CN1508161A - Catalyst composition for ethylene polymerization, and preparing method and catalyst thereof - Google Patents
Catalyst composition for ethylene polymerization, and preparing method and catalyst thereof Download PDFInfo
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- CN1508161A CN1508161A CNA021565112A CN02156511A CN1508161A CN 1508161 A CN1508161 A CN 1508161A CN A021565112 A CNA021565112 A CN A021565112A CN 02156511 A CN02156511 A CN 02156511A CN 1508161 A CN1508161 A CN 1508161A
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Abstract
The present invention provides a catalyst component for ethylene polymerization, its preparation method and catalyst. Said catalyst component includes at least one magnesium halide, at least one alcohol compound, at least one electron donor, at least one organic metal aluminium compound and reaction product of at least one titanium compound. Said catalyst has good hydrogen regulation property and higher polymerization activity, specially is applicable to series-connected reactor to prepare the wide molecular weight distribution or double-peak type polyvinyl resin.
Description
Technical field
The present invention relates to a kind ofly be used for the particularly catalyst component of vinyl polymerization or copolymerization of alkene, and the preparation method of this catalyst component and catalyzer thereof.
Technical background
Along with the polyethylene production industrial expansion, the polyvinyl production of high performance has become the emphasis that people pay close attention to.Realize the high performance of polyvinyl resin, then require when keeping polyethylene favorable mechanical performance, also must have good processing characteristics.The polyvinyl resin that the development molecular weight is broad peak distribution or bimodal distribution then can satisfy this requirement.At present, the polyvinyl polymerization process of production bimodal molecular weight distribution mainly is to adopt placed in-line staged reactor polymerization methods, the polymerization technique of double-reactor series connection commonly comprises liquid phase-liquid phase process, gas phase-gas phase process and liquid phase-gas phase process.In this double-reactor polymerization technique, mainly be by regulating two density of hydrogen and polymerizing conditions in the reactor, make the polyethylene that in different reactor, generates have different molecular weight, thereby realize that the bimodal distribution of final polymer molecular weight or broad peak distribute.
The appearance of placed in-line staged reactor polymerization technique must have corresponding catalyzer to match with it, traditional Z-N catalyzer is difficult to satisfy the requirement of this polymerization technique, this is because the decay of activity of traditional Z-N catalyzer in first reactor (density of hydrogen is higher) is bigger, cause its active on the low side in second reactor, for producing the polyvinyl resin of estimated performance, the residence time of catalyzer in second reactor certainly will will be prolonged, this means the geometrical dimension that needs to increase second reactor, cause operational process of craft to become difficult.Therefore, the catalyzer that is applicable to this placed in-line staged reactor polymerization technique not only will have higher ethylene homo and copolymerization activity, and this polymerization activity is subjected to the influence of different hydrogen concentration in the different reactor less, and promptly (different party step of reaction) all have the activity of higher stable in different reactors.
In Chinese patent CN1158136A, a kind of catalyst composition is disclosed, it has introduced the long carbochain fat alcohol compound with α-side chain in traditional Mg-Ti series catalysts component, therefore the polymerization activity and the hydrogen regulation performance of catalyzer have been improved, particularly Tu Chu characteristics are when preparation is hanged down with high-molecular weight Alathon and multipolymer, under the different hydrogen partial pressure conditions, this catalyzer can both keep high polymerization activity.But owing to used alkyl magnesium compound in catalyst preparation process, the cost of this magnesium compound is higher, thereby has increased catalyst production cost, is unfavorable for the industrial application of catalyzer.
In Chinese patent CN1085569A, though having selected cheap magnesium halide and Fatty Alcohol(C12-C14 and C12-C18) for use is the Preparation of catalysts raw material, but the alkane that needs the higher high carbon chain of use cost in preparation process is as solvent, and need dissolving (being about 140 ℃) under higher temperature, dissolution time is longer, and the polymerization activity of this catalyzer under high hydrogen concentration is also unsatisfactory.
The inventor finds by experiment repeatedly, and by using the cheap magnesium halide and long carbochain fat alcohol compound and a kind of electron donor compound of α-side chain, prepared catalyzer has good hydrogen mediation copolymerization performance when being used for the polymerization of ethene or copolymerization.And the cost of catalyzer is lower, and synthesis technique is simple, is beneficial to industrial applications.
Summary of the invention
The purpose of this invention is to provide a kind of ethylene polymerization catalysts that is used for, it comprises at least a magnesium halide, at least a alkylol cpd, the reaction product of the electron donor of at least a ester or ether, at least a organo-metallic aluminum compound and at least a titanium compound.
For improving the particle form of catalyzer, also catalyst component can be loaded on a kind of inorganic oxide carrier.This inorganic oxide carrier mainly is to be used to support active ingredient, can think, any inorganic oxide carrier of required chemical conversion reaction that do not disturb all is suitable for.The example of such inorganic oxide has silicon-dioxide, aluminum oxide, oxidation sial, magnesium oxide, titanium oxide, chromic oxide and zirconium white or the like, preferred silicon-dioxide.In general, inorganic oxide carrier should use with the particle form of exsiccant sphere or elliposoidal.Exemplary particles can have about 1 micron～about 250 microns, preferred about 10 microns～about 100 microns median size, and the specific surface area of carrier is 100-800m
2/ g, pore volume are 1-6ml/g.Dry inorganic carrier can carry out under preferred about 600 ℃ temperature at 100 ℃～1000 ℃.When inorganic carrier is that silicon-dioxide is, before use generally in 200 ℃ or more than, preferred 200 ℃～850 ℃, best 600 ℃ of heat dryings are handled.
Described halogenated magnesium compound such as general formula (I) Mg (OR
1)
2-mX
mShown in, R in the formula
1Be C
1～C
14Alkyl, X chooses from F, Cl, Br or its mixture, and m is 1 or 2.R
1Can be straight chain, side chain or cyclic alkyl, concrete compound be as magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium, chlorination butoxy magnesium etc., wherein preferred magnesium dichloride.Described halogenated magnesium compound can be used alone or as a mixture.
Described alkylol cpd such as general formula (II) R
2Shown in the OH, R in the formula
2Be C
1-C
10Secondary alkyl or tertiary alkyl, C
3-C
10Cycloalkyl, C
6-C
10Aryl, C
7-C
10Alkaryl.Preferred R
2For carbonatoms greater than 5 secondary alkyl, tertiary alkyl, cycloalkyl or alkaryl.Particular compound is as ethanol, 2-propyl alcohol, 2-methyl amyl alcohol, 2-ethylpentanol, 2-ethyl butanol, 2-Ethylhexyl Alcohol, hexalin, benzylalcohol, xylyl alcohol etc., preferred 2-Ethylhexyl Alcohol.
Described alkylol cpd can be separately and is mixed and use, in order to obtain good hydrogen regulation performance and than the catalyzer of high polymerization activity, alcohol/magnesium raw materials components mole ratio should be controlled between 1.0～3.0.
Described electron donor compound is selected from C
1～C
4The alkyl ester of aliphatic saturated monocarboxylic acid, C
7～C
8The alkyl ester of aromatic carboxylic acid, C
2～C
6Aliphatic ether, C
2～C
5Cyclic ethers, C
3～C
6A kind of in the hydrocarbyl carbonate of saturated fatty ketone, ortho-phosphoric acid or phosphorous acid or the halo hydrocarbyl carbonate or their mixture.
C wherein
1～C
4The alkyl ester of aliphatic saturated monocarboxylic acid, concrete as: CH
2COOCH
3, CH
2COOCH
2CH
3Deng; C
7～C
8The alkyl ester of aromatic carboxylic acid, concrete as: C
6H
5COOCH
3, C
6H
5COOC
2H
5Deng; C2～C6 aliphatic ether, concrete as: (C
2H
5) O, (C
3H
7) O etc., C
3～C
6Saturated fatty ketone, concrete as: CH
3COCH
3, C
2H
5COCH
3, C
2H
5COC
2H
5Deng
C wherein
2～C
5Cyclic ethers is specially: oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether, tetrahydrofuran (THF).
The wherein hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid or halo hydrocarbyl carbonate, concrete as: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, tricresyl phosphite benzene methyl
Described organo-metallic aluminum compound such as general formula (III) AlR
3 nX
3-nShown in, R in the formula
3Be identical or different C
1～C
20Alkyl can be a straight chain, and side chain or cyclic alkyl, X are halogen, n=1,2 or 3.Concrete compound is as triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, a chlorine diethyl chlorine, dichloro one ethyl chloride etc.
Described titanium compound such as general formula (IV) Ti (OR
4)
4-mX
m, R in the formula
4Be C
1～C
14Aliphatic group, X chooses from F, Cl, Br or its mixture, m is 1～4 integer.Specifically can select a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, the titanous chloride or their mixture for use, preferred titanium tetrachloride.Titanium compound should be a completely soluble liquefied compound under application of temperature, in the non-polar solvent.
Above-mentioned catalyst component of the present invention, preferably adopt the following step to be prepared:
(1) with standby after the organometallic aluminium compound treatment of inorganic oxide carrier with general formula (III).
(2) with described general formula (I) Mg (OR
1)
2-mX
mMagnesium compound, general formula (II) R
2The pure and mild electron donor of OH, interacting in non-polar solvent forms magnesium solution.Wherein non-polar solvent comprises: propane, butane, Skellysolve A, iso-pentane, hexane, heptane, octane, decane, white oil, silicone oil, hexanaphthene etc.
(3) inorganic oxide carrier that step (2) is obtained after magnesium solution and step (1) are handled contacts.
(4) the organo-metallic aluminum compound contact reacts of reaction product that step (3) is obtained and general formula (III).
(5) reaction product that step (4) is obtained and general formula (IV) Ti (OR
4)
4-mX
mTitanium compound contact obtain described catalyst component.
In the preparation process of catalyst component of the present invention, ratio between the each component is, in every mole of general formula (I) compound, general formula (II) compound is controlled at 1.0～3.0 moles, preferred 1.8～2.3 moles, the consumption of electron donor is controlled at 0.5～30.0 general formula (III) compound and is controlled at 1.0～3.0 moles, preferred 1.8～2.3 moles, general formula (IV) compound is controlled at 0.1～10, preferred 1.5～5.5 moles.
Handling in the inorganic oxide carrier process with organometallic aluminium, the nonpolar inert media consumption that is used to form slurry can change in relative broad range.Generally according to actual needs, its consumption is about 5ml/g carrier～about 200ml/g carrier.Preferred nonpolar medium is an alkane, for example pentane, hexane, iso-pentane, normal heptane, octane, nonane and decane.Before use, be used for liquid medium of the present invention and preferably should be purified, for example with silica gel or molecular sieve diafiltration, to remove minor amount of water, oxygen, polar compound and other are unfavorable for the material of catalyst activity.Reaction process is generally carried out under about 5 ℃～80 ℃ temperature range, is preferably 20 ℃～60 ℃.Reaction times also can change in relative broad range, is generally 0.5～10 hour.Drying after inorganic oxide carrier is handled can be used slight vacuum, means such as elevated temperature or nitrogen purging.
In the process of dissolving magnesium halide, the consumption of electron donor is controlled at 0.5～30 mole of every mole of magnesium halide, and its usage quantity must guarantee the abundant dissolving of magnesium halide.In order to guarantee the dissolving of magnesium halide, controlling reaction time and temperature of reaction are also very important.Reaction times was generally 1～8 hour, and preferred 2～5 hours, temperature of reaction was 30 ℃～150 ℃, preferred 50 ℃～80 ℃.
The invention still further relates to a kind of catalyzer that is used for vinyl polymerization or copolymerization, it contains the above-mentioned catalyst component of the present invention and the reaction product of alkylaluminium cpd, and the general formula of wherein used alkylaluminium cpd is AlR
3, R is 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 mix to 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, butylene, amylene, hexene, octene, the 4-methylpentene-1.
When catalyst body of the present invention ties up to catalyzed ethylene polymerization, have the advantages that high catalytic activity is all arranged under high hydrogen partial pressure or low hydrogen dividing potential drop, be specially adapted to double-reactor and prepare the polyvinyl resin that molecular weight distribution is bimodal pattern.
Embodiment
Embodiment given below is for the present invention is described, rather than limits the invention.
Testing method:
Melting index is to measure according to ASTMD1238-99
Embodiment 1:
(1) gets about 12 gram spherical silica gels (model 948, U.S. Grace company) and under nitrogen protection, activate 4 hours in 600 ℃.
(2) under the nitrogen protection, in the reaction flask after the high temperature drying of belt stirrer, add (1) the thermal activation silica gel that obtains of step 10.0 grams successively, hexane and 5.0 milliliters of AlEt after 50 milliliters of purification process
3Hexane solution (1.0mmol/ml), 50 ℃ down reaction be warming up to 70 ℃ after half an hour, nitrogen flushing is dried to into mobile powder.
(3) in another reactor, add 2.0 gram Magnesium Chloride Anhydrouss, 9.8 milliliters of 2-Ethylhexyl Alcohols, 100 milliliters of dried hexanes of purifying and 5 milliliters of mixing solutionss that tetrahydrofuran (THF) forms successively, stir 5 hours to forming clear solution 60 ℃ of reactions.
(4) with the magnesium solution of step (3) preparation and the mobile powder mixes of step (2), stirred 2 hours 60 ℃ of reactions, splash into 14.0ml tri-n-hexyl aluminum solution (1.5mmol/ml, hexane are solvent) afterwards, continued stirring reaction 1 hour.
(5) in reaction system, drip the 2.0ml titanium tetrachloride, stirred 2 hours, use 50ml hexane wash 3 times, temperature is risen to 70 ℃ at last 60 ℃ of reactions.Purge drying with high pure nitrogen, get the solids flowability powder.
Evaluating catalyst: the slurry polymerization that carries out ethene respectively under different hydrogen contents is to prepare the polyethylene of different melting index; 2L stainless steel stirring tank, the 1L hexane, poly-and stagnation pressure: 1.03MPa, the about 50mg of catalyst levels, the hexane solution of 1ml triethyl aluminum (1M), polymerization temperature: 85 ℃, polymerization time: 1 hour.
During preparation low melt index polyethylene,
During preparation high fusion index polyethylene,
Embodiment 2
Tetrahydrofuran (THF) in embodiment 1 step (3) is adjusted into epoxy chloropropane and phosphate n-butyl, and hexane is adjusted into toluene, and 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
14.0ml tri-n-hexyl aluminum in embodiment 1 step (4) is adjusted into 14.0ml aluminium diethyl monochloride (2.2mmol/ml, hexane are solvent), and 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
The amount of titanium tetrachloride in embodiment 1 step (5) is adjusted into 4ml, and 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) in reaction flask, add the 200ml hexane successively, 2.0ml toluene, the butyl octyl magnesium solution of 10mmol is lower than under 40 ℃ of situations at temperature of reaction system, slowly drips 2-ethyl-1-hexanol of 2.8ml, obtains pure magnesium complex.
(2) add the 100ml hexanes at 25 ℃ in 5.0g silicon-dioxide (600 ℃ of activation), the slow hexane solution (2M) of Dropwise 5 .0ml dichloro one aluminium triethyl then 25 ℃ of stirring reactions 0.5 hour, is warming up to 70 ℃, purges drying with high purity nitrogen.
(3) under the normal temperature, in the dried powder in (2) step, add the hexane that the 100ml purifying is crossed, under agitation add the pure magnesium complex of (1) step preparation, be warming up to 50 ℃ of stirring reactions 1.0 hours.
(4) in the reaction system in (3) step, slowly drip the titanium tetrachloride of 0.56ml,, then be warming up to 70 ℃, purge the dry pressed powder that gets with high purity nitrogen 50 ℃ of stirring reactions 1.0 hours.
The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result sees Table 1.
Comparative Examples 2
Hexane in embodiment 1 step (3) and tetrahydrofuran (THF) are adjusted into 50ml decane solvent, and the reaction whipping temp must be brought up to 140 ℃, other conditions are with implementing 1.
The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result sees Table 1.
Table 1
| Catalyzer | Low hydrogen dividing potential drop polymerization (H 2/C 2 ＝：0.28/0.75) | High hydrogen partial pressure polymerization (H 2/C 2 ＝：0.60/0.43) | ||
| ??Activity ?(gPE/g?cat) | ??MI ??(g/10min) | ??Activity ??(gPE/g?cat) | ??MI ??(g/10min) | |
| Embodiment 1 | ????4760 | ????0.96 | ????2019 | ????43.1 |
| Embodiment 2 | ????4049 | ????1.17 | ????1416 | ????23.3 |
| Embodiment 3 | ????3317 | ????0.91 | ????1288 | ????34.2 |
| Embodiment 4 | ????2521 | ????1.24 | ????1243 | ????19.0 |
| Comparative Examples 1 | ????2233 | ????0.99 | ????1035 | ????42.6 |
| Comparative Examples 2 | ????2214 | ????0.54 | ????710 | ????17.8 |
From the testing data of table 1 embodiment and Comparative Examples as can be seen, catalyzer of the present invention is compared with the disclosed catalyzer of CN1085569A (Comparative Examples 2), and polymerization activity is all higher under different density of hydrogen, and hydrogen response is better; Compare with the disclosed catalyzer of CN1158136A (Comparative Examples 1), the present invention has also shown high polymerization activity, and hydrogen regulation performance is suitable substantially, and catalyzer of the present invention has used cheap magnesium dichloride to be raw material simultaneously, and cost is lower.
Claims (15)
1, be used for the ethylene polymerization catalysts component, it comprises the reaction product of the electron donor of at least a halogenated magnesium compound, at least a alkylol cpd, at least a ester or ether, at least a organo-metallic aluminum compound and at least a titanium compound.
2, the ethylene polymerization catalysts component that is used for according to claim 1, described electron donor is selected from C
1～C
4The alkyl ester of aliphatic saturated monocarboxylic acid, C
7～C
8The alkyl ester of aromatic carboxylic acid, C
2～C
6Aliphatic ether, C
2～C
5Cyclic ethers, C
3～C
6A kind of in the hydrocarbyl carbonate of saturated fatty ketone, ortho-phosphoric acid or phosphorous acid or the halo hydrocarbyl carbonate or their mixture
3, the ethylene polymerization catalysts component that is used for according to claim 1, described halogenated magnesium compound such as general formula (I) Mg (OR
1)
2-mX
mShown in, R in the formula
1Be C
1～C
14Alkyl, X chooses from F, Cl, Br or its mixture, and m is 1 or 2, R
1Be straight chain, side chain or cyclic alkyl.
4, the ethylene polymerization catalysts component that is used for according to claim 1, wherein magnesium halide is a magnesium dichloride.
5, the ethylene polymerization catalysts component that is used for according to claim 1, wherein alkylol cpd such as general formula R
2CH
2Shown in the OH, R in the formula
2Be C
1-C
10Secondary alkyl or tertiary alkyl, C
3-C
10Cycloalkyl, C
6-C
10Aryl, C
7-C
10Alkaryl.
6, the ethylene polymerization catalysts component that is used for according to claim 5, wherein said alkylol cpd general formula R
2R among the CHOH
2For carbonatoms greater than 5 secondary alkyl, tertiary alkyl, cycloalkyl or alkaryl.
7, the ethylene polymerization catalysts component that is used for according to claim 6, wherein said alkylol cpd selects one or more in 2-methyl amyl alcohol, 2-ethylpentanol, 2-ethyl butanol, 2-Ethylhexyl Alcohol, hexalin, benzylalcohol, the xylyl alcohol.
8, the ethylene polymerization catalysts component that is used for according to claim 7, wherein alkylol cpd is a 2-Ethylhexyl Alcohol.
9, the ethylene polymerization catalysts component that is used for according to claim 1, wherein said organo-metallic aluminum compound such as general formula (III) AlR
3 nX
3-nShown in, R in the formula
3Be identical or different C
1～C
20Alkyl can be a straight chain, and side chain or cyclic alkyl, X are halogen, n=1,2 or 3.
10, the ethylene polymerization catalysts component that is used for according to claim 1, wherein said organo-metallic aluminum compound are selected from one or more in triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, a chlorine diethyl chlorine, dichloro one ethyl chloride.
11, the ethylene polymerization catalysts component that is used for according to claim 1, wherein titanium compound such as general formula (IV) Ti (OR
4)
4-mX
m, R in the formula
4Be C
1～C
14Aliphatic group, X chooses from F, Cl, Br or its mixture, m is 1～4 integer.
12, the ethylene polymerization catalysts component that is used for according to claim 11, its formula of (IV) compound is a titanium tetrachloride.
13, the ethylene polymerization catalysts component that is used for according to claim 1, wherein the ratio between the each component is, in every mole of halogenated magnesium compound, the alkylol cpd compound is controlled at 1.0～3.0 moles, the electron donor of preferred 1.8～2.3 moles, ester or ether is controlled at 0.5～30.0, the organo-metallic aluminum compound is controlled at 1.0～3.0 moles, preferred 1.8～2.3 moles and titanium compound are controlled at 0.1～10, preferred 1.5～5.5 moles.
14,, adopt the following step to be prepared according to the described ethylene polymerization catalysts component that is used for of one of claim 1-13:
(1) with standby after the organometallic aluminium compound treatment of inorganic oxide carrier with general formula (III);
(2) with described general formula (I) Mg (OR
1)
2-mX
mMagnesium compound, general formula (II) R
2The pure and mild electron donor of OH, interacting in non-polar solvent forms magnesium solution;
(3) inorganic oxide carrier that step (2) is obtained after magnesium solution and step (1) are handled contacts;
(4) the organo-metallic aluminum compound contact reacts of reaction product that step (3) is obtained and general formula (III);
(5) reaction product that step (4) is obtained and general formula (IV) Ti (OR
4)
4-mX
mTitanium compound contact obtain described catalyst component.
15, a kind of catalyzer that is used for vinyl polymerization or copolymerization, it comprises the reaction product of following component:
(a) the described ethylene polymerization catalysts component that is used for of one of claim 1-13;
(b) at least a general formula is AlR
nX
3-nOrgano-aluminium compound, R is that hydrogen or carbonatoms are 1～20 alkyl in the formula, X is a halogen, n is the number of 1＜n≤3.
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|---|---|---|---|
| CN 02156511 CN1233669C (en) | 2002-12-16 | 2002-12-16 | Catalyst composition for ethylene polymerization, and preparing method and catalyst thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02156511 CN1233669C (en) | 2002-12-16 | 2002-12-16 | Catalyst composition for ethylene polymerization, and preparing method and catalyst thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1508161A true CN1508161A (en) | 2004-06-30 |
| CN1233669C CN1233669C (en) | 2005-12-28 |
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ID=34236247
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328294C (en) * | 2004-10-27 | 2007-07-25 | 中国石油化工股份有限公司 | Ethene polymerization catalyst ingredient and its preparation method and catalyst |
| CN101148484B (en) * | 2007-08-06 | 2010-06-23 | 北京凯华创新科技有限公司 | Linear polyethylene catalyst, preparation method and application thereof |
| CN103044591A (en) * | 2011-10-11 | 2013-04-17 | 中国石油化工股份有限公司 | Polyethylene catalyst component with narrow molecular weight distribution, preparation method and application |
| CN104974282A (en) * | 2014-04-11 | 2015-10-14 | 中国石油化工股份有限公司 | Catalyst component used in ethylene polymerization reaction, preparation method and catalyst |
| CN114426609A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization and catalyst system |
-
2002
- 2002-12-16 CN CN 02156511 patent/CN1233669C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328294C (en) * | 2004-10-27 | 2007-07-25 | 中国石油化工股份有限公司 | Ethene polymerization catalyst ingredient and its preparation method and catalyst |
| CN101148484B (en) * | 2007-08-06 | 2010-06-23 | 北京凯华创新科技有限公司 | Linear polyethylene catalyst, preparation method and application thereof |
| CN103044591A (en) * | 2011-10-11 | 2013-04-17 | 中国石油化工股份有限公司 | Polyethylene catalyst component with narrow molecular weight distribution, preparation method and application |
| CN103044591B (en) * | 2011-10-11 | 2014-08-27 | 中国石油化工股份有限公司 | Polyethylene catalyst component with narrow molecular weight distribution, preparation method and application |
| CN104974282A (en) * | 2014-04-11 | 2015-10-14 | 中国石油化工股份有限公司 | Catalyst component used in ethylene polymerization reaction, preparation method and catalyst |
| 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 |
| CN114426609A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization and catalyst system |
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| Publication number | Publication date |
|---|---|
| CN1233669C (en) | 2005-12-28 |
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