CN106589174A - Catalyst component used for olefin polymerization, catalyst and preparation method of catalyst component - Google Patents
Catalyst component used for olefin polymerization, catalyst and preparation method of catalyst component Download PDFInfo
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Abstract
The invention relates to a catalyst component used for olefin polymerization, a catalyst and a preparation method of the catalyst component. The catalyst component comprises reaction products of magnesium halide, organic epoxy compounds, alcohol compounds, titanate compounds and titanium halide. According to the catalyst component used for olefin polymerization, the catalyst and the preparation method of the catalyst component, the catalyst can have high activity, polymers have the high stacking density, and the preparation process for the catalyst is simplified relatively.
Description
Technical field
The invention belongs to catalyst field, and in particular to a kind of catalytic component, catalyst for olefinic polymerization
And preparation method thereof.
Background technology
In the commercial production of polyethylene, Titanium series catalyst is obtained due to high catalytic efficiency and low price
Relatively broad application was obtained, while it is also constantly developed in application process.
The reaction mechanism of the titanium-magnesium catalyst with titanium compound and magnesium compound as solvent can be with simplified summary
It is, by various methods, titanium compound to be obtained into major catalyst in combination with magnesium compound, can adds each therebetween
Kind of auxiliary agent is modified, and then being combined with the promoter such as aluminium compound again is used for ethylene polymerization.In reality
In the selection of titanium compound, more halogenide using titanium only use on a small quantity titanate compound.
Chinese patent：Application number 201210347884.9, proposes a kind of for preparing superhigh molecular weight polyethylene
The method of the ingredient of solid catalyst of alkene, mainly by anhydrous magnesium compound, alcohol, halogenated titanium, titanate compound,
Two esters compound groups into, it is characterised in that two ester type compounds of ad hoc structure as internal electron donor, comprising
Following steps：1)CO2With alcohol and atent solvent to anhydrous magnesium compound (described anhydrous magnesium in the case of addition
Compound be alkyl magnesium, magnesium halide or alkoxyl magnesium, preferred magnesium ethylate.) processed, stir 1-2 hours；
2) above-mentioned mixed solution is added in solution of titanium halide at -30-10 DEG C, is to slowly warm up to 40-120 DEG C of addition
Two ester type compounds, react 1-3 hours, filtration washing；3) gained solid again with halogenated titanium, titanating
Compound reacts 0.5-3 hours at 90-130 DEG C；Jing is filtered, washed, vacuum drying obtains solid catalytic ingredient.
Chinese patent：Application number 201010200928.6, is related to a kind of superelevation with single active center point
Sub- polythene catalyst and preparation method thereof, the catalyst is made up of major catalyst and promoter, main catalytic
Agent is the compound with formula (1) structure being supported on magnesium halide, and the major catalyst is by following process
Prepare：(1) magnesium halide is co-mulled and made into 8-hydroxyquinoline in grinding pot, (2) are again in magnesium halide and 8- hydroxyls
Being co-mulled and made in thing for quinoline adds titanate compound to be co-mulled and made into, and (3) are in 8-hydroxyquinoline titanate esters metal-complexing
Halogenide (one or more in Silicon chloride., aluminum chloride) co-ground reaction is added in compound,
(4) major catalyst and promoter are equipped with, for polyreaction；Described promoter is alkyl aluminum chemical combination
Thing.
Chinese patent：Application number 200910079429.3, is related to a kind of extra high-molecular polythene catalyst
System, including the carrier loaded titanium catalyst solid major constituent of magnesium compound and alkyl aluminum compound promoter group
Point, it is characterised in that the carrier loaded titanium catalyst solid major constituent of described magnesium compound is mainly by the following steps
Prepare：(1)CO2With alcohol and accelerator to at the scattered anhydrous magnesium compound of atent solvent in the case of addition
Reason, is subsequently adding silicon compound and continues to react；(2) above-mentioned mixed solution is instilled into TiCl4React in solution, mistake
Filter, washing；(3) solid for obtaining step (2) and TiCl4It is (RO) with formulanTiCl4-n, wherein 0 ＜ n≤4
Titanate esters mixture reaction, wherein TiCl4It is 20: 1-1: 1 with the mol ratio of titanate esters, filter, wash,
Vacuum drying obtains the main component of catalyst solid.
Above-mentioned technology is basically used for preparing ultra-high molecular weight polyethylene, and accordingly there is polymerization activity is not too high, system
The different defects such as standby process is more complicated.
The content of the invention
For domestic catalyst research and the present situation of production, the invention provides a kind of for alkene, particularly second
Catalytic component, catalyst of alkene polyreaction and preparation method thereof.
The first aspect of the invention provides a kind of catalytic component for olefinic polyreaction, and it includes halogen
Change the product of magnesium, organic epoxy compound thing, alcohol compound, titanate compound and halogenated titanium.
The specific embodiment of catalyst according to the invention component, the magnesium halide is selected from magnesium dihalide, dihalo-
One of halogen atom is by alkyl or oxyl in the water of change magnesium and the complex and magnesium dihalide molecular formula of alcohol
At least one in the derivant replaced.The example of above-mentioned magnesium dihalide is included but is not limited to：Magnesium dichloride,
At least one in dibrominated magnesium and magnesium diiodide, preferred magnesium dichloride.
Described magnesium halide is properly added inert diluent such as when dissolving：Benzene, toluene, 1,2- dichloroethanes,
Chlorobenzene and other hydro carbons or halogenated hydrocarbon compound, so-called inertia here refers to that the diluent does not participate in reaction
And harmful effect will not be produced to the dissolving of magnesium halide.
The specific embodiment of catalyst according to the invention component, the alcohol compound can be fatty alcohol or
Aromatic alcohol.
The specific embodiment of catalyst according to the invention component, the formula of the alcohol compound is R1OH,
Wherein R1For C1-C12Aliphatic alkyl or C7-C12Aromatic hydrocarbyl.
In certain embodiments, R1It is C1-C8Alkyl, such as methyl, ethyl, n-pro-pyl, isopropyl, uncle
Butyl, normal-butyl, sec-butyl, n-pentyl, isopentyl, sec-amyl, n-hexyl, 1- methyl amyls, 2- first
It is base butyl, 2- methyl amyls, 3- methyl amyls, 4- methyl amyls, n-heptyl, different heptyl, n-octyl, different
Octyl group, 1- ethylhexyls, 2- ethylhexyls etc..
In certain embodiments, R1It is C7-C12Aromatic hydrocarbyl, such as benzyl, 2- phenylethyls, 1- phenyl
Propyl group, 2- phenyl propyl, 3- phenyl propyl, 2- methyl-benzyls, 3- methyl-benzyls, 4- methyl-benzyls etc..
Preferably, the alcohol compound is selected from ethanol, propanol, isopropanol, n-butyl alcohol, isobutanol, 2-
At least one in ethyl hexanol, benzyl alcohol and phenethanol, be preferably selected from ethanol, butanol, 2-Ethylhexyl Alcohol,
The mixture of at least one of benzyl alcohol, phenethanol, such as benzyl alcohol and ethanol.
Preferably, the alcohol compound is the mixture of aromatic alcohol and fatty alcohol, such as benzyl alcohol and C1-C8
Alkylol.According to the specific embodiment of catalytic component of the present invention, the titanate compound it is logical
Formula is TiXm(OR2)4-m, wherein X be halogen, preferred fluorine, chlorine or bromine, R2For C1-C14Aliphatic alkyl
Or C6-C14Aromatic hydrocarbyl, m is the integer of 0-3.
According to some embodiments, R2For C1-C6Aliphatic alkyl, such as methyl, ethyl, n-pro-pyl, isopropyl
Base, normal-butyl, isobutyl group, n-pentyl, isopentyl, n-hexyl etc..
According to some embodiments, m is 0,1,2 or 3.
According to some embodiments, R2For C6-C10Aryl, such as phenyl, aminomethyl phenyl, ethylphenyl etc..
Preferably, the titanate compound is selected from positive ethyl ester of metatitanic acid, tetrabutyl titanate, isopropyl titanate, titanium
The just own ester of sour isobutyl ester, metatitanic acid, metatitanic acid pentyl ester, a chlorine triethoxy titanium, dichlorodiethyl epoxide titanium and trichlorine one
At least one in ethanolato-titanium.
The specific embodiment of catalyst according to the invention component, the organic epoxy compound thing is selected from C2-C8
The oxide of aliphatic olefin, C2-C8The oxide of aliphatic diene hydrocarbon, C2-C8The oxygen of halogenated aliphatic alkene
Compound, C2-C8At least one in the oxide of halogenated aliphatic alkadienes, glycidyl ether and inner ether.
The specific embodiment of catalyst according to the invention component, the formula such as formula of the organic epoxy compound thing
(I) shown in：
Wherein, R3、R4、R5、R6Stand alone as hydrogen, halogen (such as fluorine, chlorine, bromine, iodine), C1-C6Hydrocarbon
Base or C1-C6Halohydrocarbyl.C1-C6The example of alkyl includes but is not limited to methyl, ethyl, n-pro-pyl, different
Propyl group, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-hexyl etc..C1-C6The example bag of halohydrocarbyl
Include but be not limited to chloromethyl, dichloromethyl, trichloromethyl, trifluoromethyl, a bromomethyl, two bromomethyls,
Trisbromomethyl, Chloroethyl etc..
The organic epoxy compound thing is included but is not limited to：Oxirane, expoxy propane, dioxane, epoxy
Butane, butadiene oxide, butadiene double oxide, epoxychloropropane, methyl glycidyl ether, two are shunk
At least one in glycerin ether, tetrahydrofuran, preferred tetrahydrofuran and/or epoxychloropropane.
The specific embodiment of catalyst according to the invention component, the halogenated titanium is selected from titanium tetrachloride, tetrabromo
Change titanium and at least one in titanium tetra iodide, preferred titanium tetrachloride.
The specific embodiment of catalyst according to the invention component, the feeding quantity of each component is with every mole of magnesium halide
Meter, organic epoxy compound thing is 0.01-10 mole, preferably 0.02-4 mole；Alcohol compound is 0.01-10
Mole, preferably 0.5-5 mole；Titanate compound is 0.01-1.0 mole, preferably 0.02-0.35 mole；
Halogenated titanium is 0.2-100 mole, preferably 1.0-50 mole.
The second aspect of the invention provides a kind of preparation method of above-mentioned catalytic component, methods described bag
Include：Magnesium halide is first reacted and to form homogeneous solution with organic epoxy compound thing and alcohol compound, then with titanate esters
Compound mixes, and then reacts with halogenated titanium and the catalytic component is obtained.
The inert diluent can be common aliphatic hydrocarbon or aromatic hydrocarbon.Specifically can be according to the following steps
Carry out：Magnesium halide is existed with organic epoxy compound thing and alcohol compound in the presence of stirring and inert diluent
At a temperature of 0-100 DEG C, best 40-70 DEG C of reaction forms solution, titanate compound is added, in -35-60 DEG C of temperature
Under degree, best -30-50 DEG C, titanium tetrahalide is instilled in the solution or the solution instilled in halogenated titanium, process
In can also add other electrons body compound, then heat up, then by reactant mixture in 10-150 DEG C of temperature
Under, best 20～130 DEG C, stir -10 hours 1 minute, stop stirring, sedimentation, filtration remove mother solution,
Solidss are washed with varsols such as toluene and hexanes, the catalytic component is obtained.Catalytic component can be with
The form of solidss or suspension is used.
The third aspect of the invention provides a kind of catalyst for olefinic polymerization, and it includes following components：
A. catalytic component mentioned above；With
B. organo-aluminum compound, its formula is AlRnX3-n, R is hydrogen or C in formula1-C20Alkyl, X is halogen
Element, n is the integer of 0 ＜ n≤3.
Preferably, the mol ratio of the aluminum in component B and the titanium in component A is 5:1-1000:1, preferably
20:1-800:1, more preferably 20:1-500:1.
Catalyst A, B component may be directly applied to polymerization system, also can be applied to polymerization system after first pre- complexation.
The catalyst of the present invention can be used for the homopolymerization of ethylene, it can also be used to the combined polymerization of ethylene and alpha-olefin, altogether
Polycondensation monomer can adopt propylene, butylene, amylene, hexene, octene, 4- methyl 1- amylenes.
Liquid phase polymerization can be adopted during polymerization, gas-phase polymerization may also be employed.When liquid phase polymerization is carried out, it is possible to use
Propane, hexane, heptane, hexamethylene, iso-butane, isopentane, Petroleum, raffinate oil, hydrogasoline, coal
The atent solvent such as the aliphatic saturated hydrocarbons such as oil, benzene,toluene,xylene or aromatic hydrocarbon makees reaction medium, can before polymerization
First to carry out prepolymerization.Polymerization methodses can adopt batch (-type), semi continuous or continuous way.
Polymerization temperature is -150 DEG C of room temperature, preferably 50 DEG C -100 DEG C.In order to adjust the molecular weight of polymer, adopt
Make molecular weight regulator with hydrogen.
The relative simplicity of the present invention preparation technology of catalyst, and avoid phosphorus-containing compound in preparation process
Use, be conducive to environmental conservation；Simultaneously gained catalyst has higher activity, the polymer prepared with it
With higher bulk density.
Specific embodiment
With reference to embodiment, the present invention is further illustrated.Below raw materials used for the present invention, the data are only supplied
With reference to not to raw materials used source structure restriction of the invention.
Anhydrous magnesium chloride：It is commercially available, technical grade；
Tributyl phosphate：Analyze pure, Beijing Yili Fine Chemicals Co., Ltd.；
Epoxychloropropane：Analysis is pure, Tianjin recovery fine chemistry industry institute；
Benzyl alcohol：Analyze pure, Beijing Yili Fine Chemicals Co., Ltd.；
Phenethanol：Analyze pure, Beijing Yili Fine Chemicals Co., Ltd.；
N-butyl alcohol：Analyze pure, Beijing Yili Fine Chemicals Co., Ltd.；
Butyl titanate：Analyze pure, Beijing Yili Fine Chemicals Co., Ltd.；
Dehydrated alcohol：Analyze pure, Beijing Chemical Plant；
Titanium tetrachloride：Analyze pure, Beijing Yili Fine Chemicals Co., Ltd.；
2-Ethylhexyl Alcohol；Analyze pure, Beijing Xing Jin chemical plant；
Toluene：Analyze pure, Beijing Chemical Plant；
Hexane：Technical grade, it is commercially available；
Ethylene：Polymer grade, Yanshan Petro-Chemical Industry Corporation, Jing molecular sieves, nickel accelerant purification；
Triethyl aluminum：ACROS companies of Sweden produce, and with hexane the solution of 1mol/l is made into.
(1) preparation of catalytic component
Embodiment 1：
In Jing high-purity Ns2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2、0.65mol
Toluene, stirring is lower add 0.026mol epoxychloropropane, 0.019mol benzyl alcohol, 0.044mol n-butyl alcohol,
0.060mol ethanol, is warmed up to 60 DEG C, maintains 1 hour, plus 0.0059mol tetrabutyl titanates, then should
Solution is cooled to -10 DEG C, then 0.27mol titanium tetrachlorides are instilled in it, maintains 70 minutes, then heats to
85 DEG C, maintain 1 hour, washed 4 times with hexane after filtration, be dried to obtain ingredient of solid catalyst.
Embodiment 2：
In Jing high-purity Ns2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2、0.56mol
Toluene, stirring is lower add 0.026mol epoxychloropropane, 0.019mol benzyl alcohol, 0.044mol n-butyl alcohol,
0.060mol ethanol, is warmed up to 60 DEG C, maintains 1 hour, plus 0.0029mol tetrabutyl titanates, then should
Solution is cooled to -10 DEG C, then 0.27mol titanium tetrachlorides are instilled in it, maintains 70 minutes, then heats to
85 DEG C, maintain 1 hour, washed 4 times with hexane after filtration, be dried to obtain ingredient of solid catalyst.
Embodiment 3:
In Jing high-purity Ns2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2、0.65mol
Toluene, stirring is lower to add 0.026mol epoxychloropropane, 0.019mol benzyl alcohol, 0.14mol ethanol, heats up
To 60 DEG C, maintain 2.5 hours, plus 0.0089mol tetrabutyl titanates, then the solution is cooled to into -10 DEG C,
0.54mol titanium tetrachlorides are instilled in it again, are maintained 70 minutes, then heat to 85 DEG C, maintained 1 hour,
Washed 4 times with hexane after filtration, be dried to obtain ingredient of solid catalyst.
Embodiment 4：
In Jing high-purity Ns2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2、0.65mol
Toluene, stirring is lower add 0.026mol epoxychloropropane, 0.019mol benzyl alcohol, 0.045mol isooctanol,
0.060mol ethanol, is warmed up to 60 DEG C, maintains 1 hour, plus 0.0059mol tetrabutyl titanates, then should
Solution is cooled to -10 DEG C, then 0.27mol titanium tetrachlorides are instilled in it, maintains 70 minutes, then heats to
85 DEG C, maintain 1 hour, washed 4 times with hexane after filtration, be dried to obtain ingredient of solid catalyst.
Embodiment 5：
In Jing high-purity Ns2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2、0.65mol
Toluene, stirring is lower add 0.026mol epoxychloropropane, 0.0084mol phenethanol, 0.045mol isooctanol,
0.060mol ethanol, is warmed up to 60 DEG C, maintains 1 hour, plus 0.0059mol tetrabutyl titanates, then should
Solution is cooled to -10 DEG C, then 0.27mol titanium tetrachlorides are instilled in it, maintains 70 minutes, then heats to
85 DEG C, maintain 1 hour, washed 4 times with hexane after filtration, be dried to obtain ingredient of solid catalyst.
Comparative example 1
In Jing high-purity Ns2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2、0.56mol
Toluene, stirring is lower to add 0.026mol epoxychloropropane, 0.022mol tributyl phosphates, 0.060mol ethanol,
65 DEG C, plus 0.0081mol phthalic anhydrides are warmed up to, are maintained 2.5 hours, the solution is cooled to into -10 DEG C, by 0.54mol
Titanium tetrachloride is instilled in it, is maintained 70 minutes, then heats to 85 DEG C, is maintained 1 hour, and after filtration oneself is used
Alkane is washed 4 times, is dried to obtain ingredient of solid catalyst.
Comparative example 2
In Jing high-purity Ns2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2、0.75mol
Toluene, stirring is lower to add 0.089mol epoxychloropropane, 0.033mol tributyl phosphates, is warmed up to 50 DEG C,
Maintain 3.0 hours, plus 0.0081mol phthalic anhydrides, maintain 2 hours, the solution is cooled to into -10 DEG C, by 0.36mol
Titanium tetrachloride is instilled in it, is maintained 70 minutes, then heats to 85 DEG C, is maintained 1 hour, and after filtration oneself is used
Alkane is washed 4 times, is dried to obtain ingredient of solid catalyst.
Comparative example 3
In Jing high-purity Ns2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2、0.56mol
Toluene, stirring is lower to add 0.051mol epoxychloropropane, 0.019mol benzyl alcohol, 0.071mol ethanol, rises
Temperature is maintained 1.5 hours to 60 DEG C, then the solution is cooled to into -10 DEG C, then by 0.27mol titanium tetrachlorides
Instill in it, maintain 40 minutes, then heat to 85 DEG C, maintain 1 hour, 4 are washed with hexane after filtration
It is secondary, it is dried to obtain ingredient of solid catalyst.
Comparative example 4：
In Jing high-purity Ns2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2、0.65mol
Toluene, stirring is lower to add 0.11mol n-butyl alcohol, 0.019mol benzyl alcohol, is warmed up to 100 DEG C, and maintenance 1 is little
When, then the solution is cooled to into -10 DEG C, then 0.27mol titanium tetrachlorides are instilled in it, maintain 70 minutes,
85 DEG C are then heated to, is maintained 1 hour, washed 4 times with hexane after filtration, be dried to obtain solid catalyst
Component.
(2) vinyl polymerization
Volume is 2 liters of rustless steel kettle Jing H2After being sufficiently displaced from, hexane 1000ml, triethyl group are added wherein
Aluminum 1.0ml (concentration is the hexane solution of 1mol/L), the above-mentioned prepared solid catalysts of 10mg of metering
Component, is warming up to 70 DEG C of hydrogenation to 0.26MPa (gauge pressure), then being passed through ethylene makes kettle interior up to 0.72MPa (tables
Pressure), at 80 DEG C, it is polymerized 2 hours.Polymerization result is shown in Table 1.
The polymerization result of table 1
The catalyst that can be seen that embodiment of the present invention preparation from the data of table 1 has higher activity, is used for
Vinyl polymerization, the polymer for obtaining has higher bulk density.
Claims (11)
1. a kind of catalytic component for olefinic polyreaction, it include magnesium halide, organic epoxy compound thing,
The product of alcohol compound, titanate compound and halogenated titanium.
2. catalytic component according to claim 1, it is characterised in that the organic epoxy compound thing
Selected from C2-C8The oxide of aliphatic olefin, C2-C8The oxide of aliphatic diene hydrocarbon, C2-C8Halogenated aliphatic
The oxide of race's alkene, C2-C8In the oxide of halogenated aliphatic alkadienes, glycidyl ether and inner ether extremely
Few one kind；Preferably, the organic epoxy compound thing selected from oxirane, expoxy propane, epoxychloropropane and
At least one in tetrahydrofuran.
3. catalytic component according to claim 1 and 2, it is characterised in that the magnesium halide is two
Magnesium chloride, at least one of the halogenated titanium in titanium tetrachloride, titanium tetrabromide and titanium tetra iodide, preferably
Titanium tetrachloride.
4. the catalytic component according to any one of claim 1-3, it is characterised in that the alcohols
The formula of compound is R1OH, wherein R1For C1-C12Aliphatic alkyl or C7-C12Aromatic hydrocarbyl；It is excellent
Selection of land, the alcohol compound is selected from ethanol, butanol, 2-Ethylhexyl Alcohol, benzyl alcohol and phenethanol at least
It is a kind of.
5. the catalytic component according to any one of claim 1-4, it is characterised in that the metatitanic acid
The formula of ester compounds is TiXm(OR2)4-m, wherein X be halogen, preferred fluorine, chlorine or bromine, R2For C1-C14
Aliphatic hydrocarbyl or C6-C14Aromatic hydrocarbyl, m is the integer of 0-3；Preferably, the titanate compound choosing
From the just own ester of positive ethyl ester of metatitanic acid, tetrabutyl titanate, isopropyl titanate, iso-butyl titanate, metatitanic acid, metatitanic acid pentyl ester,
At least one in one chlorine triethoxy titanium, dichlorodiethyl epoxide titanium and the ethanolato-titanium of trichlorine one.
6. the catalytic component according to any one of claim 1-5, it is characterised in that each component
In terms of every mole of magnesium halide, organic epoxy compound thing is 0.01-10 mole, preferably 0.02-4 mole to feeding quantity；
Organic Alcohol is 0.01-10 mole, preferably 0.5-5 mole；Titanate compound is 0.01-1.0 mole, preferably
For 0.02-0.35 mole；Halogenated titanium is 0.2-100 mole, preferably 1.0-50 mole.
7. the preparation method of the catalytic component any one of a kind of claim 1-6, methods described bag
Include：
Magnesium halide is first reacted and to form homogeneous solution with organic epoxy compound thing and alcohol compound, then with titanate esters
Compound mixes, and then reacts with halogenated titanium and the catalytic component is obtained.
8. preparation method according to claim 7, it is characterised in that will in the presence of inert diluent
Magnesium halide reacts to form solution at 0-100 DEG C with organic epoxy compound thing and alcohol compound, adds metatitanic acid
Ester compounds mix, and at -35-60 DEG C, halogenated titanium and above-mentioned solution reaction heat up, then reaction is mixed
Thing is stirred -10 hours 1 minute at 10-150 DEG C, sedimentation, filtration, washs solidss, and the catalysis is obtained
Agent component.
9. a kind of catalyst for olefinic polymerization, it includes following components：
A. catalytic component any one of claim 1-6 or the system by described in claim 7 or 8
The catalytic component that Preparation Method is obtained；With
B. organo-aluminum compound, its formula is AlRnX3-n, R is hydrogen or C in formula1-C20Alkyl, X is halogen
Element, n is the integer of 0 ＜ n≤3.
10. catalyst according to claim 9, it is characterised in that the aluminum in component B and component A
In titanium mol ratio be 5:1-1000:1, preferably 20:1-800:1, more preferably 20:1-500:1.
Urging described in the catalytic component or claim 9 or 10 any one of 11. claim 1-6
Agent is particularly the application of ethylene homo conjunction or copolymerization in alkene.
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| CN112661885A (en) * | 2019-10-16 | 2021-04-16 | 中国石油化工股份有限公司 | Titanium magnesium-based catalyst component for olefin polymerization, preparation method, catalyst and application |
| CN112707978A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Magnesium-based catalyst component for olefin polymerization, preparation method thereof, catalyst and application thereof |
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| CN109694423B (en) * | 2017-10-24 | 2021-07-30 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, preparation method thereof and catalyst for ethylene polymerization |
| CN110498874A (en) * | 2018-05-18 | 2019-11-26 | 中国石油化工股份有限公司 | A kind of alkoxyl magnesium particle, and its preparation method and application |
| CN112661885A (en) * | 2019-10-16 | 2021-04-16 | 中国石油化工股份有限公司 | Titanium magnesium-based catalyst component for olefin polymerization, preparation method, catalyst and application |
| CN112707978A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Magnesium-based catalyst component for olefin polymerization, preparation method thereof, catalyst and application thereof |
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Application publication date: 20170426 |