WO2002046248A2 - Materiaux supports s'utilisant avec des catalyseurs de polymerisation - Google Patents

Materiaux supports s'utilisant avec des catalyseurs de polymerisation Download PDF

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WO2002046248A2
WO2002046248A2 PCT/US2001/049703 US0149703W WO0246248A2 WO 2002046248 A2 WO2002046248 A2 WO 2002046248A2 US 0149703 W US0149703 W US 0149703W WO 0246248 A2 WO0246248 A2 WO 0246248A2
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catalyst
compound
group
catalyst system
activator
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PCT/US2001/049703
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WO2002046248A3 (fr
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Thomas Henry Peterson
Gregory T. Whiteker
Dick Alan Nagaki
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Univation Technologies, Llc
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Priority claimed from US09/731,635 external-priority patent/US6482904B2/en
Priority claimed from US09/731,639 external-priority patent/US6534608B2/en
Priority claimed from US09/731,636 external-priority patent/US20020103313A1/en
Application filed by Univation Technologies, Llc filed Critical Univation Technologies, Llc
Priority to AU2002231197A priority Critical patent/AU2002231197A1/en
Publication of WO2002046248A2 publication Critical patent/WO2002046248A2/fr
Publication of WO2002046248A3 publication Critical patent/WO2002046248A3/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
    • C08F10/02—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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • 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
    • 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
    • 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

Definitions

  • the present invention relates generally to the field of new support materials for use with polymerization catalysts.
  • the present invention is directed to new catalyst systems comprising a controlled pore glass support material, a graphite support material, or a polytetrafluoroethylene support material, and a polymerization catalyst compound, to methods for preparing these supported catalyst systems, and their use in the polymerization of olefm(s).
  • Graphite is a very soft mineral consisting of carbon having a layered structure that consists of six carbon atoms arranged in widely spaced horizontal sheets. Graphite is typically used in pencils, lubricants, crucibles, foundry facings and polishes.
  • Polytetrafluoroethylene (PTFE) sold under the trade name TEFLON, is a polymer similar in structure to polyethylene, consisting of a carbon chain with two fluorine atoms bonded to each carbon.
  • TEFLON is typically used for lubricant free bushings and bearings, liners for equipment used in the storage and transportation of strong acids and organic solvents, as electrical insulation under high-temperature conditions, and in the familiar cooking surface that does not require the use of fats or oils.
  • This invention provides a new catalyst system including controlled pore glass support materials, graphite support materials, and/or polytetrafluoroethylene support materials, a polymerization catalyst compound and an activator compound, to methods of preparing these new catalyst system and to their use in the polymerization of olefin(s).
  • the catalyst compounds which may be utilized with the new support materials of the invention to form catalyst systems include bulky ligand metallocene catalyst compounds and Group 15 containing metal compounds.
  • the ring(s) or ring system(s) are composed of carbon atoms such as but not limited to those cyclopentadienyl ligands or cyclopentadienyl-type ligand structures or other similar functioning ligand structure such as a pentadiene, a cyclooctatetraendiyl or an imide ligand.
  • the metal atom is preferably selected from Groups 3 through 15 and the lanthanide or actinide series of the Periodic Table of Elements.
  • the metal is a transition metal from Groups 4 through 12, more preferably Groups 4, 5 and 6, and most preferably the transition metal is from Group 4.
  • the new support materials of the invention may be utilized with the bulky ligand metallocene catalyst compounds represented by the formula:
  • M is a metal atom from the Periodic Table of the Elements and may be a Group 3 to 12 metal or from the lanthanide or actinide series of the Periodic Table of Elements, preferably M is a Group 4, 5 or 6 transition metal, more preferably M is zirconium, hafnium or titanium.
  • the bulky ligands, L A and L B are open, acyclic or fused ring(s) or ring system(s) and are any ancillary ligand system, including unsubstituted or substituted, cyclopentadienyl ligands or cyclopentadienyl-type ligands, heteroatom substituted and/or heteroatom containing cyclopentadienyl-type ligands.
  • Non-limiting examples of bulky ligands include cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands, indenyl ligands, benzindenyl ligands, f ⁇ uorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenyl ligands, azulene ligands, pentalene ligands, phosphoyl ligands, phosphinimine (WO 99/40125), pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzene ligands and the like, including hydrogenated versions thereof, for example tetrahydroindenyl ligands.
  • L A and L B may be any other ligand structure capable of ⁇ -bonding to M, preferably ⁇ 3 - bonding to M and most preferably ⁇ 5 -bonding .
  • the atomic molecular weight (MW) of L A or L B exceeds 60 a.m.u., preferably greater than 65 a.m.u..
  • L A and L B may comprise one or more heteroatoms, for example, nitrogen, silicon, boron, gennanium, sulfur and phosphorous, in combination with carbon atoms to form an open, acyclic, or preferably a fused, ring or ring system, for example, a hetero-cyclopentadienyl ancillary ligand.
  • Other L A and L B bulky ligands include but are not limited to bulky amides, phosphides, alkoxides, aryloxides, imides, carbolides, borollides, porphyrins, phthalocyanines, corrins and other polyazomacrocycles.
  • each L A and L B may be the same or different type of bulky ligand that is bonded to M. hi one embodiment of formula (I) only one of either L A or L B is present. [0015] Independently, each L A and L B may be unsubstituted or substituted with a combination of substituent groups R.
  • substituent groups R have up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon, that can also be substituted with halogens or heteroatoms or the like.
  • alkyl substituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, including all their isomers, for example tertiary butyl, isopropyl, and the like.
  • hydrocarbyl radicals include fluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substituted organometalloid radicals including trimethylsilyl, 1rimetb.ylgerm.yl, methyldiethylsilyl and the like; and halocarbyl-substituted organometalloid radicals including tris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and disubstitiuted boron radicals including dimethylboron for example; and disubstituted pnictogen radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, chalcogen radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and
  • Non-hydrogen substituents R include the atoms carbon, silicon, boron, aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and the like, including olefins such as but not limited to olefinically unsarurated substituents including vinyl-terminated ligands, for example but-3- enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two R groups, preferably two adjacent R groups, are joined to form a ring structure having from 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron or a combination thereof. Also, a substituent group R group such as 1-butanyl may form a carbon sigma bond to the metal M.
  • ligands may be bonded to the metal M, such as at least one leaving group Q.
  • the term "leaving group” is any ligand that can be abstracted from a bulky ligand metallocene catalyst compound to form a bulky ligand metallocene catalyst cation capable of polymerizing one or more olefin(s).
  • Q is a monoanionic labile ligand having a sigma-bond to M.
  • the value for n is 0, 1 or 2 such that formula (I) above represents a neutral bulky ligand metallocene catalyst compound.
  • Non-limiting examples of Q ligands include weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides or halogens and the like or a combination thereof, h another embodiment, two or more Q's form a part of a fused ring or ring system.
  • Q ligands include those substituents for R as described above and including cyclobutyl, cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene, pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and the like.
  • the new support materials of the invention may be utilized with the bulky ligand metallocene catalyst compounds of formula (I) where L A and L B are bridged to each other by at least one bridging group, A, as represented in the following formula:
  • L A AL B MQ n (H) are known as bridged, bulky ligand metallocene catalyst compounds.
  • L A L B , M, Q and n are as defined above.
  • Non-limiting examples of bridging group A include bridging groups containing at least one Group 13 to 16 atom, often referred to as a divalent moiety such as but not limited to at least one of a carbon, oxygen, nitrogen, silicon, aluminum, boron, gennanium and tin atom or a combination thereof.
  • bridging group A contains a carbon, silicon or germanium atom, most preferably A contains at least one silicon atom or at least one carbon atom.
  • the bridging group A may also contain substituent groups R as defined above including halogens and iron.
  • Non-limiting examples of bridging group A may be represented by R' 2 C, R' 2 Si, R' 2 Si R' 2 Si, R' 2 Ge, R'P, where R' is independently, a radical group which is hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen, or halogen or two or more R' may be joined to form a ring or ring system.
  • the bridged, bulky ligand metallocene catalyst compounds of formula (II) have two or more bridging groups A (EP 664 301 Bl).
  • the bulky ligand metallocene catalyst compounds are those where the R substituents on the bulky ligands L A and L B of formulas (I) and (H) are substituted with the same or different number of substituents on each of the bulky ligands.
  • the bulky ligands L A and L B of formulas (I) and (H) are different from each other.
  • bulky ligand metallocene catalysts compounds useful in the invention include bridged heteroatom, mono-bulky ligand metallocene compounds.
  • These types of catalysts and catalyst systems are described in, for example, PCT publication WO 92/00333, WO 94/07928, WO 91/ 04257, WO 94/03506, WO96/00244, WO 97/15602 and WO 99/20637 and U.S. Patent Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,227,440 and 5,264,405 and European publication EP-A-0 420 436, all of which are herein fully incorporated by reference.
  • J is a heteroatom containing ligand in which J is an element with a coordination number of three from Group 15 or an element with a coordination number of two from Group 16 of the Periodic Table of Elements.
  • J contains a nitrogen, phosphorus, oxygen or sulfur atom with nitrogen being most prefened.
  • the bulky ligand type metallocene catalyst compound is a complex of a metal, preferably a transition metal, a bulky ligand, preferably a substituted or unsubstituted pi-bonded ligand, and one or more heteroallyl moieties, such as those described in U.S. Patent Nos.
  • the new support materials of the invention may be utilized with the bulky ligand metallocene catalyst compounds represented by the formula:
  • M is a Group 3 to 16 metal, preferably a Group 4 to 12 transition metal, and most preferably a Group 4, 5 or 6 transition metal;
  • L D is a bulky ligand that is bonded to M; each Q is independently bonded to M and Q 2 (YZ) fonns a unicharged polydentate ligand;
  • a or Q is a univalent anionic ligand also bonded to M;
  • X is a univalent anionic group when n is 2 or X is a divalent anionic group when n is 1; n is l or 2.
  • L and M are as defined above for fonnula (I).
  • Q is as defined above for formula (I), preferably Q is selected from the group consisting of - O-, - ⁇ R-, -CR2- and -S-; Y is either C or S; Z is selected from the group consisting of -OR, -NR2, -CR3, -SR, -S1R3, -PR2, -H, and substituted or unsubstituted aryl groups, with the proviso that when Q is -NR- then Z is selected from one of the group consisting of -OR, -NR.2, -SR, -S1R3, -PR2 and -H; R is selected from a group containing carbon, silicon, nitrogen, oxygen, and/or phosphorus, preferably where R is a hydrocarbon group containing from 1 to 20 carbon atoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is an integer
  • the bulky ligand metallocene- type catalyst compounds are heterocyclic ligand complexes where the bulky ligands, the ring(s) or ring system(s), include one or more heteroatoms or a combination thereof.
  • heteroatoms include a Group 13 to 16 element, preferably nitrogen, boron, sulfur, oxygen, aluminum, silicon, phosphorous and tin. Examples of these bulky ligand metallocene catalyst compounds are described in WO 96/33202, WO 96/34021, WO 97/17379 and WO 98/22486 and EP-A1-0 874 005 and U.S. Patent No. 5,637,660, 5,539,124, 5,554,775, 5,756,611, 5,233,049, 5,744,417, and 5,856,258 all of which are herein incorporated by reference.
  • the bulky ligand metallocene catalyst compounds are those complexes known as transition metal catalysts based on bidentate ligands containing pyridine or quinoline moieties, such as those described in U.S.
  • the bulky ligand metallocene catalyst compounds are those described in PCT publications WO 99/01481 and WO 98/42664, which are fully incorporated herein by reference.
  • the controlled pore glass support materials may be utilized with the bulky ligand metallocene catalyst compounds represented by the formula:
  • the bulky ligand metallocene catalyst compounds include complexes of Ni 2+ and Pd 2+ described in the articles Johnson, et al., "New Pd(II)- and Ni(H)- Based Catalysts for Polymerization of Ethylene and a-Olefms", J. Am. Chem. Soc.
  • ligand metallocene catalyst examples include those diimine based ligands of Group 8 to 10 metal compounds disclosed in PCT publications WO 96/23010 and WO 97/48735 and Gibson, et. al, Chem. Comm., pp. 849-850 (1998), all of which are herein incorporated by reference.
  • bulky ligand metallocene catalysts are those Group 5 and 6 metal imido complexes described in EP-A2-0 816 384 and U.S. Patent No. 5,851,945, which is incorporated herein by reference, hi addition, bulky ligand metallocene catalysts include bridged bis(arylamido) Group 4 compounds described by D.H. McConville, et al., in Organometallics 1195, 14, 5478-5480, which is herein incorporated by reference. In addition, bridged bis(amido) catalyst compounds are described in WO 96/27439, which is herein incorporated by reference. Other bulky ligand metallocene catalysts are described as bis(hydroxy aromatic nitrogen ligands) in U.S.
  • Patent No. 5,852,146 which is incorporated herein by reference.
  • Other metallocene catalysts containing one or more Group 15 atoms include those described in WO 98/46651, which is herein incorporated herein by reference.
  • Still another metallocene bulky ligand metallocene catalysts include those multinuclear bulky ligand metallocene catalysts as described in WO 99/20665, which is incorporated herein by reference.
  • the bulky ligand metallocene catalysts of the invention described above include their structural or optical or enantiomeric isomers (meso and racemic isomers, for example see U.S. Patent No.
  • Group 15 Containing Polymerization Catalyst The new support materials of the invention may be utilized with Group 15 metal containing polymerization catalyst. Generally, these catalysts includes a Group 3 to 14 metal atom, preferably a Group 3 to 7, more preferably a Group 4 to 6, and even more preferably a Group 4 metal atom, bound to at least one leaving group and also bound to at least two Group 15 atoms, at least one of which is also bound to a Group 15 or 16 atom through another group. [0036] Preferably, at least one of the Group 15 atoms is also bound to a Group 15 or
  • any one of the catalyst compounds described above may have at least one fluoride or fluorine containing leaving group as described in U.S.
  • the above described polymerization catalyst compounds are typically activated in various ways to yield compounds having a vacant coordination site that will coordinate, insert, and polymerize olefin(s).
  • the catalyst system of the invention may include an activator or activators combined with the controlled pore glass, graphite, or polytetrafluoroethylene support materials.
  • activator is defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral catalyst compound to a catalytically active catalyst compound cation.
  • Non-limiting activators include alumoxanes, aluminum alkyls, and ionizing activators, which may be neutral or ionic.
  • alumoxanes activators are utilized as an activator in the
  • Alumoxanes are generally oligomeric compounds containing -Al(R)-O- subunits, where R is an alkyl group.
  • Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane.
  • Alumoxanes may be produced by the hydrolysis of the respective trialkylaluminum compound.
  • MMAO may be produced by the hydrolysis of
  • MMAO's are generally more soluble in aliphatic solvents and more stable during storage.
  • methods for preparing alumoxane and modified alumoxanes non-limiting examples of which are described in U.S. Patent No. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032,
  • a another alumoxane is a modified methyl alumoxane (MMAO)
  • the catalyst system of the invention includes an ionizing or stoichiometric activator, neutral or ionic, such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Patent No. 5,942,459) or combination thereof. It is also within an ionizing or stoichiometric activator, neutral or ionic, such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), bo
  • neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators.
  • Examples of neutral stoichiometric activators include tri-substituted boron, tellurium, aluminum, gallium and indium or mixtures thereof.
  • the three substituent groups are each independently selected from alkyls, alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy and halides.
  • the three groups are independently selected from halogen, mono or multicyclic (including halosubstituted) aryls, alkyls, and alkenyl compounds and mixtures thereof, preferred are alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20 carbon atoms (including substituted aryls). More preferably, the three groups are alkyls having 1 to 4 carbon groups, phenyl, napthyl or mixtures thereof. Even more preferably, the three groups are halogenated, preferably fluorinated, aryl groups. Most preferably, the neutral stoichiometric activator is trisperfluorophenyl boron or trisperfluoronapthyl boron.
  • Ionic stoichiometric activator compounds may contain an active proton, or some other cation associated with, but not coordinated to, or only loosely coordinated to, the remaining ion of the ionizing compound.
  • Such compounds and the like are described in European publications EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 and EP-A-0 277 004, and U.S. Patent Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. Patent Application Serial No. 08/285,380, filed August 3, 1994, all of which are herein fully incorporated by reference.
  • the stoichiometric activators include a cation and an anion component, and may be represented by the following fonnula:
  • L is an neutral Lewis base
  • H is hydrogen
  • (L-H) is a Bronsted acid
  • a d is a non-coordinating anion having the charge d-
  • d is an integer from 1 to 3.
  • the cation component, (L-H) d may include Bronsted acids such as protons or protonated Lewis bases or reducible Lewis acids capable of protonating or abstracting a moiety, such as an akyl or aryl, from the bulky ligand metallocene or Group 15 containing transition metal catalyst precursor, resulting in a catiomc transition metal species.
  • the activating cation (L-H) d + may be a Bronsted acid, capable of donating a proton to the transition metal catalytic precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums and mixtures thereof, preferably ammoniums of methylamine, aniline, dimethylamine, diethylamine, N- methylaniline, diphenylamine, trimethylamine, triethylamine, N,N- dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N- dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such as dimethyl ether diethyl ether, tefrahydrofuran and dio
  • the activating cation (L-H) d + may also be an abstracting moiety such as silver, carboniums, tropylium, carbeniums, ferroceniums and mixtures, preferably carboniums and fenoceniums. Most preferably (L-H) d + is triphenyl carbonium.
  • (A " ) is N,N-dimethylanilinium tetra(perfluorophenyl)borate or triphenylcarbenium tetra(perfluorophenyl)borate.
  • methods of activation such as using radiation (see EP-B1-0 615 981 herein incorporated by reference), electro-chemical oxidation, and the like are also contemplated as activating methods for the purposes of rendering the neutral bulky ligand metallocene catalyst compound or precursor to a bulky ligand metallocene cation capable of polymerizing olefins.
  • Other activators or methods for activating a bulky ligand metallocene catalyst compound are described in for example, U.S. Patent Nos.
  • CPG's are available, for example, from CPG, Inc, Lincoln Park, NJ, with pore diameters in the range of 65-3300 A and pore volumes from 0.4-0.8 mL/g. h addition, three particle sizes in the range 37-74 ⁇ m, 74-125 ⁇ m and 125-177 ⁇ m are also available for each material.
  • These glasses have relatively high pore volumes (> 1 mL/g) and would be expected to be more inert (they are 97% SiO 2 ) toward an electrophilic metal center when compared to a more hydroxylated support such as silica.
  • the controlled pore glass support material has a surface area in the range of from about 10 to about 700 rn ⁇ /g, pore volume in the range of from about 0.1 to about 4.0 cc/g and average particle size in the range of from about 5 to about 500 ⁇ m. More preferably, the surface area of the support material is in the range of from about 50 to about 500 nv g, pore volume of from about 0.5 to about 3.5 cc/g and average particle size of from about 10 to about 200 ⁇ m.
  • CPGs have surface functionality for the bonding of ligands.
  • the surface functionality is, for example, selected from the group consisting of amines, azides, alkylamines, thiols, alkylthiols, alcohols, diols, carboxylic acids, and combinations thereof.
  • the CPGs do not contain surface functionality hi another embodiment, the CPG includes 1142 A pores and a 37-74 ⁇ m particle size.
  • the catalyst system of the invention includes a graphite support material.
  • catalyst compounds and/or activator compounds are deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, the support material or carrier.
  • the graphite is a fluorinated graphite
  • the graphite fluorinated graphite having a low fluorine content is a fluorinated graphite having a high fluorine content.
  • the catalytic activity on the new support material will be at least 1.2 times of the catalytic activity of the same catalyst on silica. It is more preferred that the catalytic activity will be at least 2, more preferably even greater than 3 times that of the catalytic activity of the same catalysts on silica.
  • the catalyst systems of the invention described above are suitable for use in any prepolymerization and/or polymerization process over a wide range of temperatures and pressures.
  • the temperatures may be in the range of from -60 °C to about 280°C, preferably from 50°C to about 200°C, or greater than 50°C, and the pressures employed may be in the range from 1 atmosphere to about 500 atmospheres or higher.
  • Polymerization processes include solution, gas phase, slurry phase and a high pressure process or a combination thereof.
  • the process of this invention is directed toward a solution, high pressure, slurry or gas phase polymerization process of one or more olefin monomers having from 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms.
  • the invention is particularly well suited to the polymerization of two or more olefin monomers of ethylene, propylene, butene-1, pentene- 1, 4-methyl-pentene-l, hexene-1, octene-1 and decene-1.
  • Other monomers useful in the polymerization process of the invention include ethylenically unsaturated monomers, diolefms having 4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins.
  • Non- limiting monomers useful in the invention may include norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidene norbornene, dicyclopentadiene and cyclopentene.
  • a copolymer of ethylene is produced, where with ethylene, a comonomer having at least one alpha-olefm having from 4 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8 carbon atoms, is polymerized in a polymerization process.
  • ethylene or propylene is polymerized with at least two different comonomers, optionally one of which may be a diene, to form a terpolymer.
  • a continuous cycle is employed where in one part of the cycle of a reactor system, a cycling gas stream, otherwise known as a recycle stream or fluidizing medium, is heated in the reactor by the heat of polymerization. This heat is removed from the recycle composition in another part of the cycle by a cooling system external to the reactor.
  • a gas fluidized bed process for producing polymers a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. The gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer.
  • the reactor pressure in a gas phase process may vary from about 100 psig
  • the reactor temperature in a gas phase process may vary from about 30°C to about 120°C, preferably from about 60°C to about 115°C, more preferably in the range of from about 70°C to 110°C, and most preferably in the range of from about 70°C to about 95 °C.
  • gas phase processes contemplated by the process of the invention include series or multistage polymerization processes. Also gas phase processes contemplated by the invention include those described in U.S. Patent Nos. 5,627,242, 5,665,818 and 5,677,375, and European publications EP-A- 0 794 200 EP-B1-0 649 992, EP-A- 0 802 202 and EP-B- 634 421 all of which are herein fully incorporated by reference.
  • the reactor utilized in the present invention is capable and the process of the invention is producing greater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher of polymer, preferably greater than 1000 lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540 Kg/hr), even more preferably greater than 25,000 lbs/hr (11,300 Kg/hr), still more preferably greater than 35,000 lbs/hr (15,900 Kg/hr), still even more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most preferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr (45,500 Kg/hr).
  • a slurry polymerization process generally uses pressures in the range of from
  • a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which ethylene and comonomers and often hydrogen along with catalyst are added.
  • the suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor.
  • the liquid diluent employed in the polymerization medium is typically an alkane having from 3 to 7 carbon atoms, preferably a branched alkane.
  • the medium employed should be liquid under the conditions of polymerization and relatively inert.
  • a prefened polymerization technique of the invention is refened to as a particle form polymerization, or a slurry process where the temperature is kept below the temperature at which the polymer goes into solution.
  • Such technique is well known in the art, and described in for instance U.S. Patent No. 3,248,179 which is fully incorporated herein by reference.
  • Other slurry processes include those employing a loop reactor and those utilizing a plurality of stirred reactors in series, parallel, or combinations thereof.
  • Non-limiting examples of slurry processes include continuous loop or stirred tank processes.
  • other examples of slurry processes are described in U.S. Patent No. 4,613,484, which is herein fully incorporated by reference.
  • the reactor used in the slurry process of the invention is capable of and the process of the invention is producing greater than 2000 lbs of polymer per hour (907 Kg/hr), more preferably greater than 5000 lbs hr (2268 Kg/hr), and most preferably greater than 10,000 lbs/hr (4540 Kg/hr).
  • the slurry reactor used in the process of the invention is producing greater than 15,000 lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000 lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).
  • a prefened process of the invention is where the process is operated in the presence of a bulky ligand metallocene catalyst system of the invention and in the absence of or essentially free of any scavengers, such as triethylaluminum, trimethylaluminum, triisobutylaluminum and tri-n-hexylalummum and diethyl aluminum chloride, dibutyl zinc and the like.
  • a bulky ligand metallocene catalyst system of the invention and in the absence of or essentially free of any scavengers, such as triethylaluminum, trimethylaluminum, triisobutylaluminum and tri-n-hexylalummum and diethyl aluminum chloride, dibutyl zinc and the like.
  • any scavengers such as triethylaluminum, trimethylaluminum, triisobutylaluminum and tri-n-hexylalummum and diethy
  • olefin(s), preferably C2 to C30 olefin(s) or alpha-olefin(s), preferably ethylene or propylene or combinations thereof are prepolymerized in the presence of the catalyst solution or emulsion of the invention prior to the main polymerization.
  • the prepolymerization can be carried out batchwise or continuously in gas, solution or slurry phase including at elevated pressures.
  • the prepolymerization can take place with any olefin monomer or combination and/or in the presence of any molecular weight controlling agent such as hydrogen.
  • any molecular weight controlling agent such as hydrogen.
  • the polymers produced by the process of the invention can be used in a wide variety of products and end-use applications.
  • the polymers produced by the process of the invention include linear low density polyethylene, elastomers, plastomers, high density polyethylenes, medium density polyethylenes, low density polyethylenes, polypropylene and polypropylene copolymers.
  • the polymers typically ethylene based polymers, have a density in the range of from 0.86g/cc to 0.97 g/cc, preferably in the range of from 0.88 g/cc to 0.965 g/cc, more preferably in the range of from 0.900 g/cc to 0.96 g/cc, even more preferably in the range of from 0.905 g/cc to 0.95 g/cc, yet even more preferably in the range from 0.910 g/cc to 0.940 g/cc, and most preferably greater than 0.915 g/cc, preferably greater than 0.920 g/cc, and most preferably greater than 0.925 g/cc.
  • the polymers produced by the process of the invention typically have a molecular weight distribution, a weight average molecular weight to number average molecular weight (M w /M n ) of greater than 1 to about 40, preferably greater than 1.5 to about 15, more preferably greater than 2 to about 10, most preferably greater than about 2.0 to about 8.
  • M w /M n weight average molecular weight to number average molecular weight
  • the polymers of the invention typically have a narrow composition distribution as measured by Composition Distribution Breadth Index (CDBI). Further details of determining the CDBI of a copolymer are known to those skilled in the art. See, for example, PCT Patent Application WO 93/03093, published February 18, 1993, which is fully incorporated herein by reference.
  • the bulky ligand metallocene catalyzed polymers of the invention in one embodiment have CDBI's generally in the range of greater than 50% to 100%, preferably 99%, preferably in the range of 55% to 85%, and more preferably 60% to 80%, even more preferably greater than 60%, still even more preferably greater than 65%.
  • polymers produced using a bulky ligand metallocene catalyst system of the invention have a CDBI less than 50%, more preferably less than 40%, and most preferably less than 30%.
  • the polymers of the present invention in one embodiment have a melt index
  • MI MI or (I 2 ) as measured by ASTM-D-1238-E in the range of from less than 0.01 dg/min to 1000 dg/min, more preferably from about less than 0.01 dg/min to about 100 dg/min, even more preferably from about 0.1 dg/min to about 50 dg/min, and most preferably from about 0.1 dg/min to about 10 dg/min.
  • the polymers of the invention in an embodiment have a melt index ratio
  • I21/I2 I21 is measured by ASTM-D-1238-F of about 5 to less than about 2500, preferably about 15 to about 250, more preferably about 10 to about 25, more preferably from about 15 to about 25.
  • the polymers of the invention in a preferred embodiment have a melt index ratio (I2 1 /I 2 ) ( I 2 1 is measured by ASTM-D-1238-F) of from preferably greater than 10, more preferably greater than 30, even more preferably greater that 40, still even more preferably greater than 50 and most preferably greater than 65.
  • the polymer of the invention may have a narrow molecular weight distribution and a broad composition distribution or vice-versa, and may be those polymers described in U.S. Patent No. 5,798,427 incorporated herein by reference.
  • propylene based polymers are produced in the process of the invention.
  • polymers include atactic polypropylene, isotactic polypropylene, hemi-isotactic and syndiotactic polypropylene.
  • propylene polymers include propylene block or impact copolymers. Propylene polymers of these types are well known in the art see for example U.S. Patent Nos. 4,794,096, 3,248,455, 4,376,851, 5,036,034 and 5,459,117, all of which are herein incorporated by reference. [0098]
  • the polymers of the invention may be blended and/or coextruded with any other polymer.
  • Non-limiting examples of other polymers include linear low density polyethylenes produced via conventional Ziegler-Natta and/or bulky ligand metallocene catalysis, elastomers, plastomers, high pressure low density polyethylene, high density polyethylenes, polypropylenes and the like.
  • Polymers produced by the process of the invention and blends thereof are useful in such forming operations as film, sheet, and fiber extrusion and co-extrusion as well as blow molding, injection molding and rotary molding.
  • Films include blown or cast films fonned by coextrusion or by lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, membranes, etc. in food- contact and non-food contact applications.
  • Fibers include melt spinning, solution spinning and melt blown fiber operations for use in woven or non-woven form to make filters, diaper fabrics, medical garments, geotextiles, etc.
  • Extruded articles include medical tubing, wire and cable coatings, geomembranes, and pond liners. Molded articles include single and multi-layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers and toys, etc.
  • Solvents in which the catalyst system of the invention are formed can include but are not limited to: alkanes such as pentane, iso-pentane, hexane, heptane, octane, and nonane; cycloalkanes such as cyclopentane and cyclohexanes; aromatics such as benzene, toluene, ethylbenzene, and diethylbenzene; and halogen-containing solvents, such as methylene chloride and dichloromethane.
  • alkanes such as pentane, iso-pentane, hexane, heptane, octane, and nonane
  • cycloalkanes such as cyclopentane and cyclohexanes
  • aromatics such as benzene, toluene, ethylbenzene, and diethylbenzene
  • substantially uniform is meant to exclude wide variations in sizes, while allowing statistical variations, i.e. having a standard deviation of less than about 20%.
  • a silica supported catalyst system is a catalyst system supported on a silica, such as Davisson 958, purchased From Davisson, Columbia, MA. The preparation of the catalyst system is described below.
  • MAO is methylalumoxane
  • MMAO is modified methylaluminoxane
  • Cp is cyclopentadiene and Me is methyl.
  • TIBA is triisobutylaluminum
  • ZrCl 2 is bis(indenyl)zirconium dichloride.
  • Catalyst A and B, referenced in the examples, are pictured below.
  • Methylaluminoxane (MAO) and modified methylaluminoxane (MMAO) were purchased from Akzo Nobel, Houston, TX. Triisobutylaluminum was purchased from Aldrich Chemical. All catalysts were prepared from previously published procedures well known in the art or purchased from Albemarle Corporation, Baton Rouge, LA.
  • the basic reactor system consists of a one-liter stainless steel reactor vessel.
  • a purge/evacuation cycle is initiated and the reactor is heated to 95°C with nitrogen flowing through the reactor at 500 seem. Once the reactor has reached 95°C, three evacuation-refill cycles are carried out with dry nitrogen. After these cycles, the reactor is cooled to 60°C under a dry nitrogen purge at 200 seem.
  • 600 mL of hexane is charged to the reactor through a series of purification beds containing a reduced copper chromite catalyst, 13X molecular sieves and alumina.
  • 1-hexene (43 mL, dried over 13X molecular sieves) and scavenging solution are added consecutively to the reactor through a reactor port.
  • the scavenging solutions used for these experiments were modified methyl aluminoxane (MMAO, 250 equivalents, Type 3A, 1.84 M) and tri-isobutyl aluminum (TIBA, 200 equivalents).
  • MMAO modified methyl aluminoxane
  • TIBA tri-isobutyl aluminum
  • the reactor is then heated to 55°C for at least 10 minutes and is subsequently pressurized with ethylene to the set ethylene partial pressure (85 to 130 psi) (586 to 896 Kpa).
  • the catalyst solution is then charged to the reactor via a pressurized bomb.
  • Polymerization experiments are carried out for periods typically in the 30 to 40 minute range. Polymerization activities are detennined from the weight of dried polymer recovered from slurry-phase experiments.
  • a 1.00 mL sample of tri-isobutyl aluminum (1000 ⁇ mol) scavenging solution (25% TIBA in hexane) is added to the reactor.
  • the bed is stined for approximately 10 minutes while the reactor is pressurized with ethylene and brought to the run temperature.
  • the catalyst is injected into the reactor by means of a pressurized bomb injection. Catalyst activities are determined from the volume of ethylene fed as measured by calibrated Brooks mass-flow controllers.
  • Polystyrene beads were purified according to the procedure of Frechet, J. et. al. Science 1998, 280, 270-273.
  • Potassium carbonate 250 g was weighed into a IL beaker and dissolved with vigorous stirring in 500 mL of distilled water.
  • Diaion HP-20SS resin or Ambercbrom CG300s resin 200g was weighed into a 2L beaker and slurried in the potassium carbonate solution. The slurry was stirred for 30 minutes and was filtered and washed with distilled water (300 mL).
  • Concentrated hydrochloric acid 150 mL was then added to 500 mL of water in a IL beaker, combined with the resin in a 2 L beaker and then stirred for 30 minutes. The suspension was filtered and washed with distilled water (500 mL). The resin was then stirred in a 2L beaker with distilled water (500 mL) for 30 minutes.. After filtering, the resin was stirred with 600 mL methanol in a 2 L beaker for a period of 30 minutes.
  • the resin was stined in 1500 mL of methylene chloride for a period of 30 minutes and was filtered and transfened to a clean 2L beaker.
  • the resin was then stirred in a mixture of methanol and methylene chloride (300 mL methanol, 900 mL methylene chloride) for 30 minutes. After filtration, the resin was transferred to a 2L beaker and 1000 mL of methanol was added. The suspension was stirred for 30 minutes. The suspension was then filtered and washed with 100 mL of fresh methanol. The resin was then transferred into a IL round bottom flask and vacuum dried on a schlenk line overnight.
  • a catalyst solution was prepared by dissolving solid (Ind) 2 ZrCl2 (5.0 milligrams, 12.7 ⁇ mol) in toluene (2.00 mL) and modified methyl aluminoxane (1.10 mL, 150 ⁇ mol, 1.92 M). The catalyst mixture was stirred for 30 minutes. A 100 ⁇ L aliquot (0.86 ⁇ mol) was loaded into the sample portion of the bomb. The catalyst solution was injected into the 1 liter autoclave reactor via the pressurized bomb.
  • a catalyst solution was prepared by dissolving (Ind) 2 ZrCl 2 (3.37 milligrams,
  • the catalyst mixture was stined for 30 minutes. A 200 ⁇ mol aliquot (1.72 ⁇ mol) was loaded onto CPG 1142 A glass beads (200 mg). The solid mixture was shaken until the catalyst became a free flowing and powder. A 100 mg sample (0.86 ⁇ mol) of the catalyst mixture was placed into a bomb and injected into the 1 liter autoclave reactor.
  • a catalyst solution was prepared by dissolving (Ind) 2 ZrCl 2 (3.37 milligrams,
  • a catalyst solution was prepared by dissolving tetramethylbisindenylsiloxane zirconium dichloride (24.5 mg) in 1.0 mL of MAO (4.62 M solution in toluene). The catalyst mixture was stirred for 60 minutes. A 200 ⁇ L aliquot was removed and loaded onto 200 mg of controlled pore glass. The loaded catalyst was shaken until it became a free flowing and homogeneous powder and was loaded into a bomb and injected into the IL autoclave reactor.
  • Table 5 shows the activities of bis(indenyl)zirconium dichloride catalyst absorbed into other supports of Examples 15 to 18.
  • the activities of the catalysts absorbed into polytetrafluoroethylene were in the range of 10,000-50,000 g PE (mmol Zr) "1 (100 psi) " 1 h " , somewhat less than the unsupported catalyst, but clearly better than the activity of the Davisson 958 silica supported catalyst.
  • Graphite can also be used as a vehicle for solution catalyst delivery. Four different graphitic materials were examined: granular and flaked graphites and fluorinated graphites containing high and low fluorine contents. All the graphitic materials showed acceptable activity , in the range of 47,000-54,000 g PE (mmol Zr) "1 (100 psi) "1 h "1 , 1.5-2 times that of the silica supported catalyst system.

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Abstract

Cette invention concerne de nouveaux systèmes catalytiques pour polymérisation d'oléfine(s) comprenant un matériau support en verre à porosité contrôlée, un matériau support de graphite et/ou un matériau support de polytétrafluoroéthylene. L'invention concerne également des procédés de préparation du système catalytique et l'utilisation de ce système pour des opérations de polymérisation.
PCT/US2001/049703 2000-12-07 2001-11-07 Materiaux supports s'utilisant avec des catalyseurs de polymerisation WO2002046248A2 (fr)

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US6967184B2 (en) 2004-02-17 2005-11-22 Univation Technologies, Llc Fluoroalcohol leaving group for non-metallocene olefin polymerization catalysts
CN108440954A (zh) * 2018-03-15 2018-08-24 湖南格林美映鸿资源循环有限公司 一种pa6基复合材料及其制备方法
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US6967184B2 (en) 2004-02-17 2005-11-22 Univation Technologies, Llc Fluoroalcohol leaving group for non-metallocene olefin polymerization catalysts
US7163991B2 (en) 2004-02-17 2007-01-16 Univation Technologies, Llc Fluoroalcohol leaving group for non-metallocene olefin polymerization catalysts
US7196032B2 (en) 2004-02-17 2007-03-27 Univation Technologies, Llc Fluoroalcohol leaving group for non-metallocene olefin polymerization catalysts
US7479529B2 (en) 2004-02-17 2009-01-20 Univation Technologies, Llc Fluoralcohol leaving group for non-metallocene olefin polymerization catalysts
US7718566B2 (en) 2004-02-17 2010-05-18 Univation Technologies, Llc Olefin polymerization catalysts
CN110431160A (zh) * 2017-02-20 2019-11-08 埃克森美孚化学专利公司 负载型催化剂体系及其使用方法
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