WO2007092753A2 - Polymerization catalysts for producing polymers with low levels of long chain branching - Google Patents
Polymerization catalysts for producing polymers with low levels of long chain branching Download PDFInfo
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- WO2007092753A2 WO2007092753A2 PCT/US2007/061519 US2007061519W WO2007092753A2 WO 2007092753 A2 WO2007092753 A2 WO 2007092753A2 US 2007061519 W US2007061519 W US 2007061519W WO 2007092753 A2 WO2007092753 A2 WO 2007092753A2
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- C—CHEMISTRY; METALLURGY
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- 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
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
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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
- 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
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
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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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/07—Catalyst support treated by an anion, e.g. Cl-, F-, SO42-
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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
- 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
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Definitions
- This invention relates to the field of organometal compositions, olefin polymerization catalyst compositions, methods for the polymerization and copolymerization of olefins using a catalyst composition, and polyolef ⁇ ns.
- ⁇ -olefins mono- 1 -olefins
- catalyst compositions employing titanium, zirconium, vanadium, chromium, or other metals, often combined with a solid oxide and in the presence of cocatalysts.
- These catalyst compositions can be useful for both homopolymerization of ethylene, as well as copolymerization of ethylene with comonomers such as propylene, 1-butene, 1-hexene, or other higher ⁇ -olef ⁇ ns. Therefore, there exists a constant search to develop new olefin polymerization catalysts, catalyst activation processes, and methods of making and using catalysts that will provide enhanced catalytic activities and polymeric materials tailored to specific end uses.
- Polyethylene (PE) produced by any number of methods generally contains small to moderate amounts of long chain branched molecules.
- long chain branching LCB
- LCB long chain branching
- the presence of LCB is considered undesirable due to the increased elasticity that it typically imparts to the resins. Therefore the ability to control the LCB level in polyethylene using metallocene-based catalysts is a desirable goal.
- This invention encompasses catalyst compositions, methods for preparing catalyst compositions, methods for polymerizing olefins, and ethylene polymers and copolymers.
- LCB long-chain branching
- Useful metallocenes in preparing the catalyst compositions of this invention include, but are not limited to, tightly-bridged, ⁇ r ⁇ -metallocenes that comprise a pendant alkenyl (olefin-containing) group attached to at least one of the cyclopentadienyl-type moieties of the tightly-bridged ligand, and also comprises one or two aryl groups, particularly one or two phenyl groups, bonded to the bridging atom of the tightly-bridged ligand.
- the present invention encompasses a catalyst composition
- a catalyst composition comprising at least one tightly-bridged ⁇ ns ⁇ -metallocene compound containing a pendant olefin-containing moiety attached to at least one of the cyclopentadienyl-type ligands and one or two aryl groups bonded to the bridging atom of the bridging ligand; optionally, at least one organoaluminum compound; and at least one activator.
- the at least one activator can be an activator-support comprising a solid oxide treated with an electron-withdrawing anion; a layered mineral; an ion- exchangeable activator-support; an organoaluminoxane compound; an organoboron compound; an organoborate compound; or any combination of any of these activators.
- this invention comprises the contact product of at least one tightly- bridged -ws ⁇ -metallocene compound containing a pendant olefin-containing moiety attached to at least one of the cyclopentadienyl-type ligands and one or two aryl groups bonded to the bridging atom of the bridging ligand; optionally, at least one organoaluminum compound; and at least one activator, as provided herein.
- this invention encompasses a composition of matter, a catalyst composition for polymerizing olefins, a method of preparing a catalyst composition, a method of polymerizing olefins, new polymers and copolymers of ethylene, and the like, in each case encompassing at least one tightly-bridged tmy ⁇ -metallocene compound containing a pendant olef ⁇ n-containing moiety attached to at least one of the cyclopentadienyl-type ligands and one or two aryl groups bonded to the bridging atom of the bridging ligand; optionally, at least one organoaluminum compound; and at least one activator.
- the at least one activator can be a solid oxide activator-support, that is, can be an activator-support comprising a solid oxide treated with an electron-withdrawing anion.
- the catalyst composition of this invention can comprise the contact product of: 1) at least one ⁇ r ⁇ -metallocene; 2) optionally, at least one organoaluminum compound; and 3) at least one activator, wherein: a) the at least one ansa -metallocene comprises a compound having the formula: wherein M 1 is titanium, zirconium, or hafnium;
- (X 1 ) and (X 2 ) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted f ⁇ uorenyl; one substituent on (X 1 ) and (X 2 ) is a bridging group having the formula
- ER 1 R 2 wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X 1 ) and (X 2 ), and wherein R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R 1 and R 2 is an aryl group; at least one substituent on (X 1 ) or (X 2 ) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms;
- (X 3 ) and (X 4 ) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBR A 2 or SU3R A , wherein R A is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group,
- (X 5 ) is a hydrocarbyl having from 1 to 20 carbon atoms
- (X 6 ) is an alkoxide or an aryloxide, any of which having from 1 to 20 carbon atoms, halide, or hydride
- n is a number from 1 to 3, inclusive
- the at least one activator is selected independently from: i) an activator-support comprising a solid oxide treated with an electron- withdrawing anion, a layered mineral, an ion-exchangeable activator- support, or any combination thereof; ii) an organoaluminoxanc compound; iii) an organoboron or an organoborate compound; or iv) any combination thereof.
- the at least one organoaluminum compound can be optional when: 1) at least one of (X 3 ) and (X 4 ) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 2) the at least one activator comprises at least one organoaluminoxane compound; or 3) both conditions 1 and 2 exist.
- a metallocene-based composition that exhibits catalytic polymerization activity typically comprises the contact product of: 1) a metallocene component; 2) a component that provides an activatable ligand such as an alkyl or hydride ligand to the metallocene, when the metallocene compound does not already comprise such a ligand; and 3) an activator component.
- one component can function as both the component that provides an activatable ligand and the activator component, for example, an organoaluminoxane.
- these two functions can be provided by two separate components, such as an organoaluminum compound that can provide an activatable alkyl ligand to the metallocene, and a solid oxide treated with an electron- withdrawing anion that can provide the activator function.
- the metallocene compound can already comprise an activatable ligand such as an alkyl ligand, therefore, a component that provides an activatable ligand is not required, but can be an optional component of the contact product.
- this invention provides a catalyst composition comprising the contact product of at least one ⁇ wi ⁇ -metallocene, at least one organoaluminum compound, and at least one activator-support, wherein: a) the at least one ansa -metallocene comprises a compound having the formula:
- M 1 is zirconium or hafnium
- X is, independently, F, Cl, Br, or T;
- E is C or Si
- R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R 1 or R 2 is an aryl group;
- R and R are independently a hydrocarbyl group or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or hydrogen; n is an integer from 0 to 10, inclusive; and R 4A and R 4B are independently a hydrocarbyl group having up to 12 carbon atoms, or hydrogen; b) the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, rriisobutylaluminum, Irihexylaluminum, triisohexylalurninum, trioctylaluminum, diethylaluminum ethoxide, d ⁇ sobutylaluminum hydride, diethylaluminum chloride, or any combination thereof; and c) the at least one activator-support comprises a solid oxide treated with an electron-withdrawing anion, wherein the solid oxide is silic
- the present invention provides a catalyst composition comprising the contact product of: 1) at least one ⁇ s ⁇ -metallocene; and 2) at least one activator, wherein: a) the at least one ⁇ /r ⁇ -metallocene comprises a compound having the formula:
- (X 1 ) and (X 2 ) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl; one substituent on (X 1 ) and (X 2 ) is a bridging group having the formula
- ER 1 R 2 wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X 1 ) and (X 2 ), and wherein R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R 1 and R 2 is an aryl group; at least one substituent on (X 1 ) or (X 2 ) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms; (X 3 ) and (X 4 ) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which, having up to 20 carbon atoms;
- Yet another aspect of the present invention provides a catalyst composition
- a catalyst composition comprising the contact product of: 1) at least one ⁇ « ⁇ z-metallocene; and 2) at least one activator, wherein: a) the at least one ansa -metallocene comprises a compound having the formula:
- M 1 is zirconium or hafnium
- X is, independently, H, BH 4 , methyl, phenyl, benzyl, neopentyl, trimethylsilylmethyl, CH 2 CMe 2 Ph; CH 2 SiMe 2 Ph; CH 2 CMe 2 CH 2 Ph; or CH 2 SiMe 2 CH 2 Ph;
- R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R 1 or R 2 is an aryl group;
- R 3A and R 3B are independently a hydrocarbyl group or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or hydrogen; n is an integer from 0 to 10, inclusive; and
- R 4A and R 4B are independently a hydrocarbyl group having up to 12 carbon atoms, or hydrogen; and b) the at least one activator is an activator-support comprising a solid oxide treated with an electron-withdrawing anion, wherein the solid oxide is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and the electron-withdrawing anion is fluoride, chloride, bromide, iodide, phosphate, trifiate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkan
- the activator-support can comprise a solid oxide treated with an electron-withdrawing anion, wherein the solid oxide comprises silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereof.
- the electron-withdrawing anion can comprise fluoride, chloride, bromide, iodide, phosphate, trifiate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkanesulfonate, substituted or unsubstituted arenesulfonate, substituted or unsubstituted alkylsulfate, and the like, including any combination thereof.
- the activator-support can further comprises a metal or metal ion such as zinc, nickel, vanadium, tungsten, molybdenum, silver, tin, or any combination thereof.
- the electron-withdrawing anion can be fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifiuoroacetate, phosphate, fiuorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkanesulfonate, substituted or unsubstituted arenesulfonate, substituted or unsubstituted alkylsulfate, and the like, including any combination thereof.
- the activator-support can comprise a layered mineral, an ion-exchangeable activator-support, or any combination thereof.
- the activator-support can comprise a clay mineral, a pillared clay, an exfoliated clay, an exfoliated clay gelled into another oxide matrix, a layered silicate mineral, a non-layered silicate mineral, a layered aluminosilicate mineral, a non- layered aluminosilicate mineral, or any combination thereof.
- this invention further provides a process for producing a polymerization catalyst composition
- a process for producing a polymerization catalyst composition comprising contacting: at least one ansa- metallocene compound; optionally, at least one organoaluminum compound; and at least one activator; to produce the composition, wherein the at least one ansa- metallocene, the at least one organoaluminum compound, and the at least one activator are defined herein.
- this invention affords a method of polymerizing olefins, comprising contacting ethylene and an optional ⁇ -olef ⁇ n comonomer with a catalyst composition under polymerization conditions to form a polymer or copolymer; wherein the catalyst composition is provided as disclosed herein.
- the present invention provides ethylene polymers and copolymers, and articles made therefrom, produced by contacting ethylene and an optional ⁇ -olef ⁇ n comonomer with a catalyst composition under polymerization conditions to form a polymer or copolymer; wherein the catalyst composition is provided as disclosed herein.
- the activity of the catalyst compositions of this invention can be enhanced by precontacting some of the polymerization reaction components to form a first mixture, for a first period of time, before this mixture is then contacted with the remaining polymerization reaction components, forming a second mixture, for a second period of time.
- the ⁇ m- ⁇ -metallocene compound can be precontacted with some other polymerization reaction components, including, but not limited to, for example, an ⁇ -olefm monomer and an organoaluminum cocatalyst, for some period of time before this mixture is contacted with the remaining polymerization reaction components, including, but not limited to, a solid oxide activator-support.
- the first mixture is typically termed the "precontacted” mixture and comprises precontacted components
- the second mixture is typically termed the "postcontacted” mixture and comprises postcontacted components.
- the mixture of at least one metallocene, at least one olefin monomer, and at least one organoaluminum cocatalyst compound, before this mixture is contacted with the activator-support is one type of "precontacted” mixture.
- the mixture of metallocene, monomer, organoaluminum cocatalyst, and acidic activator- support, formed from contacting the precontacted mixture with the acidic activator- support, is thus termed the "postcontacted” mixture. This terminology is used regardless of what type of reaction, if any, occurs between components of the mixtures.
- the precontacted organoaluminum compound once it is admixed with the metallocene or metallocenes and the olefin monomer, to have a different chemical formulation and structure from the distinct organoaluminum compound used to prepare the precontacted mixture.
- This invention also comprises methods of making catalyst compositions that utilize at least one ⁇ mr ⁇ -metallocene catalyst, optionally at least one organoaluminum compound, and at least one activator.
- the methods of this invention include precontacting any selected catalyst components, for example, the metallocene catalyst and an organoaluminum cocatalyst with an olefin, typically but not necessarily, a monomer to be polymerized or copolymerized, prior to contacting this precontacted mixture with any remaining catalyst components, in this example, the solid oxide activator-support.
- the present invention further comprises new catalyst compositions, methods for preparing catalyst compositions, and methods for polymerizing olefins that can result in improved productivity.
- these methods can be carried out without the need for using large excess concentrations of the expensive organoaluminoxane cocatalyst such as methyl aluminoxane (MAO), or the catalyst composition can be substantially free of aluminoxanes such as MAO. That is, the catalyst compositions of this invention can have polymerization activity in the substantial absence of aluminoxanes.
- this invention also provides a catalyst composition comprising an ⁇ « ⁇ ' ⁇ -metallocene compound and an aluminoxane. Therefore, in this aspect, the catalyst composition is not required to comprise either an acidic activator-support wherein the activator-support comprises a chemically-treated solid oxide, and the catalyst composition is also not required to comprise an organoaluminum compound.
- this invention encompasses a process comprising contacting at least one monomer and the catalyst composition under polymerization conditions to produce the polymer.
- this invention comprises methods for polymerizing olefins using the catalyst compositions prepared as described herein.
- the present invention also encompasses new polyolef ⁇ ns.
- This invention also comprises an article that comprises the polymer produced with the catalyst composition of this invention.
- FIGURE 1 illustrates the structures of specific metallocenes used in the inventive Examples.
- FIGURE 2 illustrates the structures of specific metallocenes used in the comparative Examples.
- FIGURE 3 illustrates data obtained from SEC-MALS analysis of the ethylene homopolymer produced in inventive Examples 1-4 (plot of R g versus M w ).
- FIGURE 4 illustrates data obtained from SEC-MALS analysis of the ethylene homopolymer produced in inventive Examples 5-7 (plot of R g versus M w ).
- FIGURE 5 illustrates data obtained from SEC-MALS analysis of the ethylene homopolymer produced in inventive Examples 10 and 11 (plot of R g versus M w ).
- FIGURE 6 provides a plot of zero shear viscosity versus molecular weight, specifically, log( ⁇ o) versus log (M w ) for polymers prepared according to inventive Examples 1-11.
- FIGURE 7 provides a plot of zero shear viscosity versus molecular weight, specifically, log( ⁇ o) versus log (M w ) for polymers prepared according to comparative Examples 14-16.
- FIGURE 8 provides comparison gel permeation chromatograms (GPCs) for ethylene homopolymer of inventive Examples 1-11 (El-Ell) and comparative Examples 14-16 (E14-E16).
- the present invention provides new catalyst compositions, methods for preparing catalyst compositions, methods for using the catalyst compositions to polymerize olefins, olefin polymers and articles prepared, therefrom.
- this invention encompasses a catalyst composition comprising at least one tightly- bridged ⁇ ns ⁇ -metallocene compound comprising an olefm-containing moiety pendant to a cyclopentadienyl-type ligand and at least one aryl group bonded to the bridging atom of the bridging ligand, at least one activator, and optionally at least one organoaluminum compound.
- this invention comprises methods for making the catalyst composition disclosed herein, and in yet a further aspect, this invention comprises methods for polymerizing olefins employing the catalyst composition disclosed herein.
- the designation of the at least one organoaluminum compound, as an optional component in the contact product it is intended to reflect that the organoaluminum compound can be optional when it is not necessary to impart catalytic activity to the composition comprising the contact product, as understood by one of ordinary skill. A detailed description of the contact product components follows.
- the present invention provides a catalyst composition comprising at least one tightly-bridged ⁇ ns ⁇ -metallocene compound comprising an olef ⁇ n-containing moiety bonded to a cyclopentadienyl-type ligand and at least one aryl group bonded to the bridging atom of the bridging ligand, at least one activator, and optionally at least one organoaluminum compound as further disclosed herein.
- bridged or ⁇ ns ⁇ -metallocene refers simply to a metallocene compound in which the two ⁇ -cycloalkadienyl-type ligands in the molecule are linked by a bridging moiety.
- Useful ama-metallocenes are typically "tightly-bridged", meaning that the two ⁇ -cycloalkadienyl-type ligands are connected by a bridging group wherein the shortest link of the bridging moiety between the ⁇ 5 - cycloalkadienyl-type ligands is a single atom.
- the length of the bridge or the chain between the two ⁇ 5 -cycloalkadienyl-type ligands is one atom, although this bridging atom is substituted.
- the metallocenes of this invention are therefore bridged bis( ⁇ 5 -cycloalkadienyl)-type compounds, wherein the ⁇ 5 -cycloalkadienyl portions include substituted cyclopentadienyl ligands, substituted indenyl ligands, substituted fluorcnyl ligands, and the like, wherein one substitucnt on these cyclopcntadicnyl- type ligands is a bridging group having the formula ER 1 R 2 , wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and wherein E is bonded to both cyclopentadienyl-type ligands.
- R 1 and R 2 can be independently selected from an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R 1 and R 2 is an aryl group.
- one substituent on the metallocene 's cyclopentadienyl-type ligands can be a bridging group having the formula >CR 1 R 2 , >SiR 1 R 2 , >GeR 1 R 2 , or >SnR 1 R 2 , wherein R 1 and R 2 can be independently selected from an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R 1 and R 2 is an aryl group.
- Examples of bridging ER 1 R 2 groups include, but are not limited to, >CPh 2 , >SiPh 2 , >GePh 2 , >SnPh 2 , >C(tolyl) 2 , >Si(tolyl) 2 , >Ge(tolyl) 2 , >Sn(tolyl) 2 , >CMePh, >SiMePh, >GeMePh, >SnMePh, >CEtPh, >CPrPh, >CBuPh, >CMe(tolyl), >SiMe(tolyl), >GeMe(tolyl), >SnMe(tolyl), >CHPh, >CH(tolyl), and the like.
- At least one substituent on at least one of the ⁇ 5 -cycloalkadienyl-type ligands is a substituted or an un substituted olef ⁇ n-containing hydrocarbyl group, having up to 12 carbon atoms, which is referred to herein as an "alkenyl group,” regardless of the regiochemistry of the alkene functionality.
- this olef ⁇ n- containing hydrocarbyl group is bonded to one of the ⁇ 5 -cycloalkadienyl-type ligands of the bridging ligand, wherein the olef ⁇ nic bond is distal from the ⁇ 5 - cycloalkadienyl-type ligand, and therefore can be described as a pendant alkenyl group.
- one substituent on a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl of the metallocene comprises an alkenyl group, in which case the ⁇ ws ⁇ -metallocenes can be described as containing a hydrocarbyl chain attached to one of the cyclop entadienyl-type ligands which comprises an olef ⁇ nic portion.
- the at least one a/w ⁇ -mctalloccnc of this invention comprises a compound having the formula:
- (X 1 ) and (X 2 ) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl; one substituent on (X 1 ) and (X 2 ) is a bridging group having the formula
- ER 1 R 2 wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X 1 ) and (X 2 ), and wherein R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R 1 and R 2 is an aryl group; at least one substituent on (X 1 ) or (X 2 ) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms;
- (X 3 ) and (X 4 ) are independently: 1) F, Cl, Br, or 1; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBR A 2 or SO 3 R A , wherein R A is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or
- the olefm-containing hydrocarbyl group is bonded to one of the ⁇ 5 -cycloalkadienyl-type ligands of the bridging ligand, that is, the alkenyl group, can have up to about 20 carbon atoms.
- the alkenyl group can have up to about 12 carbon atoms, up to about 8 carbon atoms, or up to about 6 carbon atoms.
- alkenyl groups include, but arc not limited to, butenyl, pentenyl, hexenyl, heptenyl, or octenyl.
- the alkenyl group is 3-butenyl or 4-pentenyl.
- the pendant unsaturated group can contain the carbon-carbon double bond from about 3 to about 7 carbon atoms removed from the cyclopentadienyl-type ligand itself, and in another aspect, from 3 to about 4 carbon atoms removed from the cyclopentadienyl-type ligand itself.
- the olefin-containing hydrocarbyl group that is the alkenyl group
- any substituent on the alkenyl group when present, can be selected independently from an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, a boron group, or a substituted analog thereof, any of which having from 1 to about 20 carbon atoms; a halide; or hydrogen.
- Hydrogen is listed as a possible substituent on the alkenyl group in the context that hydrogen can add to an unsaturated moiety within the alkenyl group, as long as it does not destroy the alkenyl group.
- hydrogen is a possible substituent on any unsaturated moiety within the alkenyl group so long as it does not add across the very olefin moiety necessary for this group to be considered an alkenyl group.
- this description of other substituents on the alkenyl group atom can include substituted, unsubstituted, branched, linear, or heteroatom-substituted analogs of these moieties.
- olefmic hydrocarbyl groups specifically alkenyl groups, that can be bonded to at least one cyclopentadienyl-type moiety
- the cyclopentadienyl-type ligands can also have other substituents.
- these substituents can be selected from the same chemical groups or moieties that can serve as the (X 3 ) and (X 4 ) ligands of the ⁇ r ⁇ -metallocenes.
- any additional substituent on the cyclopentadienyl-type ligands; and any substituent on the substituted alkenyl group; and (X 3 ) and (X 4 ) can be independently selected from an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, a boron group, or a substituted analog thereof, any of which having from 1 to about 20 carbon atoms; a halide; or hydrogen; as long as these groups do not terminate the activity of the catalyst composition.
- this list includes substituents that can be characterized in more than one of these categories such as benzyl.
- This list also includes hydrogen, therefore the notion of a substituted indenyl and substituted fluorenyl includes partially saturated indenyls and fluorenyls including, but not limited to, tetrahydroindenyl groups, tetrahydrofluorenyl groups, and octahydrofluorenyl groups.
- R is independently selected from: an aliphatic group; an aromatic group; a cyclic group; any combination thereof; any substituted derivative thereof, including but not limited to, a halide-, an alkoxide-, or an amide-substituted analog or derivative thereof; any of which has from 1 to about 20 carbon atoms; or hydrogen. Also included in these groups are any unsubstituted, branched, or linear analogs thereof.
- aliphatic groups in each occurrence, include, but are not limited to, an alkyl group, a cycloalkyl group, an aikenyl group, a cycloalkenyl group, an alkynyl group, an alkadienyl group, a cyclic group, and the like, and includes all substituted, unsubstituted, branched, and linear analogs or derivatives thereof, in each occurrence having from one to about 20 carbon atoms.
- aliphatic groups include, but are not limited to, hydrocarbyls such as paraffins and alkenyls.
- aliphatic groups as used herein include methyl, ethyl, propyl, n-butyl, tert- butyl, sec-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, dodecyl, 2-ethylhexyl, pentenyl, butenyl, and the like.
- aromatic groups in each occurrence, include, but are not limited to, phenyl, naph ⁇ hyl, anthracenyl, and the like, including substituted derivatives thereof, in each occurrence having from 6 to about 25 carbons.
- Substituted derivatives of aromatic compounds include, but are not limited to, tolyl, xylyl, mesityl, and the like, including any heteroatom substituted derivative thereof.
- cyclic groups in each occurrence, include, but are not limited to, cycloparaffms, cycloolefins, cycloacetylenes, arenes such as phenyl, bicyclic groups and the like, including substituted derivatives thereof, in each occurrence having from about 3 to about 20 carbon atoms.
- heteroatom-substituted cyclic groups such as furanyl are included herein.
- aliphatic and cyclic groups are groups comprising an aliphatic portion and a cyclic portion, examples of which include, but arc not limited to, groups such as: -(CH 2 ) m C 6 HqRs -q wherein rn is an integer from 1 to about 10, and q is an integer from 1 to 5, inclusive; -(CH2) m C6H q Rn-q wherein m is an integer from 1 to about 10, and q is an integer from 1 to 11, inclusive; or -(CHz) 1n CsHqRp -4 wherein m is an integer from 1 to about 10, and q is an integer from 1 to 9, inclusive.
- R is independently selected from: an aliphatic group; an aromatic group; a cyclic group; any combination thereof; any substituted derivative thereof, including but not limited to, a halide-, an alkoxide-, or an arnide- substituted derivative or analog thereof; any of which has from 1 to about 20 carbon atoms; or hydrogen.
- aliphatic and cyclic groups include, but are not limited to: -CH 2 C 6 H 5 ; -CH 2 C 6 H 4 F; -CH 2 C 6 H 4 Cl; -CH 2 C 6 H 4 Br; -CH 2 C 6 H 4 I; - CH 2 C 6 H 4 OMe; -CH 2 C 6 H 4 OEt; -CH 2 C 6 H 4 NH 2 ; -CH 2 C 6 H 4 NMe 2 ; -CH 2 C 6 H 4 NEt 2 ; - CH 2 CH 2 C 6 H 5 ; -CH 2 CH 2 C 6 H 4 F; -CH 2 CH 2 C 6 H 4 Cl; -CH 2 CH 2 C 6 H 4 Br; -CH 2 CH 2 C 6 H 4 I; -CH 2 CH 2 C 6 H 4 OMe; -CH 2 CH 2 C 6 H 4 OEt; -CH 2 CH 2 C 6 H 4 NH 2 ; -CH 2 CH 2 C 6 H 4 NMe 2 ; -CH
- oxygen groups are oxygen-containing groups, examples of which include, but are not limited to, alkoxy or aryloxy groups (-OR) and the like, including substituted derivatives thereof, wherein R is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to about 20 carbon atoms.
- alkoxy or aryloxy groups (-OR) groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, phenoxy, substituted phenoxy, and the like.
- sulfur groups are sulfur-containing groups, examples of which include, but are not limited to, -SR and the like, including substituted derivatives thereof, wherein R in each occurrence is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to about 20 carbon atoms.
- nitrogen groups are nitrogen-containing groups, which include, but are not limited to, -NR2 or pyridyl groups, and the like, including substituted derivatives thereof, wherein R in each occurrence is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to about 20 carbon atoms.
- phosphorus groups are phosphorus-containing groups, which include, but are not limited to, -PR 2 , and the like, including substituted derivatives thereof, wherein R in each occurrence is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to about 20 carbon atoms.
- arsenic groups are arsenic-containing groups, which include, but are not limited to, -AsR 2 , and the like, including substituted derivatives thereof, wherein R in each occurrence is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to about 20 carbon atoms.
- carbon groups are carbon-containing groups, which include, but are not limited to, alkyl halide groups that comprise halide-substituted alkyl groups with 1 to about 20 carbon atoms, alkenyl or alkenyl halide groups with 1 to about 20 carbon atoms, aralkyl or aralkyl halide groups with 1 to about 20 carbon atoms, and the like, including substituted derivatives thereof.
- silicon groups are silicon-containing groups, which include, but are not limited to, silyl groups such alkylsilyl groups, arylsilyl groups, aryl alkylsilyl groups, siloxy groups, and the like, which in each occurrence have from
- silicon groups include trimethylsilyl and phenyloctylsilyl groups.
- boron groups are boron-containing groups, which include, but are not limited to, -BR 2 , -BX 2 , -BRX, wherein X is a monoanionic group such as halide, hydride, alkoxide, alkyl thiolate, and the like, and wherein R in each occurrence is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to about 20 carbon atoms.
- (X 3 ) and (X 4 ) are independently selected from an aliphatic group, a cyclic group, a combination of an aliphatic group and a cyclic group, an amido group, a phosphido group, an alkyloxide group, an aryloxide group, an alkanesulfonate, an arenesulfonate, or a trialkylsilyl, or a substituted derivative thereof, any of which having from 1 to about 20 carbon atoms; or a halide.
- (X 3 ) and (X 4 ) are independently: 1) F, Cl, Br 5 or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBR A 2 or S ⁇ 3R A , wherein R A is an alkyl group or an aryl group, any of which having up to 12 carbon atoms.
- (X 4 ) are independently selected from a hydrocarbyl having from 1 to about 10 carbon atoms, or a halide.
- (X 3 ) and (X 4 ) are independently selected from fluoride, chloride, bromide, or iodide.
- (X 3 ) and (X 4 ) are chloride.
- (X 3 ) and (X 4 ) are independently a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 .
- a further aspect of the invention provides that the at least one ansa- metallocene of this invention comprises a compound having the formula: (I), wherein:
- M 1 is zirconium or hafnium;
- X is, independently, F, Cl, Br, or I;
- E is C or Si;
- R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R 1 or R 2 is an aryl group;
- R 3A and R 3B are independently a hydrocarbyl group or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or hydrogen; n is an integer from 0 to 10, inclusive; and
- R 4A and R 4B are independently a hydrocarbyl group having up to 12 carbon atoms, or hydrogen;
- the at least one ⁇ ns ⁇ -metallocene of this invention comprises a compound having the formula:
- M 1 is zirconium or hafnium
- X is F, Cl, Br, or I
- E is C or Si
- R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R 1 or R 2 is an aryl group;
- R 3A and R 3B are independently H, methyl, allyl, benzyl, butyl, pentyl, hexyl, or trimethylsilyl;
- n is an integer from 1 to 6, inclusive;
- R 4A and R 4B are independently a hydrocarbyl group having up to 6 carbon atoms, or hydrogen.
- the at least one # « ⁇ ' «-metallocene of this invention comprises a compound having the formula:
- M 1 is zirconium or hafnium
- X is Cl, Br, or I
- E is C or Si
- R 1 and R 2 arc independently methyl or phenyl, wherein at least one of R 1 or R 2 is phenyl;
- R 3A and R 3B are independently H or methyl; n is 1 or 2; and
- R 4 ⁇ and R 4B are independently H or t-butyl.
- the at least one fir ⁇ -metallocene of this invention can comprise a compound having the formula:
- M 1 is zirconium or hafnium
- X is, independently, H, BH 4 , methyl, phenyl, benzyl, neopentyl, trimethylsilylmethyl, CH 2 CMe 2 Ph; CH 2 SiMe 2 Ph; CH 2 CMe 2 CH 2 Ph; or CH 2 SiMe 2 CH 2 Ph;
- E is C or Si
- R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R 1 or R 2 is an aryl group;
- R 3A and R 3B are independently a hydrocarbyl group or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or hydrogen; n is an integer from 0 to 10, inclusive; and
- R 4A and R 4B are independently a hydrocarbyl group having up to 12 carbon atoms, or hydrogen.
- the at least one ⁇ m «z-metallocene of this invention comprises a compound having the formula:
- the at least one ⁇ as ⁇ -metallocene of this invention can be any combination thereof.
- Yet another aspect of the present invention provides a mctalloccnc compound having the formula
- the present invention provides a catalyst composition
- a catalyst composition comprising at least one tightly-bridged ⁇ /M ⁇ -metallocene compound comprising an olefin-containing moiety bonded to a cyclopentadienyl-type ligand and at least one aryl group bonded to the bridging atom of the bridging ligand, at least one solid oxide activator-support, and optionally at least one organoaluminum compound.
- the designation of the at least one organoaluminum compound as optional is intended to reflect that the organoaluminum compound can be optional when it is not necessary to impart catalytic activity to the composition comprising the contact product, as understood by one of ordinary skill, as disclosed herein.
- Organoaluminum compounds that can be used in this invention include, but are not limited to, compounds with the formula: Al(X 5 ⁇ (X%. a , wherein (X 5 ) is a hydrocarbyl having from 1 to about 20 carbon atoms; (X 6 ) is alkoxide or aryloxide, any of which having from 1 to about 20 carbon atoms, halide, or hydride; and n is a number from 1 to 3, inclusive. In one aspect, (X 5 ) is an alkyl having from 1 to about 10 carbon atoms.
- Examples of (X 5 ) moieties include, but are not limited to, methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, and the like.
- examples of (X s ) moieties include, but are not limited to, methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, isobutyl, 1 -hexyl, 2-hexyl, 3-hexyl, isohexyl, heptyl, octyl, and the like.
- (X 6 ) can be independently selected from fluoride, chloride, bromide, methoxide, ethoxide, or hydride. In yet another aspect, (X 6 ) can be chloride.
- n is a number from 1 to 3 inclusive, and typically, n is 3.
- the value of n is not restricted to be an integer, therefore this formula includes sesquihalide compounds, other organoaluminum cluster compounds, and the like.
- organoaluminum compounds that can be used in this invention include, but are not limited to, trialkylaluminum compounds, dialkylaluminium halide compounds, dialkylaluminum alkoxide compounds, dialkylaluminum hydride compounds, and combinations thereof.
- organoaluminum compounds that are useful in this invention include, but are not limited to trimethylaluminum, triethylaluminum, tripropylaiuminum, tributylaluminum, tri-n-butylaluminum (TNBA), triisobutylaluminum (TIBA), trihexylaluminum, triisohexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof. If the particular alkyl isomer is not specified, the compound is intended to encompasses all isomers that can arise from a particular specified alkyl group .
- organoaluminum compounds that can be used in this invention include, but are not limited to, trimethylaluminum, triethylaluminum, tripropylaiuminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, triisohexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof.
- the present invention comprises precontacting the ansa- metallocene with at least one organoaluminum compound and an olefin monomer to form a precontacted mixture, prior to contact this precontacted mixture with the solid oxide activator-support to form the active catalyst.
- the catalyst composition is prepared in this manner, typically, though not necessarily, a portion of the organoaluminum compound is added to the precontacted mixture and another portion of the organoaluminum compound is added to the postcontacted mixture prepared when the precontacted mixture is contacted with the solid oxide activator.
- all of the organoaluminum compound can be used to prepare the catalyst in either the precontacting or postcontacting step. Alternatively, all the catalyst components can be contacted in a single step.
- organoaluminum compounds can be used, in either the precontacting or the postcontacting step, or in any procedure in which the catalyst components are contacted.
- the amounts of organoaluminum compound disclosed herein include the total amount of organoaluminum compound used in both the precontacted and postcontacted mixtures, and any additional organoaluminum compound added to the polymerization reactor. Therefore, total amounts of organoaluminum compounds are disclosed, regardless of whether a single organoaluminum compound is used, or more than one organoaluminum compound.
- typical organoaluminum compounds used in this invention include, but are not limited to, triethylaluminum (TEA), tri-n-butylaluminum, triisobutylaluminum, or any combination thereof.
- the present invention encompasses a catalyst composition comprising at least one tightly-bridged ⁇ ns ⁇ -mctalloccnc compound as disclosed herein; optionally, at least one organoaluminum compound; and at least one activator.
- the at least one activator can be an activator-support comprising a solid oxide treated with an electron-withdrawing anion; a layered mineral; an ion- exchangeable activator-support; an organoaluminoxane compound; an organoboron compound; an organoborate compound; or any combination of any of these activators, each of which is provided herein.
- the present invention encompasses catalyst compositions comprising an acidic activator-support, which can comprise a chemically-treated solid oxide, and which is typically used in combination with an organoaluminum compound.
- the activator-support comprises at least one solid oxide treated with at least one electron- withdrawing anion; wherein the solid oxide can be silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, and the like, or any mixture or combination thereof; and wherein the electron-withdrawing anion can be fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifiuoroacetate, phosphate, fluorophosphate, fluorozirconate,
- the activator-support includes the contact product of at least one solid oxide compound and. at least one electron-withdrawing anion source.
- the solid oxide compound comprises an inorganic oxide.
- the solid oxide can be optionally calcined prior to contacting the electron-withdrawing anion source.
- the contact product can also be calcined either during or after the solid oxide compound is contacted with the electron-withdrawing anion source.
- the solid oxide compound can be calcined or uncalcined.
- the activator-support can comprise the contact product of at least one calcined solid oxide compound and at least one electron- withdrawing anion source.
- the activator-support exhibits enhanced activity as compared to the corresponding untreated solid oxide compound.
- the activator-support also functions as a catalyst activator as compared to the corresponding untreated solid oxide. While not intending to be bound by theory, it is believed that the activator-support can function as solid oxide supporting compound with an additional ionizing, polarizing, or bond weakening function, collectively termed an "activating" function, by weakening the metal-ligand bond between an anionic ligand and the metal in the metallocene.
- the activator-support is considered to exhibit an "activating" function, regardless of whether it is ionizes the metallocene, abstracts an anionic ligand to form an ion pair, weakens the metal-ligand bond in the metallocene, simply coordinates to an anionic ligand when it contacts the activator-support, or any other mechanisms by which ionizing, polarizing, or bond weakening might occur.
- the activator- support is typically used along with a component that provides an activatable ligand such as an alkyl or hydride ligand to the metallocene, including but not limited to at least one organoaluminum compound, when the metallocene compound does not already comprise such a ligand.
- the activator-support of this invention comprises a solid inorganic oxide material, a mixed oxide material, or a combination of inorganic oxide materials, that is chemically-treated with an electron-withdrawing component, and optionally treated with at least one other metal ion.
- the solid oxide of this invention encompasses oxide materials such as alumina, "mixed oxide” compounds such as silica-alumina or silica-zirconia or silica-titania, and combinations and mixtures thereof.
- the mixed metal oxide compounds such as silica-alumina, with more than one metal combined with oxygen to form a solid oxide compound can be made by co-gellation, impregnation or chemical deposition, and are encompassed by this invention.
- the activator-support further comprises a metal or metal ion such as zinc, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, or any combination thereof.
- a metal or metal ion such as zinc, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, or any combination thereof.
- activator-supports that further comprise a metal or metal ion include, but are not limited to, zinc- impregnated chlorided alumina, zinc-impregnated fluorided alumina, zinc- impregnated chlorided silica-alumina, zinc-impregnated fluorided silica-alumina, zinc-imprcgnatcd sulfated alumina, or any combination thereof.
- the activator-support of this invention comprises a solid oxide of relatively high porosity, which exhibits Lewis acidic or Br ⁇ nsted acidic behavior.
- the solid oxide is chemically-treated with an electron-withdrawing component, typically an electron-withdrawing anion, to form a activator-support. While not intending to be bound by the following statement, it is believed that treatment of the inorganic oxide with an electron-withdrawing component augments or enhances the acidity of the oxide.
- the activator-support exhibits Lewis or Br ⁇ nsted acidity which is typically greater than the Lewis or Br ⁇ nsted acidity of the untreated solid oxide.
- One method to quantify the acidity of the chemically-treated and untreated solid oxide materials is by comparing the polymerization activities of the treated and untreated oxides under acid catalyzed reactions.
- the chemically-treated solid oxide comprises a solid inorganic oxide comprising oxygen and at least one element selected from Group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodic table, or comprising oxygen and at least one element selected from the lanthanide or actinide elements.
- the inorganic oxide comprises oxygen and at least one element selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn or Zr.
- Suitable examples of solid oxide materials or compounds that can be used in the chemically-treated solid oxide of the present invention include, but are not limited to, Al 2 O 3 , B 2 O 3 , BeO 5 Bi 2 O 3 , CdO, Co 3 O 4 , Cr 2 O 3 , CuO, Fe 2 O 3 , Ga 2 O 3 , La 2 O 3 , Mn 2 O 3 , MoO 3 , NiO, P 2 O 5 , Sb 2 O 5 , SiO 2 , SnO 2 , SrO, ThO 2 , TiO 2 , V 2 O 5 , WO 3 , Y 2 O 3 , ZnO, ZrO 2 , and the like, including mixed oxides thereof, and combinations thereof.
- mixed oxides that can be used in the activator-support of the present invention include, but are not limited to, mixed oxides of any combination of Al, B, Be, Bi, Cd, Co, Cr 5 Cu, Fe, Ga, La, Mn, Mo, Mi, P, Sb, Si, Sn, Sr, Th, Ti, V 5 W 5 Y 5 Zn, Zr, and the like.
- mixed oxides that can be used in the activator- support of the present invention also include, but are not limited to, silica-alumina, silica-titania, silica-zirconia, zeolites, many clay minerals, pillared clays, alumina- titania, alumina-zirconia, aluminophosphatc, and the like.
- the solid oxide material is chemically- treated by contacting it with at least one electron-withdrawing component, typically an electron-withdrawing anion source.
- the solid oxide material is optionally chemically-treated with at least one other metal ion, that can be the same as or different from any metal element that constitutes the solid oxide material, then calcining to form a metal-containing or metal-impregnated chemically-treated solid oxide.
- a solid oxide material and an electron- withdrawing anion source are contacted and calcined simultaneously.
- the method by which the oxide is contacted with an electron-withdrawing component includes, but is not limited to, gelling, co-gelling, impregnation of one compound onto another, and the like.
- an electron-withdrawing component typically a salt or an acid of an electron-withdrawing anion
- the electron-withdrawing component used to treat the oxide can be any component that increases the Lewis or Br ⁇ nsted acidity of the solid oxide upon treatment.
- the electron-withdrawing component is typically an electron-withdrawing anion derived from a salt, an acid, or other compound such as a volatile organic compound that can serve as a source or precursor for that anion.
- electron-withdrawing anions include, but are not limited to, fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkanesulfonate, substituted or unsubstituted arenesulfonate, substituted or unsubstituted alkylsulfate, and the like, including any mixtures and combinations thereof.
- the chemically-treated solid oxide comprises a sulfated solid oxide
- the chemically-treated oxide comprises sulfated alumina
- alkanesulfonate and alkyl sulfate refer to anions having the general formula [R 8 SO 2 O] " and [(R 5 O)SO 2 O] " , respectively, wherein R B is a linear or branched alkyl group having up to 20 carbon atoms, that is optionally substituted with at least one group selected independently from F, Cl, Br, I, OH, OMc, OEt, OCF 3 , Ph, xylyl, mesityl, or OPh.
- the alkanesulfonate and alkyl sulfate may be referred to as being either substituted or unsubstituted.
- the alkyl group of the alkanesulfonate or alkyl sulfate can have up to 12 carbon atoms. In another aspect, the alkyl group of the alkanesulfonate or alkyl sulfate can have up to 8 carbon atoms, or up to 6 carbon atoms.
- alkanesulfonates include, but are not limited to, methanes ulfonate, ethanesulfonate, 1-propanesulfonate, 2- propanesulfonate, 3-methylbutanesulfonate, trifluoromethanesulfonate, trichloro- methanesulfbnate, chloromethanesulfonate, 1-hydroxyethanesulfonate, 2-hydroxy-2- propanesulfonate, 1 -methoxy-2-propanesulfonate, and the like.
- examples of alkyl sulfates include, but are not limited to, methylsulfate, ethylsulfate, 1-propylsulfate, 2-propylsulfate, 3-methylbutylsulfate, trifluoromethanesulfate, trichloromethylsulfate, chloromethylsulfate, 1-hydroxyethylsulfate, 2-hydroxy-2- propylsulfate, l-methoxy-2-propylsulfate, and the like.
- arenesulfonate refers to anions having the general formula [Ar A S ⁇ 2 ⁇ ] " , wherein Ar A is an aryl group having up to 14 carbon atoms, that is optionally substituted with at least one group selected independently from F, Cl, Br, I, Me, Et, Pr, Bu, OH, OMe, OEt 5 OPr, OBu, OCF 3 , Ph, OPh, or R c , wherein R c is a linear or branched alkyl group having up to 20 carbon atoms.
- the arenesulfonate may be referred to as a substituted or an uns ⁇ bstituted arenesulfonate.
- the term arenesulfonate is intended to include the detergents.
- the aryl group of the arenesulfonate can have up to 10 carbon atoms. In another aspect, the aryl group of the arenesulfonate can have 6 carbon atoms.
- examples of arenesulfonates include, but are not limited to, benzenesulfonate, naphthalenesulfonate, /;-toluenesulfonate, m- toluenesulfonate, 3,5-xylenesulfonate, trifluoromethoxybenzenesulfonate, trichloro- methoxybenzenesulfonate, trifluoromethylbenzenesulfonate, trichloromethylbenzene- sulfonate, fluorobenzenesulfonate, chlorobenzenesulfonate, 1-hydroxyethane- benzenesulfonate, 3-fluoro-4-methoxybenzenesulfonate, and the like.
- the counterion or cation of that salt can be any cation that allows the salt to revert or decompose back to the acid during calcining.
- Factors that dictate the suitability of the particular salt to serve as a source for the electron-withdrawing anion include, but are not limited to, the solubility of the salt in the desired solvent, the lack of adverse reactivity of the cation, ion-pairing effects between the cation and anion, hygroscopic properties imparted to the salt by the cation, and the like, and thermal stability of the anion.
- Examples of suitable cations in the salt of the electron- withdrawing anion include, but are not limited to, ammonium, trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H + , [H(OEt 2 ⁇ ] + , and the like. Further, combinations of one or more different electron withdrawing anions, in varying proportions, can be used to tailor the specific acidity of the activator-support to the desired level. Combinations of electron withdrawing components can be contacted with the oxide material simultaneously or individually, and any order that affords the desired activator-support acidity. For example, one aspect of this invention is employing two or more electron- withdrawing anion source compounds in two or more separate contacting steps.
- an activator-support is prepared as follows.
- a selected solid oxide compound, or combination of oxide compounds is contacted with a first electron- withdrawing anion source compound to form a first mixture, this first mixture is then calcined, the calcined first mixture is then contacted with a second electron-withdrawing anion source compound to form a second mixture, followed by calcining said second mixture to form a treated solid oxide compound.
- the first and second electron-withdrawing anion source compounds are typically different compounds, although they can be the same compound.
- the solid oxide activator-support is produced by a process comprising: 1) contacting a solid oxide compound with at least one electron-withdrawing anion source compound to form a first mixture; and
- the solid oxide activator-support is produced by a process comprising: 1) contacting at least one solid oxide compound with a first electron- withdrawing anion source compound to form a first mixture; and
- the solid oxide activator-support is sometimes referred to simply as a treated solid oxide compound.
- Another aspect of this invention producing or forming the solid oxide activator-support by contacting at least one solid oxide with at least one electron- withdrawing anion source compound, wherein the at least one solid oxide compound is calcined before, during or after contacting the electron-withdrawing anion source, and wherein there is a substantial absence of aluminoxanes and organoborates.
- Calcining of the treated solid oxide is generally conducted in an ambient or inert atmosphere, typically in a dry ambient atmosphere, at a temperature from about 200 0 C to about 900°C, and for a time of about 1 minute to about 100 hours.
- calcining is conducted at a temperature from about 300 0 C to about 800°C and in another aspect, calcining is conducted at a temperature from about 400 0 C to about 700 0 C.
- calcining is conducted from about 1 hour to about 50 hours, and in another aspect calcining is conducted, from about 3 hours to about 20 hours.
- calcining can be carried out from about 1 to about 10 hours at a temperature from about 350 0 C to about 550 0 C.
- any type of suitable ambient can be used during calcining.
- calcining is conducted in an oxidizing atmosphere, such as air.
- an inert atmosphere such as nitrogen or argon, or a reducing atmosphere such as hydrogen or carbon monoxide, can be used.
- the solid oxide component used to prepare the chemically-treated solid oxide has a pore volume greater than about 0.1 cc/g. In another aspect, the solid oxide component has a pore volume greater than about 0.5 cc/g, and in yet another aspect, greater than about 1.0 cc/g. In still another aspect, the
- solid oxide component has a surface area from about 100 to about 1000 m /g. In another aspect, solid oxide component has a surface area from about 200 to about 800 m /g, and in still another aspect, from about 250 to about 600 m /g.
- the solid oxide material can be treated with a source of halide ion or sulfate ion, or a combination of anions, and optionally treated with at least one metal ion, then calcined to provide the activator-support in the form of a particulate solid.
- the solid oxide material is treated with a source of sulfate, termed a sulfating agent, a source of chloride ion, termed a chloriding agent, a source of fluoride ion, termed a fluoriding agent, or a combination thereof, and calcined to provide the solid oxide activator.
- useful acidic activator-supports include, but are not limited to: bromided alumina; chlorided alumina; fluorided alumina; sulfated alumina; bromided silica-alumina, chlorided silica-alumina; fluorided silica-alumina; sulfated silica-alumina; bromided silica-zirconia, chlorided silica-zirconia; fluorided silica-zirconia; sulfated silica-zirconia; chlorided zinc-alumina, triflate treated silica- alumina, a pillared clay such as a pillared montmorillonite, optionally treated with fluoride, chloride, or sulfate; phosphated alumina, or other aluminophosphates, optionally treated with sulfate, fluoride, or chloride; or any combination thereof. Further, any of the activ
- the treated, oxide activator-support comprises a fluorided solid oxide in the form of a particulate solid, thus a source of fluoride ion is added to the oxide by treatment with a fluoriding agent.
- fluoride ion can be added to the oxide by forming a slurry of the oxide in a suitable solvent such as alcohol or water, including, but are not limited to, the one to three carbon alcohols because of their volatility and low surface tension.
- fluoriding agents examples include, but are not limited to, hydrofluoric acid (HF), ammonium fluoride (NH 4 F), ammonium bifluoride (NH 4 HF2), ammonium tetrafluoroborate (NH 4 BF4), ammonium silicofluoride (hexafluorosilicate) ((NH 4 ⁇ SiFe), ammonium hexafluorophosphate (NH 4 PFO), tetrafluoroboric acid (HBF 4 ), ammonium hexafluorotitanate (NH 4 ⁇ TiFe, ammonium hexafluorozirconate (NHa) 2 ZrFo, analogs thereof, and combinations thereof.
- ammonium bifluoride NH 4 HF 2 can be used as the fluoriding agent, due to its case of use and ready availability.
- the solid oxide can be treated with a fluoriding agent during the calcining step.
- a fluoriding agent capable of thoroughly contacting the solid oxide during the calcining step.
- volatile organic fluoriding agents can be used.
- volatile organic fluoriding agents useful in this aspect of the invention include, but are not limited to, freons, perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, and combinations thereof.
- Gaseous hydrogen fluoride or fluorine itself can also be used with the solid oxide is fluorided during calcining.
- One convenient method of contacting the solid oxide with the fluoriding agent is to vaporize a fluoriding agent into a gas stream used to fluidize the solid oxide during calcination.
- the chemically-treated solid oxide comprises a chlorided solid oxide in the form of a particulate solid, thus a source of chloride ion is added to the oxide by treatment with a chloriding agent.
- the chloride ion can be added to the oxide by forming a slurry of the oxide in a suitable solvent.
- the solid oxide can be treated with a chloriding agent during the calcining step. Any chloriding agent capable of serving as a source of chloride and thoroughly contacting the oxide during the calcining step can be used. For example, volatile organic chloriding agents can be used.
- Gaseous hydrogen chloride or chlorine itself can also be used with the solid oxide during calcining.
- One convenient method of contacting the oxide with the chloriding agent is to vaporize a chloriding agent into a gas stream used to fluidize the solid oxide during calcination.
- the electron withdrawing anion can be typically added to the solid oxide in an amount greater than about 1% by weight of the solid oxide.
- the electron withdrawing anion can be added to the solid oxide in an amount greater than about 2% by weight of the solid oxide, greater than about 3% by weight of the solid oxide, greater than about 5% by weight of the solid oxide, or greater than about 7% by weight of the solid oxide.
- the amount of electron-withdrawing ion, for example fluoride or chloride ion, present before calcining the solid oxide is generally from about 2 to about 50% by weight, where the weight percents are based on the weight of the solid oxide, for example silica-alumina, before calcining. In another aspect, the amount of electron-withdrawing ion, for example fluoride or chloride ion, present before calcining the solid oxide is from about 3 to about 25% by weight, and in another aspect, from about 4 to about 20% by weight.
- halide ion When halide ion is used as the electron-withdrawing anion, it is used in an amount sufficient to deposit, after calcining, from about 0.1% to about 50% by weight halide ion relative to the weight of the solid oxide. In another aspect, halide is used in an amount sufficient to deposit, after calcining, from about 0.5% to about 40% by weight halide ion relative to the weight of the solid oxide, or from about 1 % to about 30% by weight halide ion relative to the weight of the solid oxide.
- the fluoride or chloride ion is added during calcining, such as when calcined in the presence Of CCl 4 , there is typically no, or only trace levels, of fluoride or chloride ion in the solid oxide before calcining.
- the halided oxide can be dried by any method known in the art including, but not limited to, suction filtration followed by evaporation, drying under vacuum, spray drying, and the like, although it is also possible to initiate the calcining step immediately without drying the impregnated solid oxide.
- the silica-alumina used to prepare the treated silica-alumina can have a pore volume greater than about 0.5 cc/g. In one aspect, the pore volume can be greater than about 0.8 cc/g, and in another aspect, the pore volume can be greater than about 1.0 cc/g. Further, the silica-alumina can have a surface area greater than about 100 m 2 /g. In one aspect, the surface area is greater than about 250 m 2 /g, and in another aspect, the surface area can be greater than about 350 m 2 /g. Generally, the silica- alumina of this invention has an alumina content from about 5 to about 95%. In one aspect, the alumina content of the silica-alumina can be from about 5 to about 50%, and in another aspect, the alumina content of the silica-alumina can be from about 8% to about 30% alumina by weight.
- the sulfated solid oxide comprises sulfate and a solid oxide component such as alumina or silica-alumina, in the form of a particulate solid.
- the sulfated oxide is further treated with a metal ion such that the calcined sulfated oxide comprises a metal.
- the sulfated solid oxide comprises sulfate and alumina.
- the sulfated alumina is formed by a process wherein the alumina is treated with a sulfate source, including for example, but not limited to, sulfuric acid or a sulfate salt such as ammonium sulfate, zinc sulfate, aluminum sulfate, nickel sulfate or copper sulfate.
- a sulfate source including for example, but not limited to, sulfuric acid or a sulfate salt such as ammonium sulfate, zinc sulfate, aluminum sulfate, nickel sulfate or copper sulfate.
- this process can be performed by forming a slurry of the alumina in a suitable solvent such as alcohol or water, in which the desired concentration of the sulfating agent has been added.
- suitable organic solvents include, but are not limited to, the one to three carbon alcohols because of their volatility and low surface tension.
- the amount of sulfate ion present before calcining is generally from about 1% to about 50% by weight, from about 2% to about 30 % by weight, of from about 5% to about 25% by weight, where the weight percents are based on the weight of the solid oxide before calcining.
- the sulfated oxide can be dried by any method known in the art including, but not limited to, suction filtration followed by evaporation, drying under vacuum, spray drying, and the like, although it is also possible to initiate the calcining step immediately.
- the solid inorganic oxide of this invention can optionally be treated with a metal source, including metal salts or metal-containing compounds.
- these compounds can be added to or impregnated onto the solid oxide in solution form, and subsequently converted into the supported metal upon calcining.
- the solid inorganic oxide can further comprise a metal selected from zinc, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, or a combination thereof.
- zinc can be used to impregnate the solid oxide because it provides good catalyst activity and low cost.
- the solid oxide can be treated with metal salts or metal-containing compounds before, after, or at the same time that the solid oxide is treated with the electron-withdrawing anion. Further, any method of impregnating the solid oxide material with a metal can be used.
- the method by which the oxide is contacted with a metal source, typically a salt or metal-containing compound includes, but is not limited to, gelling, co-gclling, impregnation of one compound onto another, and the like.
- the contacted mixture of oxide compound, electron-withdrawing anion, and the metal ion is typically calcined.
- a solid oxide material, an electron- withdrawing anion source, and the metal salt or metal-containing compound are contacted and calcined simultaneously.
- the ⁇ n ⁇ ' ⁇ -metallocene compound can be contacted with an olefin monomer and an organoaluminum cocatalyst for a first period of time prior to contacting this mixture with the acidic activator-support.
- the precontacted mixture of metallocene, monomer, and component that provides an activatable ligand to the metallocene, including but not limited to an organoaluminum cocatalyst is contacted with the acidic activator-support
- the composition further comprising the acidic activator-support is termed the "postcontacted" mixture.
- the postcontacted mixture can be allowed to remain in further contact for a second period of time prior to being charged into the reactor in which the polymerization process will be carried out.
- Various processes to prepare solid oxide activator-supports that can be employed in this invention have been reported. For example, U.S. Patent Nos.
- the activator-support used, in preparing the catalyst compositions of this invention can comprise an ion-exchangeable activator- support, including but not limited to silicate and aluminosilicate compounds or minerals, either with layered or non-layered structures, and any combination thereof.
- ion-exchangeable, layered aluminosilicates such as pillared clays can be used as activator-supports.
- the acidic activator-support comprises an ion-exchangeable activator-support, it can optionally be treated with at least one electron-withdrawing anion such as those disclosed herein, though typically the ion-exchangeable activator-support is not treated with an electron-withdrawing anion.
- the activator-support of this invention can comprise clay minerals having exchangeable cations and layers capable of expanding.
- Typical clay mineral activator-supports include, but are not limited to, ion-exchangeable, layered aluminosilicates such as pillared clays.
- support is used, it is not meant to be construed as an inert component of the catalyst composition, but rather is to be considered an active part of the catalyst composition, because of its intimate association with the ⁇ ms ⁇ 2-metallocene and the component that provides an activatable ligand to the metallocene, such as an organoaluminum.
- the ion exchangeable activator-support serves as an insoluble reactant that reacts with the ⁇ m' ⁇ -metallocene and organoaluminum components to form a catalyst composition used to produce polymer.
- the clay materials of this invention encompass materials either in their natural state or that have been treated with various ions by wetting, ion exchange, or pillaring.
- the clay material activator-support of this invention comprises clays that have been ion exchanged with large cations, including polyn ⁇ clear, highly charged metal complex cations.
- the clay material activator-supports of this invention also encompass clays that have been ion exchanged with simple salts, including, but not limited to, salts of Al(III), Fe(II), Fe(III) and Zn(II) with ligands such as halide, acetate, sulfate, nitrate, or nitrite.
- the clay activator-support of this invention comprises pillared clays.
- pillared clays is used to refer to clay materials that have been ion exchanged with large, typically polynuclear, highly charged metal complex cations. Examples of such ions include, but are not limited to, Keggin ions which can have charges such as 7+, various polyoxometallates, and other large ions.
- pillaring refers to a simple exchange reaction in which the exchangeable cations of a clay material are replaced with large, highly charged ions, such as Keggin ions.
- the pillaring process utilizes clay minerals having exchangeable cations and layers capable of expanding.
- Any pillared clay that can enhance the polymerization of olefins in the catalyst composition of the present invention can be used. Therefore, suitable clay minerals for pillaring include, but are not limited to: allophanes; smectites, both dioctahedral (Al) and tri -octahedral (Mg) and derivatives thereof such as rnontmorillonites (bentonites), nontronites, hectorites, or laponites; halloysites; vermiculites; micas; fluoromicas; chlorites; mixed-layer clays; the fiberous clays including but not limited to sepiolites, attapulgites, and palygorskites; a serpentine clay; illite; laponite; saponite; or any combination thereof.
- the pillared clay activator-support comprises bentonite or montmorillonite, noting that
- the pillared clay can be pretreated in the present invention.
- a pillared bentonite was pretreated by drying at about 300 0 C under an inert atmosphere, typically dry nitrogen, for about 3 hours, before being added to the polymerization reactor.
- This example of a pretreament is not limiting, because preheating steps such as this many be carried out at many other temperatures and times, including a combination of temperature and time steps, all of which are encompassed by this invention.
- the ion-exchangeable activator-supports such as pillared clays used to prepare the catalyst compositions of this invention can be combined with other inorganic support materials, including, but are not limited to, zeolites, inorganic oxides, phosphated inorganic oxides, and the like.
- typical support materials that can be used in this regard include, but are not limited to, silica, silica-alumina, alumina, titania, zirconia, magnesia, boria, fluorided alumina, silated alumina, thoria, aluminophosphate, aluminum phosphate, zinc aluminate, phosphated silica, phosphated alumina, silica-titania, coprecipitated silica/titania, fluorided/silated alumina, and any combination or mixture thereof.
- the amount of ⁇ /zs ⁇ -metallocene compound in relation to the ion-exchangable activator-support used to prepare the catalyst composition of this invention is typically from about 0.1 wt% to about 15 wt% ⁇ ns ⁇ -metallocene complex, based on the weight of the activator-support component (not based on the final metallocene- clay mixture). It was also found that from about 1 wt% to about 10 wt% ansa- mctalloccnc works well to afford a catalyst that operates at desired activities.
- the mixture of ⁇ ns ⁇ -metallocene and clay activator-support can be contacted and mixed for any length of time to allow thorough contact between the ansa- metallocene and activator-support.
- Sufficient deposition of the metallocene component on the clay can be achieved without heating a mixture of clay and metallocene complex.
- the ⁇ mr ⁇ -metallocene compound and the clay material are simply mixed from about room temperature to about 200 0 F in order to achieve the deposition of the ⁇ /zs ⁇ -metallocene on the clay activator-support.
- the ⁇ ws ⁇ -metallocene compound and the clay material are mixed from about 100°F to about 180 0 F in order to achieve the deposition of the ⁇ r ⁇ a-metallocene on the clay activator-support.
- the present invention encompasses catalyst compositions comprising an acidic activator-support, which can comprise a layered mineral.
- layered mineral is used herein to describe materials such as clay minerals, pillared clays, ion-exchanged clays, exfoliated clays, exfoliated clays gelled into another oxide matrix, layered minerals mixed or diluted with other materials, and the like, or any combination thereof.
- the acidic activator-support comprises a layered mineral
- it can optionally be treated with at least one electron-withdrawing anion such as those disclosed herein, though typically the layered mineral is not treated with an electron-withdrawing anion.
- at least one clay mineral can be used as the activator-support.
- Clay minerals generally include the large group of finely-crystalline, sheet-like layered minerals that are found in nature in fine-grained sediments, sedimentary rocks, and the like, and which constitute a class of hydrous silicate and aluminosilicate minerals with sheet-like structures and very high surface areas. This term is also used to describe hydrous magnesium silicates with a phyllosilicate structure.
- clay minerals examples include, but are not limited to, allophanes; smectites, both dioctahedral (Al) and tri-octahedral (Mg) and derivatives thereof such as montmorillonites (bentonites), nontronites, hectorites, or laponites; halloysites; vermiculites; micas; fluoromicas; chlorates; mixed-layer clays; the f ⁇ berous clays including but not limited to sepiolites, attapulgites, and palygorskites; a serpentine clay; illite; laponite; saponite; or any combination thereof.
- allophanes smectites, both dioctahedral (Al) and tri-octahedral (Mg) and derivatives thereof such as montmorillonites (bentonites), nontronites, hectorites, or laponites; halloysites; vermiculites; micas; fluoromicas;
- Pillared clays can also be used as the activator-support of this invention, as disclosed herein. Pillared clays comprise clay minerals, typically of the of the smectite group and other phylosilicates in addition to sepiolites and palygorskites, that have been ion exchanged with large, typically polynuclear, highly charged metal complex cations.
- the layered minerals when layered minerals are used as activator- supports or metallocene activators, the layered minerals are typically calcined prior to their use as activators. Typical calcination temperatures can range from about 100 0 C to about 700°C, from about 15O 0 C to about 500°C, or from about 200°C to about 400 0 C.
- Non-Limiting Examples of the Catalyst Composition examples include, but are not limited to the following.
- the catalyst composition can comprise, or the catalyst composition can comprise the contact product of, at least one ⁇ /r ⁇ -metallocene, at least one organoaluminum compound, and at least one activator-support, wherein: a) the at least one ansa -metallocene comprises a compound having the formula:
- M 1 is zirconium or hafnium; X is, independently, F, Cl, Br, or I; E is C or Si;
- R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R 1 or R 2 is an aryl group;
- R 3A and R 3B are independently a hydrocarbyl group or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or hydrogen; n is an integer from 0 to 10; and
- R 4A and R 4B are independently a hydrocarbyl group having up to 12 carbon atoms, or hydrogen
- the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, triisohexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof; and c) the at least one activator-support comprises a solid oxide treated with an electron-withdrawing anion, wherein the solid oxide is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytimgstates, titania, zirconia, magnesia, boria, zinc oxide, mixed
- the at least one ⁇ r ⁇ -metallocene can also comprise, or can be selected from, a compound having the formula:
- M 1 is zirconium or hafnium
- X is F, Cl, Br, or I
- R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R 1 or R 2 is an aryl group;
- R 3A and R 3B are independently H, methyl, allyl, benzyl, butyl, pentyl, hexyl, or trimethylsilyl; n is an integer from 1 to 6, inclusive; and
- R 4A and R 4B are independently a hydrocarbyl group having up to 6 carbon atoms, or hydrogen.
- the at least one ⁇ ns ⁇ -metallocene can also comprise, or can be selected from, a compound having the formula:
- M 1 is zirconium or hafnium; X is Cl, Br, or I; E is C or Si;
- R 1 and R 2 are independently methyl or phenyl, wherein at least one of R 1 or R 2 is phenyl;
- R 3A and R 3B are independently H or methyl; n is 1 or 2; and
- R 4A and R 4B are independently H or t-butyl. Also in this aspect, the at least one ⁇ ns ⁇ -mctalloccnc can also comprise, or can
- the catalyst composition can comprise, or the catalyst composition can comprise the contact product of, at least one ⁇ r ⁇ -metallocene, at least one organoaluminum compound, and at least one activator- support, wherein: a) the at least one ⁇ r ⁇ -metallocene comprises
- the at least one organoaluminum compound comprises triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof; and c) the at least one activator-support comprises a sulfated solid oxide.
- the catalyst composition can comprise, or the catalyst composition can comprise the contact product of, at least one ⁇ r ⁇ -metallocene, at least one organoaluminum compound, and at least one activator- support, wherein: a) the at least one ⁇ s ⁇ -metallocene comprises
- the at least one organoaluminum compound comprises triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof; and c) the at least one activator-support comprises sulfated alumina.
- the catalyst composition can comprise, or the catalyst composition can comprise the contact product of, at least one precontacted ar ⁇ -metallocene, at least one precontacted organoaluminum compound, at least one precontacted olefin, and at least one postcontacted activator-support, wherein each of the ⁇ ms ⁇ -metallocene, the organoaluminum compound, the olefin, and the activator-support are as disclosed herein.
- a further aspect of this invention provides for a catalyst composition
- a catalyst composition comprising the contact product of at least one tightly-bridged ⁇ ws ⁇ -metallocene compound containing a pendant olefm-containing moiety attached to at least one of the cyclopentadienyl-type ligands and one or two aryl groups bonded to the bridging atom of the bridging ligand, and at least one reagent that can function to convert the metallocene into an active catalyst that is different from the combination of the solid oxide activator-support and organoaluminum compound disclosed herein.
- the active catalyst composition can be formed typically upon activating the metallocene, which can include converting the metallocene compound to its cationic form, and by providing it with a hydrocarbyl ligand either before, after, or during its conversion to a cation that can initiate olefin polymerization.
- the at least one reagent that can convert the metallocene into an active catalyst typically includes a component that provides an activatable ligand such as an alkyl to the metallocene, when the metallocene compound does not already comprise such a ligand, and an activator component, as provided herein.
- both functions can be achieved with one component, for example, an organoaluminoxane.
- these two functions can be provided by two separate components, such as an organoaluminum compound that can provide an activatable alkyl ligand to the metallocene, and another component that can provide the activator function.
- the activator and alkylation agent for the ansa- metallocene compound can be at least one organoaluminoxane, such as methylaluminoxane or isobutylaluminoxane.
- the activator can be a Lewis acidic organoboron compound capable of abstracting an anionic ligand from the metallocene, such as tris(pentafluorophenyl)boron or triphenylcarbenium tetrakis(pentafluorophenyl)borate, that is used typically in combination with an alkylating agent such as an organoaluminum compound.
- a dialkylated tightly-bridged ⁇ ws ⁇ -metallocene compound as disclosed herein can be reacted with a Br ⁇ nsted acidic borate activator such as tri(n- butyl)ammonium tetrakis(p-tolyl)borate or N,N-dimethylanilinium tetrakis- (pentafluorophenyl)borate to remove one alkyl ligand to form an alkylated metallocene cation.
- a Br ⁇ nsted acidic borate activator such as tri(n- butyl)ammonium tetrakis(p-tolyl)borate or N,N-dimethylanilinium tetrakis- (pentafluorophenyl)borate to remove one alkyl ligand to form an alkylated metallocene cation.
- Yet another aspect provides for a dialkylated tightly-bridged ⁇ ws ⁇ -metallocene compound that can be reacted with a Lewis acidic borate activator such as triphenylcarbenium tetrakis(pentafluorophenyl)borate to remove one alkyl ligand to form an alkylated metallocene cation.
- a Lewis acidic borate activator such as triphenylcarbenium tetrakis(pentafluorophenyl)borate to remove one alkyl ligand to form an alkylated metallocene cation.
- a further aspect of this invention provides for a catalyst composition
- a catalyst composition comprising the contact product of at least one tightly-bridged ⁇ r ⁇ -metallocene comprising at least one hydrocarbyl ligand that can initiate olefin polymerization and at least one solid oxide activator-support, without the need for an organoaluminurn compound to form the contact product.
- the ⁇ r ⁇ -metallocene compound comprises a pendant olef ⁇ n-containing moiety attached to at least one of the cyclopentadienyl-type Hgands, one or two aryl groups bonded to the bridging atom of the bridging ligand, and at least one hydrocarbyl ligand that can initiate olefin polymerization.
- An organoaluminurn compound would not be required to alkylate this type of "pre-alkylated" #7M ⁇ -metallocene because it already comprises a hydrocarbyl ligand that can initiate olef
- the present invention provides a catalyst composition comprising, or a catalyst composition comprising the contact product of, at least one ⁇ s ⁇ -metallocene; optionally, at least one organoaluminurn compound; and at least one activator, wherein the activator can be selected independently from: i) an activator-support comprising a solid oxide treated with an electron-withdrawing anion, a layered mineral, an ion-cxchangcablc activator- support, or any combination thereof; ii) at least one organoaluminoxane compound; iii) at least one organoboron or organoborate compound; or iv) any combination thereof.
- the present invention provides a catalyst composition comprising the contact product of at least one ⁇ / ⁇ -metallocene; at least one organoaluminurn compound; at least one activator-support comprising a solid oxide treated with an electron-withdrawing anion; and optionally, an aluminoxane cocatalyst.
- the present invention provides a catalyst composition comprising an ⁇ ns ⁇ -metallocene compound containing a pendant unsaturated moiety, an aluminoxane cocatalyst, an optional activator-support, and an optional organoaluminum compound.
- the catalyst composition of this invention is substantially free of aluminoxanes, and in another aspect, the catalyst composition of this invention have polymerization activity in the substantial absence of aluminoxanes.
- the present invention provides a catalyst composition comprising at least one ansa-metallocens compound and an aluminoxane.
- the catalyst composition is not required to comprise either an acidic activator- support wherein the activator-support comprises a chemically-treated solid oxide, and the catalyst composition is also not required to comprise an organoaluminum compound.
- any ⁇ «.y ⁇ -metallocene compounds disclosed herein can be combined with any of the aluminoxanes (poly(hydrocarbyl aluminum oxides)) disclosed herein, or any combination of aluminoxanes disclosed herein, to form a catalyst composition of this invention.
- any ⁇ my ⁇ -metallocene compounds disclosed herein can be combined with any aluminoxane or combination of aluminoxanes, and optionally an activator-support; optionally, a layered mineral; optionally, an ion-exchangeable activator-support; optionally, at least one organoboron compound; and optionally, at least one organoborate compound, to form a catalyst composition of this invention.
- Aluminoxanes are also referred to as poly(hydrocarbyl aluminum oxides) or organoaluminoxanes.
- the other catalyst components are typically contacted with the aluminoxane in a saturated hydrocarbon compound solvent, though any solvent which is substantially inert to the reactants, intermediates, and products of the activation step can be used.
- the catalyst composition formed in this manner can be collected by methods known to those of skill in the art, including but not limited to filtration, or the catalyst composition can be introduced into the polymerization reactor without being isolated.
- the aluminoxane compound of this invention is an oligomeric aluminum compound, wherein the aluminoxane compound can comprise linear structures, cyclic, or cage structures, or typically mixtures of all three. Cyclic aluminoxane compounds having the formula:
- R is a linear or branched alkyl having from 1 to 10 carbon atoms, and n is an integer from 3 to about 10 are encompassed by this invention.
- the (AlRO) n moiety shown here also constitutes the repeating unit in a linear alun ⁇ inoxane.
- linear aluminoxanes having the formula:
- R is a linear or branched alkyl having from 1 to 10 carbon atoms, and n is an integer from 1 to about 50, are also encompassed by this invention.
- aluminoxanes can be represented generally by formulas such as (R-Al- O) D , R(R-Al-O) J1 AlR 2 , and the like, wherein the R group is typically a linear or branched Ci-C 6 alkyl such as methyl, ethyl, propyl, butyl, pentyl, or hexyl wherein n typically represents an integer from 1 to about 50.
- the aluminoxane compounds of this invention include, but are not limited to, methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propyl- aluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, iso- butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylalutninoxane, or combinations thereof.
- methyl aluminoxane (MAO), ethyl aluminoxane, or isobutyl aluminoxane are typical optional cocatalysts used in the catalyst compositions of this invention.
- These aluminoxanes are prepared from trimethylaluminum, triethylaluminum, or triisobutylaluminum, respectively, and are sometimes referred to as poly(methyl aluminum oxide), poly(ethyl aluminum oxide), and poly(isobutyl aluminum oxide), respectively.
- n is at least about 3.
- the value of n can be variable within a single sample of aluminoxane, and such a combination of organoaluminoxanes are comprised in the methods and compositions of the present invention.
- the molar ratio of the aluminum in the aluminoxane to the metallocene in the composition is usually from about 1 :10 to about 100,000:1. Tn one another aspect, the molar ratio of the aluminum in the aluminoxane to the metallocene in the composition is usually from about 5:1 to about 15,000:1.
- the amount of optional aluminoxane added to a polymerization zone is an amount within a range of about 0.01 mg/L to about 1000 mg/L, from about 0.1 mg/L to about 100 mg/L, or from about 1 mg/L to about 50 mg/L.
- Organoaluminoxanes can be prepared by various procedures which are well known in the art. Examples of organoaluminoxane preparations are disclosed in U.S. Patent Nos. 3,242,099 and 4,808,561, each of which is incorporated by reference herein, in its entirety.
- One example of how an aluminoxane can be prepared is as follows. Water, which is dissolved in an inert organic solvent, can be reacted with an aluminum alkyl compound such as AlR 3 to form the desired organoaluminoxane compound.
- organoaluminoxanes can be prepared by reacting an aluminum alkyl compound such as AlR 3 with a hydrated salt, such as hydrated copper sulfate, in an inert organic solvent.
- the present invention provides a catalyst composition comprising, or a catalyst composition comprising the contact product of, at least one ⁇ ws ⁇ -metallocene; optionally, at least one organoaluminum compound; and at least one activator.
- the activator can be selected independently from: at least one activator-support as provided herein; at least one organoal ⁇ minoxane compound; at least one organoboron or organoborate compound; or any combination thereof.
- the at least one activator can be selected from at least one organoboron compound, at least one organoborate compound, or a combination thereof.
- the present invention provides a catalyst composition comprising the contact product of at least one ⁇ ns ⁇ -metallocene; at least one organoaluminum compound; at least one activator-support comprising a solid oxide treated with an electron -with drawing anion; and optionally, an organoboron or organoborate cocatalyst.
- the present invention provides a catalyst composition comprising the contact product of: at least one ⁇ r ⁇ -metallocene compound containing a pendant unsaturated moiety; an organoboron or organoborate cocatalyst; an organoaluminum compound; and optionally, an activator-support.
- the catalyst composition is not required to comprise an activator-support.
- Any ⁇ M ⁇ 2-metallocene compound disclosed herein can be combined with any of the organoboron or organoborate cocatalysts disclosed herein, or any combination of organoboron or organoborate cocatalysts disclosed herein, along with a component that provides an activatable ligand such as an alkyl or hydride ligand to the metallocene, when the metallocene compound does not already comprise such a ligand, such as an organoaluminum compound; to form a catalyst composition.
- a component that provides an activatable ligand such as an alkyl or hydride ligand
- any ansa- metallocene compounds disclosed herein can be combined with any an organoboron or organoborate cocatalyst; an organoaluminum compound; optionally, at least one aluminoxane; and optionally, an activator-support; to form a catalyst composition of this invention.
- the catalyst composition of this invention is substantially free of organoboron or organoborate compounds, and in another aspect, the catalyst composition of this invention have polymerization activity in the substantial absence of organoboron or organoborate compounds.
- the term "organoboron" compound can be used to refer to neutral boron compounds, borate salts, or combinations thereof.
- the organoboron compounds of this invention can comprise a fluoroorgano boron compound, a fluoroorgano borate compound, or a combination thereof. Any fluoroorgano boron or fluoroorgano borate compound known in the art can be utilized.
- fluoroorgano boron compounds has its usual meaning to refer to neutral compounds of the form BY 3 .
- fluoroorgano borate compound also has its usual meaning to refer to the monoanionic salts of a fluoroorgano boron compound of the form [cation] + [BY 4 ] ⁇ , where Y represents a fluorinated organic group.
- fluoroorgano boron and fluoroorgano borate compounds are typically referred to collectively by organoboron compounds, or by either name as the context requires.
- fluorinated aryl borates such as, ⁇ iV-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarben
- any amount of organoboron compound can be utilized in this invention.
- the molar ratio of the organoboron compound to the metallocene compound in the composition is from about 0.1:1 to about 10:1.
- the amount of the fluoroorgano boron or fluoroorgano borate compound used as a cocatalyst for the metallocene is in a range of from about 0.5 mole to about 10 moles of boron compound per mole of metallocene compound.
- the amount of fluoroorgano boron or fluoroorgano borate compound used as a cocatalyst for the metallocene is in a range of from about 0.8 mole to about 5 moles of boron compound per mole of metallocene compound.
- the present invention provides a catalyst composition comprising, or a catalyst composition comprising the contact product of: 1) at least one tightly-bridged ⁇ «s ⁇ -metallocene compound comprising an olefin-containing moiety bonded to a cyclopentadienyl-type ligand and at least one aryl group bonded to the bridging atom of the bridging ligand; 2) optionally, at least one organoaluminum compound; and 3) at least one activator, as disclosed herein.
- the present invention provides a catalyst composition as disclosed herein, comprising an optional ionizing ionic compound cocatalyst in addition to these other components.
- the catalyst composition of this invention is substantially free of ionizing ionic compounds, and in another aspect, the catalyst composition of this invention have polymerization activity in the substantial absence of ionizing ionic compounds.
- the present invention provides a catalyst composition comprising at least one ⁇ / ⁇ -metallocene compound as disclosed herein, at least one ionizing ionic compound cocatalyst, optionally at least one activator-support, and optionally at least one organoaluminum compound. Examples of ionizing ionic compound arc disclosed in U.S. Patent Numbers 5,576,259 and 5,807,938.
- An ionizing ionic compound is an ionic compound which can function to enhance activity of the catalyst composition. While not bound by theory, it is believed that the ionizing ionic compound can be capable of reacting with the metallocene compound and converting the metallocene into a cationic metallocene compound. Again, while not intending to be bound by theory, it is believed that the ionizing ionic compound can function as an ionizing compound by completely or partially extracting an anionic ligand, possibly a non- ⁇ s -alkadienyl ligand such as (X 3 ) or (X 4 ), from the metallocene.
- the ionizing ionic compound is an activator regardless of whether it is ionizes the metallocene, abstracts an (X 3 ) or (X 4 ) ligand in a fashion as to form an ion pair, weakens the metal-(X 3 ) or metal-(X 4 ) bond in the metallocene, simply coordinates to an (X 3 ) or (X 4 ) ligand, or any other mechanisms by which activation can occur. Further, it is not necessary that the ionizing ionic compound activate the metallocene only. The activation function of the ionizing ionic compound is evident in the enhanced activity of catalyst composition as a whole, as compared to a catalyst composition containing catalyst composition that does not comprise any ionizing ionic compound.
- ionizing ionic compounds include, but are not limited to, the following compounds: tri(n-butyl)anxmonium tetrakis(p-tolyl)borate, tri(n-butyl)- ammonium tetrakis(m-tolyl)borate, tri(n-butyl)arnrnoniurn tetrakis(2,4- dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tri(n- butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(p-tolyl)borate, N,N-dimethylanilinium tetrakis(m-
- unsaturated reactants that are useful in the polymerization processes with catalyst compositions and processes of this invention include olefin compounds having from about 2 to about 30 carbon atoms per molecule and having at least one olefinic double bond.
- This invention encompasses homopolymerization processes using a single olefin such as ethylene or propylene, as well as copolymerization reactions with at least one different olefinic compound.
- copolymers of ethylene comprise a major amount of ethylene (>50 mole percent) and a minor amount of comonomer ⁇ 50 mole percent), though this is not a requirement.
- the comonorners that can be copolymerized with ethylene should have from three to about 20 carbon atoms in their molecular chain.
- Acyclic, cyclic, polycyclic, terminal ( ⁇ ), internal, linear, branched, substituted, unsubstituted, functionalized, and non-functionalized olefins can be employed in this invention.
- typical unsaturated compounds that can be polymerized with the catalysts of this invention include, but are not limited to, propylene, 1-butene, 2- butene, 3 -methyl- 1-butene, isobutylene, 1-pentene, 2-pentene, 3 -methyl- 1-pentene, 4- methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-l-hexene, 1-heptene, 2- hcptcnc, 3-hcptcnc, the four normal octcncs, the four normal noncncs, the five normal decenes, and mixtures of any two or more thereof.
- Cyclic and bicyclic olefins including but not limited to, cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like, can also be polymerized as described above.
- the monomer ethylene can be copolymerized with a comonomer.
- examples of the comonomer include, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl- 1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-l-pentene, 4-methyl- 1-pentene, 1- hexene, 2-hexene, 3-hexene, 3-ethyl-l-hexene, 1-heptene, 2-heptene, 3-heptene, the four normal octenes, the four normal nonenes, or the five normal decenes.
- the comonomer can be 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, or styrene.
- the amount of comonomer introduced into a reactor zone to produce the copolymer is generally from about 0.001 to about 99 weight percent comonomer based on the total weight of the monomer and comonomer. In one aspect, the amount of comonomer introduced into a reactor zone to produce the copolymer is generally from about 0.01 to about 50 weight percent comonomer based on the total weight of the monomer and comonomer. In another aspect, the amount of comonomer introduced into a reactor zone is from about 0.01 to about 10 weight percent comonomer, and in still another aspect, from about 0.1 to about 5 weight percent comonomer based on the total weight of the monomer and comonomer.
- an amount sufficient to give the above described concentrations by weight, in the copolymer produced can be used. While not intending to be bound by this theory, in the event that branched, substituted, or functionalized olefins are used as reactants, it is believed that steric hindrance can impede and/or slow the polymerization process. Thus, branched and/or cyclic portion(s) of the olefin removed somewhat from the carbon-carbon double bond would not be expected to hinder the reaction in the way that the same olefin substituents situated, more proximate to the carbon-carbon double bond might.
- At least one reactant for the catalyst compositions of this invention is ethylene, so the polymerizations are either homopolymerizations or copolymerizations with a different acyclic, cyclic, terminal, internal, linear, branched, substituted, or unsubstituted olefin.
- the catalyst compositions of this invention can be used in polymerization of diolef ⁇ n compounds, including but are not limited to, 1,3- butadiene, isoprene, 1 ,4-pentadiene, and 1 ,5-hexadiene.
- this invention encompasses a catalyst composition and a method comprising contacting at least one tightly-bridged an sa-metallocene compound, at least one activator, and optionally at least one organoaluminum compound, as disclosed herein.
- the method disclosed herein encompasses any series of contacting steps that allows contacting each of the components provided, any order of contacting components or mixtures of components. While not intending to be limiting, examples of contacting steps are typically exemplified herein using a treated solid oxide activator-support and an organoaluminum cocatalyst. These exemplary steps can encompass any number of precontacting and postcontacting steps, and can further encompass using an olefin monomer as a contact component in any of these steps. Examples of preparative methods to prepare the catalyst composition of this invention follow.
- the ansa-metallocene can be precontacted with an olefinic monomer, not necessarily the olefin monomer to be polymerized, and an organoaluminum cocatalyst for a first period of time prior to contacting this precontacted mixture with the solid oxide activator-support.
- the first period of time for contact, the precontact time, between the ansa-metallocene, the olefinic monomer, and the organoaluminum cocatalyst can typically range from time about 1 minute to about 24 hours, and from about 0.1 to about 1 hour is typical. Precontact times from about 10 minutes to about 30 minutes are also typical.
- this composition (further comprising the solid oxide activator) is termed the postcontacted mixture.
- the postcontacted mixture can be allowed to remain in contact for a second period of time, the postcontact time, prior to being initiating the polymerization process.
- postcontact times between the solid oxide activator-support and the precontacted mixture typically range from time about 1 minute to about 24 hours, and from 0.1 to about 1 hour is typical. Postcontact times from about 10 minutes to about 30 minutes are also typical.
- the various catalyst components can be contacted in the polymerization reactor simultaneously while the polymerization reaction is proceeding.
- any two or more of these catalyst components can be "precontacted” in a vessel or tube prior to their entering the reaction zone.
- This precontacting step can be a continuous process, in which the precontacted product is fed continuously to the reactor, or it can be a stepwise or batchwisc process in which a batch of precontacted product can be added to make a catalyst composition.
- This precontacting step can be carried out over a time period that can range from a few seconds to as much as several days, or longer.
- the continuous precontacting step can last typically from about 1 second to about 1 hour.
- the continuous precontacting step can last typically from about 10 seconds to about 45 minutes, or from about 1 minute to about 30 minutes.
- the precontacting process can be carried out in multiple steps, rather than a single step, in which multiple mixtures are prepared, each comprising a different set of catalyst components.
- at least two catalyst components can be contacted forming a first mixture, followed by contacting the first mixture with at least one other catalyst component forming a second mixture, and so forth.
- precontacting steps can be carried out in a single vessel or in multiple vessels. Further, multiple precontacting steps can be carried out in series (sequentially), in parallel, or a combination thereof.
- a first mixture of two catalyst components can be formed in a first vessel
- a second mixture comprising the first mixture plus one additional catalyst component can be formed in the first vessel or in a second vessel, which is typically placed downstream of the first vessel.
- one or more of the catalyst components can be split and used in different precontacting treatments. For example, part of a catalyst component can be fed into a first precontacting vessel for precontacting with at least one other catalyst component, while the remainder of that same catalyst component can be fed into a second precontacting vessel for precontacting with at least one other catalyst component, or can be fed directly into the reactor, or a combination thereof.
- the precontacting can be carried out in any suitable equipment, such as tanks, stirred mix tanks, various static mixing devices, a tube, a flask, a vessel of any type, or any combination thereof.
- a catalyst composition of this invention is prepared by contacting 1-hexene, triisobutylaluminum or tri-n-butylaluminum, and an ansa- metallocene for at least about 30 minutes, followed by contacting this precontacted mixture with a sulfated alumina activator-support for at least about 10 minutes up to one hour to form the active catalyst.
- the precontacting step typically increases the productivity of the polymer as compared to the same catalyst composition that is prepared without this precontacting step.
- the enhanced activity catalyst composition of this invention can be used for homopolymerization of an ⁇ -olefin monomer such as ethylene or copolymerization of an ⁇ -olefin and a comonomer.
- neither a precontacting step nor a postcontacting step are required for this invention.
- the postcontacted mixture can be heated at a temperature and for a duration sufficient to allow adsorption, impregnation, or interaction of precontacted mixture and the solid oxide activator-support, such that a portion of the components of the precontacted mixture is immobilized, adsorbed, or deposited thereon.
- the postcontacted mixture can be heated from between about O 0 F to about 150 0 F. Temperatures between about 4O 0 F to about 95°F are typical if the mixture is heated at all.
- the molar ratio of the ⁇ r ⁇ -metallocene compound to the organoaluminum compound can be from about 1:1 to about 1:10,000.
- the molar ratio of the ⁇ 7?s ⁇ -metallocene compound to the organoaluminum compound can be from about 1 :1 to about 1:1,000, and in another aspect, from about 1:1 to about 1:100. These molar ratios reflect the ratio of ⁇ m ⁇ -metallocene compound to the total amount of organoaluminum compound in both the precontacted mixture and the postcontacted mixture combined.
- the molar ratio of olefin monomer to ⁇ ns ⁇ -metallocene compound in the precontacted mixture can be from about 1:10 to about 100,000:1, or from about 10:1 to about 1,000:1.
- the weight ratio of the solid oxide activator to the organoaluminum compound can range from about 1 :5 to about 1 ,000:1. Tn another aspect, the weight ratio of the solid oxide activator to the organoaluminum compound can be from about 1 :3 to about 100:1, and in yet another aspect, from about 1 :1 to about 50:1.
- the weight ratio of the ans ⁇ -metallocene to solid oxide activator-support can be from about 1:1 to about 1:1,000,000.
- the weight ratio of the ⁇ r ⁇ s ⁇ -metallocene to solid oxide activator-support which can be from about 1 :10 to about 1:100,000, and in another aspect, from about 1 :20 to about 1 : 1000.
- the present invention can use AlR_ 3 -type organoaluminum compounds and an activator-support in the absence of aluminoxanes. While not intending to be bound by theory, it is believed that the organoaluminum compounds likely do not activate the metallocene catalysts in the same manner as an organoaluminoxane. Additionally, no expensive borate compounds or MgCl 2 are required to form the catalyst composition of this invention, although aluminoxane, borate compounds, MgCl 2, or any combination thereof can be used optionally in the catalyst composition of this invention.
- cocatalysts such as aluminoxanes, organoboron compounds, ionizing ionic compounds, or any combination thereof can be used as cocatalysts with the ⁇ « ⁇ 2-metallocene, either in the presence or absence of the activator support.
- cocatalysts such as aluminoxanes, organoboron compounds, ionizing ionic compounds, or any combination thereof can be used as with the ⁇ ns ⁇ -metallocene, either and in the presence or absence of an organoaluminum compound, as specified herein.
- the at least one organoaluminum compound is optional when at least one ligand on the metallocene is a hydrocarbyl group, H, or BH 4 ; when the at least one activator comprises an organoaluminoxane compound; or both these conditions are present.
- the catalyst compositions of the present invention are active in the substantial absence of cocatalysts such as aluminoxanes, organoboron compounds, ionizing ionic compounds, or any combination thereof.
- this invention provides a process to produce a catalyst composition, comprising: contacting at least one ⁇ ns ⁇ -metallocene, at least one olefin, and at least one organoaluminum compound for a first period of time to form a precontacted mixture comprising at least one precontacted ⁇ / ⁇ s ⁇ -metallocene, at least one precontacted organoaluminum compound, and at least one precontacted olefin; and contacting the precontacted mixture with at least one activator-support and optionally additional organoaluminum compound for a second period of time to form a postcontactcd mixture comprising at least one postcontactcd ⁇ ns ⁇ -mctalloccnc, at least one postcontacted organoaluminum compound, at least one postcontacted olefin, and at least one postcontacted activator-support.
- the at least one ansa-raetallocene can comprise a compound having the formula:
- (X 1 ) and (X 2 ) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fiuorenyl; one substituent on (X 1 ) and (X 2 ) is a bridging group having the formula
- ER 1 R 2 wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X 1 ) and (X 2 ), and wherein R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R 1 and R 2 is an aryl group; at least one substituent on (X 1 ) or (X 2 ) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms; (X 3 ) and (X 4 ) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4)
- the catalytic activity of the catalyst of this invention is typically greater than or equal to about 100 grams polyethylene per gram of chemically treated solid oxide per hour (abbreviated gP/(gCTSO-hr)).
- the catalyst of this invention can be characterized by an activity of greater than or equal to about 250 gP/(gCTSO-hr), and in another aspect, an activity of greater than or equal to about 500 gP/(gCTSO-hr).
- the catalyst of this invention can be characterized by an activity of greater than or equal to about 1000 gP/(gCTSO-hr), and in another aspect, an activity of greater than or equal to about 2000 gP/(gCTSO-hr).
- this activity is typically measured under slurry polymerization conditions using isobutane as the diluent, with a polymerization temperature of about 90 0 C, and an ethylene pressure of about 550 psig.
- this activity is measured under slurry polymerization conditions using isobutane as the diluent, with a polymerization temperature from about 80 0 C to about 105 °C, and an ethylene pressure from about 450 psig to about 550 psig.
- the reactor should have substantially no indication of any wall scale, coating or other forms of fouling upon making these measurements.
- the catalysts of the present invention are intended for any olefin polymerization method known in the art, using various types of polymerization reactors.
- polymerization reactor includes any polymerization reactor capable of polymerizing olefin monomers to produce homopolymers or copolymers. Such homopolymers and copolymers are referred to as resins or polymers.
- the various types of reactors include those that may be referred to as batch, slurry, gas-phase, solution, high pressure, tubular or autoclave reactors.
- Gas phase reactors may comprise fluidized bed reactors or staged horizontal reactors.
- Slurry reactors may comprise vertical or horizontal loops.
- High pressure reactors may comprise autoclave or tubular reactors.
- Reactor types can include batch or continuous processes. Continuous processes could use intermittent or continuous product discharge. Processes may also include partial or full direct recycle of un-reacted monomer, un-reacted comonomer, and/or diluent.
- Polymerization reactor systems of the present invention may comprise one type of reactor in a system or multiple reactors of the same or different type.
- Production of polymers in multiple reactors may include several stages in at least two separate polymerization reactors interconnected by a transfer device making it possible to transfer the polymers resulting from the first polymerization reactor into the second reactor.
- the desired polymerization conditions in one of the reactors may be different from the operating conditions of the other reactors.
- polymerization in multiple reactors may include the manual transfer of polymer from one reactor to subsequent reactors for continued polymerization.
- Multiple reactor systems may include any combination including, but not limited to, multiple loop reactors, multiple gas reactors, a combination of loop and gas reactors, multiple high pressure reactors or a combination of high pressure with loop and/or gas reactors.
- the polymerization reactor system may comprise at least one loop slurry reactor.
- Such reactors are known in the art and may comprise vertical or horizontal loops.
- Monomer, diluent, catalyst and optionally any comonomer may be continuously fed to a loop reactor where polymerization occurs.
- continuous processes may comprise the continuous introduction of a monomer, a catalyst, and a diluent into a polymerization reactor and the continuous removal from this reactor of a suspension comprising polymer particles and the diluent.
- Reactor effluent may be flashed to remove the solid polymer from the liquids that comprise the diluent, monomer and/or comonomer.
- Various technologies may be used for this separation step including but not limited to, flashing that may include any combination of heat addition and pressure reduction; separation by cyclonic action in either a cyclone or hydrocyclone; or separation by centrifugation.
- flashing that may include any combination of heat addition and pressure reduction; separation by cyclonic action in either a cyclone or hydrocyclone; or separation by centrifugation.
- a typical slurry polymerization process also known as the particle form process
- U.S. Patent Nos. 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191 and 6,833,415 each of which is incorporated by reference in its entirety herein.
- Suitable diluents used in slurry polymerization are well known in the art and include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquids under reaction conditions.
- suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n- pentane, isopentane, neopentane, and n-hexane.
- Some loop polymerization reactions can occur under bulk conditions where no diluent is used.
- An example is polymerization of propylene monomer as disclosed in U.S. Patent Nos. 5,455,314, which is incorporated by reference herein in its entirety.
- the polymerization reactor may comprise at least one gas phase reactor.
- Such systems are known in the art and may employ a continuous recycle stream containing one or more monomers continuously cycled through a fluidized bed in the presence of the catalyst under polymerization conditions.
- a recycle stream may be withdrawn from the fluidized bed and recycled back into the reactor.
- polymer product may be withdrawn from the reactor and new or fresh monomer may be added to replace the polymerized monomer.
- Such gas phase reactors may comprise a process for multi- step gas-phase polymerization of olefins, in which olefins are polymerized in the gaseous phase in at least two independent gas-phase polymerization zones while feeding a catalyst-containing polymer formed in a first polymerization zone to a second polymerization zone.
- One type of gas phase reactor is disclosed in U.S. Patent Nos. 5,352,749, 4588,790 and 5,436,304, each of which is incorporated by reference in its entirety herein.
- a high pressure polymerization reactor may comprise a tubular reactor or an autoclave reactor, both of which are known in the art.
- Tubular reactors may have several zones where fresh monomer, initiators, or catalysts are added.
- Monomer may be entrained in an inert gaseous stream and introduced at one zone of the reactor.
- Initiators, catalysts, and/or catalyst components may be entrained in a gaseous stream and introduced at another zone of the reactor.
- the gas streams may be intermixed for polymerization. Heat and pressure may be employed appropriately to obtain optimal polymerization reaction conditions.
- the polymerization reactor may comprise a solution polymerization reactor wherein the monomer is contacted with the catalyst composition by suitable stirring or other means.
- a carrier comprising an inert organic diluent or excess monomer may be employed.
- the monomer may be brought in the vapor phase into contact with the catalytic reaction product, in the presence or absence of liquid material.
- the polymerization zone is maintained at temperatures and pressures that will result in the formation of a solution of the polymer in a reaction medium. Agitation may be employed to obtain better temperature control and to maintain uniform polymerization mixtures throughout the polymerization zone. Adequate means arc utilized for dissipating the exothermic heat of polymerization.
- Polymerization reactors suitable for the present invention may further comprise any combination of at least one raw material feed system, at least one feed system for catalyst or catalyst components, and/or at least one polymer recovery system.
- Suitable reactor systems for the present invention may further comprise systems for feedstock purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycle, storage, loadout, laboratory analysis, and process control.
- Conditions that are controlled for polymerization efficiency and to provide resin properties include temperature, pressure and the concentrations of various reactants.
- Polymerization temperature can affect catalyst productivity, polymer molecular weight and molecular weight distribution.
- Suitable polymerization temperature may be any temperature below the de-polymerization temperature according to the Gibbs Free energy equation. Typically this includes from about 60 0 C to about 280 0 C, for example, and from about 70°C to about 110 0 C, depending upon the type of polymerization reactor.
- Suitable pressures will also vary according to the reactor and polymerization type.
- the pressure for liquid phase polymerizations in a loop reactor is typically less than 1000 psig.
- Pressure for gas phase polymerization is usually at about 200 - 500 psig.
- High pressure polymerization in tubular or autoclave reactors is generally run at about 20,000 to 75,000 psig.
- Polymerization reactors can also be operated in a supercritical region occurring at generally higher temperatures and pressures. Operation above the critical point of a pressure/temperature diagram (supercritical phase) may offer advantages.
- the concentration of various reactants can be controlled to produce resins with certain physical and mechanical properties.
- the proposed end-use product that will be formed by the resin and the method of forming that product determines the desired resin properties.
- Mechanical properties include tensile, fiexural, impact, creep, stress relaxation and hardness tests.
- Physical properties include density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, temperature melt of crystallization, density, stereoregularity, crack growth, long chain branching and rheological measurements.
- the concentrations of monomer, co-monomer, hydrogen, co-catalyst, modifiers, and electron donors are important in producing these resin properties.
- Comonomer is used to control product density.
- Hydrogen is used to control product molecular weight.
- Co-catalysts can be used to alkylate, scavenge poisons and control molecular weight.
- Modifiers can be used to control product properties and electron donors affect stereoregularity.
- the concentration of poisons must be minimized since they impact the reactions and product properties.
- the polymer or resin may be formed into various articles, including, but not limited to, bottles, drums, toys, household containers, utensils, film products, drums, fuel tanks, pipes, geomembranes, and liners.
- Various processes may be used to form these articles, including, but not limited to, blow molding, extrusion molding, rotational molding, thermoforming, cast molding and the like.
- additives and modifiers can be added to the polymer to provide better processing during manufacturing and for desired properties in the end product.
- Additives include surface modifiers such as slip agents, antiblocks, tackif ⁇ ers; antioxidants such as primary and secondary antioxidants; pigments; processing aids such as waxes/oils and fluoroelastomers; and special additives such as fire retardants, antistats, scavengers, absorbers, odor enhancers, and degradation agents.
- the ethylene polymer produced using the catalyst composition of this invention is typically characterized by lower levels of long chain branching (LCB) than are typically observed when using a tightly-bridged ⁇ msa ⁇ metal]ocene compound without an olefin-containing moiety bonded to a cyclopentadienyl-type ligand, even when the comparative metallocene comprises at least one aryl group bonded to the bridging atom of the bridging ligand.
- LLB long chain branching
- the ethylene polymer produced using the catalyst composition of this invention is typically characterized by higher molecular weights than are typically observed when using a tightly-bridged arcs ⁇ -metallocene compound without at least one aryl group bonded to the bridging atom of the bridging ligand, even when the comparative metallocene comprises an olcfm-containing moiety bonded to a cyclopcntadicnyl-typc ligand.
- Figures 3 through 8 illustrate various aspects of olefin homopolymer produced according to this invention. The combination of size exclusion chromatography (SEC) and multiangle light scattering (MALS) detection was used to detect and characterize polymer branching.
- SEC size exclusion chromatography
- MALS multiangle light scattering
- Figures 6 and 7 illustrate plots of log( ⁇ o) versus log ( ⁇ / w ) for polymers prepared according to inventive Examples 1-11 and comparative Examples 14-16, respectively, and further illustrate how reduced LCB levels are manifested (see: Table 1).
- Linear polyethylene polymers are observed to follow a power law relationship between their zero shear viscosity, ⁇ o, and their weight average molecular weight, M w , with a power very close to 3.4. This relationship is shown by a straight line with a slope of 3.4 when the logarithm of 77 0 is plotted versus the logarithm of ⁇ / w . Deviations from this linear polymer line are generally accepted as being caused by the presence of long-chain branching (LCB).
- LCB long-chain branching
- Figures 6 and 7 plot the logarithm of 770 versus the logarithm of M w for polymers prepared according to this invention, illustrating the dependence of zero shear melt viscosity on weight average molecular weight (M w ), and demonstrating that these polymers are only very slightly deviated from the well-know 3.4 power law "Arnett line" which is used as an indication of a linear polymer (J. Phys. Chem. 1980, 84, 649). Consistent with this observation, both SEC-MALS and rheology data indicate that the inventive metallocenes produce very low LCB in ethylene polymerization, as illustrated in Figure 6 for Examples 1-11. Jn contrast, polymers made according to the comparative Examples 14-16 had much lower M w relative to polymers prepared according to this invention, Examples 1-11. Typically, these polymers also had similar or slightly higher levels of LCB, as illustrated in Figure 7.
- Figure 8 demonstrates a comparison of gcl-pcrmcation chromatography (GPC) runs for the polymers produced according to Examples 1-11 and Examples 14-16, of this invention.
- GPC results Table 1 and Figure 8 indicate that the polyethylenes (PE) produced according to this invention generally have high molecular weights. While the polymers made according to comparative Examples 14- 16 were characterized by low levels of LCB ( Figure 8), these comparative polymers had relatively lower M w as compared to the polymers prepared according to this invention. Comparative Examples 12 and 13 also demonstrate that the catalyst prepared using comparative metallocene C-I exhibited poor activity (Table 1).
- polymer is used herein to mean homopolymers comprising ethylene and/or copolymers of ethylene and another olefinic comonomer. "Polymer” is also used herein to mean homopolymers and copolymers of any other polymerizable monomer disclosed herein.
- catalyst is generally used herein to refer to the organoaluminum compounds that can constitute one component of the catalyst composition, but also refers to the optional components of the catalyst composition including, but not limited to, aluminoxanes, organoboron compounds, organoborate compounds, or ionizing ionic compounds, as disclosed herein.
- cocatalysts can be organoaluminum compounds of the formula Al(X 5 ) n (X 6 )3 -n , wherein (X 5 ) is a hydrocarbyl having from 1 to about 20 carbon atoms; (X 6 ) is alkoxide or aryloxide, any of which having from 1 to about 20 carbon atoms, halide, or hydride; and n is a number from 1 to 3, inclusive.
- the term cocatalyst can be used regardless of the actual function of the compound or any chemical mechanism by which the compound might operate.
- precontacted mixture is used herein to describe a first mixture of catalyst components that are contacted for a first period of time prior to the first mixture being used to form a "postcontacted” or second mixture of catalyst components that are contacted for a second period of time.
- the precontacted mixture describes a mixture of metallocene, olefin monomer, and organoaluminum compound, before this mixture is contacted with the acidic activator-support and optionally an organoaluminum compound.
- precontacted describes components that are used to contact each other, but prior to contacting the components in the second, postcontacted mixture. Accordingly, this invention may occasionally distinguish between a component used to prepare the precontacted mixture and that component after the mixture has been prepared.
- the precontacted organoaluminum compound once it is contacted with the metallocene and the olefin monomer, to have reacted to form at least one different chemical compound, formulation, or structure from the distinct organoaluminum compound used to prepare the precontacted mixture.
- the precontacted organoaluminum compound or component is described as comprising an organoaluminum compound that was used to prepare the precontacted mixture.
- postcontacted mixture is used herein to describe a second mixture of catalyst components that are contacted for a second period of time, and one constituent of which is the "precontacted” or first mixture of catalyst components that were contacted for a first period of time.
- postcontacted mixture is used herein to describe the mixture of metallocene, olefin monomer, organoaluminum compound, and acidic activator-support, formed from contacting the precontacted mixture of a portion of these components with the any additional components added to make up the postcontacted mixture.
- the additional component added to make up the postcontacted mixture is the solid oxide activator, and optionally can include an organoaluminum compound the same or different from the organoaluminum compound used to prepare the precontacted mixture, as described herein. Accordingly, this invention may also occasionally distinguish between a component used to prepare the postcontacted mixture and that component after the mixture has been prepared.
- the term tightly-bridged ⁇ /75 «-metallocene describes a metallocene compound in which the two ⁇ 5 -cycloalkadienyl-type ligands in the molecule are linked by a bridging moiety, wherein the shortest link between the two ⁇ 5 -cycloalkadienyl-type ligands comprises one atom.
- the length of the bridge or the chain between the two cyclopentadienyl-type ligands is a single atom, although this bridging atom is substituted.
- the metallocenes of this invention are bridged bis( ⁇ - cycloalkadienyi)-type compounds, wherein the ⁇ 5 -cycloalkadienyl portions include cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, and the like, including substituted analogs and partially saturated analogs thereof.
- substituted derivatives thereof in this invention includes partially saturated ligands such as tetrahydroindenyl, tetrahydrofiuorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, substituted partially saturated indenyl, substituted partially saturated fluorenyl, and the like.
- the metallocene is referred to simply as the "catalyst", in much the same way the term “cocatalyst” is used herein to refer to the organoalumfnum compound.
- catalyst composition do not depend upon the actual product of the reaction of the components of the mixtures, the nature of the active catalytic site, or the fate of the aluminum cocatalyst, ansa- metallocene, any olefin monomer used to prepare a precontacted mixture, or the solid oxide activator after combining these components. Therefore, the terms catalyst composition, catalyst mixture, and the like include both heterogeneous compositions and homogenous compositions.
- hydrocarbyl is used to specify a hydrocarbon radical group that includes, but is not limited to aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, aralkynyl, and the like, and includes all substituted, unsubstituted, branched, linear, heteroatom substituted derivatives thereof.
- the hydrocarbyl groups of this invention typically comprise up to about 20 carbon atoms. In one aspect, hydrocarbyl groups can have up to 12 carbon atoms, up to 8 carbon atoms, or up to 6 carbon atoms.
- hydrocarbyloxide group is used generically to refer collectively to both alkoxide and aryloxide groups. Unless otherwise specified, the hydrocarbyl oxide groups of this invention typically comprise up to about 20 carbon atoms. In one aspect, hydrocarbyloxide groups can have up to 12 carbon atoms, up to 8 carbon atoms, or up to 6 carbon atoms.
- hydrocarbylamino group is used genetically to refer collectively to alkylamino (NHR), arylamino (NHAr), dialkylamino (NRa), and diatylamino (NAr 2 ) groups.
- the hydrocarbyl amino groups of this invention typically comprise up to about 20 carbon atoms.
- hydrocarbylamino groups can have up to 12 carbon atoms, up to 8 carbon atoms, or up to 6 carbon atoms.
- alkenyl is used broadly to specify a hydrocarbyl group that comprises an alkene moiety, regardless of the particular regiochemistry of the alkene moiety and encompassing all stereochemical isomers.
- the alkenyl groups of this invention typically comprise up to about 20 carbon atoms. In one aspect, alkenyl groups can have up to 12 carbon atoms, up to 8 carbon atoms, or up to 6 carbon atoms.
- solid oxide activator-support acidic activator-support, activator- support, treated solid oxide, treated solid oxide compound, and the like are used herein to indicate a treated, solid, inorganic oxide of relatively high porosity, which exhibits Lewis acidic or Br ⁇ nsted acidic behavior, and which has been treated with an electron-withdrawing component, typically an anion, and which is calcined.
- the electron-withdrawing component is typically an electron-withdrawing anion source compound.
- the treated solid oxide compound comprises the calcined contact product of at least one solid oxide compound with at least one electron-withdrawing anion source compound.
- the activator-support or "treated solid oxide compound" comprises at least one ionizing, acidic solid oxide compound.
- activator refers generally to a substance that is capable of converting the contact product of: 1) a metallocene component; and 2) a component that provides an activatable ligand such as an alkyl or hydride ligand to the metallocene, when the metallocene compound does not already comprise such a ligand; into a catalyst that can polymerize olefins.
- the contact product comprises at least one activator, which can be selected independently from: i) an activator- support comprising a solid oxide treated with an electron-withdrawing anion, a layered mineral, an ion-exchangeable activator-support, or any combination thereof; ii) an organoaluminoxane compound; iii) an organoboron or an organoborate compound; or iv) any combination of these components.
- clay is used herein to refer to that component of the catalyst composition, a substantial portion of which constitutes a clay mineral or a mixture of clay minerals that have been pretreated by either exchanging cations, pillaring or simply wetting, that can be used as a activator-support in the catalyst composition described herein.
- the transition metal compound and organometal cocatalyst are reacted with the clay activator-support to form the active catalyst.
- the clay component of the catalyst composition of this invention probably functions as a activator-support for the transition metal compound, as well as a cocatalyst from the standpoint that it is in intimate physical chemical contact with the transition metal component.
- clay mineral is used herein to describe the large group of finely-crystalline, sheet like clay minerals that are found in nature in fine-grained sediments, sedimentary rocks, and the like.
- Clay minerals are a class of hydrous silicate and aluminosilicate minerals with sheet-like structures and very high surface areas. This term is also used to describe hydrous magnesium silicates with a phyllosilicate structure. Many common clay minerals belong to the kaolinite, montmorillonite, or illite groups of clays. Thus, the term “clay mineral” is not used herein to refer to the fine-grained soil consisting of mineral particles, not necessarily clay minerals, that are less than about 0.002 mm in size.
- pillared clay is used herein to refer to a component of the catalyst composition comprising clay minerals, typically of the of the smectite group and other phylosilicates in addition to sepiolites and palygorskites, that have been ion exchanged with large, typically polynuclear, highly charged metal complex cations.
- ions include, hut are not limited to, Keggin ions which can have charges such as 7+, various polyoxometallates, and other large ions.
- pillaring refers to a simple exchange reaction in which the exchangeable cations of a clay material are replaced with large, highly charged ions, such as Keggin ions.
- pillaring and pillared clays are found in: TJ. Pinnavaia, Science 220 (4595), 365-371 (1983); J.M. Thomas, Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.) Ch. 3, pp. 55-99, Academic Press, Inc., (1972); U.S. Patent No. 4,452,910; U.S. Patent No. 5,376,611; and U.S. Patent No. 4,060,480; each of which is incorporated herein in its entirety.
- any general structure presented also encompasses all conformational isomers, regioisomers, stereoisomers, and the like, that can arise from a particular set of substituents.
- the general structure also encompasses all enantiomers, diastereomers, and other optical isomers whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as the context requires.
- the present invention is further illustrated by the following examples, which are not to be construed in any way as imposing limitations upon the scope thereof.
- MI Melt index
- High load melt index (HLMI, g/10 min) was determined in accordance with ASTM D 1238 condition E at 190 0 C with a 21 ,600 gram weight.
- Polymer density was determined in grams per cubic centimeter (g/cc) on a compression molded sample, cooled at about 15 0 C per hour, and conditioned for about 40 hours at room temperature in accordance with ASTM Dl 505 and ASTM D 1928, procedure C. Molecular weight and molecular weight distributions were obtained using a
- PL-GPC 220 Polymer Labs, UK
- TCB 1,2,4-trichlorobenzene
- BHT 2,6-di-t-butyl-4-methylphenol
- Fluff samples were stabilized with 0.1 wt% BHT dispersed in acetone and then vacuum dried before molding. Samples were compression molded at 184 0 C for a total of three minutes. The samples were allowed to melt at a relatively low pressure for one minute and then subjected to a high molding pressure for an additional two minutes. The molded samples were then quenched in a cold (room temperature) press. Disks having the size 2 mm x 25.4 mm diameter were stamped out of the molded slabs for rheological characterization. The test chamber of the rheometer was blanketed in nitrogen in order to minimize polymer degradation. The rheometer was preheated to the initial temperature of the study.
- the specimens were squeezed between the plates to a 1.6 mm thickness and the excess was trimmed.
- Strains were generally maintained at a single value throughout a frequency sweep but larger strain values were used for low viscosity samples to maintain a measurable torque. Smaller strain values were used for high viscosity samples to avoid overloading the torque transducer and to keep within the linear viscoelastic limits of the sample. The instrument automatically reduces the strain at high frequencies if necessary to keep from overloading the torque transducer.
- Viscosity data were fit with a modified Carreau-Yasuda model [R. Byron Bird, Robert C. Armstrong, and Ole Hassager, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, (John Wiley & Sons, New York, 1987), p 171-172], which is incorporated by reference herein to obtain estimates of the zero shear viscosity, viscous relaxation time, and a breadth parameter, as indicated below.
- SEC-MALS Size exclusion chromatography
- MALS multi-angle light scattering
- the mobile phase 1 ,2,4-trichlorobenzene (TCB)
- TBC 1 ,2,4-trichlorobenzene
- Polyethylene (PE) solutions with concentrations of ⁇ 1.2 mg/mL, depending on samples, were prepared at 150 °C for 4 h before being transferred to the SEC injection vials sitting in a carousel heated at 145 0 C. For polymers of higher molecular weight, longer heating times were necessary in order to obtain true homogeneous solutions.
- the weight average molecular weight (M w ), number average molecular weight (M n ), z- average molecular weight (M z ) and molecular weight distribution (M W /M ⁇ ⁇ ) were computed from these data, and are presented in various Tables.
- the Zimrn-Stockmayer approach was used to determine the amount of LCB in ethylene polymers. Since SEC-MALS measures M and R s at each slice of a chromatogram simultaneously, the branching indices, gM, as a function of M could be determined at each slice directly by determining the ratio of the mean square R s of branched molecules to that of linear ones, at the same M, as shown in equation 1 :
- LCB Ml 1 000* 14*B 3w /Mi (3) where M x is the MW of the z -th slice.
- LCBD LCB distribution across the molecular weight distribution (MWD) was thus established for a full polymer.
- a Quantachrome Autosorb-6 Nitrogen Pore Size Distribution Instrument was used to determine specific surface area ("surface area”) and specific pore volume ("pore volume”). This instrument was acquired from the Quantachrome Corporation, Syosset, N.Y. Preparation of a Fluorided Silica-Alumina Activator-Support
- the silica-alumina used to prepare the fluorided silica-alumina acidic activator-support in this Example was typically Davison silica-alumina obtained from W.R. Grace as Grade MS13-110, containing 13% alumina, having a pore volume of about 1.2 cc/g and a surface area of about 400 m 2 /g.
- This material was fluorided by impregnation to incipient wetness with a solution containing ammonium bifluoride in an amount sufficient to equal 10 wt % of the weight of the silica-alumina. This impregnated material was then dried in a vacuum oven for 8 hours at 100 0 C.
- silica-alumina samples were then calcined as follows. About 10 grams of the alumina were placed in a 1.75-inch quartz tube fitted with a sintered quartz disk at the bottom. While the silica was supported on the disk, dry air was blown up through the disk at the linear rate of about 1.6 to 1.8 standard cubic feet per hour. An electric furnace around the quartz tube was used to increase the temperature of the tube at the rate of about 400°C per hour to a final temperature of about 500 0 C. At this temperature, the silica-alumina was allowed to fluidize for about three hours in the dry air. Afterward, the silica-alumina was collected and stored under dry nitrogen, and was used without exposure to the atmosphere.
- Preparation of a Sulfated Alumina Activator-Support Sulfated alumina was formed by a process wherein alumina was chemically- treated with a sulfate or bisulfate source, typically selected from, but not limited to, sulfuric acid, ammonium sulfate, or ammonium bisulfate.
- a sulfate or bisulfate source typically selected from, but not limited to, sulfuric acid, ammonium sulfate, or ammonium bisulfate.
- a commercial alumina sold as W.R. Grace Alumina A was sulfated by impregnation with an aqueous solution containing about 15-20% (NELj) 2 SO 4 or H 2 SO 4 .
- This sulfated alumina was calcined at 550 0 C in air (240 °C/h ramp rate), with a 3 h hold period at this temperature. Afterward, the alumina was collected and stored under dry nitrogen, and was used without exposure to the atmosphere.
- Reaction products were analyzed by 1 H NMR spectroscopy (300 MHz, CDCI3 referenced against either the residual proton peak at 7.24 ppm for CHCI 3 or TMS at 0 ppm) or 13 C NMR (75 MHz, CDCl 3 , referenced against central line Of CDCl 3 at 77.00 ppm). Reported preparations were not optimized.
- n-BuLi (22.2 mL of 1.6 M in hcxancs, 35.5 rnmol) was added drop wise. After 1 hour, the bath was removed and the mixture was stirred for 48 hours at room temperature. The mixture was added to ZrCl 4 (4.37 g, 18.8 mmol) suspended in pentane (50 mL) while cooling in ice. The slurry was stirred for
- the orange slurry was stirred for 90 hours and allowed to warm to room temperature.
- the resulting slurry was centrifuged and the solid was mixed with dry methylene chloride (120 mL). The mixture was centrifuged and the solution was removed and taken to dryness under vacuum.
- the desired product (9.63 g, 48% yield) was obtained as an orange solid.
- Examples 1-16 in Table 1 illustrate ethylene polymerization runs performed in a one-gallon (3.785 liter) stainless steel autoclave reactor at various temperatures, using two liters of isobutane diluent and an aluminum alkyl cocatalyst and scavenger. No hydrogen or comonorner was added.
- Metallocene solutions (2mg/mL) were typically prepared by dissolving 30 mg of the metallocene in 15 mL of toluene.
- a typical polymerization procedure is as follows. The aluminum alkyl compound, treated solid oxide, and the metallocene solution were added through a charge port, typically in that order, while venting isobutane vapor.
- the charge port was closed and two liters of isobutane were added.
- the contents of the reactor were stirred and heated to the desired run temperature (Table 1).
- Ethylene was fed on demand to maintain the specified pressure for the specified length of the polymerization run.
- the reactor was maintained at the desired run temperature through the run by an automated heating and cooling system.
Abstract
Description
Claims
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KR1020087021468A KR101401856B1 (en) | 2006-02-02 | 2007-02-02 | Polymerization catalysts for producing polymers with low levels of long chain branching |
CA2641255A CA2641255C (en) | 2006-02-02 | 2007-02-02 | Polymerization catalysts for producing polymers with low levels of long chain branching |
JP2008553519A JP5578787B2 (en) | 2006-02-02 | 2007-02-02 | Polymerization catalyst for producing polymers with low levels of long chain branching |
EP17170893.6A EP3239190B1 (en) | 2006-02-02 | 2007-02-02 | Polymerization catalysts for producing polymers with low levels of long chain branching |
BR122017023736-5A BR122017023736B1 (en) | 2006-02-02 | 2007-02-02 | METALLOCENE COMPOUND |
BRPI0706773A BRPI0706773B1 (en) | 2006-02-02 | 2007-02-02 | catalyst composition, production process and olefin polymerization method |
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