CN104418960B - A kind of catalytic component and catalyst and its preparation method for ethylene polymerization - Google Patents
A kind of catalytic component and catalyst and its preparation method for ethylene polymerization Download PDFInfo
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- CN104418960B CN104418960B CN201310395303.3A CN201310395303A CN104418960B CN 104418960 B CN104418960 B CN 104418960B CN 201310395303 A CN201310395303 A CN 201310395303A CN 104418960 B CN104418960 B CN 104418960B
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Abstract
The invention discloses a kind of catalytic component for ethylene polymerization, the catalytic component includes the product of following component：（1）Magnesium compound；（2）Oxygen containing titanium compound；（3）Halogenated hydrocarbon compound；（4）Halide reagent.The catalytic component even particle size distribution is few for the fine polymer powder content obtained by ethylene polymerization；The catalytic component has polymerization activity higher, while hydrogen response is good；Catalyst preparation process is simple, accessory substance is few, environmentally friendly.
Description
Technical field
The present invention relates to a kind of catalytic component and catalyst for olefinic polyreaction, more specifically to one
Kind is used for Ziegler-Natta catalyst component of ethylene polymerization and preparation method thereof and catalyst.
Background technology
During the Ziegler-Natta catalyst matched with ethene polymerization process is developed, Mg-Ti systems
The research work of Ziegler-Natta catalyst composition is quite deep, and one side person skilled in art be devoted to
The polymerization catalyst activity for arriving is sufficiently high, catalyst residual in the polymer is tried one's best few；On the other hand gained polymerization is expected
The even particle distribution of thing, fine powder content are few.
United States Patent (USP) US3901863, US4617360, US4109071 disclose a kind of preparation method of Z-N catalyst, first
Liquid solution is first prepared by oxygen-containing organo-magnesium compound and oxygen-containing titanium compound, then the solution connects with chloride organo-aluminum compound
Touch reaction and form precipitation, method for preparing catalyst is simple, and activity is few compared with high, accessory substance, be adapted to the production of ethene slurry polymerization processes
Polyethylene product.But the broad particle distribution of the method gained catalyst, generally multi-modal.
United States Patent (USP) US4363746 discloses a kind of much higher catalyst of activity polymerization catalysts many than ever, will
The metal halide of magnesium such as magnesium dihalide is reacted with tetraalkoxy titanium, and then the solution is anti-with a kind of organic metal reducing agent
Should, a kind of solids is obtained, it is this then again the solids and a kind of halide ion exchanging source, such as titanium tetrachloride reaction
Although catalyst activity prepared by method is higher, fine powder content is more in the application for the catalyst.
The purpose of the present invention is to prepare a kind of even particle size distribution, the catalyst suitable for ethene slurry polymerization, is reduced poly-
Fine powder content in compound, the present inventor is had found by experiment repeatedly, by preparation method of the invention, prepared catalyst
Not only polymerization activity is improved, while hydrogen response is good, narrow particle size distribution, resulting polymers distribution of particles is concentrated, and fine powder content is few,
And catalyst preparation process is simple.
The content of the invention
A kind of present invention catalytic component and catalyst for ethylene polymerization of offer, and the catalytic component
Preparation method, the catalyst has polymerization activity higher, good hydrogen response, narrower size distribution and polymer thin
The advantages of powder content is few.
Concrete technical scheme is as follows：
An object of the present invention is to provide a kind of catalytic component for ethylene polymerization, the catalytic component bag
Include the product of following component：
（1）Magnesium compound；
（2）Oxygen containing titanium compound；
（3）Halogenated hydrocarbon compound；
（4）Halide reagent；
Component（1）Described in magnesium compound by formula (I) Mg（OR1）mCl2-mIt is shown, wherein R1It is C2~C20Alkyl,
It is saturation or undersaturated straight chain, side chain or closed chain, m is the integer of 0≤m≤2, and magnesium compound is selected from alkoxyl magnesium and dichloro
Change at least one in magnesium, alkoxyl magnesium is selected from diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium and two octyloxy magnesium
It is at least one.
Component（2）In oxygen containing titanium compound by formula (II) Ti (OR2)nCl4-nIt is shown, R in formula2It is C2~C20Hydrocarbon
Base, can be saturation or undersaturated straight chain, side chain or closed chain, and n is the integer of 0 ＜ n≤4；Preferably use titanic chemical combination
Thing, because they are generally in a liquid state at normal temperatures, and compatibility under normal conditions with some solvents is also fine.Formula
(II) in, preferably R2It is C2~C10Alkyl, n=4, wherein it is preferred that butyl titanate.
Component（3）Halogenated hydrocarbon compound may be selected from a halogenated hydrocarbons, dihalo hydrocarbon or polyhalohydrocarbon, optional self-saturation halo
Hydrocarbon, insatiable hunger and/or aromatic halohydrocarbon, may be selected from primary halogenated hydrocarbons, secondary halogenated hydrocarbons and tertiary halogenated hydrocarbons, preferably in the chloro of liquid condition
Hydrocarbon compound, specifically may be selected from 1-chlorobutane, Sec-Butyl Chloride, Isosorbide-5-Nitrae-dichloroetane, 2- chloro-2-methyl propane, carbon tetrachloride, and 1,
2- dichloroethanes, 1,2- dichloropropane, 2,2- dichloropropanes, chlorobenzene, chloroform, benzotrichloride, chlorotoluene, chlorocyclohexane
In at least one.
Component（4）Halide reagent, such as formula (III) R3 aMXbShown, M is three, four, five major elements or transition metal in formula
Element, X is halogen, R3It is to contain C2~C20The alkyl of carbon atom, a=0,1 or 2, b=1,2,3 or 4；Halide reagent is selected from dichloro
One aluminium ethide, aluminium diethyl monochloride, ethylaluminum sesquichloride, dichloro aluminium isobutyl, a chloro-di-isobutyl aluminum, two chloro isopropyls
Aluminium, a chlorine diisopropyl aluminium, silicon tetrachloride, preferably titanium tetrachloride, the aluminium ethide of dichloro one, ethylaluminum sesquichloride, dichloro isobutyl
Base aluminium, two chloro isopropyl aluminium, silicon tetrachloride, titanium tetrachloride.
During catalytic component is prepared, the feed molar ratio of various reactants, with component（1）In every mole of magnesium meter, group
Point（2）It is 0.1~20 mole, component（3）It is 0.1~20 mole, component（4）It is 0.5~50 mole, preferred ingredient（2）It is 0.5
~10 moles, component（3）It is 0.1~12 mole, component（4）It is 1.0~10 moles.
Second object of the present invention is to provide a kind of preparation method of the catalytic component for ethylene polymerization, should
Preparation method comprises the following steps：
（1）Formula (I) magnesium compound and formula (II) oxygen-containing titanium compound are reacted to form magnesium titanizing at a certain temperature
Compound clear solution；
（2）By step（1）Obtain product and react to obtain clear solution at -20~100 DEG C with formula halogenated hydrocarbon compound；
（3）By step（2）Haptoreaction forms precipitation to the solution for obtaining at a certain temperature with formula (III) compound, obtains
To the suspension of catalyst component；
（4）By step（3）The suspension for obtaining reacts certain hour at a certain temperature, then quiet heavy, washing, dry
Catalyst fines.Or by step（3）The suspension for obtaining is quiet heavy, removes a part of supernatant, adds a certain amount of dilution
Agent, then reacts certain hour at a certain temperature, quiet to sink, wash, being dried to obtain catalytic component.
The step of catalytic component is prepared（1）In, formula (I) magnesium compound and formula (II) oxygen-containing titanium compound are mutual
The temperature of contact is typically chosen to be carried out at relatively high temperatures, and temperature higher is beneficial to form magnesium titanium compound clear solution, preferably
Below the decomposition temperature of reactant, 200 DEG C are generally not more than, preferably less than 150 DEG C are carried out.Reaction is entered under agitation
OK, the time of reaction depend on reactant property and operating condition, reaction time requirement is enough to obtain transparent solution, required
Time is general at 1 to 20 hour, preferably 4 to 10 hours.Appropriate inert diluent can be as needed added, inert diluent is not
Can be chemically reacted with dissolved component, inert diluent may be selected hydro carbons such as n-hexane, hexamethylene, pentane, heptane, different
Butane, isopentane, isooctane, toluene etc. and its mixture, the dispersion for contributing to magnesium compound solution and the viscosity for reducing solution.
The step of catalytic component is prepared（2）In, by step（1）The product for obtaining and halogenated hydrocarbon compound hybrid reaction
Obtain magnesium titanium complex clear solution；Mixing temperature will be less than the decomposition temperature of magnesium compound and halogenated hydrocarbon compound, be typically chosen-
Between 20~100 DEG C, between preferably -20~60 DEG C.Incorporation time is typically chosen 30 minutes to 6 hours.
The step of preparing catalytic component（3）Alternatively referred to as settling step, completes the chlorine of magnesium titanium complex in this step
Change the alkoxy in reaction or chlorination reduction reaction, that is, chlorine element substitution magnesium titanium complex, while different halide reagents
The valence state of titanium compound can also be reverted to compared with lower valency, so that catalyst active center's group precipitates analysis from solution
Go out.Magnesium titanium complex clear solution can be carried out with the contact method of halide reagent using any of suitable method, can
With by the way of magnesium titanium complex solution is progressively added drop-wise in halide reagent solution, it would however also be possible to employ by halide reagent solution
Progressively it is added drop-wise to the mode in magnesium titanium complex solution.Rate of addition is generally selected not cause the hot-spot of reaction to be defined,
Generally it is stirred during dropwise addition and is beneficial to steadily carrying out for reaction.In the precipitation reaction step, temperature can be controlled
Between -20~100 DEG C, preferably between -20~80 DEG C.The reaction time of settling step should be long enough to obtain complete
Precipitation, the reaction time can last 1 minute to 10 hours, preferably 0.5~5 hour.
Experiment finds, after settling step, preferably suspension it is quiet it is heavy after extrude a part of supernatant, then in a constant temperature
Degree lower reaction a period of time carries out maturation process to the particle shape of catalyst than advantageous, and it can become the size distribution of catalyst
It is narrow, while the intensity of catalyst particle can also be improved, so as to reduce particle of the catalyst during catalyzed ethylene polymerization break
Broken phenomenon.The temperature of the temperature of maturation process generally greater than or equal to precipitation reaction, curing temperature can be controlled at 40~100 DEG C
Between, preferably between 40~85 DEG C.The time of slaking reaction can be controlled at 0.5~15 hour, preferably 1~5 hour.
After maturation process is carried out, typically to be washed, to remove shape in excessive reactant and preparation process
Into accessory substance, any atent solvent is used equally to this washing step, for example, can select iso-butane, pentane, n-hexane, heptan
Alkane or hexamethylene and its mixture etc., generally select the atent solvent that n-hexane is washing in experiment.After washing, catalyst hangs
Supernatant liquid can be dried by being purged with nitrogen under heating state, to obtain the powder of catalytic component.
Third object of the present invention is to provide a kind of catalyst for ethylene polymerization, and it includes following components
Product：
(a) above-mentioned catalytic component for ethylene polymerization；
B a kind of () formula is AlRnX3-nOrgano-aluminum compound, R is C that is identical or differing in formula1-8Alkyl, X is
Halogen, n is the integer of 1 ＜ n≤3.
Component (b) can be used in mixed way from one or more alkyl aluminum, preferably AlEt3、Al(iso-Bu)3、Al
(n-C6H13)3、Al(n-C8H17)3、AlEt2At least one in Cl.
Catalyst of the present invention is applied to the homopolymerization of various ethene or the combined polymerization of ethene and other α-alkene,
Wherein alpha-olefin is using the one kind in propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- octenes, 4- methylpentenes -1.This catalyst
Suitable for vapor phase method, slurry polymerization technique.
Catalytic component of the invention and its catalyst have the advantages that：
1. the catalytic component even particle size distribution, few for the fine polymer powder content obtained by ethylene polymerization；
2. the catalytic component has polymerization activity higher, while hydrogen response is good；
3. catalyst preparation process is simple, accessory substance is few, environmentally friendly.
Specific embodiment
The present invention is illustrated with embodiment below, but is not intended to limit the scope of the invention.
Method of testing：
Catalyst grain size distribution：It is measured on the MASTERSIZE2000 particles distribution instruments of Malvern company of Britain
Melt index：Determined according to ASTM D1238 standard methods
Embodiment 1
(1) magnesium dichloride 14.9g is weighed, 120ml butyl titanates are added, 140 DEG C of stirring reactions is warming up to until being formed
Clear solution, treats that solution temperature is cooled to close to room temperature, adds toluene 100ml, is uniformly mixed, and the solution for obtaining takes out standby
With.
(2) 10 milliliter is taken（1）The solution that step is obtained, plus 30 milliliters of hexane dilutions, addition 3.0ml1,4- dichloroetane,
Reaction is stirred at room temperature overnight.
(3) under normal temperature with constant pressure addition pipe to being slowly added dropwise 12.5 milliliters of Dichloroethyls of 3.0M in second step product
Aluminum solutions, after being added dropwise to complete, rise bath temperature to 45 DEG C and react 1 hour, and then 60 DEG C of stirring reactions obtain catalytic component for 4 hours and hang
Supernatant liquid.
（4）Catalytic component suspension temperature is down to room temperature, is stood, sedimentation is washed three times with hexane, each hexane
Consumption is 80 milliliters, after the completion of washing, in the case of 65 DEG C of bath temperature, drying is purged with high pure nitrogen, obtains brown solid flowing
Property powder.
Evaluating catalyst：The catalyst of 1L hexanes, 1mmol triethyl aluminums and 10-20mg is added to the stirring of 2L stainless steels
In kettle, temperature is then brought up to 90 DEG C, then the hydrogen of disposable addition 0.4MPa maintained the gross pressure of system with ethene
Polymerisation is carried out in 1.0MPa, after reacting 2 hours, stops adding ethene, cooling, pressure release, polyethylene powder to weigh, calculating is urged
The activity of agent, tests the bulk density and the melt index under 2.16Kg loads of polyethylene powder, as a result as shown in table 1.
Embodiment 2
By the 3.0ml1 in catalyst preparation step (2), 4- dichloroetane is changed to 6.0 milliliters, the same embodiment of other conditions
1.With embodiment 1, polymerization result is shown in Table 1 to the slurry polymerization appreciation condition of catalyst.
Embodiment 3
3.0 milliliters of Isosorbide-5-Nitrae-dichloroetane in catalyst preparation step (2) are changed to 2.0 milliliters of 2- chloro-2-methyl propane,
Other conditions are with embodiment 1.With embodiment 1, polymerization result is shown in Table 1 to the slurry polymerization appreciation condition of catalyst.
Embodiment 4
The Dichloroethyl aluminum solutions of 12.5 milliliters of 3.0M in catalyst preparation step (3) are changed to 10ml titanium tetrachlorides,
Other conditions are with embodiment 1.With embodiment 1, polymerization result is shown in Table 1 to the slurry polymerization appreciation condition of catalyst.
Comparative example 1
(1) 114 grams of diethoxy magnesium are weighed, 340 milliliters of butyl titanates are added, in 140 DEG C of stirring and dissolving until being formed
Clear solution, room temperature is down to by solution temperature, is added 400 milliliters to dry hexane and is diluted standby.
(2) 9 milliliter is taken（1）The solution that step is obtained, 15 milliliters of hexanes of 3M ethyl aluminum dichlorides are slowly added dropwise with buret
Solution, after being added dropwise to complete, the curing in 4 hours of 60 DEG C of stirring reactions obtains catalyst suspension.
(3) catalyst suspension temperature is down to room temperature, is stood, sedimentation is washed three times, the consumption of each hexane with hexane
It is 50 milliliters, after the completion of washing, in the case of 65 DEG C of bath temperature, drying is purged with high pure nitrogen, obtains brown solid mobility powder
End.
With embodiment 1, polymerization result is shown in Table 1 to the slurry polymerization appreciation condition of catalyst.
Comparative example 2
(1) 114 grams of diethoxy magnesium are weighed, 340 milliliters of butyl titanates are added, in 140 DEG C of stirring and dissolving until being formed
Clear solution, room temperature is down to by solution temperature, is added 400 milliliters to dry hexane and is diluted standby.
(2) 9 milliliter is taken（1）The solution that step is obtained, mixes and stands overnight with 0.5 milliliter of ethyl benzoate.By its temperature
Degree maintains 35 DEG C, and 15 milliliters of hexane solutions of 3M ethyl aluminum dichlorides are slowly added dropwise with buret, after being added dropwise to complete, 60 DEG C of stirrings
Reaction curing in 4 hours obtains catalyst suspension.
(3) catalyst suspension temperature is down to room temperature, is stood, sedimentation is washed three times, the consumption of each hexane with hexane
It is 50 milliliters, after the completion of washing, in the case of 65 DEG C of bath temperature, drying is purged with high pure nitrogen, obtains brown solid mobility powder
End.
With embodiment 1, polymerization result is shown in Table 1 to the slurry polymerization appreciation condition of catalyst.
The analysis result of table 1
Catalyst activity of the present invention is can be seen that from the experimental data of the embodiment of table 1 and comparative example keep higher level, and
The melt index of the polymer for obtaining is significantly increased, and illustrates that catalyst hydrogen response is good.The granularity point of gained catalyst of the invention
Cloth is narrower, and the bulk density of resulting polymers is improved.
Claims (16)
1. a kind of product of catalytic component for ethylene polymerization, including following component：
(1) magnesium compound
(2) oxygen containing titanium compound
(3) halogenated hydrocarbon compound
(4) halide reagent
Described magnesium compound is by formula (I) Mg (0R1)mCl2-mIt is shown, wherein R1It is C2~C20Alkyl, be saturation or insatiable hunger
The straight chain of sum, side chain or closed chain, m is the integer of 0≤m≤2；
Described oxygen containing titanium compound is by formula (II) Ti (OR2)nCl4-nIt is shown, R in formula2It is C2~C20Saturation or insatiable hunger
The straight chain of sum, side chain or ring-type chain alkylene, n is the integer of 0 ＜ n≤4；
Described halogenated hydrocarbon compound be selected from a halogenated hydrocarbons, dihalo hydrocarbon, polyhalohydrocarbon, saturated halogenated hydrocarbon, unsaturated halogenated hydrocarbons,
At least one in aromatic halohydrocarbon, primary halogenated hydrocarbons, secondary halogenated hydrocarbons and tertiary halogenated hydrocarbons；
Described halide reagent is by formula (III) R3 aMXbShown, M is three, four, five major elements or transition metal, X in formula
It is halogen, R3It is to contain C2~C20Alkyl, a=1 or 2, b=1,2 or 3；
The catalytic component is prepared from by following steps：(1) by formula (I) magnesium compound and formula (II) oxygen-containing titanium compound
Reaction forms magnesium titanium compound clear solution；(2) step (1) is obtained into product with halogenated hydrocarbon compound in -20~100 DEG C of reactions
Obtain clear solution；(3) solution for obtaining step (2) forms precipitation with formula (III) compound haptoreaction, obtains catalyst
The suspension of component；(4) suspension that step (3) is obtained is reacted into certain hour at a certain temperature, it is quiet to sink, wash, drying
Catalyst fines, or suspension that step (3) is obtained is quiet heavy, removes a part of supernatant, diluent is added, one
Determine to react certain hour at temperature, it is quiet to sink, wash, being dried to obtain catalytic component.
2. a kind of catalytic component for ethylene polymerization according to claim 1, it is characterised in that described halogen
It is in the chlorinated hydrocarbon compounds of liquid condition for hydrocarbon compound.
3. according to a kind of catalytic component for ethylene polymerization that one of claim 1-2 is described, it is characterised in that each
The material ratio of component is planted in terms of every mole of magnesium in component (1), component (2) is 0.1~20 mole, and component (3) is rubbed for 0.1~20
You, component (4) is 0.5~50 mole.
4. a kind of catalytic component for ethylene polymerization according to claim 3, it is characterised in that various components
Material ratio in terms of every mole of magnesium in component (1), component (2) is 0.5~10 mole, and component (3) is 0.1~12 mole, component
(4) it is 1.0~10 moles.
5. a kind of catalytic component for ethylene polymerization according to claim 1, it is characterised in that halo hydrocarbonylation
Compound be selected from 1-chlorobutane, Sec-Butyl Chloride, Isosorbide-5-Nitrae-dichloroetane, 2- chloro-2-methyl propane, carbon tetrachloride, 1,2- dichloroethanes,
1,2- dichloropropane, 2,2- dichloropropanes, chlorobenzene, chloroform, benzotrichloride, chlorotoluene, in chlorocyclohexane at least one
Kind.
6. a kind of catalytic component for ethylene polymerization according to claim 5, it is characterised in that halo hydrocarbonylation
Compound be selected from Isosorbide-5-Nitrae-dichloroetane, 2- chloro-2-methyl propane, 1,2- dichloroethanes, 1,2- dichloropropane, 2,2- dichloropropanes,
At least one in chlorocyclohexane.
7. a kind of catalytic component for ethylene polymerization according to claim 1, it is characterised in that halide reagent
Selected from the aluminium ethide of dichloro one, aluminium diethyl monochloride, ethylaluminum sesquichloride, dichloro aluminium isobutyl, a chloro-di-isobutyl aluminum, dichloro
Isopropyl aluminium, a chlorine diisopropyl aluminium.
8. a kind of catalytic component for ethylene polymerization according to claim 7, it is characterised in that halide reagent
Selected from the aluminium ethide of dichloro one, ethylaluminum sesquichloride, dichloro aluminium isobutyl, two chloro isopropyl aluminium.
9. a kind of catalytic component for ethylene polymerization according to claim 1, it is characterised in that oxygen-containing titanizing
R in the formula of compound2It is C2~C10Alkyl, n=4.
10. a kind of catalytic component for ethylene polymerization according to claim 9, it is characterised in that oxygen-containing titanizing
Compound is butyl titanate.
A kind of 11. catalytic components for ethylene polymerization according to claim 1, it is characterised in that magnesium compound
Selected from least one in alkoxyl magnesium and magnesium dichloride.
A kind of 12. catalytic components for ethylene polymerization according to claim 11, it is characterised in that alkoxy
Magnesium is selected from least one in diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium and two octyloxy magnesium.
The preparation method of one of the 13. claim 1-12 described catalytic component for ethylene polymerization, including it is following
Step：(1) formula (I) magnesium compound and formula (II) oxygen-containing titanium compound are reacted and forms magnesium titanium compound clear solution；(2)
Step (1) is obtained into product and reacts to obtain clear solution at -20~100 DEG C with halogenated hydrocarbon compound；(3) step (2) is obtained
Solution forms precipitation with formula (III) compound haptoreaction, obtains the suspension of catalyst component；(4) step (3) is obtained
Suspension react certain hour at a certain temperature, quiet heavy, washing, dry catalyst fines, or step (3) is obtained
Suspension it is quiet heavy, remove a part of supernatant, add diluent, certain hour is reacted at a certain temperature, it is quiet to sink, wash
Wash, be dried to obtain catalytic component.
The preparation method of 14. catalytic components for ethylene polymerization according to claim 13, it is characterised in that
The reaction temperature of step (1) is less than 200 DEG C, and the reaction time is 1 to 20 hour, and the reaction time of step (2) is 30 minutes to 6 small
When, the reaction temperature of step (3) is -20~100 DEG C, and the reaction time is 1 minute to 10 hours, and the reaction temperature of step (4) is
40~100 DEG C, the reaction time is being 0.5~15 hour.
A kind of 15. catalyst for ethylene polymerization, including one of component (a) claim 1-12 it is described for ethene
The catalytic component of polymerisation；A kind of formula of component (b) is AlRnX3-nOrgano-aluminum compound, R is identical or not phase in formula
Same C1-8Alkyl, X is halogen, and n is the integer of 1 ＜ n≤3.
The application of catalyst described in 16. claims 15 in ethylene polymerization.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1263895A (en) * | 1999-02-14 | 2000-08-23 | 中国石油化工集团公司北京化工研究院 | Catalyst for polymerization or copolymerization of ethylene and its preparing process and application |
| CN1986575A (en) * | 2005-12-22 | 2007-06-27 | 北京燕化高新催化剂有限公司 | Preparing process of slurry catalyst for gaseous ethylene polymerization |
| CN101134790A (en) * | 2006-09-01 | 2008-03-05 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization reaction and catalyst |
| CN102030845A (en) * | 2009-09-29 | 2011-04-27 | 中国石油化工股份有限公司 | Catalyst component used for vinyl polymerization reaction and catalyst thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263895A (en) * | 1999-02-14 | 2000-08-23 | 中国石油化工集团公司北京化工研究院 | Catalyst for polymerization or copolymerization of ethylene and its preparing process and application |
| CN1986575A (en) * | 2005-12-22 | 2007-06-27 | 北京燕化高新催化剂有限公司 | Preparing process of slurry catalyst for gaseous ethylene polymerization |
| CN101134790A (en) * | 2006-09-01 | 2008-03-05 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization reaction and catalyst |
| CN102030845A (en) * | 2009-09-29 | 2011-04-27 | 中国石油化工股份有限公司 | Catalyst component used for vinyl polymerization reaction and catalyst thereof |
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