CN1590415A - Preparation method of olefine polymerization catalyst solid component - Google Patents
Preparation method of olefine polymerization catalyst solid component Download PDFInfo
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- CN1590415A CN1590415A CN 03155998 CN03155998A CN1590415A CN 1590415 A CN1590415 A CN 1590415A CN 03155998 CN03155998 CN 03155998 CN 03155998 A CN03155998 A CN 03155998A CN 1590415 A CN1590415 A CN 1590415A
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Abstract
A solid catalyst component for preparing alpha-olefin homopolymer or copolymer with high catalytic activity is prepared through reacting between C2-C4 alcohol and Mg powder under existance of halomethane to obtain Mg matches solution, reacting on inorganic carrier, drying to obtain Mg carrier, and reacting on Ti(OR)nCl4-n in inertial hydrocarbon solvent, where R is C2-C8 alkyl and n=0-4.
Description
Technical field
The present invention is a kind of preparation method of catalyst solid component of olefin polymerization, specifically, is a kind of preparation method of loading type Ziegler-Natta catalyst solid ingredient.
Background technology
At present, industrial widely used efficient Ziegler-Natta catalyst system comprises Ziegler-Natta catalyst solid ingredient and promotor, is generally organo-aluminium compound.Wherein catalyst solid constituent is made of the halogenated titanium that is carried on magnesium compound or other carrier.Normally titanium tetrachloride is carried on the magnesium chloride and obtains the solid ingredient of efficient Ziegler-Natta catalyst.
The particle form of catalyst solid constituent and size distribution are most important to the use properties of catalyzer, and narrow size distribution helps the stable operation of production unit.Especially in gas-phase polyethylene technology, the catalyst solid constituent size distribution is even, can avoid occurring superfine polymer beads and wide polymer beads distribution during reaction.For this reason, many patents at first prepare the pure and mild thing carrier of spherical magnesium chloride, further again dealcoholysis and load TiCl
4Have the catalyst solid constituent of good particle form with preparation, promptly adopt this method to prepare catalyst solid constituent as USP4469648.This legal system is equipped with the complex process of the pure and mild thing coccoid of magnesium chloride, the cost height, and be difficult to obtain narrower size distribution.
USP4,698,323 usefulness dialkoxy magnesium and TiCl
4The prepared in reaction catalyst solid constituent, its used dialkoxy magnesium is dissolved in organic solvent, preferred methoxy ethoxy magnesium, diethoxy magnesium, butoxy magnesium ethylate etc.Direct reaction in the presence of hydrocarbon solvent makes dialkoxy magnesium by MAGNESIUM METAL and alkoxyl alcohol in this method.Adding iodine or mercury chloride are catalyzer during reaction, to promote the generation of alkoxide.
CN1016422B discloses a kind of preparation method of Ziegler-Natta type catalyst solid constituent, this method is in the presence of transition metal alkoxide, make the reaction of solubility dialkoxy magnesium and transition metal halide, the reusable liquid hydrocarbon is settled out solid ingredient, can obtain the spherical catalyst solid ingredient that distributes very narrow.Alkoxyl group in the dialkoxy magnesium that it adopts is the branched alkoxy that contains the line style alkoxyl group of 6-12 carbon atom or 5-12 carbon atom arranged, so that can form the pure magnesium solution that is dissolved in liquid hydrocarbon.
The another kind of method that prepare the spherical catalyst solid ingredient is to be carrier with the microsphere silica gel, makes it have activity by the muriate that forms magnesium on the silica gel surface, thus the titanium compound formation catalyzer that can load has catalytic activity.It is the activated carbon component that this method generally adopts alkoxyl magnesium or alkyl magnesium, it is dissolved in forms solution in the liquid hydrocarbon, and then, magnesium compound load on silica gel, is made catalyzer with this magnesium-containing carrier load titanium compound again with this solution-treated silica-gel carrier.Adopt alkyl magnesium and alkyl chloride reaction to make the carrier of spherical magnesium chloride as the vapor phase process catalyzer as USP4497904, and then titanium compound is reacted with it, the catalyzer that makes has narrower size distribution, can be applicable to gas phase polymerization technology fully.
CN1264393A with the reaction of orthosilicic acid tetraalkyl ester, carries dialkyl magnesium and silica supports reaction at last titanium and makes catalyzer again.This is the technology of feedstock production catalyzer with the dialkyl magnesium, because dialkyl magnesium costs an arm and a leg and is difficult to obtain and causes the catalyzer cost to raise.
CN1087304C prepares the method for catalyst solid constituent and at first handles inorganic carrier with the kelene Base Metal, and then the carrier after will handling and the compound contact reacts that contains alkyl, alkoxyl group and magnesium, final load active ingredient titanium compound.The preferred ethylaluminium dichloride of described kelene Base Metal; Described magnesium compound is made by solubility dialkyl magnesium and alcohol reaction, and preferred alkyl magnesium is dibutylmagnesium, butyl ethyl magnesium or butyl octyl magnesium, and preferred alcohol is branched-chain alcoho.In the reaction gained magnesium compound a small amount of alkyl magnesium group to be arranged, thereby will control dialkyl magnesium and pure charge ratio between 1: 2 to 1: 1.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who is applicable to the Ziegler-Natta type catalyst solid constituent of alkene gas-phase polymerization, this method preparation is simple, and raw material is easy to get.
The preparation method of catalyst solid component of olefin polymerization provided by the invention comprises the steps that titanium content is 0.5-5.0 quality % in the wherein said catalyst solid constituent, and Mg content is 0.5-10.0 quality %, preferred 1.0-5.0 quality %.
(1) in the presence of methyl halide, makes C
2-C
4Alcohol and magnesium powder press 2.0-4.0: 1 mol ratio forms uniform magnesium complex solution 20-200 ℃ of reaction, and the mass ratio of described methyl halide and magnesium powder is 10-500: 1,
(2) with the magnesium complex solution and the abundant contact reacts of inorganic carrier of above-mentioned preparation, obtain magnesium-containing carrier after the drying,
(3) in unreactive hydrocarbons solvent, magnesium-containing carrier and general formula that (2) step is made are Ti (OR)
nCl
4-nThe titanium compound contact reacts, remove and to desolvate, obtain catalyst solid constituent after the drying, R is C in the described general formula
2-C
8Alkyl, n is the integer of 0-4.
The present invention prepares the method for catalyst solid component of olefin polymerization, adopting commercially available magnesium powder is raw material, it is reacted with low carbon fat alcohol in methyl halide, prepare a kind of soluble magnesium complex solution that contains magnesium, chlorine and alkoxyl group, use this solution-treated porous inorganic carrier then, magnesium complex is loaded on the carrier, again the carrying transition metal active ingredient.The present invention compares with the method for preparing catalyst solid constituent with alkoxyl magnesium or alkyl magnesium, raw materials used cheap and easy to get, preparation is simple, convenient, and the catalyst solid constituent that makes has good particle form, narrow size distribution and excellent flowing when keeping catalytic activity.Thereby, with polymerization catalyst production polyolefin products of the present invention, can obtain having the polyolefin products of good particle form, and the fine polymer powder amount is few and have higher apparent density.
Embodiment
The at first synthetic magnesium complex that contains alkoxyl group and chlorine of the inventive method, the synthetic method is to make MAGNESIUM METAL and low-carbon alcohol reaction, and be reaction medium with the inertia halohydrocarbon that can not directly react with MAGNESIUM METAL, the reaction back generates even clarifying magnesium complex solution.After this solution drying, can record the chlorine that wherein contains 10-20 quality %, the alkoxyl group of 50-80 quality % and the magnesium of 5-15 quality %.
In the reaction of above-mentioned preparation magnesium complex solution, used haloalkane should be not and the MAGNESIUM METAL direct reaction, generates haloalkyl magnesium to avoid " grignard reaction " takes place.The used haloalkane of the present invention is a methyl halide, preferred methylene dichloride, trichloromethane or tetrachloromethane.The used methyl halide and the preferred 50-500 of mass ratio of MAGNESIUM METAL during reaction: 1.When adopting the haloalkane that can react with MAGNESIUM METAL, carry out (1) of the present invention when reaction step as n-propylcarbinyl chloride, chloric ethane etc. for solvent, the magnesium complex that contains of solubility can't be obtained, and then the even dipping of active ingredient on porous silica gel can't be realized.
The used alcohol of the inventive method (1) step reaction should be carbonatoms and is lower than six Fatty Alcohol(C12-C14 and C12-C18), preferred C
2-C
4Fatty Alcohol(C12-C14 and C12-C18), more preferably ethanol, propyl alcohol, Virahol, butanols or isopropylcarbinol.
Described (1) step the preferred 30-60 of temperature of reaction ℃.In reactant, add some initiator such as I commonly used
2, mercury chloride etc. can impel the reaction fast speeds to carry out.
(2) of the inventive method step is with magnesium complex solution inorganic carrier to be handled, so that magnesium complex is carried on process on the carrier.Load should under agitation be carried out, and magnesium complex solution is 0-100 ℃ with the temperature that contacts of inorganic carrier during load, and preferred 30-60 ℃, preferred 0.5-6.0 of reaction times hour.After the load, remove volatile matter,, promptly obtain magniferous carrier carrier drying.Mg content is 0.1-5.0 mmole/gram in the carrier.
The used preferred silicon-dioxide of inorganic carrier of above-mentioned (2) step, its specific surface area is a 100-500 rice
2/ gram, pore volume is 1-3 milliliter/gram.The spherical porous property silicon-dioxide of most commercial all can satisfy this requirement, as the silica gel of the trades mark such as the SYLOPOL 955,948 of Grace company and XPO2485.Described silicon-dioxide will activate before use, and be about to silica gel and carry out drying treatment at 100-900 ℃, so that the silica sphere hydroxy radical content is not more than 2.0 mmole/grams, preferred 0.3-2.0 mmole/gram.Generally silica gel can be reached above-mentioned requirements at dry 2-6 more than 500 ℃ hour.Raising drying treatment temperature and prolongation treatment time can make the hydroxy radical content on silica gel surface further reduce.
The inventive method (3) step is the process of supported catalyst active ingredient.Load is in the presence of unreactive hydrocarbons solvent, makes the magnesium-containing carrier and the abundant contact reacts of titanium compound of the inventive method preparation.Described unreactive hydrocarbons solvent is selected from C
5-C
8Alkane or aromatic hydrocarbons, preferred hexane, heptane or toluene.The consumption of unreactive hydrocarbons is 5-100 a times of carrier quality.Preferred titanium tetrachloride of described titanium compound or titan-alkoxide, preferred titanium butoxide of titan-alkoxide or ethanolato-titanium.The amount that adds titanium compound during load should make wherein titanium and carrier in the atomic ratio of magnesium be 0.5-20: 1.The contact reacts temperature of described titanium compound and carrier is 20-200 ℃, preferred 40-80 ℃, and preferred 0.5-6.0 of time hour.The load of described titanium can repeat one to multiple time, to meet the requirements of the titanium amount of carrying.After the load, remove unreactive hydrocarbons solvent, the gained solid is drying to obtain mobile fabulous catalyst solid constituent at 40-80 ℃.
The present invention is the titanium content in the regulation and control solid catalytic component, uses silicate ester compound that carrier is handled.This treatment step can carry out when the load magnesium complex, also can carry out when load active component.Specifically, can at the magnesium complex solution that makes of (1) step or to add general formula in (3) step during load active component be Si (OR ')
4Silicate ester compound, make in the process of load magnesium complex or titanium compound the silicate ester compound of load simultaneously.R ' is selected from C in the described silicate ester compound general formula
2-C
8Alkyl.Preferred silicate ester compound is tetramethoxy-silicane, tetraethoxysilane, tetraisopropoxysilan, tetrapropoxysilane, four butoxy silanes or their mixture, more preferably tetraethoxysilane.The consumption of silicate ester compound should make that the atomic ratio of magnesium and silicon is 0.5-5.0: 1.
Catalyst solid constituent that the present invention makes and promotor alkylaluminium cpd are used, and can be used as the catalyzer of alpha-olefin homopolymerization or copolyreaction.Preferred promotor is a trialkyl aluminium compound, as triethyl aluminum, three n-butylaluminum or triisobutyl aluminium.Al/Ti mol ratio suitable during polyreaction is 20-800, preferred 20-300.Temperature of reaction is 60-120 ℃, and preferred 80-100 ℃, pressure is 0.1-6.0MPa, preferred 0.4-2.0MPa.
Be used for the preferred C of polymeric alpha-olefin
2-C
12Alpha-olefin, as ethene, third rare, butylene, hexene or octene etc.That the used comonomer of copolymerization can be is third rare, butylene, hexene or octene.Be the molecular weight of telomerized polymer, can add chain-transfer agent during polymerization.Preferred chain-transfer agent is a hydrogen.
Further specify the present invention below by example, but the present invention is not limited to this.
Example 1
Following examples preparation magnesium complex of the present invention.
With three mouthfuls of reaction flask N that have a magnetic stirring apparatus
2Fully displacement, and at N
2Air-flow adds Mg powder 1.0 grams, I20.1 gram, 100 milliliters of methylene dichloride down.40 ℃ were stirred 2 hours, added 8 milliliters of propyl carbinol reactions 8 hours then, obtained even clear soln a.
Get 20 ml soln a at N
2The following 60 ℃ of dryings of air-flow 6 hours obtain the white solid powder, are magnesium complex, wherein contain magnesium 9.36 quality %, n-butoxy (n-BuO-) 69.08 quality %, chlorine 14.66 quality %.
Example 2
Method by example 1 prepares magnesium complex solution, and different is that the alcohol that adds is 8 milliliters of isopropylcarbinols (i-BuOH), obtains even clear soln b.
Get 20 ml soln b at N
2The following 60 ℃ of dryings of air-flow 6 hours obtain the white solid powder, are magnesium complex, wherein contain magnesium 9.68 quality %, isobutoxy (i-BuO-) 69.08 quality %, chlorine 16.66 quality %.
Example 3
Method by example 1 prepares magnesium complex solution, and the methyl chloride that adds when different is reaction is 100 milliliters of trichloromethanes, and alcohol is 8 milliliters of ethanol (EtOH), obtains even clear soln c.
Get 20 ml soln c at N
2The following 60 ℃ of dryings of air-flow 6 hours obtain the white solid powder, are magnesium complex, wherein contain magnesium 9.88 quality %, oxyethyl group (EtO-) 58.08 quality %, chlorine 19.63 quality %.
Example 4
Method by example 1 prepares magnesium complex solution, and different is that the alcohol that adds is 8 milliliters of propyl alcohol (n-PrOH), obtains even clear soln d.
Get 20 ml soln d at N
2The following 60 ℃ of dryings of air-flow 6 hours obtain the white solid powder, are magnesium complex, wherein contain magnesium 9.70 quality %, propoxy-(n-PrO-) 63.55 quality %, chlorine 18.43 quality %.
Example 5
Following examples preparation spherical catalyst solid ingredient.
(1) with three mouthfuls of reaction flask N that have a mechanical stirring device
2Fully displacement, and at N
2Air-flow adds 2.0 gram microsphere silica gels (Grace company produces, trade mark SYLOPOL 948) down.This silica gel specific surface area is 320 meters
2/ gram, pore volume are 1.6 milliliters/gram, handle 6 hours at 600 ℃ before using, and its The adsorbed hydroxyl content is 0.89 mmole/gram.
(2) 6 milliliters of examples 1 are made magnesium complex solution a and add in the reaction flask, 40 ℃ of abundant stirring reactions 30 minutes, 60 ℃ of dryings 2 hours, free mobile magnesium-containing carrier, wherein Mg content is 1.1 mmole/grams.
(3) go on foot 20 milliliters of hexanes of adding in the magnesium-containing carrier that makes, 2 milliliters of TiCl in (2)
460 ℃ of stirring reactions 1 hour, then supernatant liquid is taken away, and with hexane wash residual solid 3 times, each Xian Di is with 20 milliliters of hexanes, will wash the back solid again 60 ℃ of dryings 2 hours, 2.5 restrain the fabulous spherical catalyst solid ingredient A of flowability, wherein titaniferous 3.64 quality % contain magnesium 2.66 quality %.
Example 6
Method by example 5 prepares catalyst solid constituent, and different is the silica gel of (1) step used silica gel for the trade mark XPO2485 of Grace company production, and (2) step adds 4 milliliters of magnesium complex solution a, and Mg content is 0.8 mmole/gram in the magnesium-containing carrier that obtains.(3) step adds 1.5 milliliters of TiCl
4, get the mobile fabulous spherical catalyst solid ingredient B of 2.2 grams after the drying.Wherein the specific surface area of (1) step used silica gel is 300 meters
2/ gram, pore volume are 1.5 milliliters/gram, and 600 ℃ are handled 6 hours rear surface hydroxy radical contents is 0.43 mmole/gram.Titaniferous 3.48 quality % among the catalyst solid constituent B contain magnesium 2.12 quality %.
Example 7
Method by example 5 prepares catalyst solid constituent, different is that the magnesium complex solution that adds in (2) step is the solution b that example 2 makes, Mg content is 1.0 mmole/grams in the magnesium-containing carrier that obtains, and gets the mobile fabulous spherical catalyst solid ingredient C of 2.3 grams after (3) step is carried titanium.Wherein titaniferous 3.34 quality % contain magnesium 2.54 quality %.
Example 8
Method by example 5 prepares catalyst solid constituent, different is that the magnesium complex solution that adds in (2) step is the solution c that example 3 makes, Mg content is 1.0 mmole/grams in the magnesium-containing carrier that obtains, and gets the mobile fabulous spherical catalyst solid ingredient D of 2.6 grams after (3) step is carried titanium.Wherein titaniferous 3.75 quality % contain magnesium 2.66 quality %.
Example 9
Method by example 5 prepares catalyst solid constituent, different is that the magnesium complex solution that adds in (2) step is the solution d that example 4 makes, Mg content is 0.9 mmole/gram in the magnesium-containing carrier that obtains, and gets the mobile fabulous spherical catalyst solid ingredient E of 2.4 grams after (3) step is carried titanium.Wherein titaniferous 3.76 quality % contain magnesium 2.33 quality %.
Example 10
After by the method in example 5 (1) step the trade mark being the thermal treatment of XPO2485 silica gel, at N
2Air-flow adds down uses N
2Fully in three mouthfuls of reaction flasks of metathetical, add magnesium complex solution a, 20 milliliters of methylene dichloride and 0.25 milliliter of tetraethoxysilane that 4 milliliters of examples 1 make then.40 ℃ of abundant stirring reactions 30 minutes, 60 ℃ of dryings 2 hours, Mg content is 0.8 mmole/gram in the magnesium-containing carrier that obtains.
In the above-mentioned magnesium-containing carrier that makes, add 20 milliliters of hexanes, 0.75 milliliter of TiCl
4, 60 ℃ were reacted 1 hour, then supernatant liquid were taken away, added 20 milliliters of hexanes again, 0.75 milliliter of TiCl
4, 60 ℃ are continued reaction 1 hour, use hexane wash gained solid 3 times at last, 20 milliliters of hexanes are used in each washing, 60 ℃ of dryings 2 hours, the mobile fabulous spherical catalyst solid ingredient F of 2.2 grams, wherein titaniferous 2.28 quality % contain magnesium 2.11 quality %,
Example 11
Method by example 10 prepares catalyst solid constituent, and different is that the magnesium complex solution that adds is the solution b that example 2 makes, and Mg content is 0.9 mmole/gram in the magnesium-containing carrier that obtains.This carrier gets the mobile fabulous spherical catalyst solid ingredient G of 2.1 grams after carrying titanium and drying, wherein titaniferous 2.36 quality % contain magnesium 2.21 quality %.
Example 12-18
Following example is estimated the polymerization catalyzed performance of the catalyst solid constituent of the present invention's preparation.
2 liters of stainless steel polymermaking autoclaves are fully replaced with nitrogen, add 1 liter of exsiccant hexane, the catalyst solid constituent and 3.0 ml concns that add 40 milligrams of the present invention's preparations again are the triethyl aluminum of 1.0 mol, be warming up to 95 ℃, feed hydrogen and ethene, keeping the hydrogen dividing potential drop is 0.1MPa, feeds ethene continuously and carries out polyreaction in 2 hours, and total pressure is controlled to be 0.8MPa during reaction.Reaction finishes, and isolates polymkeric substance and dry from hexane, obtains runny ball-type polyethylene particle.Each example catalyst system therefor and activity and polymer property see Table 1.
Table 1
| Instance number | Catalyzer | Polyethylene | ||||||
| Numbering | Active | Apparent density, grams per milliliter | Size distribution, quality % | |||||
| Gram PE/ gram catalyzer | Gram PE/ gram Ti | ??＜74μm | ????74-175μm | ????175-420μm | ???＞420μm | |||
| ????12 | ??A | ?4011 | ?110192 | ??0.34 | Little | ????16.6 | ????65.0 | ???18.4 |
| ????13 | ??B | ?3368 | ?96781 | ??0.36 | ??1.0 | ????11.0 | ????78.0 | ???10.0 |
| ????14 | ??C | ?3611 | ?108113 | ??0.33 | ??0.8 | ????15.6 | ????66.3 | ???17.3 |
| ????15 | ??D | ?4630 | ?123466 | ??0.34 | ??1.2 | ????14.0 | ????80.0 | ???4.5 |
| ????16 | ??E | ?2988 | ?79468 | ??0.34 | ??2.8 | ????33.8 | ????34.9 | ???28.5 |
| ????17 | ??F | ?3657 | ?160394 | ??0.35 | Little | ????12.8 | ????79.8 | ???7.4 |
| ????18 | ??G | ?3890 | ?164830 | ??0.37 | Little | ????13.6 | ????78.6 | ???7.8 |
Claims (12)
1, a kind of preparation method of catalyst solid component of olefin polymerization comprises the steps, titanium content is 0.5-5.0 quality % in the wherein said catalyst solid constituent, and Mg content is 0.5-10.0 quality %,
(1) in the presence of methyl halide, makes C
2-C
4Alcohol and magnesium powder press 2.0-4.0: 1 mol ratio forms uniform magnesium complex solution 20-200 ℃ of reaction, and the mass ratio of described methyl halide and magnesium powder is 10-500: 1,
(2) with the magnesium complex solution and the abundant contact reacts of inorganic carrier of above-mentioned preparation, obtain magnesium-containing carrier after the drying,
(3) in unreactive hydrocarbons solvent, magnesium-containing carrier and general formula that (2) step is made are Ti (OR)
nCl
4-nThe titanium compound contact reacts, remove and to desolvate, obtain catalyst solid constituent after the drying, R is C in the described general formula
2-C
8Alkyl, n is the integer of 0-4.
2, in accordance with the method for claim 1, it is characterized in that the methyl halide described in (1) step is methylene dichloride, trichloromethane or tetrachloromethane, C
2-C
4Alcohol be selected from ethanol, propyl alcohol, Virahol, butanols or isopropylcarbinol.
3, in accordance with the method for claim 1, it is characterized in that the temperature of reaction that (1) goes on foot is 0-100 ℃.
4, in accordance with the method for claim 1, after the magnesium complex solution drying that it is characterized in that (1) step is made, wherein contain the chlorine of 10-20 quality %, the alkoxyl group of 50-80 quality % and the magnesium of 5-15 quality %.
5, in accordance with the method for claim 1, it is characterized in that described inorganic carrier of (2) step is a silicon-dioxide.
6, in accordance with the method for claim 5, it is characterized in that described silica sphere hydroxy radical content is not more than 2.0 mmole/grams.
7, in accordance with the method for claim 1, it is characterized in that (2) step magnesium complex solution is 0-100 ℃ with the temperature that contacts of inorganic carrier, Mg content is 0.1-5.0 mmole/gram in the magnesium-containing carrier.
8, in accordance with the method for claim 1, it is characterized in that described unreactive hydrocarbons solvent of (3) step is C
5-C
8Alkane or aromatic hydrocarbons, in the described titanium compound in titanium and the carrier atomic ratio of magnesium be 0.5-20: 1, the contact reacts temperature of titanium compound and carrier is 20-200 ℃.
9, in accordance with the method for claim 1, it is characterized in that described titanium compound of (3) step is selected from titanium tetrachloride.
10, in accordance with the method for claim 1, it is characterized in that adding general formula in the magnesium complex solution that makes of (1) step or the reaction of (3) step is Si (OR ')
4Silicate ester compound, make that the atomic ratio of magnesium and silicon is 0.5-5.0, R ' is selected from C in the described general formula
2-C
8Alkyl.
11, in accordance with the method for claim 9, it is characterized in that described silicate ester compound is selected from tetramethoxy-silicane, tetraethoxysilane, tetraisopropoxysilan, tetrapropoxysilane, four butoxy silanes or their mixture.
12, in accordance with the method for claim 1, it is characterized in that the used alkene of polymerization is C
2-C
12Alpha-olefin.
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100484970C (en) * | 2007-04-30 | 2009-05-06 | 中国石油化工股份有限公司 | Method for preparing solid catalyst in olefin polymerization catalyst |
| CN101205263B (en) * | 2006-12-22 | 2010-04-21 | 中国石油化工股份有限公司 | Olefin polymerization solid catalyst carrier and preparation thereof |
| CN101942053A (en) * | 2010-08-16 | 2011-01-12 | 杨波 | High-efficiency catalyst for preparing high-random alpha-olefin copolymer and preparation method thereof |
| CN101554595B (en) * | 2009-05-18 | 2011-02-02 | 中国石油化工股份有限公司 | Catalyst support used for olefinic polymerization as well as preparation method and application thereof |
| WO2011044760A1 (en) | 2009-10-16 | 2011-04-21 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst comprising the same |
| CN112812207A (en) * | 2019-11-18 | 2021-05-18 | 上海立得催化剂有限公司 | Composite type bimodal polyethylene catalyst and preparation method thereof |
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2003
- 2003-08-29 CN CN 03155998 patent/CN1261462C/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205263B (en) * | 2006-12-22 | 2010-04-21 | 中国石油化工股份有限公司 | Olefin polymerization solid catalyst carrier and preparation thereof |
| CN100484970C (en) * | 2007-04-30 | 2009-05-06 | 中国石油化工股份有限公司 | Method for preparing solid catalyst in olefin polymerization catalyst |
| CN101554595B (en) * | 2009-05-18 | 2011-02-02 | 中国石油化工股份有限公司 | Catalyst support used for olefinic polymerization as well as preparation method and application thereof |
| US9120089B2 (en) | 2009-05-18 | 2015-09-01 | China Petroleum & Chemical Corporation | Catalyst support used for olefin polymerization and preparing method and application thereof |
| WO2011044760A1 (en) | 2009-10-16 | 2011-04-21 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst comprising the same |
| WO2011044761A1 (en) | 2009-10-16 | 2011-04-21 | 中国石油化工股份有限公司 | Carrier for olefin polymerization catalyst, preparation method and application thereof |
| US9243086B2 (en) | 2009-10-16 | 2016-01-26 | China Petroleum & Chemical Corporation | Catalyst component for olefin polymerization and catalyst comprising the same |
| US9321857B2 (en) | 2009-10-16 | 2016-04-26 | China Petroleum & Chemical Corporation | Carrier for olefin polymerization catalyst, preparation method and application thereof |
| CN101942053A (en) * | 2010-08-16 | 2011-01-12 | 杨波 | High-efficiency catalyst for preparing high-random alpha-olefin copolymer and preparation method thereof |
| CN101942053B (en) * | 2010-08-16 | 2013-04-03 | 辽阳辽化奇达化工有限责任公司 | High-efficiency catalyst for preparing high-random alpha-olefin copolymer and preparation method thereof |
| CN112812207A (en) * | 2019-11-18 | 2021-05-18 | 上海立得催化剂有限公司 | Composite type bimodal polyethylene catalyst and preparation method thereof |
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