WO1998052686A1 - Procede de fabrication et d'utilisation d'un catalyseur de polymerisation d'olefines prepolymerisees - Google Patents

Procede de fabrication et d'utilisation d'un catalyseur de polymerisation d'olefines prepolymerisees Download PDF

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Publication number
WO1998052686A1
WO1998052686A1 PCT/US1997/008862 US9708862W WO9852686A1 WO 1998052686 A1 WO1998052686 A1 WO 1998052686A1 US 9708862 W US9708862 W US 9708862W WO 9852686 A1 WO9852686 A1 WO 9852686A1
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Prior art keywords
solid
liquid
fluorenyl
catalyst system
zirconium dichloride
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PCT/US1997/008862
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English (en)
Inventor
Syriac Joseph Palackal
Melvin Bruce Welch
Carlton E. Stouffer
Donald Dwight Norwood
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Phillips Petroleum Company
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Application filed by Phillips Petroleum Company filed Critical Phillips Petroleum Company
Priority to AU32129/97A priority Critical patent/AU3212997A/en
Priority to CA002287840A priority patent/CA2287840A1/fr
Priority to PCT/US1997/008862 priority patent/WO1998052686A1/fr
Publication of WO1998052686A1 publication Critical patent/WO1998052686A1/fr

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    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/49—Hafnium
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • 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
    • 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

Definitions

  • This invention relates to a new type of solid particulate metallocene catalyst system useful for the polymerization and/or copolymerization of olefins.
  • the invention is also related to a process for conducting polymerization of olefins using the inventive solid metallocene catalyst system.
  • Metallocene refers to a derivative of cyclopentadienylidene which is a metal derivative containing at least one cyclopentadienyl component which is bonded to a transition metal.
  • the transition metal is selected from Groups IVB, VB, and VIB, preferably IVB and VIB. Examples include titanium, zirconium, hafnium, chromium, and vanadium.
  • a number of metallocenes have been found to be useful for the polymerization of olefins. Generally, the more preferred catalysts are metallocenes ofZr, Hf, or Ti.
  • fouling refers to polymer buildup on the surfaces inside the reactor.
  • U.S. PatentNo. 5,498,581 discloses a new type of prepolymerized metallocene catalyst system that can be used in slurry polymerization with little if any fouling.
  • the patent teaches carrying out the prepolymerization at temperatures in the range of about - 15 °C to about +110°C or more preferably about 10°C to about 30 °C.
  • One aspect of the present invention is based upon the discovery that if one uses prepolymerization temperatures of less than 10°C there is a reduction in the amount of polymer fines produced when the catalyst system is employed in slurry polymerization.
  • Another aspect of the present invention involves employing particulate polyethylene as a feeding aid for the prepolymerized catalyst system.
  • An object of the present invention is to provide improvements to the solid metallocene catalyst systems of the type disclosed in U.S. Patent No. 5,409.581, the disclosure of which is incorporated herein by reference.
  • a method for polymerizing olefins using the new improved version of such prepolymerized metallocene is provided.
  • a solid particulate metallocene- containing catalyst system is produced by (a) combining an cocatalyst and at least one metallocene having at least one cyclopentadienyl-type ligand having at least one oleflnic unsaturated substituent in a liquid to form a liquid catalyst system, (b) conducting prepolymerization of at least one olefin in the presence of said liquid catalyst system to produce a prepolymerized solid catalyst, and (c) separating the resulting solid from the liquid and the components dissolved in the liquid, said solid being the solid particulate metallocene catalyst system, said invention being further characterized by at least one of the following improvements, namely, (1) conducting the prepolymerization by beginning at a temperature of less than 10°C and maintaining the prepolymerization temperature within the range of 3 °C to 5°C of the beginning temperature, or
  • the resulting inventive solid particulate metallocene-containing catalyst system is employed in the polymerization of an olefin by contacting the olefin with the inventive solid particulate metallocene-containing catalyst system under suitable reaction conditions.
  • the cocatalyst can be selected from any of the compounds found useful as activators for metallocenes.
  • organometallic compounds of Group IA, IIA, and IIB of the Periodic Table include organometallic halide compounds, organometallic hydride compounds, and metal halides.
  • organometallic halide compounds include organometallic hydride compounds, and metal halides.
  • organometallic hydride compounds include triethylaluminum, triisobutylaluminum, diethylaluminum chloride, diethylaluminum hydrides, and alkyl aluminoxanes.
  • fluorophenyl boron compounds that have been found suitable as cocatalysts for metallocenes.
  • triphenyl carbenium tetrakis (pentafluorophenyl) boronate as disclosed in U.S. Patent 5,155,080.
  • liquid catalyst system refers to the combination of the cocatalyst, the metallocene, and the liquid, irrespective of whether the aluminoxane and/or the metallocene are dissolved in the liquid.
  • metallocenes are considered to be applicable to the present process.
  • the essential feature is that the metallocene be one wherein at least one cyclopentadienyl-type ligand has a substituent having a polymerizable oleflnic group.
  • Some examples of such olefin-containing metallocenes are disclosed in U.S. Patent 5, 169,818 and published European Application No. 574,370.
  • the invention is considered applicable to both bridged and unbridged metallocenes.
  • the unbridged metallocenes can even include bridged ligands which contain two cyclopentadienyl-type radicals connected by a suitable bridging structure but wherein only one of the cyclopentadienyl-type radicals of that ligand is bonded to the transition metal.
  • the oleflnic substituent can be on the bridge connecting the two cyclopentadienyl-type groups.
  • the metallocenes of the type contemplated as useful for the present invention include those represented by the formula R x (Z)(Z)MeQ k wherein each Z bound to Me and is the same or different and is a cyclopentadienyl-type ligand selected from substituted or unsubstituted cyclopentadienyl, indenyl, tetrahydroindenyl, octahydrofluorenyl, and fluorenyl ligands; R is a structural bridge linking the Z's and Me is a metal selected from the group consisting of IVB, VB, and VIB metals of the periodic table, each Q is the same or different and is selected from the group consisting of hydrogen, halogens, and organo radicals; x is 1 or 0; k is a number sufficient to fill out the remaining balances of Me; further characterized by the fact that at least one Z has at least one olefmically unsaturated substituent attached.
  • this olefmically unsaturated substituent can be a branch on the bridging unit or on one or both of the cyclopentadienyl-type groups of the bridged ligands, or all three.
  • Some currently preferred units for the bridge R include divalent alkylidenes having one to four carbons, not counting the carbons of an olefmically branched substituent of the bridge.
  • a particularly preferred type of bridged metallocene includes those in which the olefmically unsaturated substituent has the formula
  • R" is a hydrocarbyl diradical having 1 to 20 carbon atoms; more preferably 2 to 10;
  • n 1 or 0, and each R' is individually selected from the group consisting of organo radicals
  • R" having 1 to 10 carbon atoms and hydrogen. Most preferably R" has at least two carbons in
  • suitable for the present invention can be prepared by reacting a dihalo oleflnic compound with an alkali metal salt of a suitable cyclopentadiene-type compound to produce a
  • the present invention thus envisions using bridged metallocenes prepared from
  • n is a number typically in the range of about 0 to 20; more preferably 2-10; R iv is Si,
  • R" and R' are each individually selected from hydrogen, or organo groups
  • R and R" components are hydrogen or alkyl
  • Z is a cyclopentadienyl-type radical as described earlier.
  • transition metal compound to yield the metallocene, using the techniques generally known
  • oleflnic unsaturation include 5-(cyclopentadienyl)-5-(9-fluorenyl)-l-hexene zirconium
  • silane zirconium dichloride bis(9-fluorenyl)(methyl)(oct-7-enyl)silane zirconium dichloride, (cyclopentadienyl)(l-allylindenyl) zirconium dichloride, bis(l-allylindenyl) zirconium
  • organo aluminoxane component used in preparing the inventive solid is aluminoxane component used in preparing the inventive solid
  • catalyst system is an oligomeric aluminum compound having repeating units of the formula
  • R-Al-0 R(R-Al-0-) n AlR 2 .
  • R is a C r C 5 alkyl radical, for example, methyl, ethyl,
  • R is methyl
  • Aluminoxanes can be prepared by various procedures known in the art. For example, an aluminum alkyl may be treated with water dissolved in an inert organic
  • a hydrated salt such as hydrated copper sulfate
  • the metallocene and aluminoxane are
  • liquid catalyst system be prepared using an organic liquid in which the aluminoxane
  • the currently preferred liquids are hydrocarbons such as hexane
  • aromatic liquid solvent typically benzene,
  • the amount should preferably be such as to dissolve
  • temperature is preferably kept below that which would cause the metallocene to decompose.
  • the temperature would be in the range of -50 °C to 100°C.
  • the temperature would be in the range of -50 °C to 100°C.
  • metallocene, the aluminoxane, and the liquid diluent are combined at room temperature, i.e.
  • reaction rate can vary depending upon the ligands of the metallocene. It is
  • the support can be any organic or inorganic solid that does not
  • porous supports such as talc
  • inorganic oxides and resinous support materials such as particulate polyolefins.
  • resinous support materials such as particulate polyolefins.
  • inorganic oxide materials include Groups II, III, IV or V metal oxides such as silica,
  • magnesium dichloride and finely divided polyolefins, such as
  • polyethylene It is within the scope of the present invention to use a mixture of one or more
  • dehydration treatment may be carried out in vacuum or while purging with a dry inert gas
  • treatment can be from about 1 to about 24 hours. However, shorter or longer times can be
  • Dehydration can also be accomplished by subjecting the solid to a chemical
  • Chemical treatment is generally capable of converting all water and hydroxyl groups in the
  • particulate material such as, for example silica
  • inert low boiling hydrocarbon such as
  • the silica should be any organic compound that can be used for example, hexane or toluene.
  • the silica should be used for example, hexane or toluene.
  • an inert hydrocarbon solution of the chemical dehydrating agent such as, for example
  • the temperature will be about
  • the solid particulate material may be filtered
  • wash solvent as well as the diluents employed to form the slurry and the
  • solution of chemical dehydrating agent can be any suitable inert hydrocarbon.
  • hydrocarbons examples include pentane, heptane, hexane, toluene, isopentane and the like.
  • silica involves reduction by contacting the solid with carbon monoxide at an elevated
  • catalyst system for the prepolymerization can vary over a wide range. Typically, however,
  • the molar ratio of aluminum in the aluminoxane to transition metal of the metallocene is in
  • a particulate solid i.e. silica
  • silica a particulate solid
  • it is used in an
  • the prepolymerization is conducted in the liquid catalyst system, which can
  • olefins be a solution, a slurry, or a gel in a liquid.
  • a wide range of olefins can be used for the
  • the prepolymerization will be conducted using an olefin
  • ethylene and non-aromatic alpha-olefins preferably selected from ethylene and non-aromatic alpha-olefins, and as propylene. It is
  • a mixture of olefins for example, ethylene and a
  • higher alpha olefin can be used for the prepolymerization.
  • the prepolymerization can be carried out in one or more prepolymerization
  • the prepolymerization steps should be conducted under relatively mild
  • the prepolymerization can be conducted over a wide range of
  • temperatures typically the temperatures would be in the range of about -15 °C to about
  • prepolymerization is begun at a temperature of less than 10°C and maintained within about
  • prepolymerization would be conducted at a temperature in the range of about
  • the amount of prepolymer can be varied but typically would be in the range
  • the resulting solid prepolymerized catalyst is separated from the liquid of the reaction mixture.
  • the material could be separated by filtration
  • the resulting solid is preferably washed with a
  • prepolymerized solid is dried by subjection to a high vacuum at a
  • a preferred technique employs at least one initial wash with an aromatic hydrocarbon, such as
  • toluene followed by a wash with a paraffinic hydrocarbon, such as hexane, and then
  • reaction mixture product with a liquid in which the prepolymer is sparingly soluble, i.e. a
  • Such a liquid is also useful for the subsequent washing of the prepolymerized solid.
  • prepolymer tends to precipitate onto the surface of the solid to aid in the recovery of the
  • the recovered solid prepolymerized catalyst system can be any suitable solid prepolymerized catalyst system. Further, if desired the recovered solid prepolymerized catalyst system can be
  • organoaluminum compounds include compounds such as triethylaluminum,
  • Trialkylaluminum compounds are currently preferred. Also,
  • the solid has been dried using one of the methods described earlier.
  • Inorganic oxides such as silica are an example.
  • fumed silica such as that
  • polyethylene fluff is used as the particulate solid flow aid. It has been found that if
  • polyethylene fluff is used it is possible to carry out the polymerizations in a continuous loop
  • particulate diluents is particularly useful in those polymerization
  • the particulate diluent serves to aid in the feeding of the catalyst
  • the particulate polyethylene used as the feed aid is preferably a polyethylene
  • the size of the polyethylene particles can vary over a wide range but typically it is
  • the particles are predominately of sizes in the range of about 1 mm to about
  • the predominate particles are those having sizes in the range of
  • the amount of polyethylene fluff combined with the catalyst can vary over a wide range; however, for best feeding results it has been found desirable to employ
  • aliphatic hydrocarbons are used as the liquid, typical
  • fluff are those made using a high activity titanium-containing catalyst such as those
  • the inventive solid prepolymerized catalyst system is particularly useful for
  • the catalysts are also useful for preparing copolymers of ethylene and propylene and
  • copolymers of ethylene or propylene and a higher molecular weight olefin are copolymers of ethylene or propylene and a higher molecular weight olefin.
  • the polymerizations can be carried out under a wide range of conditions
  • inventive catalyst system is a solid, it is considered that it is useful for
  • Typical liquid diluents include propane, butane, isobutane, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, toluene, xylene, and the like.
  • propane butane, isobutane, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, toluene, xylene, and the like.
  • the polymerization temperature can vary over a wide range, temperatures typically would be
  • the pressure of the polymerization would be in the range of from
  • the inventive catalyst system is
  • 5-hexene-2-one were dissolved in 100 mL of methanol. While cooling in ice 12.4 mL of
  • a solution was prepared by dissolving 10 g of fluorene in 100 mL of THF and then this was slowly reacted with 37.6 mL of a 1.6 molar solution of n-butyllithium in
  • the metallocene of Example II was employed to prepare solid prepolymerized catalyst systems using two different techniques which differed in that in one the
  • prepolymerization was begun at 0°C and in the other the prepolymerization was begun at
  • the catalyst preparations involved combining the metallocene and a toluene solution
  • silica specifically Davison 952 x 1836 Grade
  • silica was combined with the 10% methylaluminoxane and toluene; then the contents of the
  • Such polymer is as follows:

Abstract

On élabore un catalyseur en créant une solution catalytique selon un procédé qui consiste à combiner un aluminoxane avec un métallocène de groupe 4-6 ayant un substituant qui possède une insaturation oléfinique dans un ligand approprié, afin de former un catalyseur liquide, à effectuer la prépolymérisation d'une oléfine sur ce catalyseur liquide, et à séparer du mélange de réaction le catalyseur contenant le métallocène solide, ladite prépolymérisation étant effectuée en dessous de 15 °C à une température constante et/ou le catalyseur contenant un métallocène solide qui en résulte est combiné avec un polyéthylène particulaire. La polymérisation d'oléfines à l'aide du catalyseur solide de cette invention est également décrite.
PCT/US1997/008862 1997-05-22 1997-05-22 Procede de fabrication et d'utilisation d'un catalyseur de polymerisation d'olefines prepolymerisees WO1998052686A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU32129/97A AU3212997A (en) 1997-05-22 1997-05-22 Method for making and using a prepolymerized olefin polymerization catalyst
CA002287840A CA2287840A1 (fr) 1997-05-22 1997-05-22 Procede de fabrication et d'utilisation d'un catalyseur de polymerisation d'olefines prepolymerisees
PCT/US1997/008862 WO1998052686A1 (fr) 1997-05-22 1997-05-22 Procede de fabrication et d'utilisation d'un catalyseur de polymerisation d'olefines prepolymerisees

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PCT/US1997/008862 WO1998052686A1 (fr) 1997-05-22 1997-05-22 Procede de fabrication et d'utilisation d'un catalyseur de polymerisation d'olefines prepolymerisees

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Cited By (10)

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US6291382B1 (en) 1999-05-24 2001-09-18 Phillips Petroleum Company Metallocenes, polymerization catalyst systems, their preparation, and use
US6294496B1 (en) 1997-12-08 2001-09-25 Albemarle Corporation Particulate group 4 metallocene-aluminoxane catalyst compositions devoid of preformed support, and their preparation and their use
US6340651B1 (en) * 1999-04-26 2002-01-22 Phillips Petroleum Company Multicyclic metallocycle metallocenes and their use
US6475947B1 (en) * 1999-09-10 2002-11-05 Phillips Petroleum Company Oligomeric metallocenes and their use
US6534609B2 (en) 2001-03-13 2003-03-18 Chevron Phillips Chemical Company Lp Method for making and using a metallocene catalyst system
US6551955B1 (en) 1997-12-08 2003-04-22 Albemarle Corporation Particulate group 4 metallocene-aluminoxane catalyst compositions devoid of preformed support, and their preparation and their use
US6677265B1 (en) 1997-12-08 2004-01-13 Albemarle Corporation Process of producing self-supported catalysts
US7037872B2 (en) 2001-07-24 2006-05-02 Borealis Technology Oy Metallocene catalysts containing a cyclopentadienyl ligand substituted by a siloxy or germiloxy group containing an olefinic residue
EP2511305A1 (fr) * 2002-09-27 2012-10-17 Mitsui Chemicals, Inc. Composé de métallocènes ponté pour la polymérisation de lýoléfine et procédé de polymérisation de l'oléfine utilisant celui-ci
US8957159B2 (en) 2002-10-15 2015-02-17 Exxonmobil Chemical Patents Inc. Multiple catalyst system for olefin polymerization and polymers produced therefrom

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US5466766A (en) * 1991-05-09 1995-11-14 Phillips Petroleum Company Metallocenes and processes therefor and therewith
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US6294496B1 (en) 1997-12-08 2001-09-25 Albemarle Corporation Particulate group 4 metallocene-aluminoxane catalyst compositions devoid of preformed support, and their preparation and their use
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US6746981B2 (en) 1997-12-08 2004-06-08 Albemarle Corporation Particulate group 4 metallocene-aluminoxane catalyst compositions devoid of preformed support, and their preparation and their use
US6551955B1 (en) 1997-12-08 2003-04-22 Albemarle Corporation Particulate group 4 metallocene-aluminoxane catalyst compositions devoid of preformed support, and their preparation and their use
US6677265B1 (en) 1997-12-08 2004-01-13 Albemarle Corporation Process of producing self-supported catalysts
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US6291382B1 (en) 1999-05-24 2001-09-18 Phillips Petroleum Company Metallocenes, polymerization catalyst systems, their preparation, and use
US6482967B2 (en) * 1999-05-24 2002-11-19 Phillips Petroleum Company Metallocenes, polymerization catalyst systems, their preparation, and use
US6475947B1 (en) * 1999-09-10 2002-11-05 Phillips Petroleum Company Oligomeric metallocenes and their use
US6534609B2 (en) 2001-03-13 2003-03-18 Chevron Phillips Chemical Company Lp Method for making and using a metallocene catalyst system
US6852660B2 (en) 2001-03-13 2005-02-08 Chevron Phillips Chemical Company, Lp Solid metallocene catalyst system
US7037872B2 (en) 2001-07-24 2006-05-02 Borealis Technology Oy Metallocene catalysts containing a cyclopentadienyl ligand substituted by a siloxy or germiloxy group containing an olefinic residue
EP2511305A1 (fr) * 2002-09-27 2012-10-17 Mitsui Chemicals, Inc. Composé de métallocènes ponté pour la polymérisation de lýoléfine et procédé de polymérisation de l'oléfine utilisant celui-ci
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