CN102875705A - Catalyst component and catalyst for ethylene polymerization - Google Patents
Catalyst component and catalyst for ethylene polymerization Download PDFInfo
- Publication number
- CN102875705A CN102875705A CN2011101946943A CN201110194694A CN102875705A CN 102875705 A CN102875705 A CN 102875705A CN 2011101946943 A CN2011101946943 A CN 2011101946943A CN 201110194694 A CN201110194694 A CN 201110194694A CN 102875705 A CN102875705 A CN 102875705A
- Authority
- CN
- China
- Prior art keywords
- general formula
- catalyst component
- magnesium
- catalyst
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a catalyst component and a catalyst used for ethylene polymerization. The catalyst comprises a reaction product of the following components of (1) a magnesium compound, (2) an oxygen-containing titanium compound, (3) a halide improver, and (4) a halogenation reagent. Compared a conventional catalyst, the catalyst provided by the invention is obviously improved in activity, has the characteristics of excellent hydrogen responsiveness, relatively good bulk density of the polymerization product, etc. The fine powder content of the polymer is increased significantly; the preparation process is simple; and the catalyst is suitable for use in an apparatus of a slurry polymerization process.
Description
Technical field
The present invention relates to a kind of for olefinic polymerization particularly catalyst component and the catalyzer of vinyl polymerization, and the preparation method of this catalyzer and application.
Technical background
Mg-Ti is in the Ziegler-Natta catalyst composition production olefin polymer process in use, we wish that polymerization catalyst is active enough high, residual will as far as possible reduce of catalyzer in polymkeric substance so, the residual character that can not affect polymkeric substance of catalyzer in polymkeric substance, so just not needing to remove catalyst residue from polymkeric substance, is useful to reducing production costs and simplifying production technique.
US Patent No. 4363746 has been announced the in the past much higher catalyzer of many polymerizing catalysts of a kind of specific activity, magnesium metal halide such as magnesium dihalide and four titan-alkoxides are reacted, then this solution and a kind of organo-metallic reductive agent reaction, obtain a kind of solids, and then this solids and a kind of halide ion exchanging source, such as titanium tetrachloride reaction, although the catalyzer activity of this method preparation is higher, this catalyzer fine powder content in application is more.
In Chinese patent CN1129709, by in the catalyzer preparation, using the benzoates electronic donor compound capable, improve the tap density of activity, hydrogen response and the polymerisate of catalyzer.Wherein except alcohols, phenols, silicane and the polysiloxane-based electron donor(ED).
CN85105150 provides the polymerizing catalyst that can make productivity and fine polymer powder reach good equilibrium, with metal halide such as MgCl
2With titanium compound, such as Ti (OEt)
4Reaction, form the first catalyst component, then the first catalyst component mixes in-100 ℃～70 ℃ scopes with organo-aluminium compound, is heated 50 ℃～110 ℃ comparatively high temps again, form additional throw out, at last with gained solid and halogenating agent reaction.
The inventor is by repeatedly experiment discovery, by preparation method of the present invention, introduce the halogenide improving agent, can obtain the catalyzer that polymerization activity significantly improves, the hydrogen responsiveness is good, and the resulting polymers fine powder content compared with prior art has clear improvement, and preparation is simple.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst component for ethylene polymerization and catalyzer thereof, and the preparation method of this catalyst component, compare with existing catalyzer, this catalyst activity obviously improves, the fine polymer powder content that has simultaneously good hydrogen responsiveness and obviously improve.
A kind of catalyst component for ethylene polymerization of the present invention, this catalyst component comprises the reaction product of following component:
(1) magnesium compound is by general formula (I) Mg (0R
1)
mCl
2-mShown in, R wherein
1C
2～C
20Alkyl, optional be saturated or undersaturated straight chain, side chain or closed chain, 0≤m≤2;
(2) oxygen containing titanium compound is by general formula (II) Ti (OR
2)
nCl
4-nShown in, R in the formula
2C
2～C
20Alkyl, optional be saturated or undersaturated straight chain, side chain or closed chain, 0＜n≤4;
(3) halogenide improving agent is by general formula (III) ClOR
3 pR
4X
aOr general formula (IV) HOR
3 pR
4X
aShown in, R wherein
3Be C
1～C
6Aliphatic group or aryl radical, p=0 or 1; R
4X
aC for the halogen replacement
1～C
6Aliphatic group or aryl radical, X is F, Cl, Br, a=0 in the general formula (III), 1,2,3, a=1 in the general formula (IV), 2,3;
(4) halide reagent is by logical formula V R
5 bMX
cShown in, M is three, four, five main group element or transition metals in the formula, X is halogen, R
5To contain C
2～C
20The alkyl of carbon atom, b=0,1 or 2, c=1,2,3 or 4.
Magnesium compound described in the component (1) is by general formula (I) Mg (0R
1)
mCl
2-mShown in, R wherein
1C
2～C
20Alkyl, be saturated or undersaturated straight chain, side chain or closed chain, 0≤m≤2.Magnesium compound is selected from alkoxyl magnesium compound, halogenated magnesium compound or its miscellany, is selected from least a in magnesium dichloride, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, the two octyloxy magnesium.
Oxygen containing titanium compound is by general formula (II) Ti (OR in the component (2)
2)
nCl
4-nShown in, R in the formula
2C
2～C
20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, 0＜n≤4; The preferred tetravalent titanium compound that uses, because they are in a liquid state usually at normal temperatures, and also also fine with the consistency of some solvents under normal conditions.In the general formula (II), preferred R
2Be C
2～C
10Alkyl, n=4, wherein tetrabutyl titanate is the most commonly used.
Component (3) halogenide improving agent is by general formula (III) ClOR
3 pR
4X
aOr general formula (IV) HOR
3 pR
4X
aShown in, R wherein
3Be C
1～C
6Aliphatic group or aryl radical, p=0 or 1; R
4X
aC for the halogen replacement
1～C
6Aliphatic group or aryl radical, X is F, Cl, Br, a=0 in the general formula (III), 1,2,3, a=1 in the general formula (IV), 2,3;
By general formula (III) ClOR
3 pR
4X
aThe halogenide improving agent of explaining is acetyl halide compound or halogen acyl halide compound, specifically can be selected from ClCH
2COCl, Cl
2CHCOCl, Cl
3CCOCl, C
6H
5COCl.
General formula (IV) HOR
3 pR
4X
aShown halogenide improving agent is a class halohydrin compound, specifically can be selected from ClCH
2CH
2OH, Cl
2CHCH
2OH, Cl
3CCH
2OH, Cl
3CC (CH
3)
2OH, ClCH
2CH
2CH
2CH
2A kind of among the OH, preferred Cl
2CHCH
2OH, Cl
3CCH
2OH, Cl
3CC (CH
3)
2OH.
Halide reagent in the component (4) is such as logical formula V R
5 bMX
cShown in, M is three, four, five main group element or transition metals in the formula, X is halogen, R
5To contain C
2～C
20The alkyl of carbon atom, b=0,1 or 2, c=1,2,3 or 4; Halide reagent is selected from ethyl aluminum dichloride, aluminium diethyl monochloride, sesquialter ethylaluminium chloride, dichloro aluminium isobutyl, a chloro-di-isobutyl aluminum, two chloro isopropyl aluminium, a chlorine di-isopropyl aluminium, CCl
4, BCl
3, SiCl
4, SnCl
4, PCl
3, CH
3SiCl
3, C
2H
5SiCl
3, C
3H
7SiCl
3, TiCl
4, Si (OC
2H
5) Cl
3, preferred dichloro one aluminium triethyl, dichloro aluminium isobutyl, titanium tetrachloride, silicon tetrachloride.
In the process of Kaolinite Preparation of Catalyst component, the feed molar ratio of various reactants, in every mole of magnesium in the component (1), component (2) is 0.1～20 mole, and component (3) is 0.1～20 mole, and component (4) is 0.5～50 mole.
The present invention also provides the preparation method of above-mentioned catalyst component, and this preparation method comprises the steps:
(1) general formula (I) magnesium compound and general formula (II) being contained the oxygen titanium compound reacts at a certain temperature and forms magnesium titanium complex clear solution;
(2) step (1) is obtained product and general formula (III) or compound (IV) and react to get clear solution at-20～100 ℃;
(3) solution that step (2) is obtained and logical formula V compound at a certain temperature contact reacts form precipitation, obtain the suspension of catalyst component;
(4) suspension that step (3) is obtained reacts certain hour at a certain temperature, and quiet heavy, washing, drying obtain catalyst fines.
In the step (1) of Kaolinite Preparation of Catalyst component, general formula (I) magnesium compound and general formula (II) contain temperature that the oxygen titanium compound is in contact with one another and are typically chosen under the comparatively high temps and carry out, higher temperature is beneficial to and forms magnesium titanium compound clear solution, preferably below the decomposition temperature of reactant, generally be not higher than 200 ℃, preferably carry out below 150 ℃, reaction is carried out under agitation condition, the time of reaction is depended on character and the operational condition of reactant, reaction times requires to be enough to obtain transparent solution, required time is generally at 1 to 20 hour, preferred 4 to 10 hours.After obtaining transparent solution, can add as required an amount of inert diluent, inert diluent requires not and dissolved component generation chemical reaction, inert diluent can be selected hydro carbons such as hexane, hexanaphthene, pentane, heptane, Trimethylmethane, iso-pentane, octane-iso, toluene etc. and composition thereof, helps the dispersion of magnesium compound solution and reduces the viscosity of solution.In the step (2) of Kaolinite Preparation of Catalyst component, the product that step (1) is obtained and general formula (III) or (IV) halogenide improving agent hybrid reaction obtain magnesium titanium complex clear solution, mixing temperature will be lower than the decomposition temperature of magnesium complex and halogenide improving agent, between-20～100 ℃ of the general selections, between preferred 0～60 ℃, mixing time is generally selected 30 minutes to 6 hours.Also can be with general formula (III) or (IV) compound adding in the step (1) of preparation magnesium complex solution in the catalyst preparation process, thus the step (2) of preparation process saved.In the step (3) of Kaolinite Preparation of Catalyst component, finish chlorination reaction or the chlorination reduction reaction of magnesium titanium complex, namely the chlorine element replaces the alkoxyl group in the magnesium titanium complex, different halide reagents also can revert to the valence state of titanium compound than lower valency simultaneously, thereby makes catalyst active center's group Precipitation from solution.The contact method of magnesium titanium complex clear solution and halide reagent can adopt any known suitable method to carry out, can adopt magnesium titanium complex solution progressively is added drop-wise to mode in the halide reagent solution, also can adopt halide reagent solution progressively is added drop-wise to mode in the magnesium titanium complex solution.Rate of addition is selected to be as the criterion with the local superheating that does not induce reaction usually, usually stirs steadily carrying out of being beneficial to react in the dropping process.In this precipitin reaction step, temperature can be controlled between-20～100 ℃, preferably between-20～80 ℃.The reaction times of settling step should be long enough to obtain completely precipitation, and the reaction times can be between 1 minute to 10 hours, preferred 0.5～5 hour.
Experiment is found, after settling step, reacting at a certain temperature for some time, to carry out maturation process more favourable to the particle shape of catalyzer, it can make the size distribution narrow of catalyzer, also can improve simultaneously the intensity of catalyst particle, thereby reduce the particle fragmentation phenomenon of catalyzer in the catalyzed ethylene polymerization process.The temperature of maturation process generally is equal to or higher than the temperature of precipitin reaction, and the time of slaking reaction can be controlled at 0.5～15 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 or hexanaphthene and composition thereof etc., usually select hexane to be the inert solvent of washing in the experiment.After washing, catalyst suspension can be by carrying out drying with nitrogen purging, to obtain catalyst fines under heating state.
The present invention also provides a kind of catalyzer for vinyl polymerization, and it comprises the reaction product of following component:
(a) catalyst component that is used for vinyl polymerization of the invention described above;
(b) a kind of general formula is AlR
nX
3-nOrgano-aluminium compound, R is identical or not identical C in the formula
1-8Alkyl, X is halogen, n is the number of 1＜n≤3.
Component (b) can be selected one or more aluminum alkyls to mix and use, preferred AlEt
3, Al (iso-Bu)
3, Al (n-C
6H
13)
3, Al (n-C
8H
17)
3, AlEt
2Cl etc.
The catalyzer that the present invention relates to is applicable to the equal polymerization of various ethene or the copolymerization of ethene and other alpha-olefins, and wherein alpha-olefin adopts a kind of in propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, the 4-methylpentene-1.
Embodiment
The below illustrates the present invention with embodiment, the scope of the invention is not limited.
Testing method:
Melt index: measure according to ASTM D1238-99.
Embodiment 1
(1) take by weighing magnesium dichloride 24g, add the 195ml tetrabutyl titanate, be warming up to 140 ℃ of stirring reactions until form clear solution, treat that solution temperature is cooled near room temperature, add toluene 180ml, mix, the solution that obtains takes out for subsequent use.
(2) get the solution that 10 milliliter of (1) step obtains, add 20 milliliters of hexane dilutions, add the 1.0ml ethapon, stirring at room reaction 1 hour.
(3) slowly drip the Dichloroethyl aluminum solutions of 20 milliliters of 1.8M under the room temperature in the second step reaction product with the constant voltage minim pipette, after being added dropwise to complete, stirring at room reaction 1 hour, 60 ℃ of stirring reactions obtained catalyst component suspension in 4 hours.
(4) the catalyst component suspension temperature is down to room temperature, leaves standstill, sedimentation, with hexane washing three times, the consumption of hexane is 80 milliliters at every turn, after washing is finished, in the situation that bathe 65 ℃ of temperature, purges drying with high pure nitrogen, gets the mobile powder of brown solid.
Evaluating catalyst: the catalyzer of 1L hexane, 1mmol triethyl aluminum and 10-20mg is joined in the 2L stainless steel stirring tank, then temperature is brought up to 90 ℃, the hydrogen of disposable adding 0.4MPa, then with ethene the total pressure of system is maintained 1.0MPa 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
Change the 1.0ml ethapon in the catalyst preparation step (2) into 0.5 milliliter, other conditions are with embodiment 1.
The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result sees Table 1.
Embodiment 3
Change the 1.0ml ethapon in the catalyst preparation step (2) into 0.43 milliliter of Benzoyl chloride, other conditions are with embodiment 1.
The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result sees Table 1.
Embodiment 4
After catalyst preparation step (2) reaction finishes, solution is cooled to 0 ℃ after will reacting, slowly drip again the Dichloroethyl aluminum solutions of 20 milliliters of 1.8M in the second step reaction product with the constant voltage minim pipette, after being added dropwise to complete, 0 ℃ of stirring reaction 1 hour, stirring at room reaction 1 hour, other conditions are with embodiment 1.
The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result sees Table 1.
Comparative Examples 1
(1) takes by weighing 114 gram diethoxy magnesium, add 340 milliliters of tetrabutyl titanates, until the formation clear solution is down to room temperature with solution temperature, add 400 milliliters of dry hexane diluted for use 140 ℃ of stirring and dissolving.
(2) get the solution that 9 milliliter of (1) step obtains, slowly drip the hexane solution of 15 milliliters of 3M ethyl aluminum dichlorides with drop-burette, after being added dropwise to complete, the slaking in 4 hours of 60 ℃ of stirring reactions obtains catalyst suspension.
(3) the catalyst suspension temperature is down to room temperature, leaves standstill, sedimentation, with hexane washing three times, the consumption of hexane is 50 milliliters at every turn, after washing is finished, in the situation that bathe 65 ℃ of temperature, purges drying with high pure nitrogen, gets the mobile powder of brown solid.
The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result sees Table 1.
Comparative Examples 2
(1) take by weighing magnesium dichloride 24g, add the 195ml tetrabutyl titanate, be warming up to 140 ℃ of stirring reactions until form clear solution, treat that solution temperature is cooled near room temperature, add toluene 180ml, mix, the solution that obtains takes out for subsequent use.
(2) get the solution that 10 milliliter of (1) step obtains, add 20 milliliters of hexane dilutions, under the normal temperature with the constant voltage minim pipette to the Dichloroethyl aluminum solutions that wherein slowly drips 20 milliliters of 1.8M, after being added dropwise to complete, stirring at room reaction 1 hour, supernatant liquor is removed in press filtration behind the quiescent settling, adds the 70ml hexane, and 60 ℃ of stirring reactions obtained catalyst component suspension in 4 hours.
(3) the suspension standing sedimentation that second step is obtained extrudes supernatant liquor, and hexane washing four times adds hexane 70ml again, drips the 4.5mlTiCl of 10ml hexane dilution with constant pressure funnel
4, drip off 30 ℃ of reactions 1 hour.
(4) the catalyst component suspension temperature is down to room temperature, leaves standstill, sedimentation, with hexane washing four times, the consumption of hexane is 80 milliliters at every turn, after washing is finished, in the situation that bathe 65 ℃ of temperature, purges drying with high pure nitrogen, gets the mobile powder of brown solid.
The 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, introduce the halogenide improving agent in the preparation process of catalyzer of the present invention, catalyst activity is significantly increased, and the melting index of the polymkeric substance that obtains obviously increases, and illustrates that the hydrogen responsiveness of catalyzer has obtained increasing substantially.Fine polymer powder content relatively has clear improvement than Comparative Examples.
Claims (13)
1. a catalyst component that is used for ethylene polymerization is characterized in that, this catalyst component comprises the reaction product of following component:
(1) magnesium compound is by general formula (I) Mg (0R
1)
mCl
2-mShown in, R wherein
1C
2～C
20Alkyl, optional be saturated or undersaturated straight chain, side chain or closed chain, 0≤m≤2;
(2) oxygen containing titanium compound is by general formula (II) Ti (OR
2)
nCl
4-nShown in, R in the formula
2C
2～C
20Alkyl, optional be saturated or undersaturated straight chain, side chain or closed chain, 0＜n≤4;
(3) halogenide improving agent is by general formula (III) ClOR
3 pR
4X
aOr general formula (IV) HOR
3 pR
4X
aShown in, R wherein
3Be C
1～C
6Aliphatic group or aryl radical, p=0 or 1; R
4X
aC for the halogen replacement
1～C
6Aliphatic group or aryl radical, X is F, Cl, Br, a=0 in the general formula (III), 1,2,3, a=1 in the general formula (IV), 2,3;
(4) halide reagent is by logical formula V R
5 bMX
cShown in, M is three, four, five main group element or transition metals in the formula, X is halogen, R
5To contain C
2～C
20The alkyl of carbon atom, b=0,1 or 2, c=1,2,3 or 4.
2. catalyst component according to claim 1 is characterized in that, in the wherein said general formula (I), and R
1Be C
2～C
10Alkyl.
3. catalyst component according to claim 1 is characterized in that, wherein said general formula (I) magnesium compound is selected from alkoxyl magnesium compound, magnesium chloride or its miscellany.
4. catalyst component according to claim 3 is characterized in that, wherein said general formula (I) magnesium compound is selected from least a in magnesium dichloride, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, the two octyloxy magnesium.
5. catalyst component according to claim 1 is characterized in that, wherein said general formula (II) is titanate ester compound or its miscellany, R
2C
2～C
10Alkyl.
6. catalyst component according to claim 5 is characterized in that, wherein said titanium compound is tetrabutyl titanate.
7. catalyst component according to claim 1 is characterized in that, the halogenide improving agent that wherein said halogenide improving agent formula of (III) is explained is selected from ClCH
2COCl, Cl
2CHCOCl, Cl
3CCOCl, C
6H
5A kind of among the COCl; The halogenide improving agent that general formula (IV) is explained is selected from ClCH
2CH
2OH, Cl
2CHCH
2OH, Cl
3CCH
2OH, Cl
3CC (CH
3)
2OH, ClCH
2CH
2CH
2CH
2A kind of among the OH.
8. catalyst component according to claim 1, it is characterized in that, wherein component (4) halide reagent be selected from following one or more: ethyl aluminum dichloride, aluminium diethyl monochloride, sesquialter ethylaluminium chloride, dichloro aluminium isobutyl, a chloro-di-isobutyl aluminum, two chloro isopropyl aluminium, a chlorine di-isopropyl aluminium, CCl
4, BCl
3, SiCl
4, SnCl
4, PCl
3, CH
3SiCl
3, C
2H
5SiCl
3, C
3H
7SiCl
3, TiCl
4,, Si (OC
2H
5) Cl
3
9. catalyst component according to claim 1 is characterized in that, wherein component (4) halide reagent is a kind of or its mixture of dichloro one aluminium triethyl, dichloro aluminium isobutyl, titanium tetrachloride, silicon tetrachloride.
10. catalyst component according to claim 1, it is characterized in that, in the process of Kaolinite Preparation of Catalyst component, the feed molar ratio of various reactants, in every mole of magnesium in the component (1), component (2) is 0.1～20 mole, and component (3) is 0.1～20 mole, and component (4) is 0.5～50 mole.
11. the preparation method of the described catalyst component of claim 1～10 any one comprises the steps:
(1) general formula (I) magnesium compound and general formula (II) being contained the oxygen titanium compound reacts at a certain temperature and forms magnesium titanium compound clear solution;
(2) step (1) is obtained product and general formula (III) or compound (IV) and react to get clear solution at-20～100 ℃;
(3) solution that step (2) is obtained and logical formula V compound at a certain temperature contact reacts form precipitation, obtain the suspension of catalyst component.
(4) suspension that step (3) is obtained reacts certain hour at a certain temperature, quiet heavy, washing, dry catalyst component powder.
12. a catalyzer that is used for ethylene polymerization, it comprises the reaction product of following component:
(a) the described catalyst component for vinyl polymerization of claim 1～10;
(b) a kind of general formula is AlR
nX
3-nOrgano-aluminium compound, R is that hydrogen or carbonatoms are 1～20 alkyl in the formula, X is halogen, n is the number of 1＜n≤3.
13. the application of the described ethylene rolymerization catalyst of claim 12 in vinyl polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101946943A CN102875705A (en) | 2011-07-12 | 2011-07-12 | Catalyst component and catalyst for ethylene polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101946943A CN102875705A (en) | 2011-07-12 | 2011-07-12 | Catalyst component and catalyst for ethylene polymerization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102875705A true CN102875705A (en) | 2013-01-16 |
Family
ID=47477249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101946943A Pending CN102875705A (en) | 2011-07-12 | 2011-07-12 | Catalyst component and catalyst for ethylene polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102875705A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085739A (en) * | 2014-04-29 | 2015-11-25 | 中国石油化工股份有限公司 | Alkene polymerization catalyst composition, preparation method and application |
| CN111100218A (en) * | 2018-10-25 | 2020-05-05 | 中国石油天然气股份有限公司 | Spherical alkoxy magnesium particles and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1769308A (en) * | 2004-10-27 | 2006-05-10 | 中国石油化工股份有限公司 | Ethene polymerization catalyst ingredient and its preparation method and catalyst |
| CN101289520A (en) * | 2008-06-07 | 2008-10-22 | 淄博新塑化工有限公司 | Catalyst suitable for vinyl polymerization and copolymerisation |
| CN102059144A (en) * | 2009-11-13 | 2011-05-18 | 中国石油化工股份有限公司 | Loaded non-metallocene catalyst and preparation method and application thereof |
-
2011
- 2011-07-12 CN CN2011101946943A patent/CN102875705A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1769308A (en) * | 2004-10-27 | 2006-05-10 | 中国石油化工股份有限公司 | Ethene polymerization catalyst ingredient and its preparation method and catalyst |
| CN101289520A (en) * | 2008-06-07 | 2008-10-22 | 淄博新塑化工有限公司 | Catalyst suitable for vinyl polymerization and copolymerisation |
| CN102059144A (en) * | 2009-11-13 | 2011-05-18 | 中国石油化工股份有限公司 | Loaded non-metallocene catalyst and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085739A (en) * | 2014-04-29 | 2015-11-25 | 中国石油化工股份有限公司 | Alkene polymerization catalyst composition, preparation method and application |
| CN111100218A (en) * | 2018-10-25 | 2020-05-05 | 中国石油天然气股份有限公司 | Spherical alkoxy magnesium particles and preparation method thereof |
| CN111100218B (en) * | 2018-10-25 | 2022-05-10 | 中国石油天然气股份有限公司 | Spherical alkoxy magnesium particles and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1416438A (en) | Catalyst | |
| CN102372798A (en) | Catalyst component for olefin polymerization and preparation method thereof | |
| CN109320638B (en) | Ziegler-Natta catalyst component and catalyst for ethylene polymerization | |
| CN102875706A (en) | Catalyst component of ethylene polymerization reaction, and catalyst thereof | |
| CN101942050A (en) | Catalyst component for ethylene polymerization in slurry process and preparation method thereof | |
| CN102344508B (en) | Ethylene polymerization catalyst containing ether compound, preparation method thereof, and application thereof | |
| CN101942049A (en) | Catalyst component for ethylene polymerization, preparation method and application | |
| CN102030845B (en) | Catalyst component used for vinyl polymerization reaction and catalyst thereof | |
| CN102898558B (en) | Application of catalyst component in olefin polymerization | |
| CN102875705A (en) | Catalyst component and catalyst for ethylene polymerization | |
| CN104710549A (en) | Spherical ethylene polymerization solid titanium catalyst prepared through emulsion method, and application thereof | |
| CN102060945B (en) | Preparation and application of solid titanium catalyst component for vinyl polymerization | |
| CN102766226A (en) | Main catalyst for ethylene polymerization and catalyst containing same | |
| JPH05214025A (en) | Catalyst for polymerization of olefin | |
| CN102898555B (en) | Application of catalyst component in olefin polymerization | |
| CN102329400B (en) | Olefin polymerization catalyst containing silane compound, preparation and application thereof | |
| CN105859927B (en) | Vinyl polymerization Ziegler-Natta catalyst electron donor, catalytic component, catalyst | |
| CN107840910B (en) | Catalyst component for ethylene polymerization reaction, preparation method thereof, catalyst and application thereof | |
| CN104418961B (en) | Catalyst component for ethylene polymerization reaction as well as catalyst and preparation method of catalyst component | |
| CN103665208B (en) | The catalyst component of ethylene polymerization and catalyzer thereof | |
| WO2004009658A1 (en) | Magnesium dichloride-alcohol adducts and catalyst components obtained therefrom | |
| CN102898556B (en) | Application of catalyst component in olefin polymerization | |
| CN104418960A (en) | Catalyst component applied to ethylene polymerization, preparation method of catalyst component and catalyst | |
| CN102344515B (en) | Catalyst component for ethylene polymerization and catalyst thereof | |
| CN102321206B (en) | Vinyl polymerization catalyst, preparation and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130116 |