WO1996004318A1 - Systemes de catalyseur de polymerisation, leur production et utilisation - Google Patents

Systemes de catalyseur de polymerisation, leur production et utilisation Download PDF

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Publication number
WO1996004318A1
WO1996004318A1 PCT/US1995/009663 US9509663W WO9604318A1 WO 1996004318 A1 WO1996004318 A1 WO 1996004318A1 US 9509663 W US9509663 W US 9509663W WO 9604318 A1 WO9604318 A1 WO 9604318A1
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WIPO (PCT)
Prior art keywords
ofthe
support material
organometallic compound
metallocene
carbon atoms
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PCT/US1995/009663
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English (en)
Inventor
Main Chang
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Exxon Chemical Patents Inc.
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Publication of WO1996004318A1 publication Critical patent/WO1996004318A1/fr

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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
    • 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
    • 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61912—Component covered by group C08F4/60 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61916—Component covered by group C08F4/60 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

  • This invention relates to catalysts, catalyst systems, and to methods for their production and use in olefin polymerization.
  • this invention relates to a process for preparing a supported transition metal catalyst system for use in gas phase, slurry phase or liquid/solution phase olefin polymerization with improved reactor operability.
  • a supported catalyst In many polymerization processes, particularly a slurry phase or gas phase process, it is desirable to use a supported catalyst.
  • these catalyst systems include a metallocene and alumoxane supported on a carrier such as silica.
  • a carrier such as silica.
  • U.S. Patent No. 4,937,217 generally describes combining in solution a mixture of trimethylaluminum and triethylaluminum with an undehydrated silica. A metallocene is then added and thereafter the mixture is dried to form a free flowing powder.
  • 4,912,075, 4,935,397, and 4,937,301 generally describe the addition of trimethylaluminum to an undehydrated silica to which is then added a metallocene to form a dry supported catalyst.
  • U.S. Patent No. 4,914,253 describes adding trimethylaluminum to undehydrated silica, adding a metallocene, and then drying the catalyst.
  • U.S. Patent Nos. 4,808,561, 4,897,455 and 4,701,432 describe techniques to form a supported catalyst where the inert carrier, typically silica, is calcined and contacted with a metallocene(s) and a activator/cocatalyst component.
  • 5,238,892 describes forming a dry supported catalyst by mixing a metallocene with an alkyl aluminum then adding undehydrated silica.
  • U.S. Patent No, 5,240,894 generally describes making a supported metallocene/alumoxane catalyst system by forming a metallocene/alumoxane reaction solution, adding a porous carrier, then evaporating the resulting slurry to remove residual solvent from the carrier.
  • 5,008,228, 5,086,025 and 5,147,949 generally describe a process which involves forming a dry supported catalyst by the addition of trimethylaluminum to a water impregnated silica to form alumoxane within the silica pores and then adding the metallocene. While these supported catalysts are useful, it would be desirable to have a catalyst system that provides improved reactor operability. When catalyst systems such as those described above are used, particularly in a slurry or gas phase polymerization process, there is sometimes a tendency for the reactor to foul. During some gas phase polymerization processes, fines within the reactor accumulate and stick to the walls of the reactor, the recycling lines, and cooling systems.
  • This invention generally relates to a new polymerization catalyst system and to methods for its manufacture and use in polymerization.
  • the invention is a new method for producing a supported transition metal catalyst system made by contacting a water containing support material with an organometallic compound and at least one metallocene compound. The solid product is then recovered by drying. At some point in the process, before and/or after metallocene addition, organometallic compound is washed from the support.
  • This invention is generally directed toward a supported catalyst system useful for polymerizing olefins.
  • the method for forming the catalyst system involves supporting a metallocene compound and an organometallic compound on a support material containing water.
  • Metallocene catalysts are typically bulky ligand transition metal compounds represented by the formula:
  • L is a bulky ligand; A is at least one halogen leaving group; M is a transition metal; and m and n are such that the total ligand valency corresponds to the transition metal valency.
  • the catalyst is four co-ordinate such that the compound is ionizable to a 1 + charge state.
  • the ligands L and A may be bridged to each other.
  • the metallocene compound may be full-sandwich compounds having two or more ligands, L, which may be cyclopentadienyl ligands or cyclopentadiene derived ligands.
  • the metallocene compound may be of the half-sandwich type having one ligand, L, which is a cyclopentadienyl ligand or cyclopentadienyl derived ligand.
  • the metallocene compounds contain a multiplicity of bonded atoms, preferably carbon atoms, forming a group which can be cyclic.
  • the bulky ligand can be a cyclopentadienyl ligand or cyclopentadienyl derived ligand or any other ligand capable of ⁇ -5 bonding to the transition metal.
  • One or more bulky ligands may be ⁇ -bonded to the transition metal atom.
  • the transition metal atom may be a Group 4, 5 or 6 transition metal and/or a transition metal from the lanthanide or actinide series.
  • Other ligands may be bonded to the transition metal, such as at least one halogen which serves as a leaving group.
  • Non-limiting examples of metallocene catalysts and catalyst systems are discussed in for example, U.S. Patent Nos. 4,530,914, 4,952,716, 5,124,418, 4,808,561, 4, 897,455, 5,278,119, and 5,304,614 all of which are herein fully incorporated by reference. Further examples may be found in the disclosures of EP-A- 0129368, EP-A-0520732, EP- A- 0420436, WO 91/04257 WO 92/00333, WO 93/08221, and WO 93/08199 which are all fully incorporated herein by reference. Various forms of metallocenes may be used in the polymerization process of this invention.
  • the metallocene catalyst component can be a monocyclopentadienyl heteroatom containing compound which is typically activated by either an alumoxane, an ionic activator, a Lewis acid, or a combination thereof to form an active catalyst system.
  • catalyst systems are described in, for example, PCT International Publication WO 92/00333, WO 94/07928, and WO 91/ 04257, and WO 94/03506, U.S. Patent Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,264,405 and 5,227,440 and EP-A-0 420 436, all of which are fully incorporated herein by reference.
  • the metallocene catalysts useful in this invention can include non-cyclopentadienyl catalyst components such as boroles or carbollides in combination with a transition metal. Also useful may be those catalyst systems described in U.S. Patent Nos. 5,064,802, 5,149,819,
  • the preferred transition metal components are those of Group 4, particularly, zirconium, titanium and hafnium.
  • the transition metal may be in any oxidation state, preferably +3 or +4 or a mixture thereof. All of the catalyst systems of the invention may be prepolymerized or used in conjunction with an additive or scavenging component.
  • the term "metallocene” is defined to contain one or more unsubstituted or substituted cyclopentadienyl or cyclopentadienyl moiety in combination with a transition metal.
  • the metallocene catalyst component is represented by the formulas: (C5R , m)pR"s(C5R'm)MQ3-p- ⁇ and
  • carrier or “support” as used herein are interchangeable and can be any support material, preferably a porous support material, capable of containing water, absorbed or adsorbed, such as talc, inorganic oxides, inorganic chlorides, and resinous support materials such as polyolefin or polymeric compounds or other organic support materials.
  • the preferred support materials are inorganic oxide materials which include those from the Periodic Table of Elements of Groups 2, 3, 4, 5, 13 or 14 metal oxides.
  • Particularly preferred catalyst support materials include silica, alumina, silica-alumina, and mixtures thereof.
  • Other inorganic oxides that may be employed either alone or in combination with the silica, alumina or silica-alumina are magnesia, titania, zirconia, and the like.
  • Additional suitable support materials include finely divided polyolefins, such as polyethylene or polymeric compounds and inorganic compounds such as magnesium dichloride and the like.
  • the support material preferably has a water content in the range of from about 3 weight percent to about 27 weight percent based on the total weight of the support material and water contained therein, preferably in the range of from about 7 weight percent to about 15 weight percent, and most preferably in the range of from about 9 weight percent to about 14 weight percent.
  • the amount of water contained within the support material can be measured by techniques well known in the art.
  • the weight percent water is measured by determining the weight loss of the support material which has been heated and held at a temperature of 1000°C for 16 hours. This procedure is known as "Loss on Ignition" (LOI) and is measured in weight percent of weight lost based on the initial weight of the support material.
  • LOI Loss on Ignition
  • the support material used to make the catalyst system contains water.
  • This support may be formed by adding or removing the desired quantity of water from, for example, commercially available silica (Davidson 948).
  • the support material have a surface area in the range of from about 10 to about 700 m ⁇ /g, pore volume in the range of from about 0.1 to about 4.5 cc/g, and average particle size in the range of from about 10 to about 500 ⁇ m. More preferably, the surface area is in the range of from about 50 to about 500 m ⁇ /g, pore volume of from about 0.5 to about 4.0 cc/g, and average particle size of from about 20 to about 200 ⁇ m. Most preferably the surface area range is from about 100 to about 400 m ⁇ /g, pore volume from about 0.8 to about 3.5 cc/g, and average particle size is from about 30 to about 150 ⁇ m Method of Producing the Activator
  • the support material is first contacted with a component capable of forming an activator for the metallocene catalyst component.
  • the preferred activator component is an organometallic compound of Group 1, 2, 3 and 4 organometallic alkyls, alkoxides, and halides.
  • the preferred organometallic compounds are lithium alkyls, magnesium alkyls, magnesium alkyl halides, aluminum alkyls, silicon alkyl, silicon alkoxides and silicon alkyl halides More preferred organometallic compounds are aluminum alkyls and magnesium alkyls
  • the most preferred organometallic compounds are aluminum alkyls, for example, triethylaluminum (TEAL), trimethylaluminum (TMAL), tri-isobutylaluminum (TLBAL) and tri-n-hexylaluminum (TNHAL) and the like
  • organometallic compound when contacted with the water containing support material, forms an oxy-containing organometallic compound represented by the following general formula:
  • R (R-A]-O) n A1R which is a linear or non-cyclic compound and mixtures thereof including multi ⁇ dimensional structures
  • R is a C ⁇ to C12 alkyl group such as for example methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, and n is an integer from about 1 to 20.
  • the most preferred oxy containing organometallic compounds are alumoxanes, for example methyl alumoxane and/or ethylalumoxane
  • the support material is introduced to a solution of an organometallic compound at a temperature ranging from 0°C to 80°C. The temperature may optionally be maintained at a constant, preferably in the range of from about 0°C to about 45°C. The temperature used will depend on the quantity of the catalyst system of the invention being produced in a single batch.
  • the mole ratio of the organometallic metal to the water content of the support material is preferably in the range of from about 0.7 to about 1.5, preferably about 0.8 to about 1.3, and even more preferably in the range of from about 0.9 to about 1.3.
  • the support material is added to the organometallic compound, for example when the organometallic compound is TMAL, alumoxane, an activator, is generated predominantly inside the pores of the support material.
  • excess metal and/or organometallic compound remains unreacted.
  • the amount of excess organometallic compound naturally depends upon the initial ratio of organometallic compound to water described above. While not wishing to be bound by any particular theory, it is believed that this excess organometallic compound which fails to form activator, is at least partially responsible for reactor fouling.
  • washing is a process familiar to those skilled in the art and may be generally defined as any process by which a liquid is used to remove relatively loose components, particles, compounds, or elements from a solid material.
  • the washing process may be one involving successive slurrying and decantation as described below or the process may be involve continuous flow of fresh liquid over the solid.
  • the washing step may be performed either before or after metallocene addition or both before and after.
  • washing is accomplished by first allowing the support material to settle after reaction with the organometallic compound then decanting any supernatant.
  • the activated support is re- slurried in a suitable diluent such as a dry, oxygen-free aliphatic hydrocarbon.
  • a suitable diluent such as a dry, oxygen-free aliphatic hydrocarbon.
  • the support is again allowed to settle so that the supernatant is removed.
  • This washing process can be repeated and can be performed at any stage or in a combination of stages prior to final drying as will be more fully described below.
  • the organometallic compounds and/or metallocene compounds may be recovered from the diluent for future use or disposal.
  • the diluent may be any hydrocarbon, preferably an inert hydrocarbon of which non-limiting examples include aliphatic hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane and mixtures thereof. Dry, oxygen free, aliphatic hydrocarbons such as isobutane, isopentane, hexane, and heptane are particularly preferred.
  • the activator is formed as described above and then the metallocene catalyst component is added.
  • the supported activator can be washed and or dried before introducing the metallocene component, it can then be slurried in a suitable solvent as is known in the art and the metallocene catalyst component added thereafter.
  • the metallocene catalyst component is added to a support material/alumoxane activator solution, and is then heated to complete the reaction between the metallocene catalyst component and the alumoxane.
  • solution includes a suspension, a slurry, or a mixture.
  • the washing step may be repeated a number of times depending on the amount of organometallic compound originally used, the volume of diluent used, and the desired amount of metal removal.
  • a diluent such as hexane.
  • a porous support is contacted with a liquid comprising a metallocene catalyst and/or organometallic activator component, the total volume of the liquid being less than about four times the total pour volume of the porous support.
  • the support is thereafter washed as described above.
  • the catalyst system is then dried to remove excess liquid.
  • the catalyst system of this invention is suited for the polymerization of monomers and/or comonomers in any polymerization or prepolymerization process, gas, slurry or solution phase process.
  • the catalyst system is used in a gas phase or slurry phase polymerization process.
  • Slurry or gas phase polymerization or copolymerization reactions may involve the polymerization or optionally prepolymerization of one or more of the alpha-olefin monomers having from 2 to 20 carbon atoms, preferably 2-12 carbon atoms.
  • the invention is particularly well suited to the copolymerization reactions involving the polymerization of one or more of the monomers, for example alpha- olefin monomers of ethylene, propylene, butene-1, pentene-1, 4-methylpentene-l, hexene-1, octene-1, decene-1, and cyclic olefins such as styrene.
  • Other monomers can include polar vinyl, diolefins such as dienes, norbornene, acetylene and aldehyde monomers.
  • a copolymer of ethylene or propylene is produced.
  • the comonomer is an alpha-olefin having from 3 to 15 carbon atoms, preferably 4 to 12 carbon atoms and most preferably 4 to 10 carbon atoms.
  • ethylene is polymerized with at least two comonomers to form a terpolymer and the like.
  • the olefin(s) are prepolymerized in the presence of the catalyst system of the invention prior to the main polymerization. For details on prepolymerization see U.S. Patent No. 4,923,833 and 4,921,825 and EP-B-0279 863, published October 14, 1992 all of which are incorporated fully herein by reference.
  • novel catalyst system of this invention is effective in reducing reactor fouling, it is within the scope of this invention to also employ other methods of reducing fouling such as the use of antistatic agents or mechanical scrapers.
  • antistatic agents are described in U.S. Patent No. 5,283,278, fully incorporated herein by reference.
  • Other examples of antistatic agents include but are not limited to alcohol, thiol, silanol, ester, ketone, aldehyde, acid, amine, and ether compounds.
  • Example 1 Into a 1 liter flask equipped with mechanical stirrer, 220 ml of TMAL in heptane solution (15 wt%) and 90 ml of heptane were charged. The solution was cooled to about 50°F (10°C). A 40 g sample of silica gel (Davison D-948 with average particle size of 70 micron) which contained 12.5 wt% of water was slowly added into the flask over 70 minutes. The mole ratio TMAL/H2O was 1.13.
  • the polymer slurry was transferred into a evaporation dish.
  • the surface ofthe autoclave wall and ofthe agitator were very clean.
  • the product was recovered after letting the solvent evaporate. A total of 45 g of polymer was obtained.
  • Example 1 was repeated except that 200ml ofthe TMA solution was used. The mole ratio of TMA H2O was dropped to 1.03. The polymerization step was repeated as in Example 1. After polymerization, the surface ofthe autoclave was inspected and the autoclave wall and agitator were clean. A total of 35g of polymer was obtained.
  • Example 1 was repeated except that the washing steps after metallocene addition were deleted.
  • the aluminum content ofthe supernatant following metallocene addition was measured at 17153 ppm.
  • the solid catalyst was dried from this solution using nitrogen purging without any washing.
  • the polymerization step was repeated as in Example 1. After polymerization, the surface ofthe autoclave wall and the agitator were coated with a thick layer of polymer and most ofthe polymer product was fused together. A total of 18g of polymer was obtained.
  • Example 1 was repeated except that the washing steps were conducted before the metallocene addition.
  • the polymerization step was repeated as in
  • Example 1 After polymerization, the surface ofthe autoclave wall and agitator were clean. A total of 25g of polymer was obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention concerne généralement un système de catalyseur supporté utile pour la polymérisation d'oléfines. Le procédé de support du catalyseur selon l'invention consiste en une phase de lavage, et en la production d'un catalyseur à métaux de transition à ligand gonflant qui, lorsqu'il est utilisé dans un procédé de polymérisation, réduit sensiblement l'encrassement et l'exfoliation du réacteur dans un procédé de polymérisation en phase boueuse.
PCT/US1995/009663 1994-08-05 1995-08-01 Systemes de catalyseur de polymerisation, leur production et utilisation WO1996004318A1 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0755948A2 (fr) * 1995-06-29 1997-01-29 Ciba SC Holding AG Procédé pour la fabrication de polymères oléfiniques stabilisés
EP1731536A1 (fr) 2005-06-09 2006-12-13 Innovene Manufacturing France SAS Catalyseurs de polymérisation supportés
US7863213B2 (en) 2006-05-30 2011-01-04 Nova Chemicals (International) S.A. Supported polymerization catalysts
EP2465876A1 (fr) 2010-12-15 2012-06-20 INEOS Manufacturing Belgium NV Supports d'activation
WO2012098045A1 (fr) 2011-01-20 2012-07-26 Ineos Commercial Services Uk Limited Supports activateurs
WO2013087531A1 (fr) 2011-12-14 2013-06-20 Ineos Europe Ag Nouveaux polymères
WO2014078919A1 (fr) 2012-11-26 2014-05-30 Braskem S.A. Catalyseur métallocène supporté sur support hybride, procédé d'obtention de celui-ci, procédé de polymérisation pour l 'obtention d'un homopolymère ou d'un copolymère d'éthylène à distribution de masse molaire large ou bimodale, utilisation du catalyseur de métallocène supporté et polymère d'éthylène à distribution de masse molaire large ou bimodale

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989009237A1 (fr) * 1988-03-29 1989-10-05 Exxon Chemical Patents, Inc. Procede de preparation d'un catalyseur d'alumoxane metallocene supporte par un gel de silice
EP0545152A1 (fr) * 1991-11-29 1993-06-09 BASF Aktiengesellschaft Systèmes catalytiques supportés pour polymérisation d'alcènes en C2-C10

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989009237A1 (fr) * 1988-03-29 1989-10-05 Exxon Chemical Patents, Inc. Procede de preparation d'un catalyseur d'alumoxane metallocene supporte par un gel de silice
EP0545152A1 (fr) * 1991-11-29 1993-06-09 BASF Aktiengesellschaft Systèmes catalytiques supportés pour polymérisation d'alcènes en C2-C10

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JAMES C.W. CHIEN ET AL: "Olefin Copolymerization with Metallocene catalyst", JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY, vol. 29, 1991, XP000238172 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0755948A2 (fr) * 1995-06-29 1997-01-29 Ciba SC Holding AG Procédé pour la fabrication de polymères oléfiniques stabilisés
EP0755948A3 (fr) * 1995-06-29 1998-01-07 Ciba SC Holding AG Procédé pour la fabrication de polymères oléfiniques stabilisés
US5955522A (en) * 1995-06-29 1999-09-21 Ciba Specialty Chemicals Corporation Process for the preparation of stabilized olefin polymers
EP1731536A1 (fr) 2005-06-09 2006-12-13 Innovene Manufacturing France SAS Catalyseurs de polymérisation supportés
US7863213B2 (en) 2006-05-30 2011-01-04 Nova Chemicals (International) S.A. Supported polymerization catalysts
EP2465876A1 (fr) 2010-12-15 2012-06-20 INEOS Manufacturing Belgium NV Supports d'activation
WO2012080314A2 (fr) 2010-12-15 2012-06-21 Ineos Europe Ag Supports d'activation
WO2012098045A1 (fr) 2011-01-20 2012-07-26 Ineos Commercial Services Uk Limited Supports activateurs
WO2013087531A1 (fr) 2011-12-14 2013-06-20 Ineos Europe Ag Nouveaux polymères
WO2014078919A1 (fr) 2012-11-26 2014-05-30 Braskem S.A. Catalyseur métallocène supporté sur support hybride, procédé d'obtention de celui-ci, procédé de polymérisation pour l 'obtention d'un homopolymère ou d'un copolymère d'éthylène à distribution de masse molaire large ou bimodale, utilisation du catalyseur de métallocène supporté et polymère d'éthylène à distribution de masse molaire large ou bimodale

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