to any one of claims 1 to 6, characterized in that the internal electron donor a is selected from one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether.
8. The catalyst component according to any one of claims 1 to 6 in which in formula II R 1 And R is 2 Each independently selected from C 1 -C 10 Alkyl, C with or without substituents 2 -C 10 Alkenyl, C with or without substituents 6 -C 10 Aryl, C with or without substituents 7 -C 10 Alkylaryl, C with or without substituents 7 -C 10 Aralkyl groups with or without substituents and C 10 -C 15 With or without substituents.
9. The catalyst component according to claim 8 in which R in formula II 1 And R is 2 Wherein the substituents are selected from hydroxy, halogen, cyano, nitro, amino, mono- (C) 1 -C 6 Alkyl) amino, bis- (C 1 -C 6 Alkyl) amino, aldehyde, carboxyl.
10. The catalyst component according to any of claims 1 to 6 in which M in formula II is selected from C 1 -C 20 Alkylene, C, with or without substituents 3 -C 20 Cycloalkyl radicals and C, with or without substituents 6 -C 20 Or (a) arylene group with or without a substituent.
11. The catalyst component according to claim 10 in which in M of formula II the substituents are C 1 -C 20 One or more of the alkyl groups, and the substituents are optionally bonded to form one or more rings.
12. The catalyst component according to claim 10 in which the carbon atoms or/and hydrogen atoms in M are optionally substituted by nitrogen, oxygen, sulphur, silicon, phosphorus or halogen atoms.
13. The catalyst component according to any one of claims 1 to 6, wherein the internal electron donor b is a glycol ester compound represented by formula III,
In formula III, R 1 And R is 2 Identical or different, each independently selected from C 1 -C 10 Alkyl, C with or without substituents 2 -C 10 Alkenyl, C with or without substituents 6 -C 20 Aryl, C with or without substituents 7 -C 20 Aralkyl groups with or without substituents and C 7 -C 20 An alkylaryl group with or without a substituent; n is an integer of 0 to 10, and when n is 0, the substituent is R 3 And R is 4 Is R as carbon atom and substituent 5 And R is 6 Is bonded to a carbon atom of (c).
14. The catalyst component according to claim 13 in which in formula III, R 1 And R is 2 Each independently selected from C 1 -C 6 Alkyl, C with or without substituents 2 -C 6 Alkenyl, C with or without substituents 6 -C 10 Aryl, C with or without substituents 7 -C 10 Aralkyl groups with or without substituents and C 7 -C 10 An alkylaryl group with or without a substituent.
15. The catalyst component according to claim 14 in which R of formula III 1 And R is 2 Wherein the substituents are selected from halogen, C 1 -C 6 Alkyl and C of (C) 1 -C 6 One or more of the alkoxy groups of (a).
16. The catalyst component according to claim 13 in which in formula III, R 3 、R 4 、R 5 、R 6 And R is 1 -R 2n The same or different, each independently selected from hydrogen, halogen, C 1 -C 20 Alkyl, C with or without substituents 2 -C 10 Alkenyl, C with or without substituents 2 -C 10 Is provided with or is connected withAlkynyl having no substituent, C 6 -C 20 Aryl, C with or without substituents 7 -C 20 Alkylaryl, C with or without substituents 7 -C 20 Aralkyl groups with or without substituents and C 10 -C 20 With or without substituents.
17. The catalyst component according to claim 16 in which in formula III, R 3 、R 4 、R 5 、R 6 And R is 1 -R 2n Each independently selected from hydrogen, halogen, C 1 -C 10 Alkyl, C with or without substituents 2 -C 6 Alkenyl, C with or without substituents 2 -C 6 Alkynyl, C with or without substituents 6 -C 10 Aryl, C with or without substituents 7 -C 10 Alkylaryl, C with or without substituents 7 -C 10 Aralkyl groups with or without substituents and C 10 -C 15 With or without substituents.
18. The catalyst component according to claim 16 in which R of formula III 3 、R 4 、R 5 、R 6 And R is 1 -R 2n Wherein the substituents are selected from halogen, C 1 -C 6 Alkyl and C of (C) 1 -C 6 One or more of the alkoxy groups of (a).
19. The catalyst component according to claim 13 in which in formula III, R 3 、R 4 、R 5 、R 6 And R is 1 -R 2n Optionally containing heteroatoms which are one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus, or, in formula III, R 3 、R 4 、R 5 、R 6 And R is 1 -R 2n Form a single ring and/or multiple rings.
20. The catalyst component according to claim 19 in which the single and/or multiple rings are each independently saturated or unsaturated.
21. The catalyst component according to claim 13 in which in formula III n is an integer from 1 to 8.
22. The catalyst component according to claim 21 in which in formula III n is an integer from 2 to 6.
23. The catalyst component according to any of claims 1 to 6, characterized in that, the internal electron donor b is selected from 2, 4-pentanediol dibenzoate, 3-methyl-2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 3, 5-heptanediol diphosven methyl benzoate, 3, 5-heptanediol dibenzoate, 3, 5-heptanediol diphosven chlorobenzoate, 3, 5-heptanediol dimethoxybenzoate, 3, 5-heptanediol dibenzoate, 3, 5-heptanediol dimethoxy benzoate, 2-methyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-heptanediol dibenzoate, 6-methyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 5-ethyl-3, 5-heptanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 4-butyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-heptanediol dibenzoate, 6-dimethyl-3, 6-heptanediol dibenzoate, 4-dimethyl-5-heptanediol dibenzoate, 4-dimethyl-3, 6-heptanediol dibenzoate, 4-dimethyl-5-heptanediol dibenzoate, 6, 6-dimethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-propyl-3, 5-heptanediol dibenzoate, 4-methyl-4-propyl-3, 5-heptanediol dibenzoate, 6-methyl-2, 4-heptanediol di (p-chlorobenzoic acid) ester, 6-methyl-2, 4-heptanediol di (p-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenzoic acid) ester, 2, 6-tetramethyl-3, 5-heptanediol dibenzoate 4-methyl-3, 5-octanediol dibenzoate, 4-ethyl-3, 5-octanediol dibenzoate, 4-propyl-3, 5-octanediol dibenzoate, 4-butyl-3, 5-octanediol dibenzoate, 4-dimethyl-3, 5-octanediol dibenzoate, 4-methyl-4-ethyl-3, 5-octanediol dibenzoate, 2-methyl-6-ethyl-3, 5-octanediol dibenzoate, 5-methyl-4, 6-nonanediol dibenzoate, 5-ethyl-4, 6-nonanediol dibenzoate, 5-propyl-4, 6-nonanediol dibenzoate, 5-butyl-4, 6-nonanediol dibenzoate, 5-dimethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-ethyl-4, 6-nonanediol dibenzoate, 5-phenyl-4, 6-nonanediol dibenzoate, 4, 6-nonanediol dibenzoate and 4-butyl-3, 5-heptanediol dibenzoate, 1, 2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1, 2-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-phenylene dibenzoate, 3, 6-dimethyl-1, 2-phenylene dibenzoate, 4-tert-butyl-1, 2-phenylene dibenzoate 1, 2-naphthalene dibenzoate, 2, 3-naphthalene dibenzoate, 1, 8-naphthalate di-4-methylbenzoate, 1, 8-naphthalate di-3-methylbenzoate, 1, 8-naphthalate di-2-methylbenzoate, 1, 8-naphthalate di-4-ethylbenzoate 1, 8-naphthalene di-4-n-propylbenzoate, 1, 8-naphthalene di-4-isopropylbenzoate, 1, 8-naphthalene di-4-n-butylbenzoate, 1, 8-naphthalene di-4-isobutylbenzoate, 1, 8-naphthalene di-4-tert-butylbenzoate, 1, 8-naphthalene di-4-phenylbenzoate, one or more of di-4-fluorobenzoic acid-1, 8-naphthalene ester, di-3-fluorobenzoic acid-1, 8-naphthalene ester and di-2-fluorobenzoic acid-1, 8-naphthalene ester.
24. The catalyst component according to any one of claims 1 to 6, characterized in that the content of magnesium element is 8 to 25% by total weight of the catalyst component; the halogen content is 40-70%; the content of titanium element is 1-6%; the content of the internal electron donor a is 1 to 20 wt%; the content of the internal electron donor b is 1 to 20% by weight.
25. The catalyst component according to claim 24 in which the magnesium element is present in an amount of 10 to 22% by weight based on the total weight of the catalyst component.
26. A process for preparing a catalyst component for the preparation of a polyolefin according to any of claims 1 to 25, comprising the steps of:
step A: carrying out first contact on a magnesium halide compound, an organic phosphorus compound, an organic epoxy compound and an optional internal electron donor a in a solvent to obtain a first mixture;
and (B) step (B): in the presence of a precipitation aid, carrying out second contact on the first mixture, a titanium compound and an optional internal electron donor a to obtain a second mixture;
step C: contacting the second mixture with an internal electron donor b and optionally an internal electron donor a for a third time, washing and drying;
wherein at least one of the steps A, B and C uses an internal electron donor a,
Wherein the internal electron donor a is a diether compound shown in the formula I; the internal electron donor b is a glycol ester compound shown in a formula II,
27. the method of claim 26, wherein the magnesium halide compound has the formula MgX 2 Wherein X is bromine, chlorine or iodine.
28. The method of claim 27, wherein the magnesium halide compound is selected from one or more of magnesium dichloride, magnesium dibromide, and magnesium diiodide.
29. The method of claim 28, wherein the magnesium halide compound is magnesium dichloride.
30. The method of any one of claims 26-29, wherein the organophosphorus compound is selected from one or more of tripentyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and benzyl phosphite.
31. The method of claim 30, wherein the organophosphorus compound is tributyl phosphate or tripentyl phosphate.
32. The method of any one of claims 26-29, wherein the organic epoxy compound is C 2 -C 8 And (3) an oxidation product of an aliphatic olefin or a halogenated aliphatic olefin.
33. The method of claim 32, wherein the organic epoxy compound is one or more of ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, methyl glycidyl ether, and diglycidyl ether.
34. The method of claim 33, wherein the butadiene oxide is selected from butadiene dioxides.
35. The method of claim 33, wherein the organic epoxy compound is epichlorohydrin.
36. The process of any one of claims 26-29, wherein the solvent is selected from one or more of toluene, ethylbenzene, benzene, xylenes, chlorobenzene, hexane, heptane, octane, and decane.
37. The method of claim 36, wherein the solvent is toluene.
38. The method of any one of claims 26-29, wherein the precipitation aid is selected from one or more of an organic acid, an organic anhydride, an organic ether, and an organic ketone.
39. The method of claim 38, wherein the precipitation aid is one or more of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, diethyl ether, propyl ether, butyl ether, and amyl ether.
40. The method of claim 39, wherein the precipitation aid is phthalic anhydride.
41. The method of any one of claims 26-29, wherein the titanium compound has the formula TiX m (ORn) 4-m Wherein X is halogen and Rn is C 1 -C 20 M is an integer of 1 to 4.
42. The method of claim 41, wherein X is bromine, chlorine, or iodine.
43. The method of claim 42, wherein the titanium compound is selected from one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium chlorotriethoxide, titanium dichlorodiethoxide, and titanium trichloromonoethoxide.
44. The method of claim 43, wherein the titanium compound is titanium tetrachloride.
45. The method according to any one of claims 26 to 29, wherein the amount of the organic phosphorus compound is 0.1 to 5 moles, the amount of the organic epoxy compound is 0.2 to 10 moles, the total amount of the internal electron donor a is 0.0001 to 5 moles, the amount of the precipitation aid is 0.025 to 1 mole, the amount of the titanium compound is 0.5 to 20 moles, and the amount of the internal electron donor b is 0.0001 to 5 moles, per mole of the magnesium halide compound.
46. The method of claim 45, wherein the amount of the organic phosphorus compound is 0.3 to 3 moles, the amount of the organic epoxy compound is 0.5 to 4 moles, the total amount of the internal electron donor a is 0.01 to 1 mole, the amount of the precipitation aid is 0.05 to 0.5 mole, the amount of the titanium compound is 1 to 15 moles, and the amount of the internal electron donor b is 0.01 to 1 mole, per mole of the magnesium halide compound.
47. The method of any one of claims 26-29, wherein the conditions of the first contacting comprise: the temperature is 10-100deg.C, and the time is 0.05-6 hr.
48. The method of claim 47, wherein the conditions of the first contacting comprise: the temperature is 30-80 ℃ and the time is 0.1-2 hours.
49. The method of any one of claims 26-29, wherein the conditions of the second contacting comprise: -30 to 60 ℃ for 0.1 to 5 hours.
50. The method of claim 49, wherein the conditions of the second contacting comprise: -30 to 20 ℃ for 0.2 to 4 hours.
51. The method of any one of claims 26-29, wherein the conditions of the third contacting comprise: the temperature is 30-200deg.C, and the time is 0.5-8 hr.
52. The method of claim 51, wherein the conditions of the third contacting comprise: the temperature is 60-120 ℃ and the time is 1-6 hours.
53. The method according to any one of claims 26-29, wherein in step C, after the third contacting and before drying, the method further comprises: filtration and washing were performed.
54. An olefin polymerization catalyst comprising the following components:
(1) A catalyst component for producing polyolefin according to any one of claims 1 to 25 or a catalyst component for producing polyolefin obtained according to the production method of any one of claims 26 to 53; (2) an alkylaluminum compound; and (3) optionally an external electron donor compound.
55. The use of an olefin polymerization catalyst as claimed in claim 54 in olefin polymerization reactions.
56. The use according to claim 55, wherein the reaction is a homo-polymerization and/or copolymerization.
57. The use of claim 55 wherein the olefin comprises a compound of formula CH 2 Olefins represented by =chr, wherein R is hydrogen, C 1 -C 6 Is a hydrocarbon group.
58. The use according to claim 57 wherein the olefin is selected from the group consisting of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene.
59. The use according to claim 58 wherein the olefin is selected from one or more of ethylene, propylene, 1-n-butene, 1-n-hexene and 4-methyl-1-pentene.
60. The use according to claim 57, wherein said compound is represented by formula CH 2 The alkene represented by =chr is propylene.
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CN103012625A (en) * 2011-09-23 2013-04-03 中国石油化工股份有限公司 Olefin polymerization catalyst ingredient, preparation method and use of the olefin polymerization catalyst ingredient, catalyst system, use of the catalyst system, and olefin polymerization method
CN107129549A (en) * 2016-02-29 2017-09-05 中国石油化工股份有限公司 Ingredient of solid catalyst, catalyst and application for olefinic polymerization
CN110938162A (en) * 2018-09-25 2020-03-31 中国石油化工股份有限公司 Catalyst system for olefin polymerization and prepolymerized catalyst composition and use thereof

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Publication number Priority date Publication date Assignee Title
CN103012625A (en) * 2011-09-23 2013-04-03 中国石油化工股份有限公司 Olefin polymerization catalyst ingredient, preparation method and use of the olefin polymerization catalyst ingredient, catalyst system, use of the catalyst system, and olefin polymerization method
CN107129549A (en) * 2016-02-29 2017-09-05 中国石油化工股份有限公司 Ingredient of solid catalyst, catalyst and application for olefinic polymerization
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