CN102372802A - Catalyst ingredient for olefin polymerization and preparation method thereof - Google Patents
Catalyst ingredient for olefin polymerization and preparation method thereof Download PDFInfo
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- CN102372802A CN102372802A CN2010102596321A CN201010259632A CN102372802A CN 102372802 A CN102372802 A CN 102372802A CN 2010102596321 A CN2010102596321 A CN 2010102596321A CN 201010259632 A CN201010259632 A CN 201010259632A CN 102372802 A CN102372802 A CN 102372802A
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Abstract
The invention provides a catalyst ingredient for olefin polymerization, its preparation method and application. The ingredient comprises at least one organic magnesium compound, at least one liquid titaniferous compound, at least one hydroxyl compound, at least one chlorine-containing organosilicon compound, and at least one reaction product of a forming and precipitating aid, wherein, the forming and precipitating aid is a polystyrene block polybutadiene polymer. The prepared catalyst has good hydrogen regulation performance, good particle shape and distribution, which is advantageous for the use of the catalyst in gas phase, slurry and other polymerization devices.
Description
Technical field
The present invention relates to a kind of catalyst component and catalyzer thereof that is used for olefinic polymerization or copolymerization, and the preparation method of this catalyst component and purposes.
Technical background
After the seventies in 20th century, efficient polyolefin catalyst was succeeded in developing, great change had taken place in world's polyolefin industry.Over nearly more than 20 years; Follow the development of olefin polymetiation process; Also got significant progress with the catalyzer that polymerization technique matches, wherein effective catalyst relies on its good polymerization and sophisticated utilisation technology in the polyolefin catalyst field, still to occupy an important position.Through exploratory development for many years, Mg-Ti be the preparation method of effective catalyst also by polishing altogether, the suspension pickling process has developed into chemical reaction method.In chemical reaction method; Many patents of invention relate to chemical feedstockss such as adopting organo-metallic magnesium compound, chlorizating agent and transition metal titanium compound; Use this type reactant to prepare the catalyzer of number of different types, they are disclosed among Chinese patent CN1158136, CN1299375, CN1795213 and U.S. Pat 3787384, US4148754, US4173547, US4301029, US4508843, US4921920 and the US5124296.In such Mg-Ti catalyzer, it is to be difficult to control forming step that a fatal shortcoming is all arranged, thereby is difficult to control prepared catalyst particulate form.
Recent development is to comprise in the dispersion system of magnesium/titanium compound at catalyst precursor, adds the material of some similar emulsifying agents, makes it to form emulsion; And then reaction precipitation goes out granules of catalyst, can improve the particle form of gained catalyzer like this, like the PFPE that adopts among the EP0258089A; In Chinese patent CN1537118A, adopt PFO; These method forming step are complicated, are difficult to control, and gained granules of catalyst form is also wayward; And the material expensive that is adopted, be difficult to obtain.
In sum, still need provide a kind of preparation method simple in the Ziegler-Natta catalyst field, particle form is better, has the catalyzer of higher catalytic activity and hydrogen response.
Summary of the invention
The inventor finds through a large amount of experimental studies; Add a kind of special furtherance shape precipitation agent; Can obtain particle form better as spherical, narrow size-grade distribution, have the catalyst component of higher catalytic activity and hydrogen response, and this Preparation of catalysts method is simple.
One of the object of the invention has provided a kind of catalyst component that is used for olefinic polymerization; It is to comprise at least a organo-magnesium compound; At least a titanium-containing compound, the reaction product of at least a hydroxyl compounds, at least a chloride silicoorganic compound and at least a furtherance shape precipitation agent;
Wherein said organo-magnesium compound is like logical formula I MgR
1 nCl
2-nShown in, R in the formula
1Be C
2～C
20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, be preferably C
2～C
20Alkyl; 0＜n≤2; Concrete organo-magnesium compound such as magnesium chloride, ethyl-magnesium-chloride, dibutylmagnesium etc., at least a in the preferred dibutylmagnesium of the organo-magnesium compound that uses in the reaction, diisobutyl magnesium, dioctyl magnesium, fourth octyl group magnesium, ethyl-magnesium-chloride and the butyl magnesium chloride.
Wherein said titanium-containing compound is like logical formula II Ti (OR
2)
mCl
4-mShown in, R in the formula
2Be C
2～C
20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, 0≤m≤4; Preferred tetravalent titanium compound, because tetravalent titanium compound is in a liquid state usually at normal temperatures, and also also fine with the consistency of some solvents.The compound of m=4 and their mixture in the titanium-containing compound preferred formula (II), wherein the most commonly used is titanium tetrachloride, tetraethyl titanate and tetrabutyl titanate.
Wherein said hydroxyl compounds is like logical formula III HOR
3Shown in, R in the formula
3Be C
2～C
20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain; The hydroxyl compounds is preferably Fatty Alcohol(C12-C14 and C12-C18) or aromatic alcohol, more preferably at least a in propyl carbinol, n-hexyl alcohol, isooctyl alcohol, phenylcarbinol and the phenylethyl alcohol.
Wherein said chloride silicoorganic compound are like logical formula IV SiR
4 qCl
4-qShown in, R in the formula
4Be C
2～C
20Alkyl or alkoxyl group, 0≤q＜4.Concrete chloride silicoorganic compound are selected from least a in trichlorophenyl silane, trichloromethyl silane, trichloroethyl silane, trichlorine octyl group silane, trichlorine methoxy silane, trichlorine Ethoxysilane, trichlorine butoxy silane, dichloro dimethoxy silane, dichloro diethoxy silane and the silicon tetrachloride, at least a in preferred trichloromethyl silane, trichloroethyl silane, trichlorine methoxy silane, trichlorine Ethoxysilane and the silicon tetrachloride.
Described furtherance shape precipitation agent is PS polyhutadiene (SB) block base polymer; Comprise diblock and three blocks (SBS, BSB) and verivate thereof etc.; The block type can be linear or the form of side chain is arranged; In described PS polybutadiene block analog copolymer, the content of polyhutadiene is 3-97% (wt%), is preferably 10-90% (wt%).
Catalyst component of the present invention preferably adopts the following step to prepare:
(1) with organo-magnesium compound and the reaction of hydroxyl compounds, obtains clear solution;
(2) furtherance shape precipitation agent is dispersed in C
4～C
20In alkane or the aromatic solvent, formation solution reacts with the clear solution that step (1) obtains again, obtains mixed solution;
(3) chloride organo phosphorous compounds and titanium-containing compound are joined in the mixed solution that step (2) obtains successively, obtain catalyst component.
In the preparation process of catalyst component, the ratio between the each component is that wherein in every mole of organo-magnesium compound, titanium-containing compound is 0.01～10 mole, preferred 0.05～5 mole; The hydroxyl compounds is 0.1～20 mole, preferred 0.2～10 mole; Chloride silicoorganic compound are 0.05～50 mole, preferred 0.5～20 mole; The concentration of furtherance shape precipitation agent in reaction system is controlled at 0.001～100 grams per liter, preferred 0.01～50 grams per liter.
In step (1), the temperature of reaction of organo-magnesium compound and hydroxyl compounds is typically chosen in carries out comparatively favourablely under the higher relatively temperature, and preferably below the boiling temperature of reactant, temperature is not higher than 90 ℃ usually, generally is not higher than 70 ℃.The time of reaction is depended on the character and the operational condition of reactant, and required time is generally at 5 minutes to 2 hours, preferred 10 minutes to 1 hour.After standby magnesium compound and the reaction of hydroxyl compounds; The solution that forms can mix use with inert diluent; Inert diluent is selected from aliphatic hydrocarbon usually; For example Trimethylmethane, pentane, hexane, heptane or hexanaphthene and composition thereof, general hexane or heptane are proper inert solvents.
In step (2), furtherance shape precipitation agent is dispersed in C
4～C
20In alkane or the aromatic solvent, preferably be dispersed in hexane, heptane or toluene and composition thereof the solvent, form solution, again with step (1) in the clear solution thorough mixing that obtains, according to the kind and the different in kind of furtherance shape precipitation agent, its C
4～C
20The configuration concentration of alkane or aromatic hydrocarbons solution is controlled at 0.1～100 grams per liter, preferred 1～50 grams per liter, and the amount of adding is so that the concentration of furtherance shape precipitation agent in reaction system is 0.001～100 grams per liter, preferred 0.01～50 grams per liter.Mixing temperature generally will be lower than the boiling temperature of system, for simplicity, is typically chosen between 0～90 ℃, between preferred 10～50 ℃.Both mixing times are general selects 0.5 minute to 5 hours, preferred 10 minutes to 1 hour.
In step (3); Accomplish the uniform mixing of all materials at a certain temperature rapidly, the solution system that at first preceding two steps is obtained is reduced to certain temperature, and solution still keeps clear under this temperature; Be unlikely to become turbid or precipitate; Temperature can be controlled between-90～30 ℃, preferably between-70～0 ℃, then chloride silicoorganic compound and titanium-containing compound is progressively slowly added successively; In reinforced process, fully stir the thorough mixing that is beneficial to various materials usually, feed rate is selected to be as the criterion not cause that significant reaction or system obviously heat up usually.Behind the thorough mixing, can adopt any known suitable method to heat up, as slowly, progressively, rapidly or temperature programming; Different temperature-rising methods can obtain the totally different catalyzer of performance characteristics, in temperature-rise period; System can change muddiness into by clarification, separates out deposition, in this precipitin reaction step; The reaction times of settling step should be long enough to obtain deposition completely, and the reaction times can be lasted 1 minute to 10 hours, preferred 3 minutes～5 hours.
Experiment finds, after settling step, reacting for some time at a certain temperature, to carry out maturation process more favourable to the particle shape of catalyzer, and it can improve the intensity of catalyst particle, thereby reduces the particle fragmentation phenomenon of catalyzer in polymerization process.The temperature of maturation process generally is equal to or higher than the outlet temperature of precipitin reaction, and the time of slaking reaction can be controlled at 0.5～10 hour, preferred 1～5 hour.
After carrying out maturation process; Generally to wash; So that remove the by product that forms in excessive reactant and the preparation process, any inert solvent all can be used for this washing step, for example can select Trimethylmethane, pentane, hexane, heptane, hexanaphthene, toluene or various aromatic hydrocarbons and composition thereof etc.; Usually select in the experiment to use the hexane thorough washing own again with after twice of the toluene wash.After washing, carry out drying under the catalyst suspension nitrogen protection, to obtain catalyst fines.
In addition, the invention still further relates to a kind of catalyzer that is used for olefinic polymerization or copolymerization, it comprises the reaction product of following component:
(a) catalyst component of the invention described above;
(b) at least a general formula is AlR " '
3Organo-aluminium compound, R in the formula " ' be C identical or inequality
1-8Alkyl, one of them or two alkyl can be replaced by chlorine.Can select for use one or more aluminum alkyls to mix use, preferred AlEt
3, Al (iso-Bu)
3, Al (n-C
6H
13)
3, Al (n-C
8H
17)
3, AlEt
2Cl etc.
Catalyzer of the present invention can use according to the well-known way of this area olefinic polymerization Ziegler-Natta catalyst; As using, can also catalyzer of the present invention be mixed use with one or more Ziegler-Natta catalysts or non-Ziegler-Natta catalyst with another kind of promotor or electron donor.
Catalyzer of the present invention is applicable to various any alkene that can carry out the polycoordination reaction; Comprise a kind of equal polymerization of alkene or the copolymerization of multiple alkene; Terminal olefins such as optimal ethylene, propylene, butylene in the alkene, or the mixture of ethene, propylene, butylene and one or more terminal olefins.Comonomer is a C2-C12 alkene preferably, and preferred C4-C10 alkene is like 1-butylene, iso-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 4-methylpentene-1; Diene such as divinyl; 1,4-hexadiene and 1,7-octadiene; Cyclenes such as norbornylene, and their any mixture.
Catalyzer of the present invention can adopt conventional polymerization technique to carry out polyreaction in one or more polymerization reactors, can be gas phase, slurry or bulk polymerization, and polyreaction can be intermittence or continuous polymerization process.
To slurry or bulk reaction device, temperature of reaction is generally at 40-130 ℃, and preferred 60-110 ℃, reactor pressure is generally at 0.2-8MPa, preferred 1-6MPa, and the residence time is generally at 0.2-6 hour, preferred 0.5-3 hour.The general boiling point of selecting uses as thinner at the aliphatic hydrocarbon of-70-100 ℃ scope, and if desired, polyreaction can be carried out under super critical condition.
For Gas-phase reactor, temperature of reaction is generally at 60-130 ℃, and preferred 70-110 ℃, reactor pressure is generally at 0.5-4MPa, preferred 1-3MPa, and the residence time is generally at 0.5-10 hour, preferred 1-8 hour.If desired, select suitable aliphatic hydrocarbon to use as thinner, polyreaction can be carried out under the frozen state condition.
Catalyst levels generally depends on character, type of reactor and the operational condition of catalyzer and to the polymerisate performance demands, can use the conventional catalyst consumption.
Adopt catalyzer of the present invention, can obtain advantages of high catalytic activity and better hydrogen regulation sensitivity, the polymerisate form can be duplicated the particle form of catalyzer preferably, and promptly so-called " print effect ", so this catalyzer has excellent comprehensive performances.
Embodiment
Provide following examples so that the present invention is described better, be not used for limiting scope of the present invention.Testing method:
1, the size-grade distribution of carrier and catalyzer: MASTERSIZE particles distribution instrument, normal hexane be as dispersion agent, useful range 0.02～2000 μ m.
2, the relative weight per-cent of metal (mainly being titanium, magnesium) in the catalyst system: plasma emission spectrum (ICP).
3, the mensuration of melting index: ASTM-D 1238.
4, the mensuration of tap density: DIN-53194.
Embodiment 1:
Get dibutylmagnesium hexane solution (1M) and the 1.0ml isooctyl alcohol of 30ml hexane, 3.15ml successively, be warming up to 50 ℃ and keep stirring reaction half a hour, obtain clear solution; Add styrene butadiene triblock copolymer (wherein polybutadiene content 70% for Kraton, FG1901X) hexane solution (10g/L) 1ml then; Be cooled to-10 ℃, add 0.36 milliliter of silicon tetrachloride and 0.35ml titanium tetrachloride successively, add material after; Be rapidly heated to 50 ℃ in 10 minutes, and keep reaction 2 hours.The catalyst suspension temperature is reduced to room temperature, leave standstill, sedimentation, with hexane wash three times, the consumption of each hexane is 50 milliliters, after washing is accomplished, dry the mobile powder of brown solid, its median size is 56.2 microns.
Ultimate analysis (ICP): Ti:9.48% (weight), Mg:20.84% (weight).
Vinyl polymerization is estimated A: 1L hexane, 1mmol triethyl aluminum and a certain amount of catalyzer are joined in the 2L stainless steel stirring tank, then temperature is brought up to 85 ℃, the hydrogen of disposable adding 0.5MPa; With ethene the total pressure of system is maintained 1.03MPa then and carry out polyreaction, react after 2 hours, stop to add ethene; Cooling; Pressure release, polyethylene powder is weighed, and calculates activity of such catalysts; The tap density of test polyethylene powder and the melting index under the 2.16Kg load, the result is as shown in table 1.
Vinyl polymerization is estimated B: 1L hexane, 1mmol triethyl aluminum and a certain amount of catalyzer are joined in the 2L stainless steel stirring tank, then temperature is brought up to 85 ℃, the hydrogen of disposable adding 0.18MPa; With ethene the total pressure of system is maintained 1.03MPa then and carry out polyreaction, react after 2 hours, stop to add ethene; Cooling; Pressure release, polyethylene powder is weighed, and calculates activity of such catalysts; The tap density of test polyethylene powder and the melting index under the 2.16Kg load, the result is as shown in table 1.
Embodiment 2
In 10 minutes in the catalyst preparation process, be rapidly heated to 50 ℃, change into and being rapidly heated in 10 minutes to 70 ℃, other conditions are with embodiment 1, and its median size is 85.2 microns.
Ultimate analysis (ICP): Ti:5.12% (weight), Mg:12.81% (weight).
The ethene slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result is seen table 1.
Embodiment 3
Change the 1.0ml isooctyl alcohol in the catalyst preparation process into the 0.6ml propyl carbinol; Change hexane solution (10g/L) 1ml that adds the styrene butadiene triblock copolymer into adding 3ml; In 10 minutes, be rapidly heated, change nature into and slowly be warming up to room temperature, be heated to 50 ℃ then to 50 ℃; Other conditions are with embodiment 1, and its median size is 24.3 microns.
Ultimate analysis (ICP): Ti:11.66% (weight), Mg:24.39% (weight).
The ethene slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result is seen table 1.
Comparative Examples 1
In catalyst preparation process, remove the hexane solution that does not add the styrene butadiene triblock copolymer, other conditions are with embodiment 1, and the median size of the catalyzer that obtains is 79.46 microns, and size distribution is the multimodal distribution than broad.
Ultimate analysis (ICP): Ti:9.73% (weight), Mg:21.06% (weight).
The ethene slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result is seen table 1.
Table 1
Can find out from the experimental data of table 1 embodiment and Comparative Examples; In the Preparation of catalysts process, use SBS class furtherance type precipitation agent, the catalyzer that obtains and the particle form of polymkeric substance are good, narrow particle size distribution; (BD) is higher for the tap density of polymer resin, the catalyzer high comprehensive performance.
Claims (11)
1. the catalyst component that is used for olefinic polymerization, it is to comprise at least a organo-magnesium compound, at least a titanium-containing compound, the reaction product of at least a hydroxyl compounds, at least a chloride silicoorganic compound and at least a furtherance shape precipitation agent;
Wherein said organo-magnesium compound is like logical formula I MgR
1 nCl
2-nShown in, R in the formula
1Be C
2～C
20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, 0＜n≤2;
Wherein said titanium-containing compound is like logical formula II Ti (OR
2)
mCl
4-mShown in, R in the formula
2Be C
2～C
20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, 0≤m≤4;
Wherein said hydroxyl compounds is like logical formula III HOR
3Shown in, R in the formula
3Be C
2～C
20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain;
Wherein said chloride silicoorganic compound are like logical formula IV SiR
4 qCl
4-qShown in, R in the formula
4Be C
2～C
20Alkyl or alkoxyl group, 0≤q＜4;
Wherein said furtherance shape precipitation agent is a polystyrene block polyhutadiene base polymer (SB); Comprise diblock and three blocks (SBS, BSB) and verivate thereof; The block type can be linear or the form of side chain is arranged; In described PS polybutadiene block analog copolymer, the content of polyhutadiene is 3-97% (wt%).
2. the catalyst component that is used for olefinic polymerization according to claim 1, in the logical formula I of wherein said organo-magnesium compound, R
1Be C
2～C
20Alkyl.
3. the catalyst component that is used for olefinic polymerization according to claim 2, wherein said organo-magnesium compound are selected from least a in dibutylmagnesium, diisobutyl magnesium, dioctyl magnesium, fourth octyl group magnesium, ethyl-magnesium-chloride and the butyl magnesium chloride.
4. the catalyst component that is used for olefinic polymerization according to claim 1, in the logical formula II of wherein said titanium-containing compound, m=4.
5. the allylic olefin polymeric catalyst component that is used for according to claim 4, wherein said titanium-containing compound are selected from least a in titanium tetrachloride, tetraethyl titanate and the tetrabutyl titanate, preferred titanium tetrachloride.
6. the catalyst component that is used for olefinic polymerization according to claim 1, wherein said hydroxyl compounds are selected from least a in propyl carbinol, n-hexyl alcohol, isooctyl alcohol, phenylcarbinol and the phenylethyl alcohol.
7. the catalyzer that is used for olefinic polymerization according to claim 1; Wherein said chloride silicoorganic compound are selected from least a in trichlorophenyl silane, trichloromethyl silane, trichloroethyl silane, trichlorine octyl group silane, trichlorine methoxy silane, trichlorine Ethoxysilane, trichlorine butoxy silane, dichloro dimethoxy silane, dichloro diethoxy silane and the silicon tetrachloride, at least a in preferred trichloromethyl silane, trichloroethyl silane, trichlorine methoxy silane, trichlorine Ethoxysilane and the silicon tetrachloride.
8. the preparation method like one of claim 1-7 said catalyst component comprises the steps:
(1) organo-magnesium compound and hydroxyl compounds are reacted, obtain clear solution;
(2) furtherance shape precipitation agent is dispersed in C
4～C
20In alkane or the aromatic solvent, formation solution reacts with the clear solution that step (1) obtains again, obtains mixed solution;
(3) chloride silicoorganic compound and titanium-containing compound are joined in the mixed solution that step (2) obtains successively, obtain catalyst component.
9. preparation method according to claim 8, wherein in every mole of organo-magnesium compound, titanium-containing compound is 0.01～10 mole, preferred 0.05～5 mole; The hydroxyl compounds is 0.1～20 mole, preferred 0.2～10 mole; Chloride silicoorganic compound are 0.05～50 mole, preferred 0.1～20 mole; The concentration of furtherance shape precipitation agent in reaction system is controlled at 0.001～100 grams per liter, preferred 0.01～50 grams per liter.
10. the application of the said catalyst component of one of claim 1-7 in olefinic polymerization or copolymerization, the preferably application in ethene, propylene, butylene, hexene and octene polymerization or copolymerization.
11. a catalyzer that is used for alpha-olefine polymerizing or copolymerization, it comprises the reaction product of following component:
(a) the described catalyst component that is used for olefinic polymerization of one of claim 1-7;
(b) at least a general formula is AlR " '
3Organo-aluminium compound, R in the formula " ' be C identical or inequality
1-8Alkyl, one of them or two alkyl can be replaced by chlorine.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010259632 CN102372802B (en) | 2010-08-19 | 2010-08-19 | Catalyst ingredient for olefin polymerization and preparation method thereof |
| US13/817,610 US9068025B2 (en) | 2010-08-19 | 2011-08-19 | Catalyst component for polymerization of olefin and preparation method |
| EP11817655.1A EP2607388B1 (en) | 2010-08-19 | 2011-08-19 | Catalytic composition for polymerization of olefin and preparation method thereof |
| BR112013003741-5A BR112013003741B1 (en) | 2010-08-19 | 2011-08-19 | CATALYST COMPONENT FOR OLEFINE POLYMERIZATION, ITS PREPARATION METHODS, CATALYST FOR OLEFINE COPOLIMERIZATION OR HOMOPOLIMERIZATION, AND ITS USE |
| RU2013111930/04A RU2575167C2 (en) | 2010-08-19 | 2011-08-19 | Catalytic composition, intended for olefin polymerisation and method for obtaining thereof |
| PCT/CN2011/001389 WO2012022127A1 (en) | 2010-08-19 | 2011-08-19 | Catalytic composition for polymerization of olefin and preparation method thereof |
| MYPI2013000458A MY163741A (en) | 2010-08-19 | 2011-08-19 | Cataltic component for polymerization of olefin and preparation method thereof |
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| CN 201010259632 CN102372802B (en) | 2010-08-19 | 2010-08-19 | Catalyst ingredient for olefin polymerization and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277150A (en) * | 2013-07-01 | 2015-01-14 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method and application thereof |
| CN104277149A (en) * | 2013-07-01 | 2015-01-14 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method and application thereof |
| CN104277153A (en) * | 2013-07-01 | 2015-01-14 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method and application thereof |
| CN107880175A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and preparation method thereof and catalyst |
| CN107880188A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component and its preparation and application for olefinic polymerization |
| CN107880179A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and preparation method thereof and catalyst |
| CN107880181A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component and its preparation and application for olefinic polymerization |
| CN107880186A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component and its preparation and application for olefinic polymerization |
| CN107880176A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component and its preparation and application for olefinic polymerization |
| CN107880173A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and preparation method thereof and catalyst |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277150A (en) * | 2013-07-01 | 2015-01-14 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method and application thereof |
| CN104277149A (en) * | 2013-07-01 | 2015-01-14 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method and application thereof |
| CN104277153A (en) * | 2013-07-01 | 2015-01-14 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method and application thereof |
| CN104277150B (en) * | 2013-07-01 | 2016-05-25 | 中国石油化工股份有限公司 | For catalyst component, its preparation method and the application of olefinic polymerization |
| CN104277149B (en) * | 2013-07-01 | 2016-06-29 | 中国石油化工股份有限公司 | For the catalyst component of olefinic polymerization, its preparation method and application |
| CN104277153B (en) * | 2013-07-01 | 2016-06-29 | 中国石油化工股份有限公司 | For the catalyst component of olefinic polymerization, its preparation method and application |
| CN107880175A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and preparation method thereof and catalyst |
| CN107880188A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component and its preparation and application for olefinic polymerization |
| CN107880179A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and preparation method thereof and catalyst |
| CN107880181A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component and its preparation and application for olefinic polymerization |
| CN107880186A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component and its preparation and application for olefinic polymerization |
| CN107880176A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component and its preparation and application for olefinic polymerization |
| CN107880173A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and preparation method thereof and catalyst |
| CN107880181B (en) * | 2016-09-30 | 2020-02-18 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation and application thereof |
| CN107880176B (en) * | 2016-09-30 | 2020-07-24 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation and application thereof |
| CN107880173B (en) * | 2016-09-30 | 2020-12-18 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof and catalyst |
| CN107880188B (en) * | 2016-09-30 | 2021-04-13 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation and application thereof |
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| CN102372802B (en) | 2013-03-27 |
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