WO1996019488A1 - Procede de preparation de metallocene-alkyles racemiques de grande purete et leur utilisation - Google Patents

Procede de preparation de metallocene-alkyles racemiques de grande purete et leur utilisation Download PDF

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WO1996019488A1
WO1996019488A1 PCT/US1995/016689 US9516689W WO9619488A1 WO 1996019488 A1 WO1996019488 A1 WO 1996019488A1 US 9516689 W US9516689 W US 9516689W WO 9619488 A1 WO9619488 A1 WO 9619488A1
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bis
solvent
metallocene
dimethylsilanediyl
group
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PCT/US1995/016689
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English (en)
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Richard Allen Fisher
Terry John Burkhardt
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Exxon Chemical Patents Inc.
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Priority to AU45271/96A priority Critical patent/AU4527196A/en
Publication of WO1996019488A1 publication Critical patent/WO1996019488A1/fr

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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

Definitions

  • This invention relates generally to the preparation of metallocene alky Is, and more particularly to an improved process for preparing high purity, racemic metallocene alkyls free of inorganic salts. Certain of these metallocene alkyls are useful as catalyst components with alumoxanes or ionic activator systems for olefin polymerization.
  • Metallocene dihalides are widely used as catalyst components and are activated by alumoxanes for olefin polymerization reactions.
  • the metallocene dihalides which have found use in these applications can be synthesized by methods well known in the art. Problems inherent to these syntheses vary, but typically include low yield, difficulty in separating the metallocene dihalide from the inorganic salt byproducts of the synthesis, and complications arising, in the case of chirai, racemic metallocene dihalides, from the separation of the desired racemic isomer from racemic/meso isomeric mixtures.
  • the metallocene dialkyls are prepared from the metallocene dihalides by well known synthetic routes. Therefore, in order to utilize the chirai, racemic metallocene dialkyls as catalyst components in olefin polymerization, one is confronted with the same difficulties as they exist during the synthesis of the corresponding metallocene dihalides. Thus, many of the commercially useful chirai, racemic metallocene dialkyls are not expediently synthesized by the existing methodology. Chirai, racemic metallocene dihalides or dialkyls are useful components in stereospecific alpha-olefin polymerization catalysts.
  • '733 also discloses a preparation of chirai, silicon-bridged transition metal compounds, substantially free of meso isomer and lithium salts, but requires isolation of the metallocene dihalide racemic isomer by precipitation employing copious quantities of a non-solvent.
  • racemic isomer of chirai, racemic metallocene dihalides involves repeated recrystallizations and/or washings of the metallocene dihalide compound to isolate and purify the racemic isomer. Due to the limited solubility of the /19488 PCIYUS95/16689
  • the invention relates to a process to convert the metal salts of cyclopentadienyl ligand systems into high purity chirai, racemic metallocene alkyls while avoiding the existing problems discussed above.
  • the process comprises several steps as discussed below.
  • the high purity chirai, racemic metallocene alkyls are of sufficient purity to be used directly as catalyst components for olefin polymerization.
  • This invention provides a method for the isolation of high purity chirai, racemic metallocene alkyls based on a solubility differential wherein the solid inorganic by-products are less soluble in hydrocarbon solvents than the metallocene alkyl product, and solves the existing problem of purifying the chirai, racemic metallocene dihalides.
  • a preferred embodiment of the invention relates to a process for the preparation of chirai, racemic metallocene alkyls of Group 4-6 transition metals comprising: a. forming a reaction product in the presence of a solvent of a ligand metal salt of a represented by formula I:
  • x is 0 to 4
  • y is 1 to 4
  • T is the covalent bridging group, m is 0 or 1, and when L is a Group 1 metal, n is 2, and when L is a Group 2 metal, n is 1;
  • R and R 1 are the same or different substituents, including those selected from hydrogen, halogen, hydrocarbyl, hydrosilyl or hydrogermyl radicals, such as, for example, C ⁇ . 2 0 alkyl, C 6 . 20 aryl, C 7 . 20 arylalkyl, C 7 . 20 alkylaryl, C 2 _20 alkenyl, C ⁇ _ 2 o alkoxy, C 6 . 20 aryloxy, C 8 . 20 arylalkenyl, C 2 . 20 alkylidene, or two adjacent R or R' substituents are joined together to form a ring; and a perhalogenated Group 4-6 transition metal compound or its etherate complex; b.
  • substituents including those selected from hydrogen, halogen, hydrocarbyl, hydrosilyl or hydrogermyl radicals, such as, for example, C ⁇ . 2 0 alkyl, C 6 . 20 aryl, C 7 . 20 arylalkyl, C
  • the chirai, racemic metallocene alkyls produced are essentially free of alkali metal salts.
  • the chirai, racemic metallocene alkyls useful for stereospecific polymerizations are produced by the instant invention in isomeric purity of greater than 95% racemic isomer, in high yield, utilizing a simple synthetic process, minimum amounts of organic solvents, and without the required need for additional purification.
  • the present invention provides a process for the preparation of Group 4 transition metal chirai, racemic metallocene alkyls by a new, direct synthetic route and, more specifically, yields a much simpler purification technique to remove insoluble, inorganic by-products and the meso isomer from the racemic isomer.
  • all groups recited herein are based on the new notation of the Periodic Table of Elements as described in Hawley's Chemical Dictionary. 11th Edition, Van Nostrand Reinhold, New York, (1987).
  • the individual steps employed in the process will be described in greater detail below.
  • the products of each step do not have to be isolated. They may be optionally carried forward in-situ to the subsequent reaction step.
  • Temperature maintained during contact of components can vary widely, such as, for example, from -10 to 300°C.
  • the reaction is maintained within a temperature of from about 20°C to about 100°C, most preferably ambient temperature.
  • An embodiment of this invention involves the deprotonation of a neutral ligand precursor such as bis(2-methylbenz [e] indenyDdimethyl silane, bis(2-methylindenyl) dimethyl silane, and the like, with a suitable base, such as an alkyl lithium reagent, in a solvent, such as toluene.
  • a neutral ligand precursor such as bis(2-methylbenz [e] indenyDdimethyl silane, bis(2-methylindenyl) dimethyl silane, and the like
  • a suitable base such as an alkyl lithium reagent
  • the lithiated ligand thus obtained may be isolated or carried on in continuous sequence of steps by treatment of the nascent material with a Group 4 transition metal halide, or an etherate thereof, in a solvent such as toluene or an ether.
  • the reaction product so produced is then reacted with an alkylating agent such as an alkali metal alkyl or Grignard reagent to produce a metallocene alkyl derivative.
  • an alkylating agent such as an alkali metal alkyl or Grignard reagent
  • the metallocene alkyl remains in solution and the alkali metal salt by products are solid components which are easily removed by filtration.
  • the addition of 1,4 dioxane may facilitate the removal of magnesium salts.
  • Solvent removal yields a metallocene alkyl product as a solid, free of inorganic impurities such as alkali metal salts or alkaline earth metal salts.
  • the metallocene alkyl product obtained in the described manner may then be washed with a small amount of hydrocarbon or aromatic solvent or mixtures thereof to provide the racemic isomer of the chirai, racemic metallocene alkyl in 95% isomeric purity.
  • racemic metallocene dihalides by known methods, very little solvent is required for this wash and very little of the desired racemic isomer is lost in the process.
  • the higher solubility of the chirai, racemic metallocene alkyl derivative allows them to be readily obtained essentially free of inorganic salts.
  • the greater solubility differential between the racemic and meso isomers of the chirai, racemic metallocene alkyls as compared to the chirai, racemic metallocene dihalides allows the isomers to be separated by an exceptionally simple and convenient procedure.
  • the inventive process employs less solvent than currently used with traditional chirai, racemic metallocene dihalide syntheses, fewer purification steps, and results, generally, in higher yields than existing procedures for the purification of the racemic metallocene dihalides.
  • a further benefit of this instant invention is derived from the fact that the chirai, racemic metallocene alkyls obtained are suitable for activation with solutions of alumoxane(s), as well as discrete cocatalysts such as ion-exchange reagents or Bronstead acid salts of stable non-coordinating anions. Metallocene dihalides cannot be directly activated with discrete ionic cocatalysts and must be subjected to further synthetic manipulations (e.g., conversion to their alkyl derivative) if such cocatalysts are to be used.
  • a still further benefit of this instant invention is derived from the fact that other ligand modifications may optionally be made during the preparation of the metallocene alkyl.
  • step (a) above may be further reacted to cause a modification of the ligand system before the remainder of the steps of the invention are carried out.
  • the product of step (a) in the case were I contains a bridged bisindenyl ligand system, the product of step (a) can be further reacted with hydrogen to produce the bistetrahydroindenyl ligand system. Continuation of the process of the invention would then give the final product as a bridged bis(tetrahydroindenyl) metallocene alkyl.
  • the inventive synthetic process may occur in the presence of an organic solvent, or solvent mixture, a solution or slurry of a metal salt of the ligand with a Group 4-6 transition metal halide, preferably a titanium, zirconium, or hafnium tetrahalide, or the corresponding transition metal tetrahalide-etherate complex, for example ZrCU(THF) 2 , and in concentrations such that subsequent treatment of the reaction mixture, either before or after filtration, with an alkylating agent renders the metallocene alkyls soluble.
  • THF is tetrahydrofuran. Filtration of the reaction mixture and solvent evaporation provides the metallocene alkyl product as a solid.
  • the final step involves washing the chirai, racemic metallocene alkyl with a solvent or solvent mixtures to free the racemic isomer of the chirai, racemic metallocene from the more soluble meso isomer.
  • Suitable solvents include aromatic solvents such as benzene, toluene, xylene, as well as aliphatic hydrocarbons such as pentane, hexane, and heptane, and also mixtures of these solvents. Etherial solvents can be used, but are not required. There are rare cases where the racemic isomer is more soluble than the meso isomer (See for example, J. Organomet. Chem.. 1989, 369. 359-370).
  • one skilled in the art would know that the advantage of this invention still provides a convenient means to separate the meso isomer and the racemic isomer.
  • the ligand system and their metal salts can be readily obtained from commercial sources or synthesized. Alternately, the ligand system may be formed by other conventional methods which are well known in the art.
  • indene or 2- methylindene may be reacted with an alkyl lithium such as butyl lithium or methyl lithium in a suitable hydrocarbon, aromatic or cyclic or acyclic ether solvent to generate the corresponding lithium indenylide salt.
  • an alkyl lithium such as butyl lithium or methyl lithium in a suitable hydrocarbon, aromatic or cyclic or acyclic ether solvent
  • Treatment of these species with one-half molar equivalent of a suitable dialkyldihalosilane reagent generates the neutral alkyl siladiyl bridged bisindene ligand precursor and an alkali metal salt which is removed by filtration.
  • the bridged ligand thus formed may be transformed directly to their di-alkali metal salts (e.g. di-lithium, di-sodium, di-potassium) on treatment with an alkali metal alkyl or alkali metal hydride, in a suitable hydrocarbon or etherial solvent.
  • the di-alkali metal salts of the ligand, formed as described above, in the presence of a solvent such as toluene, ether, or other hydrocarbon is allowed to react with an equal molar quantity of the Group 4-6 metal halides, or their etherates.
  • a solvent such as toluene, ether, or other hydrocarbon
  • the volume and nature of the solvent, or solvents, is chosen such that, on ultimate conversion to the metallocene alkyl derivatives, the racemic and meso isomers are both soluble.
  • the conversion to metallocene alkyls is accomplished by treatment of the crude reaction mixture with stoichiometric quantities of an alkylating agent such as alkyl metal alkyl or Grignard reagent, or by an excess of Grigard reagent followed after reaction by treatment of small amounts of chlorotrimethylsilane. Filtration of the reaction mixture allows the metallocenes alkyls to be completely separated from the inorganic byproducts of the reaction. If a magnesium reagent is used in the alkylation step, the addition of 1,4-dioxane prior to filtration may facilitate the separation.
  • an alkylating agent such as alkyl metal alkyl or Grignard reagent
  • Grigard reagent an excess of Grigard reagent
  • a process for the preparation of a chirai, racemic metallocene alkyl compound comprising: a. forming a reaction product in the presence of a solvent of a ligand metal salt of a represented by formula I:
  • x is 0 to 4
  • y is 1 to 4
  • T is the covalent bridging group
  • m is 0 or 1, when L is a Group 1 metal, n is 2, and when L is a Group 2 metal, n is 1;
  • R and R' are the same or different substituents including those selected from hydrogen, halogen, hydrocarbyl, hydrosilyl or hydrogermyl radicals, such as, for example, C ] _.
  • a Group 4 tetrahalide is the perhalogenated Group 4-6 transition metal compound in step (a) and two molar equivalents of an alkylating agent are used in step (b).
  • Exemplary, but not limiting ligand precursors include: bis(indenyl)dimethylsilane; bis(2-methylindenyl)dimethylsilane; bis(2- methylbenz [e]indenyl] dimethylsilane; bis(indenyl)dimethylgermane; bis(2-methylindenyl)dimethylgermane; bis(2- methylbenz [e] indenyl] dimethylgermane; bis(indenyl)dimethylme thane; bis(2-methylindenyl)dimethylmethane; bis(2-methylbenz[e]indenyl]dimethylmethane, and the like.
  • Exemplary but not limiting unsymmetrical ligands include: bis(2-methylindenyl)methyl phenylsilane, (2-methylindenyl)(indenyl) dimethylsilane, and the like.
  • Exemplary but not limiting chirai metallocenes prepared in accordance with this process include the racemic isomers of: dimethyl- [1, l'-dimethylsilanediyl-bis(indenyl)] zirconium; dimethyl- [ 1, l'-dimethylgermanediyl-bis(indenyl)] zirconium; dimethyl- [1, l'-dimethylcarbyl-bis(indenyl)] zirconium; dimethyl-[l,l'-dimethylsilanediyl-bis(4,5,6,7- tetrahydroindenyl)] zirconium; dimethyl- [1, l'-dimethylgermanediyl-bis(4,5,6,7- tetrahydroindenyl)] zirconium; dimethyl- [1, l'-dimethylcarbyl-bis(4,5,6,7- tetrahydroindenyl)] zirconium; di
  • transition metal tetrahalide compounds include TiCU, ZrCl 4 , HfCl 4 .
  • titanium metallocenes can be prepared using TiCl 3 in place of TICI 4 if followed by an oxidation procedure.
  • the transition metal halide may be used in the form of an ether complex, e.g. ZrCl 4 (THF) 2 , TiCl 4 (THF) 2 , HfCl 4 (THF) 2 which can be prepared either in a hydrocarbon or halocarbon solvent and isolated from the reaction mixture or in a hydrocarbon solvent and used directly in the reaction with the ligand salt without separation from the solvent medium.
  • an ether complex e.g. ZrCl 4 (THF) 2 , TiCl 4 (THF) 2 , HfCl 4 (THF) 2 which can be prepared either in a hydrocarbon or halocarbon solvent and isolated from the reaction mixture or in a hydrocarbon solvent and used directly in the reaction with the ligand salt without separation from the solvent medium.
  • Exemplary, but non-limiting alkylating agents include any of the known alkyl-group containing organometallic compounds, for example: methyl lithium, methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, dimethyl zinc, trimethyl aluminum and the like.
  • Exemplary but not limiting covalent bridging groups, T contain atoms of silicon, carbon, oxygen, germanium, tin, or combinations thereof.
  • silicon-containing groups include dimethylsilyl, diethylsilyl, diphenylsilyl, Si-O, Si-O-C, Si-O-Si, and the like
  • carbon bridges include, methylene, ethylene, propylene, butylene and the like.
  • the reaction process may occur as an organic slurry or a solution upon the mixture of reagents. It is recommended to employ solvent in an amount sufficient to form a slurry and minirnize solvent usage.
  • Purifying the racemic metallocene alkyl may occur with a hydrocarbon such as toluene, ether, or a mixture of such solvents.
  • Concentrations of reactants based on total volume of organic solvent medium is not a necessary feature during the preparation step of the metallocene alkyl.
  • the metallocene product is not required to precipitate from the reaction mixture as it forms. Consequently, concentrations are not a critical feature provided the metallocene alkyl is soluble in the chosen solvent. Less solvent is necessary to solubilize the metallocene alkyl than the metallocene dihalide species.
  • at least one experiment may be necessary to determine amount of solvent to employ.
  • One of skill in the art has a general idea of expected solubility of the desired product and plans for concentrations relative thereto. The key is to have sufficient solvent to just dissolve the metallocene alkyl.
  • An advantage of the present invention is that the metallocene alkyl can be recovered free or substantially free of alkali metal salt by products.
  • the metallocene alkyl is preferably recovered by removal of reaction solvent.
  • the process of the present invention is suitable for the preparation of metallocene dialkyls in high purity for use in olefin polymerizations. This is of particular importance in stereospecific polymerization of alpha olefins since only the racemic form produces stereoregular polymer. Cyclic olefin copoiymers, including those of high crystalline melting point will also benefit from this method for preparing suitable metallocene catalysts where ionic catalyst system are to be used. See, for example, U. S. patent 5,324,801.
  • the Group 4 metallocene dialkyl derivatives may be activated with traditional activators, such as alumoxane activators, or with ionic activators such as described in U.S. 5,198,401 to form a catalyst system useful to polymerize olefins to polyolef ⁇ ns, e.g. polymerization of C 2 _2o olefins under suitable polymerization conditions to form homopolymers or copoiymers of polyethylene, polypropylene, and the like.
  • chirai racemic metallocene dialkyls formed are especially useful for the production of stereospecific polymer such as isotactic polypropylene.
  • the catalyst system may be placed on a support by techniques known to those of skill in the art or may further be used as-is, or prepolymerized with olefinic monomer having from 2-20 carbon atoms, preferably 2 carbon atoms.
  • ionic catalysts include ionizing anion pre-cursors which are initially neutral but form the cation and anion upon ionizing reaction with the metallocene compounds. See, EP-A-0 426 697.
  • Ionic catalysts for addition polymerization are said to be prepared by oxidation of the metal centers of transition metal compounds by anionic pre-cursors containing oxidizing groups along with the anion groups, see EP-A-0 495 375.
  • WO-A-91/09882, and WO-A-94/03506 describing suitable supporting techniques by adsorption on the surface of inert support materials.
  • Co-pending U.S. Ser. No. 031,004, equivalent WO-A- 93/11172, and U.S. Ser. No. 08/285,380, filed 8/3/94, equivalent WO-A- describe the chemical bonding of anionic activators to polymeric and metal oxide supports so as to prepare chemically bound, supported polyanionic activators.
  • the Group 4 metallocene dialkyl and activator may be used in a variety of suitable polymerization processes such as high pressure, gas, bulk, solution or slurry phase processes which may be operated in a batch or continuous fashion.
  • suitable polymerization processes such as high pressure, gas, bulk, solution or slurry phase processes which may be operated in a batch or continuous fashion.
  • Selection of metallocene compounds suitable for preparing isotactic or syndiotactic polypropylene, as well as polyolefins in general, are well-known in the art, specific reference may be made to both patent literature and academic.
  • those catalysts are stereo rigid asymmetric, chirai or bridged chirai metallocenes. See, for example, U.S. patent 5,017,714, U.S. patent 5,296,434, U.S.
  • the cyclopentadienyl (or substituted cyclopentadienyl, such as indenyl or substituted indenyl) rings when bridged to each other, will be lower alkyl-substituted (C - -Cg) in the 2 position and will additionally comprise alkyl, cycloalkyl, aryl, alkylaryl and or aryl alkyl subtituents, the latter as either of fused or pendant ring structures including multi-ring structures, for example, those of U.S. patents 5,132,262, 5,278,264 and 5,304,614
  • the invention may be further illustrated by the following examples which are presented solely for the purpose of illustration and should not be construed as limiting the invention. All the examples are carried out in a dry, oxygen-free atmosphere, standard glove box.
  • the Cp ligand system and their alkali metal salts can be readily obtained from commercial sources or synthesized. Alternately, the ligand system may be formed by other conventional methods which are well known in the art.
  • ZrCl4 (3.36g, 14.4 mmol) was added to the flask in small portions as a solid. The reaction mixture was stirred for about 72 hours after which time a bright yellow suspension had formed. The reaction was filtered and the yellow solid washed with toluene (100 ml). This material was returned to the 500 ml flask and slurried in about 200 ml of toluene. Excess CH MgBr (2.5 equivalents, 36.0 mmol, 12 ml of 3M in ether) was added dropwise to the flask and the mixture allowed to stir for about 1.5 hours. One equivalent (14.4 mmol, 1.56g, 1.83 ml) of chlorotrimethyl silane was added to the mixture.
  • Example 1 & 2 The metallocene dialkyl products formed in Example 1 & 2 were subsequently employed in solution polymerization techniques wherein either discrete ionic activators or methylalumoxane solution, respectively, were employed as activators to polymerize propylene to isotactic polypropylene.
  • the dialkyl products were also supported employing a variety of support techniques and subsequently employed in slurry polymerization reactions to polymerize propylene to isotactic polypropylene.

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Abstract

L'invention concerne une synthèse améliorée pour la préparation de métallocène-alkyles racémiques de grande pureté, sensiblement exempts de sels de métaux alcalins et de méso-isomère. Le procédé consiste à a) former dans un solvant un produit de réaction résultant d'un sel métallique d'un ligand cyclopentadiényle et d'un composé perhalogéné d'un métal de transition des groupes 4-6 ou de son complexe du type étherat; b) combiner le produit obtenu en a) avec au moins deux équivalents molaires d'un agent d'alkylation; c) séparer la solution des matières solides formées subséquemment; d) enlever le solvant pour récupérer le composé métallocène-alkyle, et e) laver le métallocène-alkyle avec un solvant ou un mélange de solvants. Les composés métallocène-alkyles sont particulièrement utiles comme catalyseurs de polymérisation d'addition ou d'insertion lorsqu'ils sont activés par un co-catalyseur de polymérisation approprié.
PCT/US1995/016689 1994-12-21 1995-12-21 Procede de preparation de metallocene-alkyles racemiques de grande purete et leur utilisation WO1996019488A1 (fr)

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AU45271/96A AU4527196A (en) 1994-12-21 1995-12-21 A method of preparing high purity racemic metallocene alkyls and use thereof

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Cited By (11)

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EP0819695A2 (fr) * 1996-07-16 1998-01-21 Montell Technology Company bv Procédé pour la modification du rapport rac/meso d'un composé metallocène
DE19726454A1 (de) * 1996-06-28 1998-02-05 Danubia Petrochem Deutschland Verfahren zur stereoselektiven Herstellung von chiralen Metallocenen
EP0835886A1 (fr) * 1996-10-09 1998-04-15 Fina Research S.A. Procédé pour la préparation et l'utilisation de composés méso/racémiques du type (bis(indényl)éthane)zirconium-dichloro
US5892077A (en) * 1996-07-16 1999-04-06 Montell Technology Company Bv Process for modifying the rac/meso ratio in a metallocene compound
US5965759A (en) * 1998-09-23 1999-10-12 Albemarle Corporation Catalytic process for isomerizing metallocenes
US6191294B1 (en) 1998-01-14 2001-02-20 Montell Technology Company Bv Process for the preparation of metallocene compounds
WO2003057705A1 (fr) * 2002-01-08 2003-07-17 Basell Polyolefine Gmbh Preparation de composes metallocenes a pont silicium
KR101712318B1 (ko) * 2016-04-29 2017-03-03 한화케미칼 주식회사 메탈로센 이성질체 촉매 및 이를 이용하여 제조된 폴리올레핀 수지
WO2019132346A1 (fr) * 2017-12-26 2019-07-04 주식회사 엘지화학 Procédé de préparation de catalyseur métallocène supporté et procédé de préparation de polypropylène à l'aide du catalyseur ainsi préparé
CN111527112A (zh) * 2017-12-26 2020-08-11 Lg化学株式会社 负载型茂金属催化剂的制备方法及使用由此制备的催化剂制备聚丙烯的方法
US11279723B2 (en) 2018-07-03 2022-03-22 Exxonmobil Chemical Patents Inc. Metallocene synthesis process

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19726454A1 (de) * 1996-06-28 1998-02-05 Danubia Petrochem Deutschland Verfahren zur stereoselektiven Herstellung von chiralen Metallocenen
EP0819695A2 (fr) * 1996-07-16 1998-01-21 Montell Technology Company bv Procédé pour la modification du rapport rac/meso d'un composé metallocène
EP0819695A3 (fr) * 1996-07-16 1998-04-22 Montell Technology Company bv Procédé pour la modification du rapport rac/meso d'un composé metallocène
US5892077A (en) * 1996-07-16 1999-04-06 Montell Technology Company Bv Process for modifying the rac/meso ratio in a metallocene compound
EP0835886A1 (fr) * 1996-10-09 1998-04-15 Fina Research S.A. Procédé pour la préparation et l'utilisation de composés méso/racémiques du type (bis(indényl)éthane)zirconium-dichloro
US6191294B1 (en) 1998-01-14 2001-02-20 Montell Technology Company Bv Process for the preparation of metallocene compounds
US5965759A (en) * 1998-09-23 1999-10-12 Albemarle Corporation Catalytic process for isomerizing metallocenes
US7002031B2 (en) 2002-01-08 2006-02-21 Basell Polyolefine Gmbh Preparation of silicon-bridged metallocene compounds
WO2003057705A1 (fr) * 2002-01-08 2003-07-17 Basell Polyolefine Gmbh Preparation de composes metallocenes a pont silicium
KR101712318B1 (ko) * 2016-04-29 2017-03-03 한화케미칼 주식회사 메탈로센 이성질체 촉매 및 이를 이용하여 제조된 폴리올레핀 수지
WO2019132346A1 (fr) * 2017-12-26 2019-07-04 주식회사 엘지화학 Procédé de préparation de catalyseur métallocène supporté et procédé de préparation de polypropylène à l'aide du catalyseur ainsi préparé
CN111527112A (zh) * 2017-12-26 2020-08-11 Lg化学株式会社 负载型茂金属催化剂的制备方法及使用由此制备的催化剂制备聚丙烯的方法
US11504706B2 (en) 2017-12-26 2022-11-22 Lg Chem, Ltd. Method of preparing supported metallocene catalyst and method of preparing polypropylene using catalyst prepared thereby
CN111527112B (zh) * 2017-12-26 2023-01-06 Lg化学株式会社 负载型茂金属催化剂的制备方法及使用由此制备的催化剂制备聚丙烯的方法
US11731123B2 (en) 2017-12-26 2023-08-22 Lg Chem, Ltd. Method of preparing supported metallocene catalyst and method of preparing polypropylene using catalyst prepared thereby
US11279723B2 (en) 2018-07-03 2022-03-22 Exxonmobil Chemical Patents Inc. Metallocene synthesis process

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