CN1061994C - Syndiotactic selective compound metallocene catalyst - Google Patents
Syndiotactic selective compound metallocene catalyst Download PDFInfo
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- CN1061994C CN1061994C CN95107482A CN95107482A CN1061994C CN 1061994 C CN1061994 C CN 1061994C CN 95107482 A CN95107482 A CN 95107482A CN 95107482 A CN95107482 A CN 95107482A CN 1061994 C CN1061994 C CN 1061994C
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
Abstract
The present invention relates to a compound metallocene catalyst for preparing syndiotactic polyolefin, which is a three-component compound of metallocene, ether and inorganic salt and has the following general formula of Ar2C[Cp-9-Flu]MeQ2. RXR'. nMe'Q2/n, wherein the definition of each symbol is disclosed in the specification. The catalyst can be exposed to air for several hours or stored in nitrogen for a long time. A preparation method of the catalyst is convenient without separation and purification. Reaction conditions are milder than that of the prior art, and the product yield of the catalyst is high. When the catalyst is used as a main catalyst and methylaluminoxane, etc. are used as cocatalysts, syndiotactic polyolefin with favorable performance can be prepared at a low aluminum/zirconium ratio.
Description
The invention relates to a kind of syndiotactic selective compound metallocene catalyst, its preparation method and the application in olefinic polymerization thereof.
It is 70% syndiotactic polypropylene that J.A.Ewen etc. find to use the catalyzer of being made up of transistion metal compound with asymmetric ligand and aikyiaiurnirsoxan beta can obtain five unit syndiotactic regularities first.The representative instance of described transistion metal compound has isopropylidene (cyclopentadienyl fluorenyl) zirconium dichloride and isopropylidene (cyclopentadienyl fluorenyl) hafnium dichloride (J.Am.Chem. Soc., 110,6255-6256 (1988)).Some similar transistion metal compounds are also disclosed in patent, for example (EP387690, EP387691, EP0516019A2) such as aminomethyl phenyl methylene radical (cyclopentadienyl fluorenyl) zirconium dichloride, phenylbenzene methylene radical (cyclopentadienyl fluorenyl) zirconium dichloride and phenylbenzene methylene radical (cyclopentadienyl fluorenyl) hafnium dichloride.
Above-mentioned these transistion metal compounds generally are to replace the fulvene reaction by fluorenes and two to obtain two cyclopentadienyl ligands, and the reaction of two cyclopentadienyl ligands and zirconium tetrachloride or hafnium tetrachloride is made.For making fluorenes and two replace easier the carrying out of reaction of fulvene, at first fluorenes should be made the form of negative ion, the most frequently used is the fluorenyl lithium, it normally with fluorenes with etc. the hexane solution of the diethyl ether solution of mole lithium methide or butyllithium react and obtain.Wherein the diethyl ether solution of lithium methide reacts down at lesser temps (10 ℃) with methyl iodide and metallic lithium and obtains, because methyl coupling side reaction is inevitable in reaction, thereby yield is lower, and the reaction raw materials methyl iodide is more expensive, so cost is higher.Though the hexane solution of butyllithium has higher chemically reactive, but under the condition of not controlling rate of addition and temperature, single electron transfer can or take place with other more active hydrogen effects in the fluorenes and generate free radical in the butyllithium of local overrich, so that influenced the unicity of reaction, the transformation efficiency that causes reacting reduces.
Dialkyl group replaces the addition reaction of fulvene and fluorenyl lithium and generally carry out (CN1040036A) under-78 ℃, and this is because alkyl fulvenes contains the elimination reaction that α hydrogen easily takes place active α hydrogen under the effect of strong basicity reagent fluorenyl lithium.This reaction is restricted by kinetic factor mainly, thereby low temperature can suppress this elimination reaction.Different with dialkyl group replacement fulvene, diaryl replaces fulvene and does not contain acid α hydrogen.Thereby can under relatively mild condition, carry out the fluorenes negative ion to two strong additions (EP0516019A2) outside the fulvene ring.
Part pairs of anion and zirconium tetrachloride (ZrCl are disclosed among the CN1040036A
4) reaction two kinds of a kind of methods of method be with ZrCl
4React generation ZrCl in advance with tetrahydrofuran (THF) (THF)
4(THF)
2, then itself and part pairs of anion being reacted, the luxuriant productive rate of gained zirconium is 30～40%, and THF is bonded in the final coordination compound catalyzer; Another kind method is with ZrCl
4Under-78 ℃ in methylene dichloride the furnishing pulpous state, under-78 ℃, make the dichloromethane solution reaction of this slurry and part pairs of anion then, the luxuriant productive rate of gained zirconium-as be 40-50%.
EP0516019A
2In describe the preparation method of phenylbenzene methylene radical (cyclopentadienyl-9-fluorenyl) zirconium dichloride in detail, wherein the fluorenes negative ion by fluorenes with wait the mole n-Butyl Lithium to react to obtain, fluorenyl lithium and two addition reactions that replace fulvene are at room temperature carried out, and the yield of two cyclopentadienyl ligands is 42%; Being reflected among the THF of two cyclopentadienyl ligands and zirconium tetrachloride carried out under-78 ℃, and the luxuriant productive rate of zirconium only is 36%.
Though metalloscene catalyst is that the preparation syndiotactic polyolefins is indispensable, its preparation condition harshness, yield is low.(needing vacuum to desolventize separates to separate the purification process complexity, purify with the alkane extraction or with the aromatic hydrocarbons recrystallization or with the method for ion-exchanger chromatography), even and this catalyzer is very unstable in air also can slowly decompose, bring very big inconvenience to practical application under nitrogen atmosphere
The purpose of this invention is to provide a kind of class of metallocenes catalyzer of how stablizing than prior art.
Another object of the present invention provides a kind of method that purification, high productivity prepare this class of metallocenes catalyzer of need not separating under mild conditions.
The 3rd purpose of the present invention provides the application of this class of metallocenes catalyzer in the preparation syndiotactic polyolefins.
We find, adopt the phenyl lithium and the fluorenes that are different from prior art lithium methide and butyllithium to react the fluorenyl lithium that can obtain high yield.This reaction process is steady, at room temperature carries out can reaching stoichiometric reaction in 4 hours.
We also find, coordination pairs of anion and ZrCl
4The solid product that obtains after the reaction in weak lewis base medium (as ether) has good syndiotactic polymerization catalytic performance, but promptly can be used as catalyzer and stable existence in air without purifying.
Finished the present invention based on above-mentioned test-results.
The catalyzer that is used to prepare syndiotactic polyolefins provided by the invention is the metallocenes-ether-inorganic salt three component mixtures with following general formula:
Ar
2C[Cp-9-Flu]MeQ
2·RXR′·nMe′Q
2/n
Wherein Ar comprises phenyl, aromatic cluste or heterocyclic radical such as naphthyl, pyridyl etc. for replacing or unsubstituted aryl, preferred phenyl; Cp is for replacing or unsubstituted cyclopentadienyl, and its substituting group is selected from C
1～C
12Alkyl, alkoxyl group, silylation, aryl, aralkoxy and hydroxyl or halogen etc.; Flu is for replacing or unsubstituted fluorenyl, and its substituting group is selected from C
1～C
12Alkyl, alkoxyl group, silylation, aryl, aralkoxy and hydroxyl or halogen etc.; Me is the metal that is selected from IVB family element in the periodic table of elements, wherein preferred zirconium or hafnium, particularly zirconium; Q represents halogen, preferred chlorine; R and R ' can be identical or different, are selected from C
1～C
6Alkyl, preferred ethyl; X is oxygen or sulphur, preferred oxygen; Me ' is basic metal or alkaline earth metal atom, preferred lithium, magnesium, particularly lithium; The value of n is 1 or 2, and n is 2 when Me ' is basic metal, and n is 1 when Me ' alkaline-earth metal.
The X-ray diffraction analysis that composite catalyst sample provided by the invention is carried out shows that this catalyzer has certain degree of crystallinity.In ' HNMR (nucleus magnetic resonance) spectrum, can be observed tangible RXR ' characteristic peak.Ultimate analysis shows that its chemical constitution is Ar
2C[Cp-9-Flu] MeQ
2RXR ' nMe ' Q
2/nWhen extracting with the luxuriant solvent of easy dissolution of metals (as methylene dichloride, toluene etc.), it is very sensitive to air to separate the metallocenes that obtains, and illustrates in this catalyzer to exist Intermolecular Forces between three components that this reactive force has improved the stability of metallocenes.Component beyond the metallocenes has no adverse effect to polyreaction except that stable metal is luxuriant.
Above-mentioned Preparation of catalysts method provided by the invention comprises:
(1) in ether solvent, will replace or the reaction of unsubstituted fluorenes and highly basic, will react the fluorenes negative ion of gained and substitution in ring or unsubstituted diaryl fulvene again and at room temperature react, obtain two cyclopentadienyl ligands;
(2) in inert solvent, with two cyclopentadienyl ligands and alkaline reagents reaction, the two cyclopentadienyl ligand pairs of anion and the chemical formula that will react gained again are MeQ
4Metallic compound reaction, wherein Me is selected from the metal of IVB family in the periodic table of elements, Q is a halogen.
In the step poly-(1), ether solvent is an ether solvent commonly used in this area, as tetrahydrofuran (THF), ether etc.Highly basic can be lithium alkylide, as lithium methide, butyllithium etc.; Also can be lithium aryl, as phenyl lithium etc.; The preferred phenyl lithium that uses among the present invention.The example of the substitution in ring base of fluorenes and diaryl fulvene has C
1～C
12Alkyl, alkoxyl group, silylation, aryl, aralkoxy, and hydroxyl, halogen etc.The preferred phenylbenzene fulvene of diaryl fulvene.
In the step poly-(2), inert solvent is selected from the solvent of formula RXR ' expression, and wherein R and R ' can be identical or different, are selected from C
1～C
6Alkyl, preferred ethyl; X is oxygen or sulphur, preferred oxygen; Preferred ether among the present invention.Alkaline reagents is normally used lithium alkylide, lithium aryl etc., generally uses butyllithium.At chemical formula is MeQ
4Metallic compound in, the preferred zirconium of Me or hafnium, particularly zirconium; The preferred chlorine of Q.
The method of the above-mentioned class of metallocenes Preparation of Catalyst of usefulness provided by the invention syndiotactic polyolefins is to be Primary Catalysts with catalyzer provided by the present invention, be aided with the promotor of one of the mixture that is selected from methylaluminoxane, aluminum alkyls and methylaluminoxane or Lewis acid, make olefinic polymerization obtain syndiotactic polyolefins.Wherein preferably use methylaluminoxane to make promotor, the amount ratio of promotor and Primary Catalysts is about 300 with Al/Zr (mole) expression and is advisable.
Said alkene can be ethene or C
3～C
8Alpha-olefin, preferred propylene.
Polyreaction can adopt mode well known in the art to carry out, and preferably adopts solution polymerization process or slurry polymerization process.Solvent for use can be aliphatic hydrocrbon or aromatic hydrocarbon, for example hexane, toluene etc.
Metallocenes composite catalyst provided by the invention has the stability much higher than prior art, this catalyzer can be in air adherence hour or deposit in the nitrogen atmosphere midium or long term.This Preparation of catalysts mild condition provided by the invention need not complicated tediously long separation, purify to go on foot and gather, and the luxuriant productive rate of zirconium can reach about 85%.With catalyzer of the present invention is Primary Catalysts, and methylaluminoxane is a promotor when being used for the syndiotactic polymerization of alkene, the syndiotactic polyolefins that aluminium zirconium that can be lower is better than obtained performance.
Fig. 1 is obtain among the embodiment 2 polyacrylic
13CNMR (NMR (Nuclear Magnetic Resonance) spectrum spectrogram.
Fig. 2 is polyacrylic IR (infrared spectra) spectrogram that obtains among the embodiment 2.
Further specify the present invention below by preferred embodiment, but the present invention is not subjected to the restriction of these embodiment.
Embodiment 1
Catalyst P h provided by the present invention
2C[Cp-9-Flu] ZrCl
2Et
2O2LiCl's is synthetic
In the 250mlSchlenk reaction flask, add 5.10g (30.7mmol) fluorenes, after 60ml anhydrous tetrahydro furan (THF) dissolving, under room temperature, add the phenyl lithium diethyl ether solution of 38.4ml (30.7mmol) 0.8M by constant pressure funnel, at room temperature reacted 2 hours.Add 7.07g (30.7mmol) phenylbenzene fulvene then, at room temperature continue reaction after 12 hours, add the suitable quantity of water hydrolysis.Tell organic phase, with the mixed solution recrystallization of methyl alcohol and chloroform, obtain white powder two cyclopentadienyl ligands of 62g (productive rate is 51%) behind the vacuum concentration, the result of ultimate analysis and nucleus magnetic resonance shows that this two cyclopentadienyl ligand has following The Nomenclature Composition and Structure of Complexes: Ph
2C[Cp-9-Flu].
The above-mentioned part that obtains of 2.0g (5.0mmol) is dissolved in the 20ml ether, and at 0 ℃ of n-buli hexane solution 6.4ml (10mmol) that adds 1.6M down, reaction was cooled to-50 ℃ with gained suspension after 15 hours under the room temperature, added 1.16g (5.0mmol) ZrCl
4,, under agitation make mixture slowly rise to room temperature, filter and with a small amount of ether washing leaching cake, obtain the catalyzer provided by the invention of 3.1g solid powdery after the drying.
X-ray diffraction analysis shows that this catalyzer has certain degree of crystallinity, and electronic microscope photos shows at analyzed area interior element Zr of institute and Cl and is evenly distributed.By
1Can be observed tangible Et in the HNMR spectrum
2O (ether) characteristic peak.Ultimate analysis shows that its chemical constitution is Ph
2C[Cp-9-Flu] ZrCl
2Et
2O2LiCl.The result who analyzes with inductively coupled plasma atomic emission spectrum (ICP-AES) shows that the Zr content in this catalyzer is 11.0%, and the yield of catalyzer counts 85% with the weight of Zr.
Example 2
The test of normal pressure propylene polymerization
In the 500ml there-necked flask that has purified with high purity nitrogen in advance, under propylene atmosphere, add catalyzer and the 2 gram methylaluminoxane of 100ml toluene, 50 milligrams of embodiment 1.Feed propylene gas continuously.In 40 ℃ of following polymerization under atmospheric pressure hour, obtain 52 grams (dry back) polymkeric substance.Then this polymkeric substance is carried out
13CNMR, IR, DSC (differential scanning calorimetric), GPC (gel permeation chromatography) analyze.
Fig. 1's
13CH among the CNMR
3Chemical shift and the characteristic peak 977cm in the IR of Fig. 2 spectrum
-1And 963cm
-1Prove that all this polypropylene is a syndiotactic polypropylenes.Recording this polyacrylic fusing point by dsc analysis is 107 ℃.Gpc analysis shows that its weight-average molecular weight (Mw) is 220,000, and molecular weight distribution (MWD) is 2.By
13The CNMR spectrum is known three unit syndiotactic regularity n%＞8% by inference.
Embodiment 3
The test of high pressure propylene polymerization
In advance in the autoclave of 1 liter that high purity nitrogen has purified, after adding 400ml toluene and making toluene saturated, add the catalyzer of 2.0g methylaluminoxane and 0.100g embodiment 1 with propylene gas.Keeping monomer pressure is 0.7 MPa, 35 ℃ of reactions 1 hour down,, add ethanol and separate out polymkeric substance with the methanol solution stopped reaction of hydrochloric acid, with polymer precipitation with washing with alcohol after, dry under vacuum, obtain the 10g polypropylene.Dsc analysis shows that this polyacrylic fusing point is 139 ℃; Gpc analysis shows that its Mw is 450,000, MWD is 229; By
13The CNMR spectrum is known this polyacrylic syndiotactic regularity n+m+mr%＞92% by inference.
Embodiment 4
The test of high pressure liquid phase bulk propylene polymerization
Catalyzer and the 2g methylaluminoxane of 50mg embodiment 1 are dissolved in the 30ml toluene, contact 2 hours in advance.
In advance in the autoclave of 5 liters that high purity nitrogen has purified, add and contain the toluene solution 20ml of 1g methylaluminoxane, and then add above-mentioned pre-contact liquid and liquid propene 3 liters, system is warming up to 70 ℃.Polyreaction was carried out 1 hour under the mixing speed of 70 ℃, 2.9 MPas and 250 rev/mins.Termination reaction is discharged unnecessary propylene, obtains polymer powder, with its dilute hydrochloric acid solution and washing with alcohol of using methyl alcohol successively, obtain after the drying syndiotactic polypropylene (
13CNMR characterizes).Gpc analysis shows that its Mw is 410,000, MWD is 2.3; Recording its fusing point with DSC is 139 ℃.
Claims (12)
1. syndiotactic selective compound metallocene catalyst is characterized in that this catalyzer is the metallocenes-ether-inorganic salt three component mixtures with following general formula:
Ar
2C[Cp-9-Flu] MeQ
2RXR ' nMe ' Q
2/ n wherein, Ar is for replacing or unsubstituted aryl; Cp is for replacing or unsubstituted cyclopentadienyl, and its substituting group is selected from C
1～C
12Alkyl, alkoxyl group, silylation, aryl, aralkoxy and hydroxyl or halogen; Flu is for replacing or unsubstituted fluorenyl, and its substituting group is selected from C
1～C
12Alkyl, alkoxyl group, silylation, aryl, aralkoxy and hydroxyl or halogen etc.; Me is a kind of element that is selected from IVB family in the periodic table of elements; Q is a halogen; R and R ' can be identical or different, are selected from C
1～C
6Alkyl; X is oxygen or sulphur; Me ' is basic metal or alkaline earth metal atom; The value of n is 1 or 2.
2. according to the described catalyzer of claim 1, it is characterized in that the Ar in the formula is a phenyl, Cp is a cyclopentadienyl, and Flu is a fluorenyl, and Me is a zirconium, and Q is a halogen, and R and R ' are ethyl, and X is an oxygen, and Me ' is an alkali metal atom, and n is 2.
3. according to the described catalyzer of claim 2, it is characterized in that the Q in the formula is a chlorine.
4. according to the described catalyzer of claim 2, it is characterized in that the Me ' in the formula is a lithium.
5. claim 1 Preparation of catalysts method is characterized in that this method comprises:
(1) in ether solvent, make to replace or unsubstituted fluorenes and highly basic reaction, fluorenes negative ion that again reaction is obtained and substitution in ring or unsubstituted diaryl fulvene at room temperature react, and obtain two cyclopentadienyl ligands;
(2) be in the inert solvent of RXR ' in expression formula, make the reaction of two cyclopentadienyl ligands and alkaline reagents, the two cyclopentadienyl ligand pairs of anion and the chemical formula that will react gained again are MeQ
4Metallic compound reaction, wherein, R and R ' can be selected from C identical or differently
1～C
6Alkyl, X is oxygen or sulphur, and Me is selected from the metal of IVB family in the periodic table of elements, and Q is selected from halogen.
6. according to the described preparation method of claim 5, it is characterized in that wherein said ether solvent is selected from tetrahydrofuran (THF) or ether.
7. according to the described preparation method of claim 5, it is characterized in that wherein said highly basic is selected from lithium alkylide or lithium aryl.
8. according to the described preparation method of claim 5, it is characterized in that wherein said alkaline reagents is selected from lithium alkylide or lithium aryl.
9. the preparation method of a syndiotactic polyolefins, it is characterized in that this method comprises that the catalyzer with claim 1 is a Primary Catalysts, material with one of the mixture that is selected from methylaluminoxane, aluminum alkyls and methylaluminoxane or Lewis acid is a promotor, makes alkene carry out polymerization.
10. in accordance with the method for claim 9, it is characterized in that wherein said alkene is selected from ethene, C
3～C
8Alpha-olefin.
11. in accordance with the method for claim 10, it is characterized in that said alkene is propylene.
12. in accordance with the method for claim 9, it is characterized in that said Primary Catalysts is phenylbenzene methylene radical (cyclopentadienyl-9-fluorenyl) zirconium dichloride-ether-lithium chloride with following expression formula:
Ph
2C[Cp-9-Flu] ZrCl
2Et
2O2LiCl, promotor are methylaluminoxane.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95107482A CN1061994C (en) | 1995-07-14 | 1995-07-14 | Syndiotactic selective compound metallocene catalyst |
| DE19627662A DE19627662C2 (en) | 1995-07-14 | 1996-07-09 | Syndiospecific metallocene adduct catalyst, process for the preparation of the catalyst and its use for the production of syndiotactic polyolefin |
| IT96TO000601A IT1290802B1 (en) | 1995-07-14 | 1996-07-12 | SYNDIOSPECIFIC METALLOCENE ADDUCT CATALYST |
| JP18388796A JP3192090B2 (en) | 1995-07-14 | 1996-07-12 | Syndio-specific metallocene adduct catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95107482A CN1061994C (en) | 1995-07-14 | 1995-07-14 | Syndiotactic selective compound metallocene catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1140720A CN1140720A (en) | 1997-01-22 |
| CN1061994C true CN1061994C (en) | 2001-02-14 |
Family
ID=5076335
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95107482A Expired - Fee Related CN1061994C (en) | 1995-07-14 | 1995-07-14 | Syndiotactic selective compound metallocene catalyst |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP3192090B2 (en) |
| CN (1) | CN1061994C (en) |
| DE (1) | DE19627662C2 (en) |
| IT (1) | IT1290802B1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049437C (en) * | 1997-07-28 | 2000-02-16 | 中国石油化工总公司 | Process for preparing syndiotactic selective metallocene catalyst |
| CN1060780C (en) * | 1998-05-08 | 2001-01-17 | 中国石油化工集团公司 | Metallocene adduct, its preparation and use in olefin synthesis |
| US6057467A (en) * | 1998-07-17 | 2000-05-02 | Research Institute Of Petroleum Processing, Sinopec | Metallocene adduct, its preparation and its application in olefin polymerization |
| US6288181B1 (en) * | 1999-03-30 | 2001-09-11 | Eastman Chemical Company | Process for producing polyolefins |
| SG85150A1 (en) * | 1999-11-15 | 2001-12-19 | China Petrochemical Corp | Metallocene adduct, its preparation and its application in olefin polymerization |
| EP1903061A1 (en) * | 2006-09-25 | 2008-03-26 | Total Petrochemicals Research Feluy | Preparation of diphenyl-bridged substituted cyclopentadienyl-fluorenyl ligands |
| CN108298417B (en) | 2017-01-11 | 2020-09-25 | 奥的斯电梯公司 | Passenger transportation system and start-stop control method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0426643A1 (en) * | 1989-10-30 | 1991-05-08 | Fina Research S.A. | Process for the preparation of metallocenes |
| EP0582114A1 (en) * | 1992-08-03 | 1994-02-09 | Albemarle Corporation | Process for preparing metallocenes |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3907965A1 (en) * | 1989-03-11 | 1990-09-13 | Hoechst Ag | METHOD FOR PRODUCING A SYNDIOTACTIC POLYOLEFIN |
| DE3907964A1 (en) * | 1989-03-11 | 1990-09-13 | Hoechst Ag | METHOD FOR PRODUCING A SYNDIOTACTIC POLYOLEFIN |
-
1995
- 1995-07-14 CN CN95107482A patent/CN1061994C/en not_active Expired - Fee Related
-
1996
- 1996-07-09 DE DE19627662A patent/DE19627662C2/en not_active Expired - Fee Related
- 1996-07-12 IT IT96TO000601A patent/IT1290802B1/en active IP Right Grant
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0426643A1 (en) * | 1989-10-30 | 1991-05-08 | Fina Research S.A. | Process for the preparation of metallocenes |
| EP0582114A1 (en) * | 1992-08-03 | 1994-02-09 | Albemarle Corporation | Process for preparing metallocenes |
Also Published As
| Publication number | Publication date |
|---|---|
| ITTO960601A0 (en) | 1996-07-12 |
| ITTO960601A1 (en) | 1998-01-12 |
| JPH0948810A (en) | 1997-02-18 |
| JP3192090B2 (en) | 2001-07-23 |
| CN1140720A (en) | 1997-01-22 |
| DE19627662A1 (en) | 1997-01-16 |
| DE19627662C2 (en) | 2003-08-21 |
| IT1290802B1 (en) | 1998-12-11 |
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