EP0885248A1 - Systemes catalyseurs metallocenes stables - Google Patents

Systemes catalyseurs metallocenes stables

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Publication number
EP0885248A1
EP0885248A1 EP97908032A EP97908032A EP0885248A1 EP 0885248 A1 EP0885248 A1 EP 0885248A1 EP 97908032 A EP97908032 A EP 97908032A EP 97908032 A EP97908032 A EP 97908032A EP 0885248 A1 EP0885248 A1 EP 0885248A1
Authority
EP
European Patent Office
Prior art keywords
metallocene
days
catalyst
catalyst system
methyl
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.)
Ceased
Application number
EP97908032A
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German (de)
English (en)
Inventor
Anthony N. Speca
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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Filing date
Publication date
Application filed by Exxon Chemical Patents Inc filed Critical Exxon Chemical Patents Inc
Publication of EP0885248A1 publication Critical patent/EP0885248A1/fr
Ceased legal-status Critical Current

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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
    • 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
    • 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
    • C08F4/62—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
    • C08F4/65916—Component covered by group C08F4/64 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
    • C08F4/62—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

Definitions

  • This invention relates to stabilized metallocene catalyst systems and to methods for their production and use.
  • these catalyst systems comprise metallocene and alkylalumoxane wherein the ratio of the aluminum of the alkylalumoxane to the transition metal of the metallocene used to prepare the catlayst system is in the range of from about 80: 1 to about 200: 1.
  • These catalyst systems retain their activity and may be used directly in polymerization after storage for periods of up to two months or more.
  • U. S. Patent No. 5,393,851 describes a concentrated stock metallocene alumoxane solution which may be stored for up to 14 days. Before use in polymerization, this solution must be diluted with additional alumoxane. Additionally, these concentrated solutions must be stored in a relatively cool environment in order to retain activity and there can be an activity loss of from 20 to 30 percent before the solution becomes stable.
  • This invention relates to a method for polymerizing olefins comprising polymerizing one or more olefins under suitable polymerization conditions in the presence of an active metallocene catalyst system comprising metallocene and an alkylalumoxane which active catalyst system has been stored for at least two days.
  • This invention also relates to stabilized metallocene catalyst systems comprising metallocene, alkylalumoxane and optionally support material wherein the ratio of the aluminum of the alkylalumoxane to the transition metal of the metallocene used to prepare the catalyst system is in the range of from about 80: 1 to about 200: 1.
  • this invention relates to a method for preparing a metallocene catalyst system, said method comprising the steps of: (a) combining a metallocene catalyst component with an alkylalumoxane wherein the ratio of the aluminum of the alkylalumoxane to the transition metal of the metallocene used to prepare the catalyst system is in the range of from about 80: 1 to about 200: 1 ; and (b) storing the combination for a time period of at least about two days.
  • the metallocene catalyst systems of this invention comprises metallocene and alkylalumoxane wherein the ratio of the aluminum of the alkylalumoxane to the transition metal of the metallocene used to prepare the catalyst system is in the range of from about 80: 1 to about 200: 1.
  • This catalyst system can be stored for at least about two days at relatively high temperatures without substantial loss in activity.
  • "storing" or “stored” means allowed to sit without being used as a catalyst system or component.
  • the ratio of the aluminum of the alkylalumoxane to the transition metal of the metallocene used to prepare the catalyst system is in the range of from about 85:1 to about 150:1, more preferably from about 90:1 to about 125:1.
  • the composition may be stored for at least about two days, or up to about 5 days, about 7 days, about 14 days, about 21 days, about 28 days, about 35 days, about 42 days, about 49 days, about 56 days, about 63 days, about 70 days, about 77 days, about 84 days or even about 91 days or more.
  • the weight percent of metal on the finished catalyst system is in the range of from about 0.20 to about 1.0, more preferably from about 0.25 to about 0.85, and most preferably from about 0.30 to about 0.70.
  • the temperature during storage may be up to 60°C, preferably up to 45°C, more preferably ambient temperature or from about 20°C to about 45°C.
  • the catalyst system may be stored at high ambient temperatures, higher productivity is likely to be retained if the catalyst sytem is stored under the coolest conditions practicable.
  • the catalyst system may be warehoused outside or only partially sheltered in most climates. Any suitable container may be used for storage. To preserve activity, the container should be air-tight and the storage atmosphere should be free of oxygen and/or water.
  • the catalyst system After storage, the catalyst system retains at least about 50% of its original productivity, preferably at least about 60%, more preferably at least about 70%, even more preferably at least about 75%, even more prefereably at least about 80%, even more preferably at least about 90% and most preferably at least about 95 percent of its original productivity, i.e., its productivity when less than 1 day old.
  • the metallocene and alkylalumoxane are preferably combined with a support either before or after storage, preferably before storage.
  • a support is defined as any material upon which metallocenes and/or activators may be fixed.
  • the support material is a porous particulate material, such as talc, inorganic oxides, inorganic chlorides and resinous materials such as polyolefin or polymeric compounds. Such materials are generally commercially available.
  • the preferred support materials are porous inorganic oxide materials, which include those from the Periodic Table of Elements of Groups 2, 3, 4, 5, 13 or 14 metal oxides. Silica, alumina, silica-alumina, and mixtures thereof are most preferred. 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.
  • metallocene includes a single metallocene composition or two or more metallocene compositions.
  • Metallocenes are typically bulky ligand transition metal compounds generally represented by the formula: [ ] m M[A] n where L is a bulky ligand; A is 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 ligands L and A may be bridged to each other, and if two ligands L and/or A are present, they may be bridged.
  • the metallocene compound may be full-sandwich compounds having two or more ligands L which may be cyclopentadienyl ligands or cyclopentadiene derived ligands or half-sandwich compounds having one ligand L, which is a cyclopentadienyl ligand or cyclopentadienyl derived ligand.
  • the transition metal atom may be a Group 4, 5 or 6 transition metal and/or a metal from the lanthanide and actinide series.
  • Zirconium, titanium, and hafnium are often preferred.
  • Other ligands may be bonded to the transition metal, such as a leaving group, such as but not limited to hydrocarbyl, hydrogen or any other univalent anionic ligand.
  • metallocenes are discussed in United States Patent Nos. 4,530,914;
  • the metallocene catalyst component of the invention can be a monocyclopentadienyl heteroatom containing compound. This heteroatom is activated by either an alumoxane, an ionizing activator, a Lewis acid or a combination thereof to form an active polymerization catalyst system.
  • metallocene catalysts useful in this invention can include non-cyclopentadienyl catalyst components, or ancillary ligands such as boroles or carbollides in combination with a transition metal.
  • the metallocene is represented by the formula:
  • M is a metal of Group 4, 5, or 6 of the Periodic Table preferably, zirconium, hafnium and titanium, most preferably zirconium;
  • R* and R2 are identical or different, are one of a hydrogen atom, a Cj-Cio alkyl group, preferably a C1-C3 alkyl group, a CI -CJO alkoxy group, preferably a C1-C3 alkoxy group, a C ⁇ -Cjo aryl group, preferably a Cg-Cg aryl group, a C ⁇ - Cjo aryloxy group, preferably a C ⁇ -Cg aryloxy group, a C2-C10 alkenyl group, preferably a C2-C4 alkenyl group, a C7-C40 arylalkyl group, preferably a C7-C10 arylalkyl group, a C7-C40 alkylaryl group, preferably a C7-C12 alkylaryl group, a Cg-C4o arylalkenyl group, preferably a Cg-C ⁇ 2 arylalkenyl group, or a hal
  • R3 and R ⁇ are hydrogen atoms
  • R5 and R > are identical or different, preferably identical, are one of a halogen atom, preferably a fluorine, chlorine or bromine atom, a C i -C ⁇ Q alkyl group, preferably a C1-C4 alkyl group, which may be halogenated, a Cg-C 10 aryl group, which may be halogenated, preferably a Cg-Cg aryl group, a C2-C10 alkenyl group, preferably a C2-C4 alkenyl group, a C7-C40 -arylalkyl group, preferably a C7-C1 Q arylalkyl group, a C7-C40 alkylaryl group, preferably a C7- C12 alkylaryl group, a Cg-C4o arylalkenyl group, preferably a Cg-C 12 arylalkenyl group, a -NR2 15 , -SR 15 , -OR 15
  • ⁇ is silicon, germanium or tin, preferably silicon or germanium, most preferably silicon;
  • R8 and R ⁇ are identical or different and have the meanings stated for R 1 ! ;
  • n and n are identical or different and are zero, 1 or 2, preferably zero or 1, m plus n being zero, 1 or 2, preferably zero or 1 ;
  • R ⁇ are identical or different and have the meanings stated for R 1 ⁇ , R 1 ⁇ and R 1 ⁇ .
  • Two adjacent R 1 ⁇ radicals can be joined together to form a ring system, preferably a ring system containing from about 4-6 carbon atoms.
  • Alkyl refers to straight or branched chain substituents.
  • Halogen halogenated is fluorine, chlorine, bromine or iodine atoms, preferably fluorine or chlorine.
  • Particularly preferred metallocenes are compounds of the structures: iO
  • M 1 is Zr or Hf
  • R 1 and R 2 are methyl or chlorine
  • R 5 , R 6 R 8 , R 9 ,R 10 , R * and R 2 have the above-mentioned meanings.
  • These chiral metallocenes may be used as a racemate for the preparation of highly isotactic polypropylene copolymers. It is also possible to use the pure R or S form. An optically active polymer can be prepared with these pure stereoisomeric forms. Preferably the meso form of the metallocene is removed to ensure the center (i.e., the metal atom) provides stereoregular polymerization. Separation of the stereoisomers can be accomplished by known literature techniques. For special products it is also possible to use rac/meso mixtures.
  • the metallocenes are prepared by a multi-step process involving repeated deprotonations/metallations of the aromatic ligands and introduction of the bridge and the central atom by their halogen derivatives.
  • the following reaction scheme illustrates this generic approach:
  • metallocenes include: Dimethylsilandiylbis (2-methyl-4-phenyl- 1 -indenyl)ZrCl2 Dimethylsilandiyibis(2-methyl-4, 5-benzoindenyl)ZrCl2 ; Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyI)ZrCl2; ⁇ Q-
  • alkylalumoxane may be used as an activator for the metallocene.
  • alkylalumoxanes contain about 5 to 40 of the repeating units:
  • R is a Cj-Cg alkyl including mixed alkyls. Particularly preferred are the compounds in which R is methyl.
  • Alumoxane solutions, particularly methylalumoxane solutions which are preferred, may be obtained from commercial vendors as solutions having various concentrations. There are a variety of methods for preparing alumoxane, non-limiting examples of which are described in U.S. Patent No.
  • U.S. Patent No. 5,157,137 discloses a process for forming clear, gel- free solutions of alkylalumoxane by treating a solution of alkylalumoxane with an anhydrous salt and/or hydride of an alkali or alkaline earth metal.
  • the metallocene, alkylalumoxane and support material may be combined in any manner or order.
  • suitable support techniques are described in U. S. Patent Nos. 4,808,561 and 4,701,432 (each fully incorporated herein by reference).
  • the metallocene and alkylalumoxane are combined first and their reaction product combined with the support material.
  • Suitable examples of this technique are described in U. S. Patent No. 5,240,894 and WO 94/28034, WO 96/00243, and WO 96/00245 (each fully incorporated herein by reference).
  • a porous support such as silica is used and the volume of metallocene and activator combined with the support is less than about 4.0 times the total pore volume of the support, more preferably less than about 3.0 times the total pore volume of the support, even more preferably less than about 2.5 times the total pore volume of the support.
  • the procedure for measuring the total pore volume of a porous support is well known in the art. Details of one of these procedures are discussed in Volume 1, Experimental Methods in Catalytic Research (Academic Press, 1968) (specifically see pages 67-96). This preferred procedure involves the use of a classical BET apparatus for nitrogen absorption. Another method well know in the art is described in Innes, Total porosity and Particle Density of Fluid Catalysts By Liquid Titration, Vol. 28, No. 3, Analytical Chemistry 332-334 (March, 1956).
  • the support When the volume of solution combined with porous support material is less than one times the total pore volume of the support, the support appears completely dry and free-flowing and is consequently easy to mix and transfer. When volumes above one times the total pore volume of the porous support are used, the support becomes progressively more difficult to mix and transfer as volume increases because it has the consistency of damp or wet mud. At greater volumes of solution, a slurry is eventually formed such that one can observe separation of the solution and support as the silica settles. At the slurry stage, the support is easier to mix and handle. These factors should be considered when choosing solution volumes.
  • the support and solution such that the solution is evenly distributed among the support particles.
  • the catalyst system is preferably dried at least to a free flowing powder prior to storage.
  • Heat and/or vacuum may be used to dry the catalyst.
  • temperature in the range of from about 25°C to about 100°C is used for a time period ranging from about 4 to about 36 hours. It may be advantageous to dry the catalyst without vacuum or with a flow of warm inert gas such as nitrogen.
  • the final weight ratio of the aluminum of the alkylalumoxane to the metal of the metallocene as determined by elemental analysis is preferably in the range of from about 15 to about 170, more preferably from about 50 to about 150, even more preferably from about 80 to about 125.
  • the catalyst systems of this invention may be used directly in polymerization after storage or the catalyst system may be prepolymerized before or after storage using methods well known in the art. For details regarding prepolymerization, see United States Patent Nos. 4,923,833 and 4,921,825, EP 0 279 863 and EP 0 354 893 each of which is fully incorporated herein by reference.
  • the catalyst systems of this invention may also be combined before or after storage with one or more additives such as scavengers.
  • suitable scavenging compounds include triethylaluminum (TEAL), trimethylaluminum (TMAL), tri- isobutylaluminum (TIBAL), tri-n-hexylaluminuim (TNHAL) and the like.
  • the catalyst system of this invention may be used in the polymerization of any monomer and optionally comonomers in any process including gas, slurry or solution phase or high pressure autoclave processes.
  • polymerization includes copolymerization and “monomer” includes comonomer.
  • a gas or slurry phase process is used, most preferably a bulk liquid propylene polymerization process is used.
  • this invention is directed toward the bulk liquid polymerization and copolymerization of propylene or ethylene, particularly propylene, in a slurry or gas phase polymerization process, particularly a slurry polymerization process.
  • Another embodiment involves copolymerization reactions of propylene or ethylene, particularly propylene, with one or more of the alpha- oiefin monomers having from 4 to 20 carbon atoms, preferably 4-12 carbon atoms, for example alpha-olefin comonomers of ethylene, butene- 1 , pentene- 1 , 4- 19 methylpentene-l, hexene-1, octene-1, decene-1, and olefins such as styrene, cyclopentene or norbomene.
  • Suitable monomers include vinyl, diolefins such as dienes, for example, 1,3-butadiene, 1,4-hexadiene, norbornadiene or vinylnorbornene, acetylene, ethylidene norbornene and aldehyde monomers.
  • a continuous cycle is employed where in one part of the cycle of a reactor, a cycling gas stream, otherwise known as a recycle stream or fluidizing medium, is heated in the reactor by the heat of polymerization.
  • the recycle stream usually contains one or more monomers continuously cycled through a fiuidized bed in the presence of a catalyst under reactive conditions. This heat is removed in another part of the cycle by a cooling system external to the reactor.
  • the recycle stream is withdrawn from the fiuidized bed and recycled back into the reactor.
  • polymer product is withdrawn from the reactor and new or fresh monomer is added to replace the polymerized monomer.
  • a slurry polymerization process generally uses pressures in the range of about 1 to about 500 atmospheres or even greater and temperatures in the range of -60°C to about 280°C.
  • a suspension of solid, particulate polymer is formed in a liquid polymerization medium to which ethylene and comonomers and often hydrogen along with catalyst are added.
  • the liquid employed in the polymerization medium can be, for example, an alkane or a cycloalkane.
  • the medium employed should be liquid under the conditions of polymerization and relatively inert. Non-limiting examples of liquid mediums include hexane and isobutane. ⁇
  • the catalyst system after storage has a productivity of at least about 2000 g polymer/g catalyst, preferably at least about 2500 g polymer/g catalyst, most preferably at least about 3000 g polymer/g catalyst.
  • Table I summarizes stability of catalyst activity after aging at 100°F (34°C).
  • Example 1 having a lower Aluminum to Zirconium molar ratio was stable to heat aging at 100°F (34°C) while the catalyst VI- of Comparative Example 3 at three times the ratio lost 30% catalyst activity after 40 hours and about 45% after about 2 weeks.
  • Example 4 having an Al/Zr molar ratio of 126 was more stable to activity loss than the catalyst of Comparative Example 5.
  • the latter having an Al/Zr of 210 lost about 50% activity after heat aging for 2 months while the catalyst with the ratio of the instant invention maintained about 85% activity in about the same time period.

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Polymerization Catalysts (AREA)

Abstract

L'invention concerne des systèmes catalyseurs métallocènes stabilisés, ainsi que des procédés permettant leur production et leur utilisation. Spécifiquement, ces systèmes catalyseurs comprennent un métallocène, un alkyl-alumoxane et éventuellement un matériau support. Le rapport de l'aluminium de l'alkyl-alumoxane sur le métal de transition du métallocène utilisé pour préparer ce dernier est compris entre 80:1 et 200:1 environ. Ces catalyseurs conservent leur activité et peuvent être utilisés directement pour la polymérisation après stockage pendant deux mois ou davantage à température ambiante.
EP97908032A 1996-03-04 1997-03-04 Systemes catalyseurs metallocenes stables Ceased EP0885248A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US1276096P 1996-03-04 1996-03-04
US12760P 1996-03-04
PCT/US1997/003486 WO1997032906A1 (fr) 1996-03-04 1997-03-04 Systemes catalyseurs metallocenes stables

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EP0885248A1 true EP0885248A1 (fr) 1998-12-23

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EP (1) EP0885248A1 (fr)
JP (1) JP2000506212A (fr)
KR (1) KR19990087458A (fr)
CN (1) CN1214055A (fr)
AU (1) AU1988097A (fr)
CA (1) CA2243519A1 (fr)
EA (1) EA199800808A1 (fr)
WO (1) WO1997032906A1 (fr)

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AU2007319883B2 (en) * 2006-11-14 2012-12-13 Univation Technologies, Llc. Catalyst systems and polymerization processes
EP2573091A1 (fr) 2011-09-23 2013-03-27 Lummus Novolen Technology Gmbh Procédé de recyclage de ligand libre provenant de leurs complexes de métallocènes correspondants
WO2020056119A1 (fr) 2018-09-14 2020-03-19 Fina Technology, Inc. Mélanges de polymères de polypropylène à rhéologie contrôlée et de polyéthylène et procédés d'utilisation
WO2020172306A1 (fr) 2019-02-20 2020-08-27 Fina Technology, Inc. Compositions polymères à faible gauchissement
BR112023019645A2 (pt) 2021-04-26 2023-11-07 Fina Technology Folhas de polímero catalisadas de sítio único finas

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JP2000506212A (ja) 2000-05-23
CA2243519A1 (fr) 1997-09-12
EA199800808A1 (ru) 1999-04-29
AU1988097A (en) 1997-09-22
CN1214055A (zh) 1999-04-14
KR19990087458A (ko) 1999-12-27
WO1997032906A1 (fr) 1997-09-12

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