CN105085735B - A kind of preparation method of catalytic component for olefinic polymerization - Google Patents
A kind of preparation method of catalytic component for olefinic polymerization Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of the catalytic component for olefinic polymerization, including elder generation with anhydrous magnesium halide is dissolved in the mixed solvent comprising oxygen-containing organic titanic compound, organic epoxy compound object, hydroxyl class compound and inert diluent and forms a kind of magnesium halide solution, and the in the mixed solvent is free of phosphate compounds；The magnesium halide solution mixes precipitation solid with halogenation organo-aluminum compound and obtains the catalytic component again；The wherein described halogenation organo-aluminum compound is such as formula AlR5 nX3‑nShown compound, R in formula5It is C1~C20Alkyl, the direct-connected or branched hydrocarbyl of preferably not higher than 6 carbon atoms, wherein 0.5≤n≤2.5, X are halogen.There is catalytic component prepared by the present invention preferable particle shape, excellent hydrogen regulation performance to be conducive to use of the catalyst on slurry or gas-phase polymerization process device.
Description
Technical field
The present invention relates to a kind of preparation methods of the catalytic component for alkene homopolymerization or combined polymerization.
Background technology
With the development of olefin polymetiation process, the catalyst to match with polymerization technique has also got significant progress,
Middle effective catalyst still occupies by its excellent polymerization and ripe application technology in polyolefin catalyst field
Consequence.Especially people increasingly pay close attention to the production development of new structure vistanex, to olefin polymerization catalysis
Comprehensive performance require also higher and higher, not only to adapt to process unit, but also adjustable to resin structure controllable.Through excessive
The exploratory development in year, shows that Mg-Ti systems effective catalyst is relatively suitble to this application.
The method that the preparation method of Mg-Ti systems effective catalyst mostly uses solution modeling at present, i.e., first make magnesium compound molten
In certain solvent, then reprecipitation be precipitated method.Such as day tekiaki 54-40293 propositions metatitanic acid liposoluble solution magnesium compound,
It proposes day tekiaki 56-811 and day tekiaki 58-83006 to dissolve magnesium compound with compounds such as alcohol, aldehyde, amine, carboxylic acids, day is special
Clear 58-19307 propositions organic phosphorus compound dissolving magnesium compound is opened, day tekiaki 58-183708 proposes organic epoxidation
The schemes such as object and organic phosphorus compound (phosphate compounds) mixed dissolution magnesium compound of conjunction.
Although above-mentioned magnesium compound dissolving method can also overcome the shortcomings that grinding method to a certain extent, but still have one
Serial deficiency has much room for improvement, as described in day tekiaki 54-40293, day tekiaki 58-19307, day tekiaki 58-183708
Magnesium compound solution is used for catalysis in olefine polymerization after catalyst is precipitated, and catalytic activity is relatively low, and when extending polymerization time
Activity is decreased obviously, and the bulk density of polymer is relatively low.
Secondly Mg-Ti systems effective catalyst also mostly uses the preparation method of chemical reaction.In chemical reaction method, many hairs
Bright patent is related to using chemical raw materials such as organic metal magnesium compound, chlorinating agent and transition metal titanium compounds, with this kind of reaction
Object has prepared a variety of different types of catalyst, they be disclosed in Chinese patent CN1158136, CN1299375,
In CN1795213 and United States Patent (USP) US3787384, US4148754, US4173547, US4508843 and 5124296.This
In the Mg-Ti catalyst of type, although the performance of catalyst is easy modulation, generally existing gained catalyst granules form is not
Well, the problem of wider distribution, some even multi-modals are unfavorable for the long period even running of polyplant.
The present inventor selects suitable magnesium halide solution modeling by testing discovery repeatedly in the preparation process of catalyst
System can obtain the catalyst system for olefinic polymerization or combined polymerization well.This catalyst system and catalyzing has very high polymerization
Activity, and kinetics of polymerization is steady, and decay of activity is slow, and hydrogen response is good；Catalyst granules form is good, particle diameter distribution
It is narrow, cause morphology preferable, particle diameter distribution is narrow, and fine powder is few, large bulk density, is conducive to the long period of polyplant
Even running；Carbon number is very high in the stereospecificity of 3 or 3 or more olefin polymer.In addition, in catalyst synthesis processes Central Plains
Material consumption is few, and utilization rate of equipment and installations is high, has easy to operate, environmental-friendly advantage.
Invention content
The present invention provides a kind of preparation method of the catalytic component for olefinic polymerization, including elder generation is molten with anhydrous magnesium halide
In the mixed solvent comprising oxygen-containing organic titanic compound, organic epoxy compound object, hydroxyl class compound and inert diluent and
A kind of magnesium halide solution is formed, and the in the mixed solvent is free of phosphate compounds；The magnesium halide solution again with halogenation
Organo-aluminum compound mixing is precipitated solid and obtains the catalytic component；Wherein organic epoxy compound object is as shown in general formula I
Ternary epoxide, R in formula I2And R3Independently selected from H or C1~C10Alkyl or halohydrocarbyl, can be saturation or insatiable hunger
Straight chain, branch or the closed chain of sum；Or the organic epoxy compound object is 4~8 yuan of epoxides；The organic calorize of halogenation
It is such as formula AlR to close object5 nX3-nShown compound, R in formula5It is C1~C20Alkyl, preferably not higher than 6 carbon atoms it is direct-connected
Or branched hydrocarbyl, wherein 0.5≤n≤2.5, X are halogen.
The magnesium halide solution obtained in the present invention is amorphous magnesium halide form, that is to say, that magnesium halide solution of the invention
In do not contain crystalline state magnesium halide.In the present invention, Materials Absolute magnesium halide be crystalline state magnesium halide, can be α, β or
A variety of crystalline forms such as γ.In the present invention, the mixed solvent can also wrap other than above-mentioned essential four kinds of organic solvents
Containing other organic solvents, it is for example, selected from the organic solvent of the compounds such as esters, ketone and amine.These other organic solvents
Dosage is not premised on influencing the phase of final magnesium halide solution product.
In the present invention, in the mixed solvent is free of phosphate compounds, and the obtained magnesium halide solution is in downstream
Have in application process and more preferably show, such as it is used in catalyst preparation so that solid component is easy to be precipitated and make corresponding
The activity of catalyst improves；And avoid the phosphorus containg substances that residual toxicity is big in the catalyst prod in downstream.In the present invention
Phosphate compounds are, for example, tributyl phosphate, three iso-butyl ester of phosphoric acid, tricresyl phosphate propyl ester, triethyl phosphate or tripotassium phosphate
Ester.
Preferably, in the present invention, the magnesium halide solution be with anhydrous magnesium halide be dissolved in by oxygen-containing organic titanic compound,
Organic epoxy compound object, hydroxyl class compound and inert diluent composition mixed solvent and formed.That is, it is preferred that originally
The in the mixed solvent of invention only includes above-mentioned essential four kinds of organic solvents.
In a specific embodiment, the general formula of the magnesium halide is MgX2, X is halogen in formula.Described oxygen-containing have
Machine titanium compound such as general formula Ti (OR1)nX4-nIt is shown, R in formula1It is C1~C20Alkyl, can be saturations or undersaturated straight chain,
Branch or closed chain, 0<N≤4, X are halogens.It is preferable to use tetravalent titanium compounds, because they are usually in a liquid state at normal temperatures,
And there is good compatibility with some solvents in general.In reaction in specifically used titanium compound preferred formula
The compound of n=4 and their mixture, wherein butyl titanate are the most commonly used.The hydroxyl class compound formula is
HOR4, R in formula4It is C1~C20Alkyl, can be saturations or undersaturated straight chain, branch or closed chain；The inert diluent
For C3~C100Aliphatic hydrocarbon or its halogenated hydrocarbons, or be aromatic hydrocarbon or its halogenated hydrocarbons, can be saturations or undersaturated straight chain,
Branch or closed chain；It is preferred that the inert diluent is C4~C20Hydrocarbon compound.
Preferably, the magnesium halide is magnesium chloride, magnesium bromide, magnesium iodide and its mixture, is more preferably used in reaction
Magnesium halide is the mixture of magnesium chloride or magnesium chloride containing；The oxygen-containing organic titanic compound is metatitanic acid lipoid substance and its mixing
Object, preferably tetraethyl titanate, tetraisopropyl titanate, butyl titanate, four different monooctyl ester of metatitanic acid；The hydroxyl class compound is fat
Fat alcohol, aromatic alcohol or phenols, preferably methanol, ethyl alcohol, isopropanol, n-butanol, n-hexyl alcohol, isooctanol, benzyl alcohol and benzyl carbinol；Institute
It states inert diluent and is selected from benzene,toluene,xylene, normal butane, iso-butane, isopentane, pentane, n-hexane, hexamethylene, heptan
Alkane, octane, decane, 1,2- dichloroethanes, chlorobenzene and its mixture.
The present invention in a specific embodiment, in terms of every mole of magnesium halide, oxygen-containing organic titanic compound is
0.01~2.0 mole, preferably 0.1~1.5 mole；Organic epoxy compound object be 0.01~10 mole, preferably 0.1~6.5 mole,
Hydroxyl class compound is 0.01~20 mole, and preferably 0.1~15 mole, halogenation organo-aluminum compound is 0.1~100 mole,
It is preferred that 0.5~50 mole.
In a specific embodiment, the molar concentration of magnesium halide is 0.0001~20mol/L in magnesium halide solution,
Preferably 0.001~10mol/L.
In the present invention, it is preferred that organic epoxy compound object shown in general formula I includes aliphatic of the carbon atom number 2~8
The compounds such as the oxide of alkene, alkadienes or halogenated aliphatic olefins or alkadienes, glycidol ether, inner ether.It is preferred that described have
Machine epoxide is selected from ethylene oxide, propylene oxide, epoxy butane, butadiene oxide, butadiene double oxide, epoxy chlorine
It is one or more in propane, methyl glycidyl ether, diglycidyl ether and tetrahydrofuran.
In the present invention, the preferably described halogenation organo-aluminum compound is selected from ethyl aluminum dichloride, ethylaluminum sesquichloride, chlorination two
At least one of aluminium ethide and dichloro aluminium isobutyl, wherein ethyl aluminum dichloride or dichloro aluminium isobutyl are preferred.
In the step of present invention prepares magnesium halide solution, magnesium compound, organic epoxy compound object, hydroxyl class compound
The property that reactant is depended on the temperature that organic titanic compound contacts with each other, is typically chosen and carries out at a relatively high temperature
Dissolving advantageously, preferably in the decomposition temperature of reactant hereinafter, temperature is normally no higher than 200 DEG C, is generally not more than 150 DEG C.
The time of dissolving depends on the property and operating condition of reactant, and general selection of time is can obtain fully transparent solution
Until, required time is generally 10 minutes to 24 hours, preferably 2 to 16 hours.Inertia as described above can be added when dissolving
Diluent.
Second step prepared by catalytic component is alternatively referred to as settling step, completes magnesium titanium complex solution in this step
Chlorination reaction makes liquid complex Precipitation from solution.The contact of magnesium titanium complex solution and halogenation organo-aluminum compound
Method may be used any of suitable method and carry out, and may be used and magnesium titanium complex solution is gradually added drop-wise to halogenation has
Mode in machine aluminium compound solution, can also be molten using halogenation organo-aluminum compound solution is gradually added drop-wise to magnesium titanium complex
Mode in liquid.Rate of addition generally selects the hot-spot be subject to and do not cause reaction, is usually stirred during being added dropwise
Mix the steady progress in favor of reaction.In the precipitation reaction step, temperature can control between -40~100 DEG C, preferably
Between -20~80 DEG C.The reaction time of settling step should be long enough to obtain complete precipitation, and the reaction time can last 1
Minute to 10 hours, preferably 0.5~8 hour.
Experiment is found, after settling step, a period of time of reaction at a certain temperature carries out maturation process to catalyst
Particle shape than advantageous, while the intensity of catalyst particle can also be improved, to reduce catalyst in catalyzed ethylene polymerization mistake
Particle fragmentation phenomenon in journey.The temperature of the temperature of maturation process generally greater than or equal to precipitation reaction, the time of slaking reaction
It can control at 0.5~15 hour, preferably 1~10 hour.
It after carrying out maturation process, generally to be washed, to remove shape in excessive reactant and preparation process
At by-product, any atent solvent is used equally for this washing step, such as can select benzene,toluene,xylene, isobutyl
Alkane, pentane, hexane, heptane or hexamethylene and its mixture etc., hexane is generally selected in experiment, toluene be washing inertia it is molten
Agent.After washing, catalyst suspension can directly carry out repeatedly carrying titanium processing, can also be by using nitrogen under heating state
Purging is dried, and directly obtains catalyst fines.
The present invention also provides a kind of catalyst for olefinic polymerization, and it includes the reaction products of following components：
(a) catalytic component that the above method is prepared；
(b) at least one general formula is AlRmX3-mOrgano-aluminum compound, the hydrocarbon that R is hydrogen or carbon atom number is 1~20 in formula
Base, X are halogen, m 0<The number of m≤3.
In the present invention, one or more kinds of organo-aluminum compounds can be selected to be used in mixed way, preferably AlEt3、Al
(iso-Bu)3、Al(n-C6H13)3、Al(n-C8H17)3、AlEt2Cl etc..
Catalytic component or catalyst of the present invention are suitable for various olefinic polymerizations or copolymerization；It is preferred that in second
Application in alkene, propylene, butylene, hexene and octene homopolymerization or copolymerization.Especially the homopolymerization of ethylene or ethylene with
The combined polymerization of other alpha-olefins, wherein alpha-olefin are using one in propylene, butylene, amylene, hexene, octene, 4- methylpentenes -1
Kind.
Specific implementation mode
Test method：
1, the size distribution of carrier and catalyst：MASTERSIZE particles distribution instruments, n-hexane measure model as dispersant
Enclose 0.02~2000 μm.
2, the relative weight percents of metal in catalyst system (mainly titanium, magnesium)：Plasma emission spectrum (ICP).
3, the measurement of melt index：ASTM-D1238.
4, the measurement of bulk density：DIN-53194.
Example given below rather than is limited the invention in order to illustrate the present invention.
Embodiment 1
The preparation of catalytic component：1.2 grams of anhydrous magnesium chlorides are weighed, 4.4 milliliters of butyl titanates, 1.0 milliliters of rings are added
Oxygen chloropropane, 1.1 milliliters of absolute ethyl alcohols and 50 milliliters of hexanes are kept stirring dissolving at 60 DEG C until forming clear solution.Then
100 milliliters of hexanes are added again, solution temperature are down to 0 DEG C, the hexane that 18 milliliters of ethyl aluminum dichlorides are slowly added dropwise with buret is molten
Liquid (3M) after being added dropwise to complete, maintains 0 DEG C of reaction half an hour, then is warming up to 65 DEG C and maintains reaction 3 hours, obtains catalyst suspension
Liquid.Catalyst suspension being stood, sedimentation, is washed four times with hexane, the dosage of each hexane is 50 milliliters, after the completion of washing,
In the case of 65 DEG C of bath temperature, purges drying with high pure nitrogen, obtain mobility powder, i.e., catalytic component of the present invention,
Average grain diameter is 15.68 μm.Elemental analysis (ICP)：Ti:11.48% (weight), Mg:13.78% (weight).
Evaluating catalyst：1L hexanes, 1mmol triethyl aluminums and a certain amount of catalyst are added to 2L stainless steel stirred tanks
In, temperature is then increased to 90 DEG C, is added at one time the hydrogen of 0.4MPa, is then maintained the gross pressure of system with ethylene
1.0MPa carries out polymerisation, after reacting 2 hours, stops that ethylene, cooling is added, pressure release, polyethylene powder is weighed, and is calculated and is catalyzed
The activity of agent, the bulk density (BD) for testing polyethylene powder and the melt index (MI under 2.16Kg loads2.16), as a result such as
Shown in table 1.
Embodiment 2
The preparation of catalytic component：" solution temperature is down to 0 DEG C " in 1 preparation process of embodiment is adjusted to " will be molten
Liquid temperature is down to 45 DEG C " and accordingly " 0 DEG C of reaction half an hour of maintenance " it will be changed to " maintaining 45 DEG C of reaction half an hour ", other conditions are same
Embodiment 1.The average grain diameter of gained catalytic component is 14.77 μm.Elemental analysis (ICP)：Ti:7.64% (weight), Mg:
16.06% (weight).
Evaluating catalyst：For the slurry polymerization evaluation condition of catalyst with embodiment 1, polymerization result is shown in Table 1.
Embodiment 3
The preparation of catalytic component：" 4.4 milliliters of butyl titanates " in 1 preparation process of embodiment is adjusted to " 2.8 millis
Rise tetraethyl titanate ", other conditions are the same as embodiment 1.The average grain diameter of gained catalytic component is 21.64 μm.Elemental analysis
(ICP)：Ti:10.92% (weight), Mg:16.33% (weight).
Evaluating catalyst：For the slurry polymerization evaluation condition of catalyst with embodiment 1, polymerization result is shown in Table 1.
Embodiment 4
The preparation of catalytic component：" 1.1 milliliters of absolute ethyl alcohols " in 1 preparation process of embodiment is adjusted to " 2.3 milliliters
N-butanol ", and " solution temperature is down to 0 DEG C " is adjusted to " solution temperature is down to 45 DEG C " and accordingly " 0 DEG C of reaction will be maintained
Half an hour " is changed to " maintaining 45 DEG C of reaction half an hour ", and other conditions are the same as embodiment 1.The average grain diameter of gained catalytic component is
16.84μm.Elemental analysis (ICP)：Ti:8.19% (weight), Mg:12.57% (weight).
For the slurry polymerization evaluation condition of catalyst with embodiment 1, polymerization result is shown in Table 1.
Table 1
Claims (14)
1. a kind of preparation method of catalytic component for olefinic polymerization, including first anhydrous magnesium halide is dissolved in by oxygen-containing organic
The mixed solvent of titanium compound, organic epoxy compound object, hydroxyl class compound and inert diluent composition, forms a kind of halogenation
Magnesium solution, and the in the mixed solvent is free of phosphate compounds；The magnesium halide solution again with halogenation organo-aluminum compound
Mixing is precipitated solid and obtains the catalytic component；
Wherein, when the anhydrous magnesium halide being dissolved in the mixed solvent, solution temperature is controlled at 60 DEG C or less；
Wherein organic epoxy compound object is the ternary epoxide as shown in general formula I,
R in formula I2And R3Independently selected from H or C1~C10Alkyl or halohydrocarbyl, can be saturations or undersaturated straight chain, branch
Chain or closed chain；Or the organic epoxy compound object is 4~8 yuan of epoxides；
The halogenation organo-aluminum compound is such as formula AlR5 nX3-nShown compound, R in formula5It is C1~C20Alkyl, wherein 0.5
≤ n≤2.5, X are halogen.
2. according to the method described in claim 1, it is characterized in that, the halogenation organo-aluminum compound is such as formula AlR5 nX3-nInstitute
Show compound, R in formula5It is no greater than the direct-connected or branched hydrocarbyl of 6 carbon atoms.
3. according to the method described in claim 1, it is characterized in that, the magnesium halide solution is to be dissolved in anhydrous magnesium halide by containing
Oxygen organic titanic compound, organic epoxy compound object, hydroxyl class compound and inert diluent composition mixed solvent and formed.
4. according to the method described in claim 1, it is characterized in that, the general formula of the magnesium halide is MgX2, X is halogen in formula；Institute
State oxygen-containing organic titanic compound such as general formula Ti (OR1)nX4-nIt is shown, R in formula1It is C1~C20Alkyl, can be saturation or insatiable hunger
Straight chain, branch or the closed chain of sum, 0<N≤4, X are halogens.
5. according to the method described in claim 1, it is characterized in that, the hydroxyl class compound formula is HOR4, R in formula4It is
C1~C20Alkyl, can be saturations or undersaturated straight chain, branch or closed chain；The inert diluent is C3~C100's
Aliphatic hydrocarbon or its halogenated hydrocarbons, or be aromatic hydrocarbon or its halogenated hydrocarbons, can be saturations or undersaturated straight chain, branch or ring-type
Chain.
6. according to the method described in claim 5, it is characterized in that, the inert diluent is C4~C20Hydrocarbon compound.
7. according to the method described in claim 1, it is characterized in that, the magnesium halide be magnesium chloride, magnesium bromide, magnesium iodide and its
Mixture；The oxygen-containing organic titanic compound is metatitanic acid lipoid substance and its mixture；The hydroxyl class compound is fat
Fat alcohol, aromatic alcohol or phenols；The inert diluent is selected from benzene,toluene,xylene, normal butane, iso-butane, isopentane, positive penta
Alkane, n-hexane, hexamethylene, heptane, octane, decane, 1,2- dichloroethanes, chlorobenzene and its mixture.
8. the method according to the description of claim 7 is characterized in that the oxygen-containing organic titanic compound is tetraethyl titanate, titanium
Sour tetra-isopropyl, butyl titanate, four different monooctyl ester of metatitanic acid；The hydroxyl class compound is methanol, ethyl alcohol, isopropanol, positive fourth
Alcohol, n-hexyl alcohol, isooctanol, benzyl alcohol and benzyl carbinol.
9. according to the method described in claim 1, it is characterized in that, in terms of every mole of magnesium halide, oxygen-containing organic titanic compound is
0.01~2.0 mole；Organic epoxy compound object is 0.01~10 mole；Hydroxyl class compound is 0.01~20 mole；Halogenation
Organo-aluminum compound is 0.1~100 mole.
10. according to the method described in claim 9, it is characterized in that, in terms of every mole of magnesium halide, oxygen-containing organic titanic compound is
0.1~1.5 mole；Organic epoxy compound object is 0.1~6.5 mole；Hydroxyl class compound is 0.1~15 mole；Halogenation has
Machine aluminium compound is 0.5~50 mole.
11. the method according to any one of claim 1~10, which is characterized in that the organic epoxy compound object choosing
From ethylene oxide, propylene oxide, epoxy butane, butadiene oxide, butadiene double oxide, epoxychloropropane, methylglycidyl
It is one or more in glycerin ether, diglycidyl ether and tetrahydrofuran.
12. the method according to any one of claim 1~10, which is characterized in that the halogenation organo-aluminum compound
Selected from least one of ethyl aluminum dichloride, ethylaluminum sesquichloride, diethylaluminum chloride and dichloro aluminium isobutyl.
13. the method according to any one of claim 1~10, which is characterized in that the olefinic polymerization is ethylene, third
The homopolymerization or combined polymerization of alkene, butylene, hexene and octene.
14. a kind of catalyst for olefinic polymerization, it includes the reaction products of following components：
(a) catalytic component that one of claim 1~13 the method is prepared；
(b) at least one general formula is AlRmX3-mOrgano-aluminum compound, the alkyl that R is hydrogen or carbon atom number is 1~20 in formula, X
For halogen, m 0<The number of m≤3.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410176105.2A CN105085735B (en) | 2014-04-29 | 2014-04-29 | A kind of preparation method of catalytic component for olefinic polymerization |
| JP2016565201A JP6706582B2 (en) | 2014-04-29 | 2015-04-29 | Method for preparing catalyst component for olefin polymerization |
| RU2016146550A RU2673609C2 (en) | 2014-04-29 | 2015-04-29 | Method for preparation of a catalyst component used for polymerization of olefin |
| SG11201609010RA SG11201609010RA (en) | 2014-04-29 | 2015-04-29 | Method for preparation of a catalyst component used for olefin polymerization |
| MYPI2016703972A MY187602A (en) | 2014-04-29 | 2015-04-29 | Preparation method of a catalyst component for olefin polymerization |
| EP15785255.9A EP3138856B1 (en) | 2014-04-29 | 2015-04-29 | Method for preparation of a catalyst component used for olefin polymerization |
| PCT/CN2015/077844 WO2015165405A1 (en) | 2014-04-29 | 2015-04-29 | Method for preparation of a catalyst component used for olefin polymerization |
| CA2947189A CA2947189C (en) | 2014-04-29 | 2015-04-29 | Preparation method of a catalyst component for olefin polymerization |
| US15/307,209 US10174141B2 (en) | 2014-04-29 | 2015-04-29 | Preparation method of a catalyst component for olefin polymerization |
| BR112016025376-0A BR112016025376B1 (en) | 2014-04-29 | 2015-04-29 | METHOD OF PREPARING A CATALYST COMPONENT FOR OLEFIN POLYMERIZATION |
| KR1020167033297A KR102172790B1 (en) | 2014-04-29 | 2015-04-29 | Method for preparation of a catalyst component used for olefin polymerization |
| PH12016502158A PH12016502158A1 (en) | 2014-04-29 | 2016-10-28 | Preparation method of a catalyst component for olefin polymerization |
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| CN112646064B (en) * | 2019-10-11 | 2023-01-03 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof, catalyst and application |
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| CN102344508A (en) * | 2011-06-23 | 2012-02-08 | 中国石油天然气股份有限公司 | Ethylene polymerization catalyst containing ether compound, preparation method thereof, and application thereof |
| CN102453171A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method thereof |
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| CN102453128B (en) * | 2010-10-19 | 2013-07-03 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst thereof |
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| CN102453171A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method thereof |
| CN102344508A (en) * | 2011-06-23 | 2012-02-08 | 中国石油天然气股份有限公司 | Ethylene polymerization catalyst containing ether compound, preparation method thereof, and application thereof |
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