CN102372802B - 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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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 for olefinic polymerization or copolymerization and catalyzer thereof, and the preparation method of this catalyst component and purposes.
Technical background
After the efficient polyolefin catalyst of 20 century 70s was succeeded in developing, great change had occured in world's polyolefin industry.Over nearly more than 20 years, follow the development of olefin polymetiation process, the catalyzer that matches with polymerization technique has also been got significant progress, and wherein effective catalyst relies on its good polymerization and ripe utilisation technology still to occupy an important position in the polyolefin catalyst field.Through exploratory development for many years, Mg-Ti be the preparation method of effective catalyst also by common polishing, the Suspension method 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, prepared the catalyzer of number of different types with this class reactant, they are disclosed among Chinese patent CN1158136, CN1299375, CN1795213 and US Patent No. 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 arranged, thereby is difficult to control the form of prepared catalyst particle.
Recent development is to comprise in the dispersion system of magnesium/titanium compound at catalyst precursor, the material that adds some similar emulsifying agents, make it to form emulsion, and then reaction precipitation goes out granules of catalyst, can improve like this particle form of gained catalyzer, such as the PFPE that adopts among the EP0258089A, in Chinese patent CN1537118A, adopt PFO, these method forming step are complicated, be difficult to control, gained granules of catalyst form is also wayward, and the material price that adopts is high, is difficult to obtain.
In sum, still need to 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 is by a large amount of experimental studies have found that, 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 the preparation method of this catalyzer is simple.
One of purpose of the present invention has provided a kind of catalyst component 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 such as logical formula I MgR
1 nCl
2-nShown in, R in the formula
1C
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 such as logical formula II Ti (OR
2)
mCl
4-mShown in, R in the formula
2C
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 such as logical formula III HOR
3Shown in, R in the formula
3C
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 such as logical formula IV SiR
4 qCl
4-qShown in, R in the formula
4C
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 polystyrene polyhutadiene (SB) block base polymer, comprise diblock and three blocks (SBS, BSB) and derivative thereof etc., the block type can be linear or the form of side chain is arranged, in described polystyrene 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 be prepared:
(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 successively in the mixed solution that step (2) obtains, 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 relatively high 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 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 with inert diluent use, 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 that obtains fully mix, according to 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), finish rapidly at a certain temperature the even mixing of all substances, the solution system that at first first two steps is obtained is reduced to certain temperature, 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 are progressively slowly added successively, usually fully stir the abundant mixing that is beneficial to various materials in reinforced process, feed rate is selected to be as the criterion not cause that significant reaction or system obviously heat up usually.After fully 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 precipitation, in this precipitin reaction step, the reaction times of settling step should be long enough to obtain completely precipitation, and the reaction times can be lasted 1 minute to 10 hours, preferred 3 minutes～5 hours.
Experiment finds, after settling step, reacting at a certain temperature for some time, 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, in order to remove the by product that forms in excessive reactant and the preparation process, any inert solvent all can be used for this washing step, such as selecting Trimethylmethane, pentane, hexane, heptane, hexanaphthene, toluene or various aromatic hydrocarbons and composition thereof etc., usually select in the experiment with after twice of the toluene wash, fully wash oneself with hexane again.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 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 identical or not identical C
1-8Alkyl, wherein one or two alkyl can be replaced by chlorine.Can select 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 with another kind of promotor or electron donor, catalyzer of the present invention can also be mixed use with one or more Ziegler-Natta catalysts or non-Ziegler-Natta catalyst.
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, the alpha-olefins such as optimal ethylene, propylene, butylene in the alkene, or the mixture of ethene, propylene, butylene and one or more alpha-olefins.Comonomer is C2-C12 alkene preferably, preferred C4-C10 alkene, such as 1-butylene, iso-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 4-methylpentene-1, diene such as divinyl, Isosorbide-5-Nitrae-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 necessary, 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 necessary, 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 requirement of polymerisate performance, can use the conventional catalyst consumption.
Adopt catalyzer of the present invention, can obtain higher catalytic activity and hydrogen response preferably, the polymerisate form can copy the particle form of catalyzer preferably, i.e. and so-called " print effect ", so this catalyzer has good over-all properties.
Embodiment
Provide following examples the present invention is described better, be not used for limiting the scope of the 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 successively dibutylmagnesium hexane solution (1M) and the 1.0ml isooctyl alcohol of 30ml hexane, 3.15ml, be warming up to 50 ℃ and keep stirring reaction half an hour, obtain clear solution, then add styrene butadiene triblock copolymer (Kraton, FG1901X, wherein polybutadiene content 70%) hexane solution (10g/L) 1ml, be cooled to-10 ℃, add successively 0.36 milliliter of silicon tetrachloride and 0.35ml titanium tetrachloride, after adding material, be rapidly heated to 50 ℃ in 10 minutes, and keep reaction 2 hours.The catalyst suspension temperature is down to room temperature, leaves standstill, sedimentation, with hexane washing three times, the consumption of each hexane is 50 milliliters, after washing is finished, the dry mobile powder of brown solid that gets, 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, then with ethene the total pressure of system is maintained 1.03MPa and carry out polyreaction, react after 2 hours, stop to add ethene, cooling, pressure release, polyethylene powder is weighed, calculate the activity of catalyzer, 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, then with ethene the total pressure of system is maintained 1.03MPa and carry out polyreaction, react after 2 hours, stop to add ethene, cooling, pressure release, polyethylene powder is weighed, calculate the activity of catalyzer, 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
Be rapidly heated to 50 ℃ in 10 minutes in the catalyst preparation process, 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 sees 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 to 50 ℃, change nature into and slowly be warming up to room temperature, then be heated 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 sees Table 1.
Comparative Examples 1
Except the hexane solution that does not add the styrene butadiene triblock copolymer, other conditions are with embodiment 1 in catalyst preparation process, and the median size of the catalyzer that obtains is 79.46 microns, and size distribution is that wider multimodal distributes.
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 sees Table 1.
Table 1
Can find out from the experimental data of table 1 embodiment and Comparative Examples, use SBS class furtherance type precipitation agent in the preparation process of catalyzer, 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 (15)
1. be used for the catalyst component of 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 silicon compound and at least a furtherance shape precipitation agent;
Wherein said organo-magnesium compound is such as logical formula I MgR
1 nCl
2-nShown in, R in the formula
1C
2～C
20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, 0＜n≤2;
Wherein said titanium-containing compound is such as logical formula II Ti (OR
2)
mCl
4-mShown in, R in the formula
2C
2～C
20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, 0≤m≤4;
Wherein said hydroxyl compounds is such as logical formula III HOR
3Shown in, R in the formula
3C
2～C
20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain;
Wherein said chloride silicon compound is such as logical formula IV SiR
4 qCl
4-qShown in, R in the formula
4C
2～C
20Alkyl or alkoxyl group, 0≤q＜4;
Wherein said furtherance shape precipitation agent is polystyrene polybutadiene block analog copolymer, described block analog copolymer is diblock and derivative or three blocks and derivative thereof, the block type is linear or the form of side chain is arranged, in described polystyrene polybutadiene block analog copolymer, the content of polyhutadiene is 3-97%(wt%).
2. the catalyst component for olefinic polymerization according to claim 1, in the logical formula I of wherein said organo-magnesium compound, R
1C
2～C
20Alkyl.
3. the catalyst component 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 for olefinic polymerization according to claim 1, in the logical formula II of wherein said titanium-containing compound, m=4.
5. the catalyst component for olefinic polymerization according to claim 1, wherein said titanium-containing compound are selected from least a in titanium tetrachloride, tetraethyl titanate and the tetrabutyl titanate.
6. the catalyst component for olefinic polymerization according to claim 5, wherein said titanium-containing compound is titanium tetrachloride.
7. the catalyst component 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.
8. the catalyst component for olefinic polymerization according to claim 1, wherein said chloride silicon compound are selected from least a in trichlorophenyl silane, trichloroethyl silane, trichlorine octyl group silane, trichlorine Ethoxysilane, trichlorine butoxy silane, dichloro diethoxy silane and the silicon tetrachloride.
9. the catalyst component for olefinic polymerization according to claim 8, wherein said chloride silicon compound are selected from least a in trichloroethyl silane, trichlorine Ethoxysilane and the silicon tetrachloride.
10. the preparation method such as catalyst component as described in one of claim 1-9 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 silicon compound and titanium-containing compound are joined successively in the mixed solution that step (2) obtains, obtain catalyst component.
11. preparation method according to claim 10, wherein in every mole of organo-magnesium compound, titanium-containing compound is 0.01～10 mole; The hydroxyl compounds is 0.1～20 mole; Chloride silicon compound is 0.05～50 mole; The concentration of furtherance shape precipitation agent in reaction system is controlled at 0.001～100 grams per liter.
12. preparation method according to claim 11, wherein in every mole of organo-magnesium compound, titanium-containing compound is 0.05～5 mole; The hydroxyl compounds is 0.2～10 mole; Chloride silicon compound is 0.1～20 mole; The concentration of furtherance shape precipitation agent in reaction system is controlled at 0.01～50 grams per liter.
13. the application of the described catalyst component of one of claim 1-9 in olefinic polyreaction.
14. the application that is applied as in ethene, propylene, butylene, hexene and octene polyreaction according to claim 13.
15. a catalyzer that is used for alpha-olefin polymerization, it comprises the reaction product of following component:
(a) the described catalyst component for olefinic polymerization of one of claim 1-9;
(b) at least a general formula is AlR " '
3Organo-aluminium compound, R in the formula " ' be identical or not identical C
1-8Alkyl, wherein one 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 |
| 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 |
| MYPI2013000458A MY163741A (en) | 2010-08-19 | 2011-08-19 | Cataltic component for polymerization of olefin and preparation method thereof |
| 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 |
| 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 |
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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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| CN102372802B true CN102372802B (en) | 2013-03-27 |
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| 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 |
| 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 |
| 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 |
| 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 |
| CN107880186B (en) * | 2016-09-30 | 2020-05-12 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation and application thereof |
| CN107880179B (en) * | 2016-09-30 | 2021-02-05 | 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 |
| CN107880175B (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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5298474A (en) * | 1991-07-12 | 1994-03-29 | Ecp Enichem Polimeri S.R.L. | Supported catalyst for the (co)polymerization of ethylene |
| EP1187857B1 (en) * | 1999-06-07 | 2004-01-21 | Eastman Chemical Company | Process for producing ethylene/olefin interpolymers |
| CN1537118A (en) * | 2001-06-20 | 2004-10-13 | Olefin polymerization catalyst component and preparating the same |
-
2010
- 2010-08-19 CN CN 201010259632 patent/CN102372802B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5298474A (en) * | 1991-07-12 | 1994-03-29 | Ecp Enichem Polimeri S.R.L. | Supported catalyst for the (co)polymerization of ethylene |
| EP1187857B1 (en) * | 1999-06-07 | 2004-01-21 | Eastman Chemical Company | Process for producing ethylene/olefin interpolymers |
| CN1537118A (en) * | 2001-06-20 | 2004-10-13 | Olefin polymerization catalyst component and preparating the same |
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