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EP1455940A1 - Heterogenisation de composants catalytiques - Google Patents

Heterogenisation de composants catalytiques

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Publication number
EP1455940A1
EP1455940A1 EP02795096A EP02795096A EP1455940A1 EP 1455940 A1 EP1455940 A1 EP 1455940A1 EP 02795096 A EP02795096 A EP 02795096A EP 02795096 A EP02795096 A EP 02795096A EP 1455940 A1 EP1455940 A1 EP 1455940A1
Authority
EP
European Patent Office
Prior art keywords
oxide
reaction
general formula
compound
refunctionalized
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02795096A
Other languages
German (de)
English (en)
Inventor
Katrin Köhler
Eike Poetsch
Herbert Schumann
Birgit Wassermann
Katharina Lange
Ralf Widmaier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP1455940A1 publication Critical patent/EP1455940A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0209—Impregnation involving a reaction between the support and a fluid
    • 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
    • C08F110/02—Ethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • 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
    • C08F4/65925—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 non-bridged
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a method for the refunctionalization of chemically inert, thermally pretreated metal oxides with an increased number of coreactive groups on the oxide surface without producing by-products which deactivate catalytic components.
  • the invention further relates to the use of the refunctionalized metal oxides as catalyst supports for olefin polymerization.
  • Heterogeneous catalysts have the great practical advantage that the catalyst fixed on a surface can be separated from the product very easily after the reaction. Intensive efforts have been made in recent years in order to enable a more cost-effective and efficient separation or reuse of homogeneous catalysts. Et al the principles of two-phase catalysis and the covalent immobilization of homogeneous catalysts on solid phases were developed. [W. A. Herrmann, B. Cornils, Angew. Chem. 1997, 109, 1074-1095; Davis, M.E., Chemtech 1992, 22, (8), 498]
  • the catalyst is chemisorbed on a carrier material by covalent, ionic or coordinative binding.
  • the catalyst can also be linked to the the carrier surface must be bound.
  • the carrier material can be both organic and inorganic in nature.
  • the surface hydroxyl groups are reacted, for example, with metal alkyls, halides or alcoholates or functionalized alkoxysilanes to form organo-functionalized surfaces.
  • inorganic support materials have a more or less large number of reactive OH groups on the surface, which can form a bond with catalytically active organic or organometallic components.
  • this number is about 4.4 - 8.5 per nm 2 .
  • Siloxane bridges Si-O-Si
  • Si-O-Si can be broken on the surface of Si0 2 networks by alkali organyls such as phenyllithium or butyl lithium.
  • alkali organyls such as phenyllithium or butyl lithium.
  • this reaction leads to a partial detachment of SiR 4 from the surface, with vonSi-OLi building blocks remaining on the surface.
  • a method was described in P19802753 of how the number of active OH groups on the oxide surface is increased by reaction of the oxide material with a strongly basic reagent MR such as alkali or alkaline earth metal hydrides, oxides or organyls and subsequent protonation with HX and can adjust.
  • a strongly basic reagent MR such as alkali or alkaline earth metal hydrides, oxides or organyls and subsequent protonation with HX and can adjust.
  • a salt MX is formed as a by-product in all cases, which in many cases, in particular with subsequent catalyst attachment leads to partial or complete poisoning of the catalyst in the case of extremely reactive, Lewis acidic catalysts. This is the case, for example, in the coordinative olefin polymerization using Lewis acidic metal-containing catalysts from group IVb of the periodic table of the elements.
  • catalysts can only be used using a support, since the catalyst support prevents reactor fouling and prevents agglomeration of the catalytically active centers. Consequently, catalyst supports are required which contain no deactivating components, but at the same time have a sufficiently high number of coreactive groups on the support surface for the subsequent covalent attachment of the catalytic components.
  • the support should disintegrate into small particles during the polymerization, which are evenly distributed in the resulting polymer, which presupposes that the catalytic components are also bound in the pores and fissures of the support. This is very important for the further processing of the polymer, since larger carrier particles include optical properties such.
  • the object of the present invention was therefore to develop a process which increases the number of coreactive groups on the surface of support materials without simultaneously introducing deactivating by-products.
  • the process is also intended specifically to provide those carrier materials with a sufficiently large number of coreactive groups on the surface which have been given a chemically inert surface by thermal pretreatment to remove the by-products resulting from the carrier production processes. ben.
  • These coreactive groups on the support surface should be capable of further covalent attachment of catalytic components, in particular for the coordinative olefin polymerization.
  • Other goals were to use carrier materials with good thermal conductivity and low swellability, an inexpensive and simple one
  • the supported catalysts produced should advantageously be able to be used in the polymerization of olefins.
  • the present object is achieved by a simple method which refunctionalises chemically inert, thermally pretreated metal oxides with an increased number of coreactive groups on the oxide surface without generating deactivating by-products.
  • R, R ', R "independently of one another A, OA, OAIA 2 , NA 2 , PA 2 , and
  • a branched or unbranched C 1 -C 2 alkyl A branched or unbranched C 1 -C 2 alkyl
  • Cycloalkyl, alkenyl, cycloalkenyl, aryl or alkynyl are the subject of the present application.
  • the invention interpret, subject of the present application.
  • the invention of this application also encompasses the special embodiments of this method as claimed in claims 2 to 14 and reproduced in the following description.
  • the present invention includes the catalyst supports produced or refunctionalized by the process according to the invention, but also their use in polymerization, metathesis, hydrogenation, coupling, oxidation and hydroformylation reactions or in metallocene-mediated olefin polymerization or as support materials for singles -site catalysts.
  • T metal atom of the oxide from the group Ha - IVa and IVb of the periodic table of the elements;
  • R, R ⁇ R "independently of one another A, OA, OAIA 2) NA 2 , PA 2 ;
  • Ci - C 12 alkyl A branched or unbranched Ci - C 12 alkyl, cycloalkyl,
  • Alkenyl, cycloalkenyl, aryl or alkynyl are alkyl, the radicals methyl, ethyl, i- and n-propyl, n-, i- and tert-butyl, pentyl, hexyl, heptyl, octyl, as cycloalkyl radicals the radicals cyclopropyl, cyclobutyl , Cyclopentyl, cyclohexyl or cycloheptyl, as alkenyl radicals the radicals ethylene, propenyl, butenyl, butadienyl,
  • A is particularly preferably to be understood as the radicals methyl, ethyl, i-propyl.
  • the reaction according to the invention can be used in a simple process in that a metal oxide from one of the groups Ha - IVa or IVb of the periodic table of the elements, optionally after previous thermal pretreatment in a high vacuum at temperatures in the range from 20 to 1000 ° C. in an aprotic solvent with a Compound of the general formula (1) RR'AIH, in which R and R 'have the meanings given above, reacted and stirred at a temperature in the range from 0 to 150 ° C. for 5 minutes to 2 days. It is preferably stirred at a temperature in the range from 50 to 120 ° C. for 1 to 8 hours.
  • the reaction product formed can be separated off, washed with the same solvent and dried in an oil pump vacuum and then or directly or in-situ with a compound of the general formula (2) RR'AIOR "in which R and R 'have the meanings given above
  • a suspension of the reaction product obtained by the reaction with the compound of the general formula (1) is prepared and this is at a temperature in the range from 0 to 150 ° C. for 5 Stirred for min to 3 days, preferably in the range of 30 to 80 ° C for 5 to 30 hours.
  • the resulting product is separated.
  • Both the reaction of a metal oxide with a compound of the general formula (1) and the reaction with compounds of the general formula (2) are preferably carried out under a protective gas atmosphere.
  • Inert gases can be nitrogen or argon.
  • Solvents suitable for carrying out the process can be hydrocarbons or aprotic nonpolar solvents such as, for example, diethyl ether, dioxane, tetrahydrofuran or carbon tetrachloride, or mixtures of these solvents.
  • the hydrocarbons can be both aliphatic and aromatic hydrocarbons.
  • Suitable hydrocarbons include Pentane, hexane, heptane, benzene, toluene and xylene.
  • Other suitable hydrocarbons are known to the person skilled in the art and can be selected depending on the starting compounds.
  • Metal oxides from one of the groups Ha - IVa or IVb of the Periodic Table of the Elements can serve as catalyst supports, such as oxides of silicon, aluminum, magnesium, titanium and zirconium and mixed oxides of silicon-aluminum, silicon-titanium and silicon-zirconium. Oxides of silicon such as silica gels, broken SiO 2 , spherical SiO 2 , monolithic SiO 2 , spherical monodisperse SiO 2 and aluminum are preferred.
  • Oxides are particularly preferred, in particular that of silicon with a particle size of 10 nm to 250 ⁇ m, a particle surface of 10 to 1000 m 2 / g and a pore volume of 0 - 15 ml / g, preferably with a pore volume of 0 - 5 ml / G.
  • Other suitable metal oxides are known to the person skilled in the art and can be selected depending on the subsequent application of the refunctionalized carriers.
  • the oxide surfaces refunctionalized with RR'AI building blocks can be converted into a large number of coreactive groups on the oxide surface by reaction with compounds which contain acidic hydrogen atoms, which groups can be used to attach ligands and / or catalytic components.
  • acidic hydrogen atoms preference is given to compounds having acidic hydrogen atoms from the Group water, alcohols, amines, carboxylic acids and acetylenes used. Alcohols and water are most preferred.
  • Other suitable compounds are known to the person skilled in the art and can be selected depending on the subsequent application of the refunctionalized carriers.
  • the refunctionalized supports obtained by the process according to the invention can be used as catalyst supports in particular for polymerization, metathesis, hydrogenation, coupling, oxidation or hydroformylation reactions. It has been found that the refunctionalized oxide materials serve as support materials for single-site catalysts.
  • the method according to the invention for carrier preparation for catalytic olefin polymerization is particularly suitable. Particularly good results are achieved when the refunctionalized supports are used in metallocene-mediated olefin polymerization.
  • the catalytic components consisting of a cocatalyst such as e.g. Methylaluminoxane and a catalyst such as e.g. a metallocene compound are immobilized on the refunctionalized carrier materials.
  • Other suitable cocatalysts and catalysts for olefin polymerization are known to the person skilled in the art and can be selected depending on the polymerization process.
  • Corresponding supported catalysts can be used in the polymerization reactions of olefins.
  • A is branched or unbranched C 1 -C 12 -alkyl or aryl and compound of the general formula (2) RR'AIOR ", in which R, R ', R" independently of one another A, OA;
  • Ci - C 12 alkyl or aryl mean be used.
  • Aluminum tribute oxide can be used particularly well for the refunctionalization of metal oxides.
  • Diethyl aluminum ethoxide are suitable for this purpose and lead to a high number of coreactive dialkylaluminium components on the metal oxide surface.
  • the gradual thermal pretreatment of the Si0 2 carrier in a high vacuum at temperatures in the range from 20 ° C to 1000 ° C with subsequent cooling in a protective gas atmosphere leads to the removal of the surface-bound reactive silanol groups to remove the physisorbed, volatile components such as water, Al - alcohols, ammonia and polar solvents resulting from the carrier manufacturing process.
  • the thermal pretreatment has an extremely advantageous effect on the subsequent heterogenization of catalytic and cocatalytic components, since the proportion of potential catalyst poisons in the support material is greatly reduced.
  • the process described here for the refunctionalization of the chemically inactive metal oxide surface present after drying produces a coreactive functionalized SiO 2 surface which has a higher number of coreactive groups on the surface (based on aluminum 6-8 per nm 2 , based on hydroxyl groups 12 -16 nm) compared to Si0 2 materials at room temperature with only 4 hydroxyl groups per nm 2 surface or compared to Si0 2 materials pretreated at 1000 ° C with no hydroxyl group on the surface.
  • This process also enables chemical refunctionalization of the metal oxide surfaces without generating deactivating by-products that act as potential catalyst poisons.
  • the refunctionalized oxide materials serve as support materials for, for example, single-site catalysts.
  • the refunctionalized carriers loaded with diorganylaluminum were partially hydrolyzed and reacted with the cocatalytic component methylaluminoxane (MAO) and the precatalytic component zirconocene dichloride [( ⁇ 5 -C 5 H 5 ) 2 ZrCI 2 3 and used for catalytic olefin polymerization for the production of polyethylene :
  • the refunctionalized metal oxide supports lead in the ethylene polymerization in combination with aluminum-containing cocatalysts and metalocene catalysts to an activity increase of 25% in comparison to the carrier-free homogeneous system ( ⁇ 5 -C 5 H 5 ) 2 ZrCl 2 / MAO.
  • the process according to the invention is thus particularly suitable for the reactivation and chemical functionalization of oxidic catalyst support materials which have lost their active surface functions, for example as a result of a drying process, but which are necessary for the physisorption or chemisorption of homogeneous or else heterogeneous catalyst systems or components.
  • the SiO 2 (Monospher 250) is dried in a Schlenk flask at 150 ° C for 6 hours in a vacuum of 10 "2 - 10 " 3 mbar (weight loss 3-4%). Then you bring the dried Si0 2 on a porcelain boat, which is in a quartz tube with ground caps and taps. In a tube furnace, the quartz tube with the Si0 2 is heated to 1000 ° C for 24 hours in a vacuum of 10 "2 - 10 " 3 mbar. The heating phase is regulated via a temperature ramp of 1 ° C / min. After the heating phase at 1000 ° C has ended, the cooling phase takes place under an inert gas atmosphere (N 2 ). There is a drying loss of 8% based on the Si0 2 pretreated at 150 ° C.
  • R iso-butyl
  • R ' OAl'ßuz
  • R " ethyl
  • the carrier dried in an oil pump vacuum, is then suspended in 20 ml of toluene in a 100 ml Schlenk flask.
  • 20 ml of a 1.6 M toluene solution of 5 Et 2 AIOEt are added dropwise through a septum using a syringe.
  • the cooled ones are worked up Suspension by filtration or centrifugation.
  • the solvent freed from Si0 2 is washed three times with 20 ml of toluene and three times with 10 ml of hexane and then dried in an oil pump vacuum.
  • a toluene methylaluminoxane solution is placed in an 11 Büchi glass autoclave and the organoaluminum-functionalized support based on SiO 2 (Monospher 250) described in Example 1 is added as a toluene suspension and then stirred at 30 ° C. for half an hour.
  • a toluene Cp 2 ZrCl 2 solution is then injected and the mixture is stirred for a further ten minutes. 2 bar of ethylene are injected and the pressure and temperature are kept constant throughout the polymerization. After an hour of reaction, the polymerization is terminated by releasing the pressure and adding ethanol.
  • the toluene polymer suspension is stirred for several hours with dilute hydrochloric acid and then filtered, washed until neutral and dried to constant weight.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerization Catalysts (AREA)

Abstract

La présente invention concerne un procédé pour refonctionnaliser des oxydes métalliques chimiquement inertes, ayant subi un traitement thermique et présentant un nombre élevé de groupes organoaluminium coréactifs à leur surface, sans produire de sous-produits désactivant des composants catalytiques. La présente invention concerne également l'utilisation des oxydes métalliques refonctionnalisés en tant que support de catalyseur pour une polymérisation d'oléfines.
EP02795096A 2001-12-21 2002-12-04 Heterogenisation de composants catalytiques Withdrawn EP1455940A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10163457 2001-12-21
DE10163457A DE10163457A1 (de) 2001-12-21 2001-12-21 Heterogenisierung von katalytischen Komponenten
PCT/EP2002/013711 WO2003053578A1 (fr) 2001-12-21 2002-12-04 Heterogeneisation de composants catalytiques

Publications (1)

Publication Number Publication Date
EP1455940A1 true EP1455940A1 (fr) 2004-09-15

Family

ID=7710500

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02795096A Withdrawn EP1455940A1 (fr) 2001-12-21 2002-12-04 Heterogenisation de composants catalytiques

Country Status (6)

Country Link
US (1) US20050085374A1 (fr)
EP (1) EP1455940A1 (fr)
JP (1) JP2005513205A (fr)
AU (1) AU2002360957A1 (fr)
DE (1) DE10163457A1 (fr)
WO (1) WO2003053578A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX363101B (es) 2012-11-26 2019-03-08 Braskem Sa Catalizador de metaloceno soportado por medios de soporte hibridos, procesos para producir el mismo, procesos de polimerizacion para producir un homopolimero o copolimero de etileno con distribucion de masa molar amplia o bimodal, uso del catalizador de metaloceno soportado y polimero de etileno con distribucion de masa molar amplia o bimodal.
US20220098034A1 (en) * 2018-12-17 2022-03-31 King Abdullah University Of Science And Technology Heterogeneous catalysts for hydrogen generation from formic acid

Family Cites Families (8)

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Publication number Priority date Publication date Assignee Title
US4347157A (en) * 1979-04-25 1982-08-31 Sumitomo Chemical Company, Limited Catalysts for the polymerization of olefins
US4295999A (en) * 1979-10-17 1981-10-20 Shell Oil Company Polymerization catalyst
JP2826362B2 (ja) * 1990-02-13 1998-11-18 三井化学株式会社 オレフィン重合用固体触媒の製造方法、オレフィン重合用固体触媒およびオレフィンの重合方法
TW218884B (fr) * 1991-05-01 1994-01-11 Mitsubishi Kakoki Kk
WO1999010389A1 (fr) * 1997-08-21 1999-03-04 Sumitomo Chemical Company, Limited Particules modifiees, vehicule prepare a partir de ces particules, constituant de catalyseur de polymerisation d'olefine ainsi prepare, catalyseur de polymerisation d'olefine ainsi prepare et procede de preparation d'un polymere d'olefine
US6159888A (en) * 1998-09-09 2000-12-12 Phillips Petroleum Company Polymerization catalyst systems, their preparation, and use
DE10149785A1 (de) * 2001-10-09 2003-04-10 Merck Patent Gmbh Katalysatorsysteme für die Ziegler-Natta-Propen-Polymerisation
US7238757B2 (en) * 2002-09-13 2007-07-03 Merck Patent Gesellschaft Oxygen-containing organoaluminium complexes as cocatalysts

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03053578A1 *

Also Published As

Publication number Publication date
AU2002360957A1 (en) 2003-07-09
DE10163457A1 (de) 2003-07-03
WO2003053578A1 (fr) 2003-07-03
JP2005513205A (ja) 2005-05-12
US20050085374A1 (en) 2005-04-21

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