CN105330770B - A kind of catalyst and its application for ethylene slurry polymerization - Google Patents
A kind of catalyst and its application for ethylene slurry polymerization Download PDFInfo
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- CN105330770B CN105330770B CN201410273530.3A CN201410273530A CN105330770B CN 105330770 B CN105330770 B CN 105330770B CN 201410273530 A CN201410273530 A CN 201410273530A CN 105330770 B CN105330770 B CN 105330770B
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Abstract
The invention proposes a kind of for the carried catalyst of ethylene slurry polymerization and the composition of the catalyst and preparation method, and wherein catalyst is grouped as by tri- groups of A, B, C.Wherein component A is that magnesium halide is dissolved in organic epoxy compound object, organic phosphorus compound, electron donor compound to form homogeneous solution, by TiCl4It is slowly reacted at low temperature with magnesium halide homogeneous solution, photocatalyst crystals is precipitated, then pass through strict control temperature reaction, and obtain catalytic component A, B component is organo-aluminum compound, and component C is halogenated hydrocarbon compound, and there are two types of component C usage modes, (1) after component C is mixed with B component, it is added in ethylene polymerization system, (2) are separately added into A, B in polymerization reaction, C, three components.Polyethylene of the catalyst for ethylene slurry polymerization to obtain shows good mechanical property, while the polymerization activity of catalyst increases.
Description
Technical field
The present invention relates to a kind of systems for the olefinic polymerization especially catalyst of ethylene slurry polymerization and the catalyst
Preparation Method and application.
Background technique
Traditional Z-N catalyst is by classical titanium-Al catalysts, have developed to by the compound activatings such as magnesium chloride,
Other various organic compounds modified stage；And by simple raising catalyst activity, develops to and urged by adjusting
Agent improves the performances of polymeric articles.
Since the seventies, the companies such as Mitsui petro chemical industry Co., Ltd. succeed in developing a variety of is with magnesium chloride
The Ti-Mg high-effective carrier catalyst of carrier makes world's slurry process production polyolefin industry obtain quick development.
The method of vinyl polymerization disclosed in Japan Patent JP49-51378 and combined polymerization, the catalyst are that Ti/Mg is efficient
Carried catalyst.The catalyst preparation process is simple, and reaction condition is not harsh, and operation is easier to.But since the catalyst is adopted
Magnesium halide is dissolved with the biggish alcohols of different polarities and alkane solvents, prevent magnesium halide generates equal from being dissolved completely
Phase solution is only the magnesium halide slurries for generating a kind of particulate soliquid or swelling.Thus give prepared catalyst strips
Carry out some disadvantages related with magnesium halide stratiform crystallization property, if prepared polymer apparent density is lower, particle shape and
It is distributed bad etc..
CN1229092A proposes a kind of preparation of catalyst and the catalyst for ethylene homo conjunction or combined polymerization
Method, wherein catalyst be organic epoxy compound object is dissolved in by magnesium halide, organic phosphorus compound adds the electron bodily form
It at homogeneous solution, then acts on and obtains at least one precipitation additive and the halide of transition metals Ti or derivatives thereof, gather
When conjunction in conjunction with organo-aluminum compound.The catalyst preparation process is simple, shows very high activity for vinyl polymerization, simultaneously
The particle shape of resulting polymers is preferable, and apparent density is higher, but catalyst is not good enough to the sensibility of hydrogen.
Halogenated hydrocarbons is successfully used for vanadium series catalyst as the accelerative activator of catalyst, and has been successfully applied to gas phase
Method polyethylene industrial production.Vanadium series catalyst activity can be made to improve 4-10 times due to joined promotor.Chinese patent
CN1189505A is disclosed, and traditional titanium Z/N type catalyst is rubbed using suitable halogenated hydrocarbons with titanium when being used for ethene gas-phase polymerization
You than when, catalyst activity improve 80-200%.
The present invention introduces halogenated hydrocarbon compound in special catalyst system, is found by lot of experiments, halogenated hydrocarbons
The addition activity of catalyst not only can be improved, and polyethylene can be improved mechanical property obtain its tensile yield strength
To raising.
Summary of the invention
The object of the present invention is to provide a kind of catalyst systems for slurry olefin polymerization, in catalyst system
Halogenated hydrocarbon compound is introduced, the mechanical property that the activity of catalyst not only can be improved, but also polyethylene can be improved makes its drawing
Yield strength is stretched to be improved.
A kind of catalyst system for slurry olefin polymerization of the present invention, including following components：
(A) ingredient of solid catalyst of titaniferous is that organic epoxy compound object, organic phosphorus chemical combination are dissolved in by magnesium halide
Object add electron donor formed homogeneous solution, be slowly added in above-mentioned homogeneous solution transition metals Ti halide or its spread out
Biology is washed with inert diluent, obtains ingredient of solid catalyst；
(B) organo-aluminum compound；
(C) halogenated hydrocarbon compound.
The molar ratio of the halogenated hydrocarbon compound and titanium is 0.01~50, preferably 0.1~10.
The general formula of the halogenated hydrocarbon compound is R1R2X4-b, R in formula1It is C1~C20Alkyl or aromatic radical, R2It is C1~
C20Alkyl, b 1,2 or 3, X are F, Cl, Br.Particular compound includes monochlorethane, a chloropropane, a chlorobutane, a chlorine penta
Alkane, a chlorohexane, 1,2- dichloroethanes, 1,3- dichloropropane, 1,4- dichloroetane, 1,5- dichloropentane, 1,6- dichloro hexane,
One or more of chloroform, monochloro-benzene, dichloro-benzenes.
The halogenated hydrocarbon compound using when can have following several method：(1) first by organo-aluminum compound when polymerizeing
React to obtain mixture in advance with halogenated hydrocarbon compound, preparation method is halogenated hydrocarbons after diluting at -10~10 DEG C, with 0
~60 DEG C are to be slowly dropped in organo-aluminum compound under optimum condition, and rate of addition is 0.1~0.5ml/min；(2) it polymerize
When organo-aluminum compound and halogenated hydrocarbon compound be separately added into paradigmatic system.
Magnesium halide described in component (A) includes the complex compounds such as magnesium dihalide, the water of magnesium dihalide or alcohol, magnesium dihalide point
The derivative that one of halogen atom is replaced by oxyl or halocarbon oxygroup in minor, above-mentioned magnesium dihalide are specially dichloride
Magnesium, magnesium dibromide, magnesium diiodide.It wherein, is best with magnesium dichloride.
The magnesium halide granularity used is to stir preferably lower easy dissolution, and solution temperature is -10 DEG C~150 DEG C, with 20 DEG C
~130 DEG C preferably.It can add when dissolution or inert diluent is not added such as：Benzene,toluene,xylene, 1,2- dichloroethanes, chlorobenzene with
And other hydro carbons or halogenated hydrocarbon compound.Wherein, benzene,toluene,xylene is preferable, and toluene, dimethylbenzene are best.
Organic epoxy compound object described in component (A) includes aliphatic olefin of the carbon atom number 2~8, alkadienes halogen
The compounds such as the oxide of fat subsitutes race alkene or alkadienes, glycidol ether, inner ether.Particular compound is such as：Ethylene oxide, ring
Ethylene Oxide, epoxy butane, epoxychloropropane, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran etc..Wherein, preferably
Be ethylene oxide, propylene oxide, epoxychloropropane, tetrahydrofuran, be best with tetrahydrofuran, epoxychloropropane.
Organic phosphorus compound described in component (A) includes the hydrocarbyl carbonate or halogenation hydrocarbyl carbonate of orthophosphoric acid or phosphorous acid.Tool
Body is such as：Orthophosphoric acid trimethyl, orthophosphoric acid triethyl, orthophosphoric acid tributyl, triphenyl phosphite, Trimethyl phosphite, phosphorous acid
Triethyl, tributyl phosphite, triphenyl phosphite, phosphorous acid benzene methyl etc..Wherein, preferably orthophosphoric acid trimethyl, just
Triethyl phosphate and orthophosphoric acid tributyl, orthophosphoric acid tributyl are best.
Electron donor described in component (A) can be selected from C1~C20Alcohol or isomery alcohol, such as：Methanol, ethyl alcohol, third
Alcohol, isopropanol, butanol, isobutanol, 2-Ethylhexyl Alcohol, n-octyl alcohol, lauryl alcohol, glycerine, amylalcohol, decyl alcohol, dodecanol, 18
Alkanol, Bian alcohol, benzyl carbinol, with C1~C8Straight chain alcohol be best.
Alkyl metal cpd can be also added in magnesium halide described in component (A) during dissolution forms homogeneous solution
Such as zinc alkyl and/or alkyl aluminum.
Organo-silicon compound can also be added in component (A), the general formula of organo-silicon compound is R1 XR2 YSi(OR3)z, wherein
R1And R2Respectively alkyl or halogen, R3For alkyl, 0≤x≤2,0≤y≤2 and 0≤z≤4, and x+y+z=4.Particular compound
Including：Tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silicon, silicon tetrachloride etc..
In terms of every mole of magnesium halide, organic epoxy compound object 0.01~10 rubs molar ratio in component (A) between each component
You, preferably 0.02~4 mole；0.01~10 mole of organic phosphorus compound, preferably 0.02~4 mole；Electron donor 0.005
~15 moles, preferably 0.05~10 mole；0~2 mole of alkyl metal cpd, preferably 0~0.5 mole；Transition metal
The halide of titanium or 0.2~20 mole of derivative；Organo-silicon compound are 0.05~1 mole.Titaniferous amount is in component (A)
1wt%~8wt%.
The preparation method of component A：Magnesium halide is dissolved in organic epoxy compound object and organic phosphorus compound under stiring
Electron donor is added, homogeneous transparent solution is formed, adds or be not added alkyl metal cpd, at a temperature of -35~60 DEG C, most
It is -30~10 DEG C good, the halide of transition metals Ti or derivative are instilled into magnesium halide homogeneous solution, can be added at -30~110 DEG C
Enter organo-silicon compound, be filtered, washed, obtains component A solids.
Component (B) organo-aluminum compound is alkyl aluminum compound.Wherein the molar ratio computing of aluminium and titanium be 100~
0.001, preferably 10~0.01, preferably 1~0.1.
Catalyst A, B of the present invention, component C may be directly applied to polymerization system, and condensate is applied to after can also being first complexed in advance
System.
Catalyst of the invention can be used for the homopolymerization of ethylene, it can also be used to which the combined polymerization of ethylene and alpha-olefin, copolymerization are single
Propylene, butylene, amylene, hexene, octene, 4- methyl 1- amylene can be used in body.
Polymerization process includes the following steps：(1) preparation of component A：Magnesium halide is dissolved in organic epoxidation under stiring
It closes and adds electron donor in object and organic phosphorus compound, form homogeneous transparent solution, add or be not added alkyl metal cpd,
At a temperature of -35~60 DEG C, best -30~10 DEG C, it is uniformly molten that the halide of transition metals Ti or derivative are instilled into magnesium halide
Liquid can be filtered, washed in -30~110 DEG C of addition organo-silicon compound, obtain component A solids；(2) in reaction unit
In, component B organo-aluminum compound, component C halogenated hydrocarbon compound are mixed with component A, carry out vinyl polymerization.
Component B organo-aluminum compound and component C halogenated hydrocarbon compound in step (2) can also be reacted in advance and be mixed
Then object is mixed with component A again, carry out vinyl polymerization.
When using the method that halogenated titanium is added dropwise, time for adding was preferably controlled within 5 hours, when being gradually warmed up, was risen
Warm speed to heat up preferably 4~100 DEG C per hour.
By above-mentioned steps, (A) component of invention catalyst system is made, this component can be with solids or suspension
Form use.
Liquid phase polymerization can be used when polymerization, gas-phase polymerization can also be used.When carrying out liquid phase polymerization, can be used propane,
Hexane, heptane, hexamethylene, iso-butane, isopentane, naphtha, raffinate oil, hydrogasoline, kerosene, benzene,toluene,xylene etc. it is full
Make reaction medium with atent solvents such as aliphatic hydrocarbon or aromatic hydrocarbon, prepolymerization can be first carried out before polymerization.Polymerization methods can use
Intermittent, semi continuous or continous way.Polymerization temperature is room temperature~150 DEG C, preferably 50 DEG C~100 DEG C.In order to adjust polymerization
The molecular weight of object makees molecular weight regulator using hydrogen.
Due to the component A in catalyst system and organo-aluminum compound and halogenated hydrocarbon compound collective effect, institute of the present invention
When the catalyst system stated is used for slurry polymerization, higher catalytic activity is not only embodied, but also obtained polymer has
Higher tensile yield strength.
Specific embodiment
Following embodiment is to describe to more detailed citing of the invention, but the invention is not limited to these embodiments.
Embodiment 1
The preparation of catalytic component (A)：Through high-purity N2In the reactor being sufficiently displaced from, it is anhydrous to sequentially add 4.0g
MgCl2, 50mL toluene, 2.0mL epoxychloropropane, 3.0mL tributyl phosphate, be warming up to 50 DEG C under stirring, and maintain 15 minutes,
Add 6.0mL ethyl alcohol, the reaction was continued 15 minutes, which is cooled to -5~0 DEG C, then 30mL titanium tetrachloride is added dropwise to above-mentioned chlorine
Change in magnesium homogeneous solution, add 5ml tetraethoxy-silicane, solution is warming up to 80 DEG C, removes mother liquor.4 times are washed with hexane, very
Sky is dry, obtains ingredient of solid catalyst A.
Vinyl polymerization 1：Hexane 1000mL, metering is added after H2 is sufficiently displaced from the stainless steel kettle that volume is 2 liters wherein
Containing 0.5mmolTi above-mentioned prepared ingredient of solid catalyst A, triethyl aluminum 1.0mmol.1,2- dichloroethanes, which is added, makes it
It is 1.5 with catalyst Ti molar ratio, is warming up to 70 DEG C plus hydrogen 0.26MPa, then is passed through ethylene to make to reach 0.73MPa (gauge pressure) in kettle,
At 85 DEG C, it polymerize 2 hours.
Vinyl polymerization 2：Hexane 1000mL is added wherein, urges after ethylene is sufficiently displaced from for the stainless steel kettle that volume is 2 liters
Agent (B) component triethyl aluminum 2.0mL, metering containing the above-mentioned prepared ingredient of solid catalyst A of 0.5mmolTi, be added 1,
2- dichloroethanes makes itself and catalyst Ti molar ratio 1.5, is warming up to 70 DEG C plus hydrogen 0.15MPa (gauge pressure), then be passed through ethylene to make
0.25MPa (gauge pressure) is reached in kettle, at 85 DEG C, is polymerize 2 hours.
Embodiment 2
Catalytic component (A) with embodiment 1, only will polymerization 1 and 2 in 1,2- dichloroethanes is added and make its in catalyst
The molar ratio of Ti is changed to 1.0.
Embodiment 3
Catalytic component (A) with embodiment 1, only will polymerization 1 and 2 in 1,2- dichloroethanes is added and make its in catalyst
The molar ratio of Ti is changed to 2.0.
Embodiment 4
Catalytic component (A) will be added chloroform and it made to rub with Ti in catalyst with embodiment 1 in polymerization 1 and 2
You are than being 1.0.
Embodiment 5
Catalytic component (A) will be added chloroform and it made to rub with Ti in catalyst with embodiment 1 in polymerization 1 and 2
You are changed to 1.5 by ratio.
Embodiment 6
Catalyst (A) component will be added chloroform and it made to rub with Ti in catalyst with embodiment 1 in polymerization 1 and 2
You are changed to 2.0 by ratio.
Embodiment 7
Catalyst (A) component will be added chloroform and make itself and catalyst Ti with embodiment 1 in polymerization 1 and 2, mole
Than being changed to 2.5.
Embodiment 8
Catalyst (A) component will be added chloroform and it made to rub with Ti in catalyst with embodiment 1 in polymerization 1 and 2
You are changed to 3.0 by ratio.
Embodiment 9
Catalyst (A) component will polymerize mole that 1- chlorobenzene is added in 1 and 2 and makes itself and Ti in catalyst with embodiment 1
Than being changed to 2.0.
Comparative example：Catalyst is synthesized with embodiment 1 (A) component,
Vinyl polymerization 1：Hexane 1000mL, metering is added after H2 is sufficiently displaced from the stainless steel kettle that volume is 2 liters wherein
Containing the above-mentioned prepared ingredient of solid catalyst of 0.5mmolTi, triethyl aluminum 1.0mmol.It is warming up to 70 DEG C plus hydrogen 0.26MPa
(gauge pressure), then being passed through ethylene keeps kettle interior up to 0.73MPa (gauge pressure), at 85 DEG C, polymerize 2 hours.
Vinyl polymerization 2：Hexane 1000mL is added wherein, urges after ethylene is sufficiently displaced from for the stainless steel kettle that volume is 2 liters
Agent (B) component 2.0mL, metering containing the above-mentioned prepared ingredient of solid catalyst of 0.5mmolTi, be warming up to 70 DEG C plus hydrogen
0.15MPa (gauge pressure), then being passed through ethylene keeps kettle interior up to 0.25MPa (gauge pressure), at 85 DEG C, polymerize 2 hours.
Test the tensile yield strength of polyethylene:By 1 powder 53% of polymerization, the ratio of 2 powders 47% of polymerization weighs poly- second
Alkene powder carries out Mechanics Performance Testing after evenly mixing.
Experimental result is shown in Table 1
1 polymerization result 1 of table
2 polymerization result 2 of table
When can be seen that catalyst system of the invention for slurry polymerization from the data of Tables 1 and 2, not only embody
Higher catalytic activity, and obtained polymer tensile yield strength with higher.
Claims (19)
1. a kind of catalyst for ethylene slurry polymerization, including following components：(A) ingredient of solid catalyst of titaniferous is
Be dissolved in organic epoxy compound object by magnesium halide, organic phosphorus compound add electron donor formed homogeneous solution, above-mentioned
It is slowly added to the halide or derivatives thereof of transition metals Ti in homogeneous solution, is washed with inert diluent, obtains consolidating for titaniferous
Body catalyst component；(B) organo-aluminum compound；(C) halogenated hydrocarbon compound is R selected from general formula1R2X4-bHalogenated hydrocarbon compound,
Chloroform, monochloro-benzene and dichloro-benzenes, R in formula1It is C1~C20Alkyl or aromatic radical, R2It is C1~C20Alkyl, b 1,2 or
3, X be F, Cl, Br.
2. a kind of catalyst for ethylene slurry polymerization according to claim 1, it is characterised in that the halogenated hydrocarbons
Compound is selected from monochlorethane, a chloropropane, a chlorobutane, a chloropentane, a chlorohexane, 1,2- dichloroethanes, 1,3- dichloro
Propane, Isosorbide-5-Nitrae-dichloroetane, 1,5- dichloropentane, 1,6- dichloro hexane, chloroform, monochloro-benzene, at least one in dichloro-benzenes
Kind.
3. a kind of catalyst for ethylene slurry polymerization according to claim 1, it is characterised in that the halogenated hydrocarbons
The molar ratio of compound and titanium is 0.01~50, and the dosage of component B is with the molar ratio computing of aluminium and titanium for 100~0.001.
4. a kind of catalyst for ethylene slurry polymerization according to claim 1, it is characterised in that the halogenated hydrocarbons
The molar ratio of compound and titanium is 0.1~10, and the dosage of component B is with the molar ratio computing of aluminium and titanium for 1~0.1.
5. a kind of catalyst for ethylene slurry polymerization according to claim 1, it is characterised in that the component (A)
In include general formula be R1 XR2 YSi(OR3)zOrgano-silicon compound, wherein R1And R2Respectively alkyl or halogen, R3For alkyl, 0≤
X≤2,0≤y≤2 and 0≤z≤4, and x+y+z=4.
6. a kind of catalyst for ethylene slurry polymerization according to claim 5, it is characterised in that the organosilicon
Compound is selected from tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silicon, silicon tetrachloride.
7. a kind of catalyst for ethylene slurry polymerization according to claim 1, it is characterised in that the magnesium halide
Including one of halogen atom in magnesium dihalide, the water of magnesium dihalide or alcohol complex, magnesium dihalide molecular formula by oxyl or
The derivative that halocarbon oxygroup is replaced.
8. a kind of catalyst for ethylene slurry polymerization according to claim 1, it is characterised in that organic ring
Oxygen compound include carbon atom number 2~8 aliphatic olefin, alkadienes, halogenated aliphatic alkene or alkadienes oxide,
Glycidol ether, interior ether compound.
9. a kind of catalyst for ethylene slurry polymerization according to claim 1, it is characterised in that described is organic phosphorus
Compound includes the hydrocarbyl carbonate or halogenation hydrocarbyl carbonate of orthophosphoric acid or phosphorous acid.
10. a kind of catalyst for ethylene slurry polymerization according to claim 1, it is characterised in that the component
It (A) further include alkyl metal cpd in.
11. a kind of catalyst for ethylene slurry polymerization according to claim 1, it is characterised in that with every mole of halogenation
Magnesium meter, 0.01~10 mole of organic epoxy compound object；0.01~10 mole of organic phosphorus compound；Electron donor 0.005~15 rubs
You；The halide of transition metals Ti or 0.2~20 mole of derivative.
12. a kind of catalyst for ethylene slurry polymerization according to claim 11, it is characterised in that with every mole of halogen
Change magnesium meter, 0.02~4 mole of organic epoxy compound object.
13. a kind of catalyst for ethylene slurry polymerization according to claim 11, it is characterised in that with every mole of halogen
Change magnesium meter, 0.02~4 mole of organic phosphorus compound.
14. a kind of catalyst for ethylene slurry polymerization according to claim 11, it is characterised in that with every mole of halogen
Change magnesium meter, 0.05~10 mole of electron donor.
15. a kind of catalyst for ethylene slurry polymerization according to claim 1, it is characterised in that by the halogen after dilution
It for hydrocarbon compound under the conditions of -10~10 DEG C, is slowly dropped in organo-aluminum compound, rate of addition is 0.1~0.5ml/
Min, then again with component A haptoreaction.
16. a kind of catalyst for ethylene slurry polymerization according to claim 1, it is characterised in that by organo-aluminium chemical combination
Object and halogenated hydrocarbon compound respectively with component A haptoreaction.
17. the application described in claim 1 for the catalyst of ethylene slurry polymerization in slurry polymerization, including following step
Suddenly：(1) preparation of component A：Magnesium halide is dissolved in organic epoxy compound object and organic phosphorus compound under stiring and is added
Electron donor forms homogeneous transparent solution, adds or be not added alkyl metal cpd, at a temperature of -35~60 DEG C, by transition metal
The halide or derivative of titanium instill magnesium halide homogeneous solution and are filtered, washed, obtain in 30~110 DEG C of addition organo-silicon compound
To component A solids；(2) in reaction unit, component B organo-aluminum compound, component C halogenated hydrocarbon compound are mixed with component A,
Carry out vinyl polymerization.
18. application of the catalyst described in claim 17 for ethylene slurry polymerization in slurry polymerization, it is characterised in that
In step (1) at a temperature of -30~10 DEG C, the halide of transition metals Ti or derivative are instilled into magnesium halide homogeneous solution.
19. the application according to claim 17 for the catalyst of ethylene slurry polymerization in slurry polymerization, feature
It is that component B organo-aluminum compound and component the C halogenated hydrocarbon compound in step (2) react in advance and obtains mixture, then again
It is mixed with component A, carries out vinyl polymerization.
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| CN101139407A (en) * | 2006-09-07 | 2008-03-12 | 北京金鼎科化工科技有限公司 | Catalyst active component for ethylene polymerization or copolymerization and catalyst precursor comprising the active component and preparation method thereof |
| CN102977232A (en) * | 2011-09-02 | 2013-03-20 | 中国石油化工股份有限公司 | Catalyst system for ethylene polymerization |
| CN102977235A (en) * | 2011-09-02 | 2013-03-20 | 中国石油化工股份有限公司 | Titanium-containing solid catalyst component for ethylene polymerization and catalyst system composed of the titanium-containing solid catalyst component |
| CN103772543A (en) * | 2012-10-19 | 2014-05-07 | 中国石油化工股份有限公司 | Ethylene polymerization catalyst and production method thereof |
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| CN1189505A (en) * | 1997-01-31 | 1998-08-05 | 台湾聚合化学品股份有限公司 | Ti family catalyst system capable of polymerizing olefines |
| CN1086191C (en) * | 1998-03-17 | 2002-06-12 | 中国石油化工集团公司 | Catalyst for ethylene polymerization or copolymerization and preparation method thereof |
| CN103772550B (en) * | 2012-10-23 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of catalyst component for polymerization of ethylene and catalyst thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101139407A (en) * | 2006-09-07 | 2008-03-12 | 北京金鼎科化工科技有限公司 | Catalyst active component for ethylene polymerization or copolymerization and catalyst precursor comprising the active component and preparation method thereof |
| CN102977232A (en) * | 2011-09-02 | 2013-03-20 | 中国石油化工股份有限公司 | Catalyst system for ethylene polymerization |
| CN102977235A (en) * | 2011-09-02 | 2013-03-20 | 中国石油化工股份有限公司 | Titanium-containing solid catalyst component for ethylene polymerization and catalyst system composed of the titanium-containing solid catalyst component |
| CN103772543A (en) * | 2012-10-19 | 2014-05-07 | 中国石油化工股份有限公司 | Ethylene polymerization catalyst and production method thereof |
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