CN102453171B - Catalyst component for olefin polymerization and preparation method thereof - Google Patents
Catalyst component for olefin polymerization and preparation method thereof Download PDFInfo
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Abstract
The invention provides a catalyst component for olefin polymerization, a preparation method thereof and a purpose thereof. The catalyst component is a reaction product prepared from at least one organic magnesium compound, at least one liquid titanium-containing compound, at least one hydroxyl-containing compound, at least chlorine-containing organic aluminum compound, at least one acyl chloride compound and at least one modified additive, wherein the modified additive is a polystyrene-segmented polybutadiene polymer. Good hydrogen regulation performances, and good particle forms and good particle distributions of the prepared catalyst are in favor of the use of the catalyst in process devices gas-phase polymerization, slurry polymerization and the like.
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 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, 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 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, 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 the particle form of gained catalyzer like this, as the PFPE that adopts among the EP-A-258089, in Chinese patent CN1537118A, adopt PFO, these method forming step complexity, 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 addition, in the recent period studies show that adding the electron donor compound at the catalyst component preparatory phase can regulate and control the polymerization activity of catalyzer, adjusts the hydrogen regulation performance of catalyzer and reduce oligomer in the polymerisate etc.
In Chinese patent CN1129709A, by in Preparation of Catalyst, using the electron donor compound, can improve the tap density of activity of such catalysts, hydrogen response and polymerisate.The electron donor compound that uses in this patent contains the organic compound of one or more pairs of unbound electrons, mainly refers to the acylate compounds.
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 property-modifying additive, can obtain particle form preferably as spherical, narrow size-grade distribution, the catalyst component with higher catalytic activity, simultaneously, if in the Preparation of catalysts process, select suitable adding step to add the acyl chloride compound, can obviously improve the hydrogen response of catalyzer.This Preparation of catalysts method is simple, because the catalyzer of preparation also has good particle form and distribution simultaneously, thereby more is conducive to the use of catalyzer on polymerization technique devices such as gas phase, slurry except having good hydrogen regulation performance.
A kind of catalyst component for olefinic polymerization of the present invention, 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 organo-aluminium compound, at least a acyl chloride compound and at least a property-modifying additive;
(1) organo-magnesium compound is by general formula (I) MgR
1 nCl
2-nShown in, R in the formula
1Be C
2～C
20Alkyl, optional be saturated or undersaturated straight chain, side chain or closed chain, 0＜n≤2;
(2) titanium-containing compound is by logical formula II Ti (OR
2)
mCl
4-mShown in, R in the formula
2Be C
2～C
20Alkyl, optional be saturated or undersaturated straight chain, side chain or closed chain, 0≤m≤4;
(3) the hydroxyl compounds is by logical formula III HOR
3Shown in, R in the formula
3Be C
2～C
20Alkyl, optional be saturated or undersaturated straight chain, side chain or closed chain;
(4) chloride organo-aluminium compound is by logical formula IV AlR
4 pCl
3-pShown in, R in the formula
4Be C
2～C
20Alkyl, 0.5≤p≤2.5;
(5) the acyl chloride compound is by shown in general formula (V) RCOCl, and R is C in the formula
2～C
20Alkyl, optional be saturated or undersaturated straight chain, side chain or closed chain;
(6) property-modifying additive is polybutadiene block polyethylene oxide base polymer, comprise diblock and three blocks and derivative thereof, the block type of optional is linear or the form side chain form or star is arranged, in described polybutadiene block polyethylene oxide analog copolymer, the content of polyhutadiene is 3-97% (wt%).
Described organo-magnesium compound such as general 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 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.
Described titanium-containing compound is as 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.Tetravalent titanium compound 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 as 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.
Described chloride organo-aluminium compound is as logical formula IV AlR
4 pCl
3-pShown in, R in the formula
4Be C
2～C
20Alkyl, preferred C
2～C
6The alkyl of direct-connected or side chain, 0.5≤p≤2.5.Concrete chloride organo-aluminium compound comprises ethyl aluminum dichloride, sesquialter ethylaluminium chloride, diethylaluminum chloride, dichloro aluminium isobutyl, wherein preferred ethyl aluminum dichloride or dichloro aluminium isobutyl.
Described acyl chloride compound is shown in general formula (V) RCOCl, and R is C in the formula
2～C
20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain.Concrete acyl chloride compound comprises formyl chloride, Acetyl Chloride 98Min., propionyl chloride, butyryl chloride, Benzoyl chloride, phenyllacetyl chloride, phenylpropyl alcohol acyl chlorides, benzene butyryl chloride, at least a in preferred formyl chloride, Acetyl Chloride 98Min., Benzoyl chloride and the phenyllacetyl chloride.
Described property-modifying additive is polybutadiene block polyoxy ethane (PB-b-POE) base polymer, comprise diblock and three blocks (PB-b-POE-b-PB, POE-b-PB-b-POE) and derivative thereof etc., can be linear, side chain arranged or star etc. other form.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) organo-magnesium compound and hydroxyl compounds are reacted, obtain clear solution;
(2) property-modifying additive is dispersed in C
4～C
20In alkane or the aromatic solvent, formation solution reacts with the clear solution that acyl chloride compound and step (1) obtain again, obtains mixed solution;
(3) chloride organo-aluminium compound 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 organo-aluminium compound is 0.1～50 mole, preferred 0.5～20 mole; The acyl chloride compound is 0.001～20 mole, preferred 0.01～10 mole; The concentration of property-modifying additive 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 relative higher 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 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), property-modifying additive 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, formation solution reacts with the clear solution that acyl chloride compound and step (1) obtain again, obtains mixed solution.According to kind and the different in kind of property-modifying additive, the control of its solution allocation concentration is at 0.1～100 grams per liter, preferred 1～50 grams per liter, and the amount of adding is so that the concentration of property-modifying additive 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 the even mixing of all substances at a certain temperature rapidly, at first the solution system that first two steps are 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 chlorine organo-aluminium 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 precipitation 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, 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, for example can select 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 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 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, a-alkene such as optimal ethylene, propylene, butylene in the alkene, or the mixture of ethene, propylene, butylene and one or more a-alkene.Comonomer is C2-C12 alkene preferably, preferred C4-C10 alkene, 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, 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.
Catalyzer of the present invention has advantages of high catalytic activity and higher hydrogen response, and the polymerisate form can copy the particle form of catalyzer preferably, i.e. and so-called " print effect ", so this catalyzer has excellent comprehensive performances.
Embodiment
Provide following examples in order to 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 pattern of catalyzer and polymkeric substance: scanning electron microscope (SEM).
4, the mensuration of melting index: ASTM-D 1238.
5, 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 an hour, obtain clear solution, add 0.2ml Benzoyl chloride and polybutadiene block polyethylene oxide copolymer (polybutadiene content 75wt%) hexane solution (10g/L) 3ml then, be cooled to-50 ℃, the hexane solution (2M) and the 0.35ml titanium tetrachloride that add 1.6 milliliters of ethyl aluminum dichlorides successively, keep low-temp reaction after half an hour, naturally slowly heat up, after rising to room temperature, 50 ℃ of reactions 2 hours are kept in heating.The catalyst suspension temperature is down to room temperature, leaves standstill, hexane wash three times are used in sedimentation, and the consumption of each hexane is 50 milliliters, after washing is finished, and the dry mobile powder of brown solid that gets, its median size is 11.23 microns.
Ultimate analysis (ICP): Ti:11.14% (weight), Mg:13.32% (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, temperature is brought up to 85 ℃ then, 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, calculate 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, temperature is brought up to 85 ℃ then, 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, calculate 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
Change the 0.2ml Benzoyl chloride in the catalyst preparation process into the 0.5ml Benzoyl chloride, 1.6 other conditions of hexane solution (2M) that the hexane solution (2M) of milliliter ethyl aluminum dichloride changes 1.6 milliliters of dichloro aluminium isobutyl into are with embodiment 1, its median size is 13.8 microns.
Ultimate analysis (ICP): Ti:10.18% (weight), Mg:12.05% (weight).
The ethene slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result sees Table 1.
Embodiment 3
Change 0.2ml Benzoyl chloride in the catalyst preparation process into the 0.2ml Acetyl Chloride 98Min., other conditions are with embodiment 1, and its median size is 9.88 microns.
Ultimate analysis (ICP): Ti:10.37% (weight), Mg:12.89% (weight).
The ethene slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result sees Table 1.
Comparative Examples 1
Removing in catalyst preparation process do not add the 0.2ml Benzoyl chloride, and other conditions are with embodiment 1, and its median size is 17.3 microns.
Ultimate analysis (ICP): Ti:10.83% (weight), Mg:13.57% (weight).
The ethene slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result sees Table 1.
Table 1
From the experimental data of table 1 embodiment and Comparative Examples as can be seen, in the Preparation of catalysts process, use the acyl chloride compound, the catalyzer that obtains and polymkeric substance except particle form good, narrow particle size distribution, and the hydrogen response of polymer resin is better, the catalyzer high comprehensive performance is convenient to develop the resin product innovation of unique properties.
Claims (16)
1. 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 organo-aluminium compound, at least a acyl chloride compound and at least a property-modifying additive;
(1) organo-magnesium compound is by logical formula I MgR
1 nCl
2-nShown in, R in the formula
1Be C
2～C
20Alkyl, optional be saturated or undersaturated straight chain, side chain or closed chain, 0＜n≤2;
(2) titanium-containing compound is by logical formula II Ti (OR
2)
mCl
4-mShown in, R in the formula
2Be C
2～C
20Alkyl, optional be saturated or undersaturated straight chain, side chain or closed chain, 0≤m≤4;
(3) the hydroxyl compounds is by logical formula III HOR
3Shown in, R in the formula
3Be C
2～C
20Alkyl, optional be saturated or undersaturated straight chain, side chain or closed chain;
(4) chloride organo-aluminium compound is by logical formula IV AlR
4 pCl
3-pShown in, R in the formula
4Be C
2～C
20Alkyl, 0.5≤p≤2.5;
(5) the acyl chloride compound is by shown in general formula (V) RCOCl, and R is C in the formula
2～C
20Alkyl, optional be saturated or undersaturated straight chain, side chain or closed chain;
(6) property-modifying additive is polybutadiene block polyethylene oxide base polymer, be diblock and three blocks and derivative thereof, the block type of optional is linear or the form side chain form or star is arranged, in described polybutadiene block polyethylene oxide base polymer, 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
1Be C
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 di-n-butyl magnesium, 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, wherein said titanium-containing compound are selected from least a in titanium tetrachloride, tetraethyl titanate and the tetrabutyl titanate.
5. the catalyst component for olefinic polymerization according to claim 4, wherein said titanium-containing compound is titanium tetrachloride.
6. 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.
7. the catalyst component for olefinic polymerization according to claim 1, in the logical formula IV of wherein said chloride organo-aluminium compound, R
4Be C
2～C
6The alkyl of straight or branched.
8. the catalyst component for olefinic polymerization according to claim 7, wherein said chloride organo-aluminium compound are selected from least a in ethyl aluminum dichloride, sesquialter ethylaluminium chloride, diethylaluminum chloride and the dichloro aluminium isobutyl.
9. the catalyst component for olefinic polymerization according to claim 1, wherein said acyl chloride compound are selected from least a in propionyl chloride, butyryl chloride, Benzoyl chloride, phenyllacetyl chloride, phenylpropyl alcohol acyl chlorides and the benzene butyryl chloride.
10. the catalyst component for olefinic polymerization according to claim 9, wherein said acyl chloride compound are selected from least a in Benzoyl chloride and the phenyllacetyl chloride.
11. the catalyst component for olefinic polymerization according to claim 1, the content of polyhutadiene is 10-90%(wt% in the wherein said polybutadiene block polyethylene oxide base polymer).
12. the preparation method of the described catalyst component of one of claim 1-11 comprises the steps:
(1) organo-magnesium compound and hydroxyl compounds are reacted, obtain clear solution;
(2) property-modifying additive is dispersed in C
4～C
20In alkane or the aromatic solvent, formation solution reacts with the clear solution that acyl chloride compound and step (1) obtain again, obtains mixed solution;
(3) chloride organo-aluminium compound and titanium-containing compound are joined successively in the mixed solution that step (2) obtains, obtain catalyst component.
13. the preparation method of catalyst component according to claim 12, 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 organo-aluminium compound is 0.1～50 mole; The acyl chloride compound is 0.001～20 mole; The concentration control of property-modifying additive in reaction system is at 0.001～100 grams per liter.
14. the preparation method of catalyst component according to claim 13, 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 organo-aluminium compound is 0.5～20 mole; The acyl chloride compound is 0.01～10 mole; The concentration control of property-modifying additive in reaction system is at 0.01～50 grams per liter.
15. one kind is used for the equal polymerization of alpha-olefin or the catalyzer of copolymerization, it comprises the reaction product of following component:
(a) the described catalyst component for olefinic polymerization of one of claim 1-11;
(b) at least a general formula is AlR'''
3Organo-aluminium compound, R''' is C identical or inequality in the formula
1-8Alkyl, one of them or two alkyl can be replaced by chlorine.
16. claim 15 described for alpha-olefin equal polymerization or the catalyzer of copolymerization in the application of the equal polymerization of alpha-olefin or copolymerization, described alkene is ethene, propylene, butylene, hexene and/or octene.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010511365 CN102453171B (en) | 2010-10-19 | 2010-10-19 | Catalyst component 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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| CN104277155B (en) * | 2013-07-01 | 2016-07-06 | 中国石油化工股份有限公司 | For the catalyst component of olefinic polymerization, its preparation method and application |
| CN104974282B (en) * | 2014-04-11 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of catalytic component for ethylene polymerization, preparation method and catalyst |
| CN105085735B (en) * | 2014-04-29 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of preparation method of catalytic component for olefinic polymerization |
| CN107880169B (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 |
| CN107880172B (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 |
| CN107880195B (en) * | 2016-09-30 | 2020-05-12 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof and catalyst |
| CN107880183B (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 |
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| CN1537118A (en) * | 2001-06-20 | 2004-10-13 | Olefin polymerization catalyst component and preparating the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1537118A (en) * | 2001-06-20 | 2004-10-13 | Olefin polymerization catalyst component and preparating the same |
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