CN101245115A - Homopolymerization and combined polymerization catalyst of ethylene and preparation method thereof - Google Patents
Homopolymerization and combined polymerization catalyst of ethylene and preparation method thereof Download PDFInfo
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- CN101245115A CN101245115A CNA2008100889138A CN200810088913A CN101245115A CN 101245115 A CN101245115 A CN 101245115A CN A2008100889138 A CNA2008100889138 A CN A2008100889138A CN 200810088913 A CN200810088913 A CN 200810088913A CN 101245115 A CN101245115 A CN 101245115A
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Abstract
The invention pertains to a ball-shaped solid titanium complex catalyst used for vinyl polymerization or copolymerization. The catalyst is prepared by the following method: (1) homogeneous magnesium solution is prepared by dissolving magnesium halide into alcoholic compound; (2) at least one organoboron compound without inactive hydrogen is added into the homogeneous magnesium solution; (3) the ball-shaped solid titanium complex catalyst is prepared by reaction of the said magnesium combination solution and titanium compound through recrystallization. The ball-shaped solid titanium complex catalyst demonstrates high catalytic activity of solid titanium complex catalyst used for vinyl polymerization or copolymerization, can be used for polymerization and copolymerization of ethylene to produce polymers with high bulk density, narrow particle size distribution and low fines content.
Description
Technical field
The present invention relates to a kind of solid titanium catalyst that is used for vinyl polymerization and copolymerization.Described solid titanium catalyst is used for vinyl polymerization and copolymerization demonstrates high catalytic activity, can produce high-bulk-density, narrow size-grade distribution and the few polymkeric substance of fine powder content.
Technical background
In recent years, the research of olefin polymerization catalysis is the hot issue in the polyolefine research field always.Exploitation high catalytic activity, hydrogen response be good, obtain the polyolefin catalyst that polymer particle size is evenly distributed, fine powder is few is the target that the scientific research personnel pursues.Bibliographical information the magniferous Ti-base catalyst of many usefulness as olefinic polymerization and copolymerization method with catalyzer.These catalyzer can provide high catalytic activity, produce the polymkeric substance of high-bulk-density, go for the slurry and the vapour phase polymerization of ethene.As obtaining to produce in the catalyzer of high-bulk-density olefin polymer, make magnesium compound and give electron compound prepared in reaction magnesium solution with magnesium solution.Used comprises alcohol, amine, cyclic ethers or organic carboxyl acid to electron compound.Usually magnesium solution prepares in the presence of hydrocarbon solvent.Magnesium-supported catalyzer can prepare by magnesium solution and halogen titanium compound such as titanium tetrachloride reaction.The method for preparing magnesium solution with alcohol is disclosed among US3642746, US 4336360, US 4330649 and the US 5106807.US 4477639 and US 4518706 also disclose with tetrahydrofuran (THF) or the cyclic ester method as the solvent of the described magnesium compound of dissolving.Though these catalyzer can be produced the polymkeric substance of high-bulk-density, but still described catalyzer need improved aspect the catalytic activity of catalyzer.In addition, wide size-grade distribution is arranged and contain many fine powders with the polymkeric substance of above-mentioned Catalyst Production, this makes troubles for the production quiet run at the easy blocking pipeline of production process.The Preparation of catalysts method of disclosed vinyl polymerization and copolymerization among the Japanese Patent JP 4951378 is: magnesium dichloride through grinding and ethanol synthesis generate MgCl
26C
2H
5OH alcohol adduct slurries, again with aluminium diethyl monochloride generation esterification, last and TiCl
4Carry the titanium reaction, obtain MgCl
2Carrier loaded Titanium series catalyst.This method for preparing catalyst is simple, the reaction conditions gentleness, and activity is very high during the catalyst vinyl polymerization.But this preparation method exists the carrier magnesium chloride can not dissolve in mineral oil, the irregular platy shaped particle that produces when there be former grinding in magnesium chloride in the slurry reaction system, cause the solid catalyst particle form that obtains relatively poor, thickness is inhomogeneous, thereby polymer morphology is also bad, fine powder is more, easily produces static and easy blocking pipe.This catalyzer oligomer in the solvent when polymerization is more simultaneously, easily blocking pipe and brought bigger trouble for aftertreatment.
For improving these problems, US 4311414 proposes a kind of by making the magnesium hydroxide dry air prepare the method for catalyzer, can produce the improved polymkeric substance of narrow particle size distribution and mean particle size.US 3953414 and US 4111835 also reported by making hydration magnesium dichloride dry air prepare the method for catalyzer, but the production special shape, the great polymkeric substance of mean particle size.But these methods need optional equipment such as air dry-set, and prepared catalyst activity is lower, and the polymkeric substance that obtains contains very big particle makes the melting process of polymkeric substance become difficulty.Therefore, needing can be by the simple method catalyzer that is used for vinyl polymerization and copolymerization preparation, that high polymerization activity and hydrogen response are arranged.In addition, also need to produce narrow size-grade distribution of polymerisate and the few catalyzer of fine particle content.
Summary of the invention
The objective of the invention is to solve the deficiency of above-mentioned art methods, a kind of catalyzer that is used for vinyl polymerization and copolymerization is provided.More particularly, the objective of the invention is to provide have desired high catalytic activity in vinyl polymerization and the copolymerization, catalyzer that hydrogen response is good, and make resulting polymers have high-bulk-density, narrow size-grade distribution and the few catalyzer of fine powder content.
Catalyzer of the present invention prepares by following steps: (1) makes halogenated magnesium compound be dissolved in preparation homogeneous phase magnesium solution in the alkylol cpd; (2) make the organoboron compound reaction of described homogeneous phase magnesium solution and at least a non-activity hydrogen produce magnesium compositions solution; (3) make the reaction of described magnesium compositions solution and titanium compound produce solid titanium catalyst, can carry out once, also can carry out repeatedly with the reaction of titanium compound.Described magnesium compound can be a halogenated magnesium compound.The type that is used for halogenated magnesium compound of the present invention can comprise following type: magnesium dihalide compound such as magnesium chloride, magnesium iodide, magnesium fluoride and magnesium bromide; Halogenated alkyl magnesium compound such as methylmagnesiumhalide, ethyl-magnesium-halide, halogenation propyl group magnesium, butyl Grignard reagent, halogenation isobutyl-magnesium, halogenation hexyl magnesium and halogenation amyl group magnesium; Halogenated alkoxy magnesium compound such as halogenation magnesium methylate, halogenation magnesium ethylate, halogenation isopropoxy magnesium, halogenation butoxy magnesium and halogenation octyloxy magnesium; Halogenation aryloxy magnesium such as halogenation phenoxy group magnesium and halogenation methylphenoxy magnesium.These magnesium compounds can the simplification compound or with two or the form of mixtures of multiple compound use.In addition, above-mentioned magnesium compound can be effectively to use with the coordination compound form of other metal.Other magnesium compound comprises the compound that exists by can be dependent on the magnesium compound preparation method but can not represent with molecular formula, generally can be considered the mixture of magnesium compound.For example, available following compound is as magnesium compound: the compound that obtains by magnesium compound and polysiloxane compound, the silane compound that comprises halogen, ester or alcohol reaction; In the presence of halogenated silanes, phosphorus pentachloride or thionyl chloride, react the compound that obtains by MAGNESIUM METAL and alcohol, phenol or ether.Described magnesium compound can be magnesium halide, especially magnesium chloride or the alkyl magnesium chloride that the alkyl of 1～10 carbon atom is arranged; The chlorination alkoxyl magnesium that the alkoxyl group of 1～10 carbon atom is arranged; The chlorination aryloxy magnesium that the aryloxy of 6～20 carbon atoms is arranged.Used magnesium solution can be made solution and prepares by making described magnesium compound be dissolved in alcohol under the situation that has or do not exist varsol.The type that is used for varsol of the present invention can be aliphatic hydrocrbon such as pentane, hexane, heptane, octane, decane and kerosene; Clicyclic hydrocarbon is as ring benzene, methyl ring benzene, hexanaphthene and methylcyclohexane; Aromatic hydrocarbon such as benzene,toluene,xylene, ethylbenzene etc.; Halohydrocarbon such as propylene dichloride, Ethylene Dichloride, trieline, tetracol phenixin and chlorobenzene etc.Preparing magnesium solution by magnesium compound can make solvent with alcohol and carry out under the situation that adds or do not add varsol.The type of alcohol can comprise alcohol such as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, octanol, decyl alcohol, dodecanol, Stearyl alcohol, benzylalcohol, phenylethyl alcohol, Isobutyl Benzyl Carbinol and the cumic alcohol that contains 1～20 carbon atom, the alcohol of optional self-contained 1～12 carbon atom of preferred alcohol.The mean particle size of gained catalyzer and size-grade distribution can be depending on the ratio of the type of consumption, magnesium compound of type, alcohol of used alcohol and magnesium compound and alcohol.In the process of preparation magnesium solution, magnesium compound can carry out in the presence of hydrocarbon with the reaction of alcohol.Though temperature of reaction can change according to the type and the consumption of used alcohol, can be at least about-25 ℃, preferred-10 to 200 ℃ or more preferably from about 0 to 150 ℃ approximately.Reaction times can be about 15 minutes to 5 hours or preferred about 30 minutes to 4 hours.
The organoboron compound of described no reactive hydrogen is R as general formula
1 xR
2 yB (OR
3)
zShown organoboron compound, wherein R
1And R
2Be respectively carbonatoms and be 1～10 alkyl,-oxyl, aryl or halogen, R
3For carbonatoms is 1～10 alkyl, 0≤x≤3,0≤y≤3 and 0≤z≤3, and x+y+z=3;
The represented boron compound of above-mentioned general formula comprises: comprise trimethyl-boron, triethyl-boron, methyl diethyl boron, trimethyl borate, triethyl borate, tributyl borate, triphenyl borate and boric acid three monooctyl esters, diethoxymethyl boron, diethoxy ethyl boron, dibutoxy ethyl boron, dibutoxy butyl boron, two Phenoxyphenyl boron, oxyethyl group diethyl boron, oxyethyl group dibutyl boron, phenoxy group phenylbenzene boron, chlorination diethoxy boron, bromination diethoxy boron, diphenyl antimony chloride oxygen base boron, dichloride oxyethyl group boron, dibrominated oxyethyl group boron, dichloride butoxy boron, dichloride phenoxy group boron and tonsilon oxyethyl group boron etc.
Described titanium compound general formula is Ti (OR)
aX
b, R is C in the formula
1～C
10Aliphatic group or aryl, X is a halogen, a is 0,1,2 or 3, b is 1 to 4 integer, a+b=3 or 4;
When described magnesium combination compound solution and titanium compound reaction, the shape of the solid titanium catalyst component of separating out and size depend primarily on the condition of reaction.In order to control particle shape, may preferably make the mixture of described magnesium compound solution and titanium compound, organoboron compound under enough low temperature, react the generation solid substance composition.Described boron compound can also can contact back adding system at magnesium compound solution in magnesium compound solution and adding system before titanium compound contacts with titanium compound.Described temperature of reaction can be-70 to 70 ℃ approximately, more preferably from about-50 to 50 ℃.After the described contact reacts, described temperature of reaction is slowly raise to continue about 0.5～5 hour abundant reaction down at about 50 to 150 ℃.The solid catalyst particle that obtains is as mentioned above reacted with additional titanium compound again.Used titanium compound can be halogenated titanium or halogenated alkoxy titanium, and wherein alkoxy-functional has 1～20 carbon atom.Also can use the mixture of these compounds in the time of suitably.In these compounds, halogenated titanium or wherein alkoxy-functional have the halogenated alkoxy titanium of 1～8 carbon atom to be fit to, preferred compound is a titanium tetrahalide.Can be used for the polymerization and the copolymerization of ethene by the catalyzer of the method for the invention preparation.Especially, described catalyzer can be used for the homopolymerization of ethene, also can be used for ethene and has 3 or the alpha-olefin of more carbon atoms such as the copolymerization of propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene or 1-hexene.Use the polyreaction useful catalyst system of catalyzer of the present invention to carry out, described catalyst system comprises: (1) magnesium, titanium and solid titanium complex catalyst of giving electron compound of comprising described herein; (2) alkyl metal cpd or alumina metal compound.Described organometallic compound is the trialkylaluminium that the alkyl of 1～6 carbon atom is arranged, as triethyl aluminum and triisobutyl aluminium or its mixture.In the time of suitably, also can use the organo-aluminium compound of one or more halogen or hydrogen foundation group, as ethylaluminium dichloride, diethylaluminum chloride, sesquialter ethylaluminium chloride or diisobutylaluminium hydride.Be used for before the polyreaction, can make solid titanium complex catalyst component described herein and ethene or alpha-olefin pre-polymerization.Described pre-polymerization can be in the presence of varsol such as the hexane, under the enough low temperature, carrying out under the pressure of ethene or alpha-olefin and in the presence of above-mentioned catalyst component and organo-aluminium compound such as triethyl aluminum.In the polymerization reaction system in organo-aluminium compound and the solid titanium complex catalyst mol ratio of titanium be 1～1000, preferred 20～200.For guaranteeing high polymerization rate, described polyreaction needs to carry out under sufficiently high temperature, and usually, the temperature that is fit to is about 20 to 200 ℃, more preferably from about 60 to 95 ℃.The monomer pressure that is fit in the polymerization process is 1～100atm, 2～50atm more preferably from about.
With embodiment the present invention is described below, but and unrestricted invention scope.
Embodiment 1 is heated to 130 ℃ to 4.76 gram (50mmol) Magnesium Chloride Anhydrouss, 75 milliliters of decane and 16.3 gram (125mmol) isooctyl alcohol, makes it to react 3 hours, obtains a kind of homogeneous phase solution.In this solution, add the tributyl borate of 15mmol and stir 2 hours so that tributyl borate is dissolved in this solution down at 50 ℃.Above-mentioned all homogeneous phase solutions that obtain are cooled to room temperature, in 1 hour, while stirring it are added drop-wise to then in the 150mL titanium tetrachloride that temperature remains 0 ℃.Mixture temperature was kept 1 hour down at 0 ℃, under agitation in 2 hours, temperature is carried to 120 ℃ then, and this temperature was kept 2 hours.After reaction in 2 hours finishes, the solid that generates is carried out heat filtering separate.With hexane and decane solid catalyst is carried out thorough washing respectively,, obtain a kind of solid titanium catalyst component after drying until in scavenging solution, can not detecting the titanium compound of separating out.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, adding hexane 1L and concentration is the triethyl aluminum 1.0mL of 1M, the catalyzer that adds the above-mentioned preparation of accurate weighing with syringe, be warming up to 75 ℃, feed hydrogen and make the still internal pressure reach 0.28MPa, feed ethene again and make the interior stagnation pressure of still reach 0.73MPa (gauge pressure), polymerization is 2 hours under 80 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 2 is heated to 130 ℃ to 4.76 gram (50mmol) Magnesium Chloride Anhydrouss, 75 milliliters of decane and 16.3 gram (125mmol) isooctyl alcohol, makes it to react 3 hours, obtains a kind of homogeneous phase solution.In this solution, add the phenyl-boron dihydroxide diethyl ester of 15mmol and stir 2 hours down so that the phenyl-boron dihydroxide diethyl ester is dissolved in this solution at 50 ℃.Above-mentioned all homogeneous phase solutions that obtain are cooled to room temperature, in 1 hour, while stirring it are added drop-wise to then in the 150mL titanium tetrachloride that temperature remains 0 ℃.Mixture temperature was kept 1 hour down at 0 ℃, under agitation in 2 hours, temperature is carried to 120 ℃ then, and this temperature was kept 2 hours.After reaction in 2 hours finishes, the solid that generates is carried out heat filtering separate.With hexane and decane solid catalyst is carried out thorough washing respectively,, obtain a kind of solid titanium catalyst component after drying until in scavenging solution, can not detecting the titanium compound of separating out.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, the triethyl aluminum 1.0mL that adds hexane 1L and concentration 1M, the catalyzer that adds the above-mentioned preparation of accurate weighing with syringe, be warming up to 75 ℃, feed hydrogen and make the still internal pressure reach 0.28MPa, feed ethene again and make the interior stagnation pressure of still reach 0.73MPa (gauge pressure), polymerization is 2 hours under 80 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 3 is with embodiment 1, and difference is that the add-on of tributyl borate is 20mmol.Polymerization result sees Table 1.
Embodiment 4 is with embodiment 1, and difference is that the add-on of tributyl borate is 10mmol.Polymerization result sees Table 1.
Embodiment 5 is with embodiment 1, and difference is that the add-on of decane is 50mL.Polymerization result sees Table 1.
Embodiment 6 is heated to 130 ℃ to 4.76 gram (50mmol) Magnesium Chloride Anhydrouss, 75 milliliters of decane and 16.3 gram (125mmol) isooctyl alcohol, makes it to react 3 hours, obtains a kind of homogeneous phase solution.In this solution, add the triphenyl borate of 15 mmoles and stir 2 hours so that triphenyl borate is dissolved in this solution down at 50 ℃.Above-mentioned all homogeneous phase solutions that obtain are cooled to room temperature, in 1 hour, while stirring it are added drop-wise to then in the 150mL titanium tetrachloride that temperature remains 0 ℃.Mixture temperature was kept 1 hour down at 0 ℃, under agitation in 2 hours, temperature is carried to 120 ℃ then, and this temperature was kept 2 hours.After reaction in 2 hours finishes, the solid that generates is carried out heat filtering separate.With hexane and decane solid catalyst is carried out thorough washing respectively,, obtain a kind of solid titanium catalyst component after drying until in scavenging solution, can not detecting the titanium compound of separating out.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, the triethyl aluminum 1.0mL that adds hexane 1L and concentration 1M, the catalyzer that adds the above-mentioned preparation of accurate weighing with syringe, be warming up to 75 ℃, feed hydrogen and make the still internal pressure reach 0.28MPa, feed ethene again and make the interior stagnation pressure of still reach 0.73MPa (gauge pressure), polymerization is 2 hours under 80 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 7 is heated to 130 ℃ to 4.76 gram (50mmol) Magnesium Chloride Anhydrouss, 75 milliliters of decane and 16.3 gram (125mmol) isooctyl alcohol, makes it to react 3 hours, obtains a kind of homogeneous phase solution.In this solution, add the methyl-boron-dihydroxide dibutylester of 15 mmoles and stir 2 hours so that the methyl-boron-dihydroxide dibutylester is dissolved in this solution down at 50 ℃.Above-mentioned all homogeneous phase solutions that obtain are cooled to room temperature, in 1 hour, while stirring it are added drop-wise to then in the 150mL titanium tetrachloride that temperature remains 0 ℃.Mixture temperature was kept 1 hour down at 0 ℃, under agitation in 2 hours, temperature is carried to 120 ℃ then, and this temperature was kept 2 hours.After reaction in 2 hours finishes, the solid that generates is carried out heat filtering separate.With hexane and decane solid catalyst is carried out thorough washing respectively,, obtain a kind of solid titanium catalyst component after drying until in scavenging solution, can not detecting the titanium compound of separating out.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add hexane 1L, the triethyl aluminum 1.0mL of concentration 1M adds the catalyzer of the above-mentioned preparation of accurate weighing with syringe, is warming up to 75 ℃, feeding hydrogen makes the still internal pressure reach 0.28MPa, feed ethene again and make the interior stagnation pressure of still reach 0.73MPa (gauge pressure), polymerization is 2 hours under 80 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 8 Preparation of catalysts are with embodiment 1, and difference is that the boron-containing compound that adds is a sec.-propyl boric acid dibutylester.Vinyl polymerization is with embodiment 1, and polymerization result sees Table 1.
Embodiment 9 Preparation of catalysts are with embodiment 1, and difference is that the boron-containing compound that adds is a triethyl borate.The embodiment of vinyl polymerization department 1, polymerization result sees Table 1.
Embodiment 10 is heated to 130 ℃ to 4.76 gram (50mmol) Magnesium Chloride Anhydrouss, 75 milliliters of decane and 16.3 gram (125mmol) isooctyl alcohol, makes it to react 3 hours, obtains a kind of homogeneous phase solution.In this solution, add the tributyl borate of 15mmol and stir 2 hours so that tributyl borate is dissolved in this solution down at 50 ℃.Above-mentioned all homogeneous phase solutions that obtain are cooled to 0 ℃, and the 150mL titanium tetrachloride that will remain 0 ℃ then in 1 hour while stirring is added drop-wise in the above-mentioned homogeneous phase solution.Mixture temperature was kept 1 hour down at 0 ℃, under agitation in 2 hours, temperature is carried to 120 ℃ then, and this temperature was kept 2 hours.After reaction in 2 hours finishes, the solid that generates is carried out heat filtering separate.With hexane and decane solid catalyst is carried out thorough washing respectively,, obtain a kind of solid titanium catalyst component after drying until in scavenging solution, can not detecting the titanium compound of separating out.
Vinyl polymerization is with embodiment 1, and polymerization result sees Table 1.
Claims (6)
1. a solid titanium catalyst component that is used for vinyl polymerization and copolymerization, preparation as follows: the preparation of (1) homogeneous phase magnesium solution is that magnesium halide is dissolved in alkylol cpd; (2) in above-mentioned magnesium compound, add a kind of boron compound at least; (3) make the reaction of described magnesium compositions solution and titanium compound produce the spherical titanium catalyst of solid kind through recrystallization;
Wherein said liquid magnesium compound is that magnesium halide is dissolved in resulting product in the organic alcohol solvent system; Dissolution process can carry out in the presence of thinner.
Described organic alcohol compound is that carbonatoms is that alkyl alcohol, cycloalkanol and the carbonatoms of 1～10 straight chain, side chain is that 6～20 fragrant and mellow or aralkyl is pure, and the halides of above-mentioned organic alcohol;
Described titanium compound general formula is Ti (OR)
aX
b, R is C in the formula
1～C
10Aliphatic group or aryl, X is a halogen, a is 0,1,2 or 3, b is 1 to 4 integer, a+b=3 or 4;
The organoboron compound of described no reactive hydrogen such as general formula are R
1 xR
2 yB (OR
3)
zShown organoboron compound, wherein R
1And R
2Be respectively carbonatoms and be 1～10 alkyl,-oxyl, aryl or halogen, R
3For carbonatoms is 1～10 alkyl, 0≤x≤3,0≤y≤3 and 0≤z≤3, and x+y+z=3;
2. the catalyst component that is used for vinyl polymerization or copolymerization according to claim 1 is characterized in that described organoboron compound preferably is selected from one or more in trimethyl borate, triethyl borate, tripropoxy-boron, tributyl borate or boric acid three monooctyl esters.
3. the catalyst component that is used for vinyl polymerization or copolymerization according to claim 1, it is characterized in that described organic alcohol compound, preferably be selected from one or more of methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, 2-methyl amyl alcohol, 2-ethyl butanol, enanthol, 2-Ethylhexyl Alcohol, octanol and decyl alcohol.
4. according to the described catalyst component that is used for vinyl polymerization or copolymerization of one of claim 1～3, ratio between each reactant is in every mole in magnesium compound magnesium halide, organic alcohol compound is: 0.1～10.0 mole, boron compound is 0.05～1.0 mole, and titanium compound is 1.0～15.0 moles.
5. catalyzer that is used for vinyl polymerization or copolymerization, it comprises the reaction product of following component:
(1) the described catalyst component of claim 1～4;
(2) 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, 0＜n≤3.
6. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 5, wherein the mol ratio of the middle titanium of aluminium and component (1) is 10～1000 in the component (2).
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100889138A CN101245115A (en) | 2008-04-07 | 2008-04-07 | Homopolymerization and combined polymerization catalyst of ethylene and preparation method thereof |
| CN2009801146559A CN102272172A (en) | 2008-04-07 | 2009-04-07 | Method for preparing a titanium catalyst component, titanium catalyst component, method for preparing a titanium catalyst and titanium catalyst |
| PCT/EP2009/002566 WO2009124722A1 (en) | 2008-04-07 | 2009-04-07 | Method for preparing a titanium catalyst component, titanium catalyst component, method for preparing a titanium catalyst and titanium catalyst |
| DE112009000794T DE112009000794T5 (en) | 2008-04-07 | 2009-04-07 | A process for producing a titanium catalyst component, a titanium catalyst component, a process for producing a titanium catalyst, and a titanium catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100889138A CN101245115A (en) | 2008-04-07 | 2008-04-07 | Homopolymerization and combined polymerization catalyst of ethylene and preparation method thereof |
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| CN101245115A true CN101245115A (en) | 2008-08-20 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009132825A1 (en) * | 2008-04-29 | 2009-11-05 | Süd-Chemie AG | Method for preparing a titanium catalyst component, titanium catalyst component, method for preparing a titanium catalyst and titanium catalyst |
| CN102272172A (en) * | 2008-04-07 | 2011-12-07 | 南方化学股份公司 | Method for preparing a titanium catalyst component, titanium catalyst component, method for preparing a titanium catalyst and titanium catalyst |
| CN102372799A (en) * | 2010-08-19 | 2012-03-14 | 中国石油化工股份有限公司 | Catalyst ingredient used for alkene polymerization and preparation method thereof |
| CN102372800A (en) * | 2010-08-19 | 2012-03-14 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method thereof |
| CN102453169A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Catalyst ingredient for olefin polymerization and preparation method thereof |
| US9068025B2 (en) | 2010-08-19 | 2015-06-30 | China Petroleum & Chemical Corporation | Catalyst component for polymerization of olefin and preparation method |
| CN104829758A (en) * | 2015-05-17 | 2015-08-12 | 北京化工大学 | Alkene polymerization catalyst as well as preparation method and application thereof |
| CN114539449A (en) * | 2020-11-24 | 2022-05-27 | 中国石油天然气股份有限公司 | Titanium catalyst component for ethylene polymerization and preparation method and application thereof |
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2008
- 2008-04-07 CN CNA2008100889138A patent/CN101245115A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102272172A (en) * | 2008-04-07 | 2011-12-07 | 南方化学股份公司 | Method for preparing a titanium catalyst component, titanium catalyst component, method for preparing a titanium catalyst and titanium catalyst |
| WO2009132825A1 (en) * | 2008-04-29 | 2009-11-05 | Süd-Chemie AG | Method for preparing a titanium catalyst component, titanium catalyst component, method for preparing a titanium catalyst and titanium catalyst |
| CN102372799A (en) * | 2010-08-19 | 2012-03-14 | 中国石油化工股份有限公司 | Catalyst ingredient used for alkene polymerization and preparation method thereof |
| CN102372800A (en) * | 2010-08-19 | 2012-03-14 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method thereof |
| CN102372799B (en) * | 2010-08-19 | 2013-03-27 | 中国石油化工股份有限公司 | Catalyst ingredient used for alkene polymerization and preparation method thereof |
| CN102372800B (en) * | 2010-08-19 | 2013-03-27 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method thereof |
| US9068025B2 (en) | 2010-08-19 | 2015-06-30 | China Petroleum & Chemical Corporation | Catalyst component for polymerization of olefin and preparation method |
| CN102453169A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Catalyst ingredient for olefin polymerization and preparation method thereof |
| CN102453169B (en) * | 2010-10-19 | 2013-02-27 | 中国石油化工股份有限公司 | Catalyst ingredient for olefin polymerization and preparation method thereof |
| CN104829758A (en) * | 2015-05-17 | 2015-08-12 | 北京化工大学 | Alkene polymerization catalyst as well as preparation method and application thereof |
| CN114539449A (en) * | 2020-11-24 | 2022-05-27 | 中国石油天然气股份有限公司 | Titanium catalyst component for ethylene polymerization and preparation method and application thereof |
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