WO2010008515A1 - Half-metallocene catalyst compositions and their polymer products - Google Patents

Half-metallocene catalyst compositions and their polymer products Download PDF

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Publication number
WO2010008515A1
WO2010008515A1 PCT/US2009/004047 US2009004047W WO2010008515A1 WO 2010008515 A1 WO2010008515 A1 WO 2010008515A1 US 2009004047 W US2009004047 W US 2009004047W WO 2010008515 A1 WO2010008515 A1 WO 2010008515A1
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Prior art keywords
group
compound
activator
catalyst composition
substituted
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PCT/US2009/004047
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French (fr)
Inventor
Max P. Mcdaniel
Matthew G. Thorn
Elizabeth A. Benham
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Chevron Phillips Chemical Company Lp
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Application filed by Chevron Phillips Chemical Company Lp filed Critical Chevron Phillips Chemical Company Lp
Priority to BRPI0916802-8A priority Critical patent/BRPI0916802B1/en
Priority to MX2011000546A priority patent/MX2011000546A/en
Priority to ES09788901.8T priority patent/ES2529469T3/en
Priority to EP09788901.8A priority patent/EP2310124B1/en
Priority to RU2011105195/04A priority patent/RU2504556C2/en
Priority to AU2009271628A priority patent/AU2009271628B2/en
Priority to CA2730726A priority patent/CA2730726C/en
Publication of WO2010008515A1 publication Critical patent/WO2010008515A1/en
Priority to EG2011010085A priority patent/EG26533A/en

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    • C08F10/02—Ethene
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    • C08F4/00—Polymerisation catalysts
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    • 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
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    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0286—Complexes comprising ligands or other components characterized by their function
    • B01J2531/0294—"Non-innocent" or "non-spectator" ligands, i.e. ligands described as, or evidently, taking part in the catalytic reaction beyond merely stabilizing the central metal as spectator or ancilliary ligands, e.g. by electron transfer to or from the central metal or by intra-/intermolecular chemical reactions, e.g. disulfide coupling, H-abstraction
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
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    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
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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

  • the present invention relates generally to the field of olefin polymerization catalysis, catalyst compositions, methods for the polymerization and copolymerization of olefins, and polyolefins. More specifically, this invention relates to half- metallocene compounds with a heteroatom-containing ligand bound to the transition metal, and catalyst compositions employing such hybrid compounds.
  • Polyolefins such as high density polyethylene (HDPE) homopolymer and linear low density polyethylene (LLDPE) copolymer can be produced using various combinations of catalyst systems and polymerization processes.
  • One method that can be used to produce such polyolefins employs a chromium -based catalyst system.
  • HDPE and LLDPE resins produced using a chromium-based catalyst system generally have a broad molecular weight distribution. For instance, resins having a polydispersity index (PDI) greater than 6 are not unusual. Polyolefin resins produced using a chromium catalyst also can have a low level of long chain branching. This combination of properties is difficult to duplicate with other commercially viable catalyst systems.
  • Metallocene catalysts for example, generally produce polyolefins with a much narrower molecular weight distribution and either have too little, or too much, long chain branching.
  • Ziegler-type catalyst systems produce polyolefin resins which are typically much narrower in molecular weight distribution and have substantially no long chain branching. Polyolefin resins produced using a ballard catalyst are generally too high in molecular weight, too broad in molecular weight distribution, and contain too much long chain branching.
  • the present invention generally relates to new catalyst compositions, methods for preparing catalyst compositions, methods for using the catalyst compositions to polymerize olefins, the polymer resins produced using such catalyst compositions, and articles produced using these polymer resins.
  • the present invention relates to half-metallocene compounds with a heteroatom-containing ligand bound to the transition metal, and catalyst compositions employing such hybrid metallocene compounds.
  • Catalyst compositions of the present invention which contain these hybrid metallocene compounds can be used to produce, for example, ethylene-based homopolymers and copolymers.
  • the present invention discloses novel hybrid metallocene compounds having a metallocene moiety and a heteroatom-containing ligand. According to one aspect of the present invention, these unbridged hybrid metallocene compounds have the formula:
  • M is Zr, Hf, or Ti
  • X 1 and X 2 independently are a halide or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;
  • X 3 is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X 3 independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;
  • R A is an aryl group substituted with alkenyl substituent, any substituents on R A other than the alkenyl substituent independently are a hydrogen atom or a substituted or unsubstituted alkyl, alkenyl, or alkoxy group; and
  • R B and R c independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof.
  • Catalyst compositions containing these unbridged hybrid metallocene compounds are also provided by the present invention.
  • a catalyst composition which comprises a contact product of a hybrid metallocene compound and an activator.
  • This catalyst composition can further comprise an organoaluminum compound.
  • the activator can be an activator-support, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or combinations thereof.
  • a catalyst composition comprising a contact product of a hybrid metallocene compound and an activator.
  • the hybrid metallocene compound is:
  • Ph is an abbreviation for phenyl.
  • This catalyst composition can further comprise an organoaluminum compound, and the activator can be an activator-support, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or combinations thereof.
  • the activator can be an activator-support, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or combinations thereof.
  • the present invention also contemplates a process for polymerizing olefins in the presence of a catalyst composition, the process comprising contacting the catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce a polymer or copolymer.
  • the catalyst composition can comprise a contact product of a hybrid metallocene compound and an activator.
  • organoaluminum compounds can be employed in this process.
  • the activator can be an activator-support, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or a combination thereof.
  • Polymers produced from the polymerization of olefins, resulting in either homopolymers or copolymers, can be used to produce various articles of manufacture.
  • FIG. 1 presents a plot of the molecular weight distributions of the polymers of Example 3 and Example 4.
  • FIG. 2 presents a plot of the molecular weight distributions of the polymers of
  • FIG. 3 presents a dynamic melt viscosity versus frequency plot, measured at 190 0 C, for the polymers of Examples 4-7.
  • FIG. 4 presents a plot of the molecular weight distributions of the polymers of Examples 8-12.
  • polymer means homopolymers comprising ethylene and copolymers of ethylene and a comonomer. "Polymer” also means homopolymers and copolymers of any olefin monomer disclosed herein (e.g., propylene).
  • co-catalyst generally refers to organoaluminum compounds that can constitute one component of a catalyst composition. Additionally, “co-catalyst” can refer to other components of a catalyst composition including, but not limited to, aluminoxanes, organoboron or organoborate compounds, ionizing ionic compounds, as disclosed herein.
  • co-catalyst is used regardless of the actual function of the compound or any chemical mechanism by which the compound may operate. In one aspect of this invention, the term “co-catalyst” is used to distinguish that component of the catalyst composition from the hybrid metallocene compound.
  • fluoroorgano boron compound is used with its ordinary 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. Materials of these types are generally and collectively referred to as "organoboron or organoborate compounds.”
  • contact product describes compositions wherein the components are contacted together in any order, in any manner, and for any length of time.
  • the components can be contacted by blending or mixing.
  • contacting of any component can occur in the presence or absence of any other component of the compositions described herein.
  • Combining additional materials or components can be done by any suitable method.
  • the term “contact product” includes mixtures, blends, solutions, slurries, reaction products, and the like, or combinations thereof. Although “contact product” can include reaction products, it is not required for the respective components to react with one another.
  • precontacted mixture is used 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 compound (or compounds), olefin monomer, and organoaluminum compound (or compounds), before this mixture is contacted with an activator-support and optional additional 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.
  • the precontacted mixture can describe a mixture of metallocene compound, olefin monomer, and activator-support, before this mixture is contacted with an organoaluminum co-catalyst.
  • postcontacted mixture is used 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 compound, olefin monomer, organoaluminum compound, and activator-support (e.g., chemically-treated solid oxide), formed from contacting the precontacted mixture of a portion of these components with any additional components added to make up the postcontacted mixture.
  • the additional component added to make up the postcontacted mixture can be a chemically-treated solid oxide, and, optionally, can include an organoaluminum compound which is the same as 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.
  • hybrid metallocene describes an unbridged half-metallocene compound with a heteroatom-containing ligand bound to the transition metal.
  • the hybrid metallocenes of this invention contain one ⁇ 3 to ⁇ 5 -cyclopentadienyl-type moiety, wherein ⁇ 3 to ⁇ 5 -cycloalkadienyl moieties include cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, and the like, including partially saturated or substituted derivatives or analogs of any of these.
  • substituted derivatives thereof in this invention comprises partially saturated ligands such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, substituted partially saturated indenyl, substituted partially saturated fluorenyl, and the like.
  • the hybrid metallocene is referred to simply as the "catalyst,” in much the same way the term “co-catalyst” is used herein to refer to, for example, an organoaluminum compound. Unless otherwise specified, the following abbreviations are used: Cp for cyclopentadienyl; Ind for indenyl; and Flu for fluorenyl.
  • catalyst composition do not depend upon the actual product resulting from the contact or reaction of the components of the mixtures, the nature of the active catalytic site, or the fate of the co-catalyst, the hybrid metallocene compound, any olefin monomer used to prepare a precontacted mixture, or the activator-support, after combining these components. Therefore, the terms “catalyst composition,” “catalyst mixture,” “catalyst system,” and the like, can include both heterogeneous compositions and homogenous compositions.
  • hydrocarbyl specifies 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.
  • chemically-treated solid oxide "solid oxide activator-support,”
  • treated solid oxide compound indicates a 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 chemically-treated solid oxide compound comprises a calcined contact product of solid oxide compound with electron-withdrawing anion source compound.
  • the chemically-treated solid oxide comprises ionizing, acidic solid oxide compound.
  • support and “activator-support” are not used to imply these components are inert, and such components should not be construed as an inert component of the catalyst composition.
  • the activator-support of the present invention can be a chemically- treated solid oxide.
  • any structure presented also encompasses all conformational isomers, regioisomers, and stereoisomers that may arise from a particular set of substituents.
  • the structure also encompasses all enantiomers, diastereomers, and other optical isomers whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as would be recognized by a skilled artisan.
  • Applicants disclose or claim a range of any type Applicants' intent is to disclose or claim individually each possible number that such a range could reasonably encompass, including end points of the range as well as any sub-ranges and combinations of sub-ranges encompassed therein.
  • Applicants disclose or claim a chemical moiety having a certain number of carbon atoms Applicants' intent is to disclose or claim individually every possible number that such a range could encompass, consistent with the disclosure herein.
  • a moiety is an aliphatic group having from 1 to 20 carbon atoms, as used herein, refers to a moiety that can be selected independently from an aliphatic group having 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms, as well as any range between these two numbers (for example, an aliphatic group having 3 to 6 carbon atoms), and also including any combination of ranges between these two numbers (for example, an aliphatic group having 2 to 4 carbon atoms and an aliphatic group having 8 to 12 carbon atoms).
  • the weight ratio of organoaluminum to activator-support in a catalyst composition provided in one aspect of this invention.
  • the weight ratio of organoaluminum compound to activator-support is in a range from about 10:1 to about 1:1000
  • Applicants intend to recite that the weight ratio can be selected from about 10:1, about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1:1, about 1:5, about 1:10, about 1:25, about 1:50, about 1:75, about 1:100, about 1:150, about 1:200, about 1:250, about 1:300, about 1:350, about 1:400, about 1:450, about 1:500, about 1:550, about 1:600, about 1:650, about 1:700, about 1:750, about 1:800, about 1:850, about 1:900, about 1:950, or about 1:1000.
  • the weight ratio can be within any range from about 10:1 to about 1:1000 (for example, the weight ratio is in a range from about 3:1 to about 1:100), and this also includes any combination of ranges between about 10:1 to about 1:1000. Likewise, all other ranges disclosed herein should be interpreted in a manner similar to these two examples.
  • the present invention is directed generally to new catalyst compositions, methods for preparing catalyst compositions, methods for using the catalyst compositions to polymerize olefins, the polymer resins produced using such catalyst compositions, and articles produced using these polymer resins.
  • the present invention relates to half-metallocene compounds with a heteroatom- containing ligand bound to the transition metal, and catalyst compositions employing such hybrid metallocene compounds.
  • the present invention discloses novel hybrid metallocene compounds having a metallocene moiety and a heteroatom-containing ligand, and methods of making these compounds. For convenience, these compounds will be referred to herein as hybrid metallocene compounds.
  • the unbridged hybrid metallocene compounds have the formula:
  • M is Zr, Hf, or Ti
  • X 1 and X 2 independently are a halide or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;
  • X 3 is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X 3 independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;
  • R A is an aryl group substituted with an alkenyl substituent, any substituents on R A other than the alkenyl substituent independently are a hydrogen atom or a substituted or unsubstituted alkyl, alkenyl, or alkoxy group; and
  • R B and R c independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof.
  • Formula (I) above is not designed to show stereochemistry or isomeric positioning of the different moieties (e.g., this formula is not intended to display cis or trans isomers, or R or S diastereoisomers), although such compounds are contemplated and encompassed by this formula.
  • the metal in formula (I), M is selected from Zr, Hf, or Ti. In one aspect of the present invention, M is either Zr or Ti.
  • X 1 and X 2 independently can be a halide, such as a fluorine, chlorine, bromine, or iodine atom.
  • an aliphatic group includes linear or branched alkyl and alkenyl groups. Generally, the aliphatic group contains from 1 to 20 carbon atoms. Unless otherwise specified, alkyl and alkenyl groups described herein are intended to include all structural isomers, linear or branched, of a given moiety; for example, all enantiomers and all diastereomers are included within this definition.
  • propyl is meant to include n-propyl and iso-propyl
  • butyl is meant to include n-butyl, iso- butyl, t-butyl, sec-butyl, and so forth.
  • octyl isomers include 2-ethyl hexyl and neooctyl.
  • suitable alkyl groups which can be employed in the present invention include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl, and the like.
  • alkenyl groups within the scope of the present invention include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, and the like.
  • Aromatic groups and combinations with aliphatic groups include aryl and arylalkyl groups, and these include, but are not limited to, phenyl, alkyl-substituted phenyl, naphthyl, alkyl-substituted naphthyl, phenyl-substituted alkyl, naphthyl- substituted alkyl, and the like. Generally, such groups and combinations of groups contain less than 20 carbon atoms.
  • non-limiting examples of such moieties that can be used in the present invention include phenyl, tolyl, benzyl, dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl, propyl-2- phenylethyl, and the like.
  • Cyclic groups include cycloalkyl and cycloalkenyl moieties and such moieties can include, but are not limited to, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, and the like.
  • One example of a combination including a cyclic group is a cyclohexylphenyl group.
  • any substituted aromatic or cyclic moiety used herein is meant to include all regioisomers; for example, the term tolyl is meant to include any possible substituent position, that is, ortho, meta, or para.
  • X 1 and X 2 independently are a substituted or unsubstituted aliphatic group having from 1 to 20 carbon atoms.
  • X 1 and X 2 independently are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl.
  • either X 1 or X 2 , or both are trimethylsilylmethyl.
  • X 1 and X 2 independently are ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl.
  • X 1 and X 2 independently are a substituted or unsubstituted aromatic group, for example, having up to 20 carbon atoms, in another aspect of the present invention.
  • X 1 and X 2 are both chlorine atoms.
  • X 1 and X 2 independently can be selected from phenyl, naphthyl, tolyl, benzyl, dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl, propyl-2-phenylethyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, or cyclohexylphenyl in other aspects of this invention.
  • X 1 and X independently are methyl, phenyl, benzyl, or a halide.
  • X 1 and X 2 independently can be methyl, phenyl, benzyl, or a chlorine atom in another aspect of the present invention.
  • X is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group.
  • X 3 is a substituted or unsubstituted cyclopentadienyl group.
  • X 3 is a substituted or unsubstituted indenyl group.
  • X can be an unsubstituted cyclopentadienyl, indenyl, or fluorenyl group.
  • X 3 can have one or more substituents. Any substituents on X 3 independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof. Hydrogen is included, therefore the notion of a substituted indenyl and substituted fluorenyl includes partially saturated indenyls and fluorenyls including, but not limited to, tetrahydroindenyls, tetrahydrofluorenyls, and octahydrofluorenyls.
  • Exemplary aliphatics which can be employed in the present invention include alkyls and alkenyls, examples of which include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl, and the like.
  • Illustrative aromatic groups and combinations with aliphatic groups, as discussed above, can include phenyl, tolyl, benzyl, and the like. Cyclic substituents are also contemplated herein, and non-limiting examples were also provided above, including moieties such as cyclopentyl and cyclohexyl.
  • each substituent on X independently is a hydrogen atom, or a methyl, ethyl, propyl, n-butyl, t-butyl, or hexyl group.
  • substituents on X 3 are selected independently from a hydrogen atom, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl.
  • R A is an aryl group substituted with an alkenyl substituent.
  • suitable alkenyl group substituents include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, and the like.
  • the alkenyl substituent on R A is an ethenyl, a propenyl, or a butenyl.
  • R A contains no further substitutions.
  • R A can be further substituted with a hydrogen atom or a substituted or unsubstituted alkyl, alkenyl, or alkoxy group.
  • suitable alkyls that can be substituents on R A include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl, and the like.
  • R A can have additional alkenyl substituents selected from, for example, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, and a decenyl group, and the like.
  • Alkoxy substituents generally have between 1 and 20 carbons atoms and include, but are not limited to, methoxy, ethoxy, propoxy, or butoxy, and the like.
  • each substituent on R A other than the alkenyl substituent independently is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group.
  • X 4 can be -O-R A .
  • Non-limiting examples of X 4 in this aspect of the invention include the following moieties:
  • R B and R c independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof.
  • Exemplary aliphatics which can be employed as R B and/or R c include the alkyl and alkenyl selections discussed above.
  • Illustrate aromatic groups and combinations with aliphatic groups can include phenyl, benzyl, tolyl, xylyl, and the like.
  • cyclic substituents can also be employed, and as discussed above, non-limiting examples include cyclopentyl, cyclohexyl, and the like.
  • a non-limiting example of X 4 in this aspect of the invention is the following moiety:
  • substituted aliphatic, aromatic, or cyclic groups are disclosed, as well as substituted alkyl, alkenyl, or alkoxy groups.
  • substituted alkyl, alkenyl, or alkoxy groups are intended to include substituted analogs with substitutions at any position on these groups that conform to the normal rules of chemical valence.
  • groups substituted with one or more than one substituent are contemplated.
  • Such substituents when present, are independently selected from an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, a germanium group, a tin group, a lead group, a boron group, an aluminum group, an inorganic group, an organometallic group, or a substituted derivative thereof, any of which having from 1 to 20 carbon atoms; a halide; or hydrogen; as long as these groups do not terminate the activity of the catalyst composition.
  • substituent groups include, but are not limited to, the following groups.
  • Examples of halide substituents, in each occurrence, include fluoride, chloride, bromide, and iodide.
  • oxygen groups are oxygen-containing groups, examples of which include, but are not limited to, alkoxy or aryloxy groups (-OR X ), -OSiR 5 S, - OPR X 2 , -OA1R X 2 , and the like, including substituted derivatives thereof, wherein R x in each occurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to 20 carbon atoms.
  • alkoxy or aryloxy groups (-OR X ) 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 X and the like, including substituted derivatives thereof, wherein R x in each occurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to 20 carbon atoms.
  • nitrogen groups are nitrogen-containing groups, which include, but are not limited to, -NR X 2 and the like, including substituted derivatives thereof, wherein R x in each occurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to 20 carbon atoms.
  • phosphorus groups are phosphorus-containing groups, which include, but are not limited to, -PR X 2 , -P(OR X ) 2 , and the like, including substituted derivatives thereof, wherein R x in each occurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to 20 carbon atoms.
  • arsenic groups are arsenic-containing groups, which include, but are not limited to, -AsR 2 , -As(0R x ) 2 , and the like, including substituted derivatives thereof, wherein R x in each occurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to 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 20 carbon atoms, aralkyl groups with 1 to 20 carbon atoms, -
  • silicon groups are silicon-containing groups, which include, but are not limited to, silyl groups such as alkylsilyl groups, arylsilyl groups, arylalkylsilyl groups, siloxy groups, and the like, which in each occurrence have from
  • germanium groups are germanium-containing groups, which include, but are not limited to, germyl groups such as alkylgermyl groups, arylgermyl groups, arylalkylgermyl groups, germyloxy groups, and the like, which in each occurrence have from 1 to 20 carbon atoms.
  • tin groups are tin-containing groups, which include, but are not limited to, stannyl groups such as alkylstannyl groups, arylstannyl groups, arylalkylstannyl groups, stannoxy (or "stannyloxy”) groups, and the like, which in each occurrence have from 1 to 20 carbon atoms.
  • tin groups include, but are not limited to, stannoxy groups.
  • lead groups are lead-containing groups, which include, but are not limited to, alkyllead groups, aryllead groups, arylalkyllead groups, and the like, which in each occurrence, have from 1 to 20 carbon atoms.
  • boron groups are boron-containing groups, which include, but are not limited to, -BR X 2 , -BX 2 , -BR X X, and the like, wherein X is a monoanionic group such as hydride, alkoxide, alkyl thiolate, and the like, and wherein R x in each occurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to 20 carbon atoms.
  • aluminum groups are aluminum-containing groups, which include, but are not limited to, -A1R X , -AlX 2 , -A1R X X, wherein X is a monoanionic group such as hydride, alkoxide, alkyl thiolate, and the like, and wherein R x in each occurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to 20 carbon atoms.
  • inorganic groups that may be used as substituents, in each occurrence include, but are not limited to, -OAlX 2 , -OSiX 3 , -OPX 2 , -SX, -AsX 2 , -PX 2 , and the like, wherein X is a monoanionic group such as hydride, amide, alkoxide, alkyl thiolate, and the like, and wherein any alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl group or substituent on these ligands has from 1 to 20 carbon atoms.
  • organometallic groups that may be used as substituents, in each occurrence, include, but are not limited to, organoboron groups, organoaluminum groups, organogallium groups, organosilicon groups, organogermanium groups, organotin groups, organolead groups, organo-transition metal groups, and the like, having from 1 to 20 carbon atoms.
  • M is Zr or Ti in formula (I), and both X 1 and X 2 are methyl groups, phenyl groups, or benzyl groups.
  • X 3 is an unsubstituted cyclopentadienyl or indenyl group
  • X 4 is -O-R A .
  • R A is an aryl group substituted with one alkenyl substituent, such as propenyl or butenyl. Further, R A can be additionally substituted with, for example, a methyl or methoxy group.
  • M is Zr or Ti in formula (I), and both X 1 and X 2 are methyl groups, phenyl groups, or benzyl groups.
  • X 3 is an unsubstituted cyclopentadienyl or indenyl group
  • R B and R c independently are a phenyl group, a benzyl group, a tolyl group, or a xylyl group.
  • hybrid metallocene compounds of the present invention include (Ind)(X )Zr(CH 2 Ph) 2 , wherein Ind is an abbreviation for indenyl, Ph is an abbreviation for phenyl, and X 4 is one of the following moieties:
  • One such method for synthesizing a hybrid metallocene compound of the present invention involves first the synthesis of, for example, half- metallocene compounds CpZr(CH 2 Ph) 3 or IndZr(CH 2 Ph) 3 .
  • These half-metallocene compounds can be synthesized in accordance with the procedures described in Scholz et al., "Benzyl compounds of electron-deficient transition metals.
  • the molecular structure of Cp 2 Ti(CH 2 Ph) 2 and CpZr(CH 2 Ph) 3 ,” is disclosed in Journal of Organometallic Chemistry (1993), 443(1), 93-9.
  • This procedure employs initial reactant materials which are commercially available, for instance, benzylmagnesium chloride (PhCH 2 MgCl), cyclopentadienylzirconium trichloride (CpZrCl 3 ), and indenylzirconium trichloride (IndZrCl 3 ).
  • initial reactant materials which are commercially available, for instance, benzylmagnesium chloride (PhCH 2 MgCl), cyclopentadienylzirconium trichloride (CpZrCl 3 ), and indenylzirconium trichloride (IndZrCl 3 ).
  • Synthesis of a hybrid metallocene compound of the present invention from CpZr(CH 2 Ph) 3 or IndZr(CH 2 Ph) 3 can be accomplished using a representative procedure described in Thorn et al., "Synthesis, structure and molecular dynamics of ⁇ 2 -iminoacyl compounds [Cp(ArO)Zr( ⁇ ⁇ Bu 1 NCCH 2 Ph)(CH 2 Ph)] and
  • the present invention also relates to catalyst compositions employing these half-metallocene compounds having a heteroatom-containing ligand.
  • a catalyst composition which comprises a contact product of a hybrid metallocene compound and an activator.
  • This catalyst composition can further comprise an organoaluminum compound.
  • the activator can be an activator-support, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or a combination thereof.
  • catalyst compositions can be used to produce polyolefins, both homopolymers and copolymers, for a variety of end-use applications.
  • the hybrid metallocene compound in these catalyst compositions has the formula:
  • M is Zr, Hf, or Ti;
  • X 1 and X independently are a halide or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;
  • X 3 is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X 3 independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;
  • R A is an aryl group substituted with an alkenyl substituent, any substituents on R A other than the alkenyl substituent independently are a hydrogen atom or a substituted or unsubstituted alkyl, alkenyl, or alkoxy group; and
  • R B and R c independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof.
  • the catalyst compositions disclosed herein can contain additional bridged or unbridged metallocene compounds as well as more than one activator. Additionally, more than one organoaluminum compound is also contemplated.
  • a catalyst composition which comprises a contact product of a hybrid metallocene compound, an activator- support, and an organoaluminum compound, wherein this catalyst composition is substantially free of aluminoxanes, organoboron or organoborate compounds, and ionizing ionic compounds.
  • the catalyst composition has catalyst activity, to be discussed below, in the absence of these additional materials.
  • these compounds can be employed as activators.
  • a catalyst composition comprising a hybrid metallocene compound and an activator is contemplated, and in this aspect, the activator is an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof. More than one activator or co-catalyst can be present in the catalyst composition.
  • a catalyst composition which comprises a contact product of a hybrid metallocene compound and an activator, wherein the hybrid metallocene compound is:
  • this catalyst composition can further comprise an organoaluminum compound.
  • the present invention encompasses various catalyst compositions containing an activator, which can be an activator-support.
  • the activator-support comprises a chemically-treated solid oxide.
  • 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.
  • the activator-support contains Br ⁇ nsted acid groups.
  • the chemically-treated solid oxide exhibits enhanced acidity as compared to the corresponding untreated solid oxide compound.
  • the chemically-treated solid oxide also functions as a catalyst activator as compared to the corresponding untreated solid oxide. While the chemically-treated solid oxide activates the metallocene in the absence of co-catalysts, it is not necessary to eliminate co-catalysts from the catalyst composition.
  • the activation function of the activator-support is evident in the enhanced activity of catalyst composition as a whole, as compared to a catalyst composition containing the corresponding untreated solid oxide.
  • the chemically-treated solid oxide can function as an activator, even in the absence of an organoaluminum compound, aluminoxanes, organoboron compounds, ionizing ionic compounds, and the like.
  • the chemically-treated solid oxide can comprise solid oxide treated with electron-withdrawing anion. While not intending to be bound by the following statement, it is believed that treatment of the solid oxide with an electron-withdrawing component augments or enhances the acidity of the oxide.
  • the activator- support exhibits Lewis or Br ⁇ nsted acidity that is typically greater than the Lewis or Br ⁇ nsted acid strength of the untreated solid oxide, or the activator-support has a greater number of acid sites than the untreated solid oxide, or both.
  • Chemically-treated solid oxides of this invention are formed generally from an inorganic solid oxide that exhibits Lewis acidic or Br ⁇ nsted acidic behavior and has a relatively high porosity.
  • the solid oxide is chemically-treated with an electron- withdrawing component, typically an electron-withdrawing anion, to form an activator-support.
  • the solid oxide used to prepare the chemically-treated solid oxide has a pore volume greater than 0.1 cc/g. According to another aspect of the present invention, the solid oxide has a pore volume greater than 0.5 cc/g. According to yet another aspect of the present invention, the solid oxide has a pore volume greater than 1.0 cc/g.
  • the solid oxide has a surface area of from 100 to 1000 m 2 /g. In yet another aspect, the solid oxide has a surface area of from 200 to 800 m 2 /g. In still another aspect of the present invention, the solid oxide has a surface area of from 250 to 600 m 2 /g.
  • the chemically-treated solid oxide can comprise a solid inorganic oxide comprising oxygen and an element selected from Group 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, or 15 of the periodic table, or comprising oxygen and an element selected from the lanthanide or actinide elements.
  • a solid inorganic oxide comprising oxygen and an element selected from Group 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, or 15 of the periodic table, or comprising oxygen and an element selected from the lanthanide or actinide elements.
  • the inorganic oxide can comprise oxygen and an 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 to form the chemically-treated solid oxide include, but are not limited to, AI 2 O3, B 2 O 3 , BeO, 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.
  • the solid oxide can be silica, alumina, silica-alumina, aluminum phosphate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof.
  • the solid oxide of this invention encompasses oxide materials such as alumina, "mixed oxide” compounds thereof such as silica-alumina, and combinations and mixtures thereof.
  • the mixed oxide compounds such as silica-alumina can be single or multiple chemical phases with more than one metal combined with oxygen to form a solid oxide compound.
  • Examples of mixed oxides that can be used in the activator-support of the present invention include, but are not limited to, silica- alumina, silica-titania, silica-zirconia, zeolites, various clay minerals, alumina-titania, alumina-zirconia, zinc-aluminate, and the like.
  • the electron-withdrawing component used to treat the solid oxide can be any component that increases the Lewis or Br ⁇ nsted acidity of the solid oxide upon treatment (as compared to the solid oxide that is not treated with an electron- withdrawing anion).
  • the electron- withdrawing component is an electron-withdrawing anion derived from a salt, an acid, or other compound, such as a volatile organic compound, that serves as a source or precursor for that anion.
  • electron-withdrawing anions include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, trifluoroacetate, triflate, and the like, including mixtures and combinations thereof.
  • ionic or non-ionic compounds that serve as sources for these electron-withdrawing anions also can be employed in the present invention.
  • the chemically-treated solid oxide used in the catalyst compositions of the present can be fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, and the like, or combinations thereof.
  • the counterion or cation of that salt can be selected from 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.
  • 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.
  • combinations of one or more different electron-withdrawing anions 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 in any order that affords the desired chemically-treated solid oxide acidity.
  • one aspect of this invention is employing two or more electron-withdrawing anion source compounds in two or more separate contacting steps.
  • a chemically-treated solid oxide is prepared is 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 calcined and then contacted with a second electron-withdrawing anion source compound to form a second mixture; the second mixture is then calcined to form a treated solid oxide compound.
  • the first and second electron-withdrawing anion source compounds can be either the same or different compounds.
  • the chemically-treated solid oxide 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 a metal source, including metal salts, metal ions, or other metal-containing compounds.
  • a metal source including metal salts, metal ions, or other metal-containing compounds.
  • the metal or metal ion include zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, and the like, or combinations thereof.
  • Examples of chemically-treated solid oxides that contain a metal or metal ion include, but are not limited to, zinc-impregnated chlorided alumina, titanium-impregnated fluorided alumina, zinc-impregnated fluorided alumina, zinc-impregnated chlorided silica- alumina, zinc-impregnated fluorided silica-alumina, zinc-impregnated sulfated alumina, chlorided zinc aluminate, fluorided zinc aluminate, sulfated zinc aluminate, and the like, or any combination thereof.
  • any method capable 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, can include, but is not limited to, gelling, co- gelling, impregnation of one compound onto another, and the like.
  • the metal-containing compound is added to or impregnated into 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, titanium, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, and the like, or combinations of these metals.
  • 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.
  • 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 chemically-treated solid oxide can comprise the contact product of a solid oxide compound and an electron-withdrawing anion source. It is not required that the solid oxide compound be calcined prior to contacting the electron-withdrawing anion source.
  • the contact product typically is 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 solid oxide material is chemically-treated by contacting it with an electron-withdrawing component, typically an electron-withdrawing anion source. Further, the solid oxide material optionally is chemically treated with a metal ion, and then calcined to form a metal- containing or metal-impregnated chemically-treated solid oxide. According to another aspect of the present invention, the solid oxide material and electron- withdrawing anion source are contacted and calcined simultaneously.
  • an electron-withdrawing component typically an electron-withdrawing anion source.
  • the solid oxide material optionally is chemically treated with a metal ion, and then calcined to form a metal- containing or metal-impregnated chemically-treated solid oxide.
  • the solid oxide material and electron- withdrawing anion source are contacted and calcined simultaneously.
  • the method by which the oxide is contacted with the electron-withdrawing component can include, but is not limited to, gelling, co-gelling, impregnation of one compound onto another, and the like.
  • the contacted mixture of the solid oxide, electron-withdrawing anion, and optional metal ion is calcined.
  • the solid oxide activator-support i.e., chemically-treated solid oxide
  • the solid oxide activator-support thus can be produced by a process comprising: 1) contacting a solid oxide compound with an electron-withdrawing anion source compound to form a first mixture; and
  • the solid oxide activator- support (chemically-treated solid oxide) is produced by a process comprising: 1) contacting a solid oxide compound with a first electron- withdrawing anion source compound to form a first mixture;
  • the chemically- treated solid oxide is produced or formed by contacting the solid oxide with the electron-withdrawing anion source compound, where the solid oxide compound is calcined before, during, or after contacting the electron-withdrawing anion source, and where there is a substantial absence of aluminoxanes, organoboron or organoborate compounds, and ionizing ionic compounds.
  • Calcining of the treated solid oxide generally is conducted in an ambient atmosphere, typically in a dry ambient atmosphere, at a temperature from 200 0 C to 900 0 C, and for a time from 1 minute to 100 hours. Calcining can be conducted at a temperature of from 300 0 C to 800 0 C, or alternatively, at a temperature from 400 0 C to 700 0 C. Calcining can be conducted for 1 hour to 50 hours, or for 3 hours to 20 hours. Thus, for example, calcining can be carried out for 1 to 10 hours at a temperature of from 350 0 C to 550 0 C. Any suitable ambient atmosphere can be employed during calcining. Generally, calcining is conducted in an oxidizing atmosphere, such as air.
  • the solid oxide material is treated with a source of halide ion, sulfate ion, or a combination of anions, optionally treated with a metal ion, and then calcined to provide the chemically-treated solid oxide 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.
  • a source of sulfate termed a "sulfating agent”
  • chloride ion termed a "chloriding agent”
  • fluoride ion termed a "fluoriding agent”
  • 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; 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 of the above.
  • any of these activator-supports optionally can be treated with a metal ion.
  • the chemically-treated solid oxide can comprise a fluorided solid oxide in the form of a particulate solid.
  • the fluorided solid oxide can be formed by contacting a solid oxide with a fluoriding agent.
  • the 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 not limited to, the one to three carbon alcohols because of their volatility and low surface tension.
  • fluoriding agents include, but are not limited to, hydrofluoric acid (HF), ammonium fluoride (NH 4 F), ammonium bifluoride (NH 4 HF 2 ), ammonium tetrafluoroborate (NH 4 BF 4 ), ammonium silicofluoride (hexafluorosilicate) ((NH 4 ⁇ SiF 6 ), ammonium hexafluorophosphate (NH 4 PF 6 ), analogs thereof, and combinations thereof.
  • HF hydrofluoric acid
  • NH 4 F ammonium fluoride
  • NH 4 HF 2 ammonium bifluoride
  • NH 4 HF 2 ammonium tetrafluoroborate
  • NH 4 BF 4 ammonium silicofluoride
  • ammonium bifluoride NH 4 HF 2 can be used as the fluoriding agent, due to its ease of use and availability.
  • the solid oxide is 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, an the like, and combinations thereof.
  • Gaseous hydrogen fluoride or fluorine itself also can be used with the solid oxide if fluorided while calcining.
  • the chemically-treated solid oxide comprises a chlorided solid oxide in the form of a particulate solid.
  • the chlorided solid oxide is formed by contacting a solid oxide 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.
  • volatile organic chloriding agents can be used.
  • suitable volatile organic chloriding agents include, but are not limited to, certain freons, perchlorobenzene, chloromethane, dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, and the like, or any combination thereof.
  • Gaseous hydrogen chloride or chlorine itself also can 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 while calcination.
  • the amount of fluoride or chloride ion present before calcining the solid oxide generally is from 2 to 50% by weight, where the weight percent is based on the weight of the solid oxide, for example, silica-alumina, before calcining. According to another aspect of this invention, the amount of fluoride or chloride ion present before calcining the solid oxide is from 3 to 25% by weight, and according to another aspect of this invention, from 4 to 20% by weight.
  • the halided oxide can be dried by any suitable method 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 typically has a pore volume greater than 0.5 cc/g. According to one aspect of the present invention, the pore volume is greater than 0.8 cc/g, and according to another aspect of the present invention, greater than 1.0 cc/g. Further, the silica-alumina generally has a surface area greater than 100 m 2 /g. According to another aspect of this invention, the surface area is greater than 250 m /g. Yet, in another aspect, the surface area is greater than 350 m /g.
  • the silica-alumina utilized in the present invention typically has an alumina content from 5 to 95% by weight.
  • the alumina content of the silica-alumina is from 5 to 50%, or from 8% to 30%, alumina by weight.
  • high alumina content silica-alumina compounds can be employed, in which the alumina content of these silica-alumina compounds typically ranges from 60% to 90%, or from 65% to 80%, alumina by weight.
  • the solid oxide component comprises alumina without silica, and according to another aspect of this invention, the solid oxide component comprises silica without alumina.
  • 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 treated further 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, for example, sulfuric acid or a sulfate salt such as ammonium sulfate.
  • This process is generally 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 from 0.5 parts by weight to 100 parts by weight sulfate ion to 100 parts by weight solid oxide.
  • the amount of sulfate ion present before calcining is from 1 part by weight to 50 parts by weight sulfate ion to 100 parts by weight solid oxide, and according to still another aspect of this invention, from 5 parts by weight to 30 parts by weight sulfate ion to 100 parts by weight solid oxide. These weight ratios are based on the weight of the solid oxide before calcining.
  • the sulfated oxide can be dried by any suitable method 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 activator-support used in preparing the catalyst compositions of this invention comprises an ion- exchangeable activator-support, including but not limited to silicate and aluminosilicate compounds or minerals, either with layered or non-layered structures, and combinations thereof.
  • ion-exchangeable, layered aluminosilicates such as pillared clays are used as activator-supports.
  • the acidic activator-support comprises an ion-exchangeable activator-support, it can optionally be treated with anelectron-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 comprises 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 unbridged metallocene component.
  • 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 polynuclear, 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 activator-support comprises a pillared clay.
  • pillared clay 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 montmorillonites (bentonites), nontronites, hectorites, or laponites; halloysites; vermiculites; micas; fluoromicas; chlorites; mixed-layer clays; the fibrous clays including but not limited to sepiolites, attapulgites, and palygorskites; a serpentine clay; illite; laponite; saponite; and any combination thereof.
  • allophanes smectites, both dioctahedral (Al) and tri-octa
  • the pillared clay activator-support comprises bentonite or montmorillonite.
  • the principal component of bentonite is montmorillonite.
  • the pillared clay can be pretreated if desired.
  • a pillared bentonite is pretreated by drying at 300 0 C under an inert atmosphere, typically dry nitrogen, for 3 hours, before being added to the polymerization reactor.
  • an exemplary pretreatment is described herein, it should be understood that the preheating can be carried out at many other temperatures and times, including any combination of temperature and time steps, all of which are encompassed by this invention.
  • the activator-support used to prepare the catalyst compositions of the present invention can be combined with other inorganic support materials, including, but not limited to, zeolites, inorganic oxides, phosphated inorganic oxides, and the like.
  • typical support materials that are used include, but are not limited to, silica, silica-alumina, alumina, titania, zirconia, magnesia, boria, thoria, aluminophosphate, aluminum phosphate, silica-titania, coprecipitated silica/titania, mixtures thereof, or any combination thereof.
  • one or more of the hybrid metallocene compounds can be precontacted with an olefin monomer and an organoaluminum compound for a first period of time prior to contacting this mixture with the activator-support.
  • the composition further comprising the activator-support is termed a "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.
  • one or more of the hybrid metallocene compounds can be precontacted with an olefin monomer and an activator-support for a first period of time prior to contacting this mixture with the organoaluminum compound.
  • the composition further comprising the organoaluminum is termed a "postcontacted" mixture.
  • the postcontacted mixture can be allowed to remain in further contact for a second period of time prior to being introduced into the polymerization reactor.
  • organoaluminum compounds that can be used with the present invention include, but are not limited to, compounds having the formula:
  • R 2 is an aliphatic group having from 2 to 6 carbon atoms.
  • R can be ethyl, propyl, butyl, hexyl, or isobutyl.
  • Other organoaluminum compounds which can be used in accordance with the present invention include, but are not limited to, compounds having the formula:
  • X 5 is a hydrocarbyl
  • X 6 is an alkoxide or an aryloxide, a halide, or a hydride
  • m is from 1 to 3, inclusive.
  • X is a hydrocarbyl having from 1 to 20 carbon atoms.
  • X 5 is an alkyl having from 1 to 10 carbon atoms.
  • X 5 can be ethyl, propyl, n-butyl, sec-butyl, isobutyl, or hexyl, and the like, in yet another aspect of the present invention.
  • X is an alkoxide or an aryloxide, any one of which has from 1 to 20 carbon atoms, a halide, or a hydride.
  • X 6 is selected independently from fluorine or chlorine.
  • X is chlorine.
  • m is a number from 1 to 3, inclusive, and typically, m is 3.
  • the value of m is not restricted to be an integer; therefore, this formula includes sesquihalide compounds or other organoaluminum cluster compounds.
  • organoaluminum compounds suitable for use in accordance with the present invention include, but are not limited to, trialkylaluminum compounds, dialkylaluminum halide compounds, dialkylaluminum alkoxide compounds, dialkylaluminum hydride compounds, and combinations thereof.
  • suitable organoaluminum compounds include trimethylaluminum (TMA), triethylaluminum (TEA), tripropylaluminum, diethylaluminum ethoxide, tributylaluminum, diisobutylaluminum hydride, triisobutylaluminum, diethylaluminum chloride, and the like, or combinations thereof.
  • the present invention contemplates a method of precontacting an unbridged hybrid metallocene compound with an organoaluminum compound and an olefin monomer to form a precontacted mixture, prior to contacting this precontacted mixture with the activator-support to form a catalyst composition.
  • 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- support.
  • the entire organoaluminum compound can be used to prepare the catalyst composition in either the precontacting or postcontacting step. Alternatively, all the catalyst components are contacted in a single step.
  • organoaluminum compound can be used in either the precontacting or the postcontacting step.
  • 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 or more than one organoaluminum compound is used.
  • the present invention provides a catalyst composition which contains an activator, and in some aspects of the invention, the activator comprises an aluminoxane compound.
  • aluminoxane refers to aluminoxane compounds, compositions, mixtures, or discrete species, regardless of how such aluminoxanes are prepared, formed or otherwise provided.
  • a catalyst composition comprising an aluminoxane compound can be prepared in which aluminoxane is provided as the poly(hydrocarbyl aluminum oxide), or in which aluminoxane is provided as the combination of an aluminum alkyl compound and a source of active protons such as water.
  • Aluminoxanes are also referred to as poly(hydrocarbyl aluminum oxides) or organoaluminoxanes.
  • the other catalyst components typically are contacted with the aluminoxane in a saturated hydrocarbon compound solvent, though any solvent that is substantially inert to the reactants, intermediates, and products of the activation step can be used.
  • the catalyst composition formed in this manner is collected by any suitable method, for example, by filtration. Alternatively, the catalyst composition is introduced into the polymerization reactor without being isolated.
  • aluminoxane compound of this invention can be an oligomeric aluminum compound comprising linear structures, cyclic structures, or cage structures, or 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 p is an integer from 3 to 20, are encompassed by this invention.
  • the AlRO moiety shown here also constitutes the repeating unit in a linear aluminoxane.
  • linear aluminoxanes having the formula:
  • R is a linear or branched alkyl having from 1 to 10 carbon atoms, and q is an integer from 1 to 50, are also encompassed by this invention.
  • aluminoxanes can have cage structures of the formula R' 5r+ ⁇ R b r .
  • R' is a terminal linear or branched alkyl group having from 1 to 10 carbon atoms
  • R b is a bridging linear or branched alkyl group having from 1 to 10 carbon atoms
  • r is 3 or 4
  • ⁇ is equal to « A I(3) - «o(2) + «O(4) > wherein « A i(3) is the number of three coordinate aluminum atoms, /io( 2 ) is the number of two coordinate oxygen atoms, and «o( 4 ) is the number of 4 coordinate oxygen atoms.
  • aluminoxanes which can be employed in the catalyst compositions of the present invention are represented generally by formulas such as (R-A1-O) P , R(R- Al-O) q AlR 2 , and the like.
  • the R group is typically a linear or branched Ci-C 6 alkyl, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl.
  • aluminoxane compounds that can be used in accordance with the present invention include, but are not limited to, methylaluminoxane, ethylaluminoxane, n- propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, t-butyl- aluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, 1 -pentylaluminoxane, 2- pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, and the like, or any combination thereof.
  • Methylaluminoxane, ethylaluminoxane, and iso-butylaluminoxane are prepared from trimethylaluminum, triethylaluminum, or triisobutylaluminum, respectively, and sometimes are referred to as poly(methyl aluminum oxide), poly(ethyl aluminum oxide), and poly(isobutyl aluminum oxide), respectively. It is also within the scope of the invention to use an aluminoxane in combination with a trialkylaluminum, such as that disclosed in U.S. Patent No. 4,794,096.
  • the present invention contemplates many values of p and q in the aluminoxane formulas (R-Al-O) p and R(R-Al-O) q AlR 2 , respectively.
  • p and q are at least 3.
  • the value of p and q can vary within a single sample of aluminoxane, and such combinations of organoaluminoxanes are contemplated herein.
  • the molar ratio of the total moles of aluminum in the aluminoxane (or aluminoxanes) to the total moles of hybrid metallocene compound (or compounds) in the composition is generally between 1 : 10 and 100,000: 1. In another aspect, the molar ratio is in a range from 5: 1 to 15,000: 1.
  • aluminoxane can be added to a polymerization zone in ranges from 0.01 mg/L to 1000 mg/L, from 0.1 mg/L to 100 mg/L, or from 1 mg/L to 50 mg/L.
  • Organoaluminoxanes can be prepared by various procedures. Examples of organoaluminoxane preparations are disclosed in U.S. Patent Nos. 3,242,099 and 4,808,561. For example, water in an inert organic solvent can be reacted with an aluminum alkyl compound, such as (R 2 ⁇ Al, to form the desired organoaluminoxane compound. While not intending to be bound by this statement, it is believed that this synthetic method can afford a mixture of both linear and cyclic R-Al-O aluminoxane species, both of which are encompassed by this invention. Alternatively, organoaluminoxanes can be prepared by reacting an aluminum alkyl compound, such as (R 2 ) 3 A1 with a hydrated salt, such as hydrated copper sulfate, in an inert organic solvent.
  • a hydrated salt such as hydrated copper sulfate
  • the catalyst composition can comprise an organoboron or organoborate activator.
  • Organoboron or organoborate compounds include neutral boron compounds, borate salts, and the like, or combinations thereof.
  • fluoroorgano boron compounds and fluoroorgano borate compounds are contemplated.
  • fluorinated aryl borates such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium te
  • fluoroorgano boron compounds that can be used as optional co-catalysts in the present invention include, but are not limited to, tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)- phenyljboron, and the like, or mixtures thereof.
  • fluoroorgano borate and fluoroorgano boron compounds, and related compounds are thought to form "weakly- coordinating" anions when combined with organometal or metallocene compounds, as disclosed in U.S. Patent 5,919,983.
  • Applicants also contemplate the use of diboron, or bis-boron, compounds or other bifunctional compounds containing two or more boron atoms in the chemical structure, such as disclosed in J. Am. Chem. Soc, 2005, 127, pp. 14756-14768.
  • any amount of organoboron compound can be used.
  • the molar ratio of the total moles of organoboron or organoborate compound (or compounds) to the total moles of hybrid metallocene compound (or compounds) in the catalyst composition is in a range from 0.1 : 1 to 15: 1.
  • the amount of the fluoroorgano boron or fluoroorgano borate compound used as a co-catalyst for the hybrid metallocene is from 0.5 moles to 10 moles of boron/borate compound per mole of unbridged hybrid metallocene compound.
  • the amount of fluoroorgano boron or fluoroorgano borate compound is from 0.8 moles to 5 moles of boron/borate compound per mole of hybrid metallocene compound.
  • the present invention further provides a catalyst composition which can comprise an ionizing ionic compound.
  • An ionizing ionic compound is an ionic compound that can function as an activator or co-catalyst to enhance the activity of the catalyst composition. While not intending to be bound by theory, it is believed that the ionizing ionic compound is capable of reacting with a metallocene compound and converting the metallocene into one or more cationic metallocene compounds, or incipient cationic metallocene compounds.
  • the ionizing ionic compound can function as an ionizing compound by completely or partially extracting an anionic ligand, possibly a non- alkadienyl ligand such as X 1 or X 2 , from the hybrid metallocene.
  • the ionizing ionic compound is an activator regardless of whether it ionizes the hybrid metallocene, abstracts an X or X ligand in a fashion as to form an ion pair, weakens the metal-X 1 or metal-X 2 bond in the hybrid metallocene, simply coordinates to an X 1 or X 2 ligand, or activates the hybrid metallocene compound by some other mechanism.
  • the ionizing ionic compound activate the hybrid metallocene compound only.
  • the activation function of the ionizing ionic compound can be evident in the enhanced activity of catalyst composition as a whole, as compared to a catalyst composition that does not contain an ionizing ionic compound.
  • ionizing ionic compounds include, but are not limited to, the following compounds: tri(n-butyl)ammonium tetrakis(p-tolyl)borate, tri(n-butyl) ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammonium 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-tolyl)
  • Unsaturated reactants that can be employed with catalyst compositions and polymerization processes of this invention typically include olefin compounds having from 2 to 30 carbon atoms per molecule and having an olef ⁇ nic double bond.
  • This invention encompasses homopolymerization processes using a single olefin such as ethylene or propylene, as well as copolymerization reactions with a different olef ⁇ nic compound.
  • the resulting copolymers generally contain a major amount of ethylene (>50 mole percent) and a minor amount of comonomer ( ⁇ 50 mole percent), though this is not a requirement.
  • the comonomers that can be copolymerized with ethylene often have from 3 to 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 catalyst compositions of this invention include, but are not limited to, ethylene, propylene, 1-butene, 2-butene, 3-methyl-l-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-heptene, 3-heptene, the four normal octenes, the four normal nonenes, the five normal decenes, and the like, or mixtures of two or more of these compounds.
  • Cyclic and bicyclic olefins including but not limited to, cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like, can also be polymerized as described above.
  • Styrene can also be employed as a monomer in the present invention.
  • the monomer can be, for example, ethylene or propylene, which is copolymerized with a comonomer.
  • olefin comonomers include, but are not limited to, 1-butene, 2-butene, 3-methyl-l-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-l-pentene, 4-methyl-l-pentene, 1 - hexene, 2-hexene, 3-ethyl-l-hexene, 1-heptene, 2-heptene, 3-heptene, 1 -octene, and the like.
  • the comonomer is selected from 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, and styrene, or any combination thereof.
  • the amount of comonomer introduced into a reactor zone to produce the copolymer is from 0.01 to 50 weight percent of the comonomer based on the total weight of the monomer and comonomer.
  • the amount of comonomer introduced into a reactor zone is from 0.01 to 40 weight percent comonomer based on the total weight of the monomer and comonomer.
  • the amount of comonomer introduced into a reactor zone is from 0.1 to 35 weight percent comonomer based on the total weight of the monomer and comonomer.
  • the amount of comonomer introduced into a reactor zone is from 0.5 to 20 weight percent comonomer based on the total weight of the monomer and comonomer.
  • a monomer/reactant is ethylene, so the polymerizations are either a homopolymerization involving only ethylene, 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 the polymerization of diolef ⁇ n compounds including, but not limited to, 1 ,3-butadiene, isoprene, 1 ,4-pentadiene, and 1,5-hexadiene.
  • the present invention encompasses a catalyst composition comprising a contact product of an unbridged hybrid metallocene compound and an activator.
  • a composition can further comprise an organoaluminum compound.
  • Suitable activators include, but are not limited to, activator-supports, aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, and the like, or combinations thereof.
  • This invention further encompasses methods of making these catalyst compositions, such as, for example, contacting the respective catalyst components in any order or sequence.
  • a hybrid metallocene compound can be precontacted with an olef ⁇ nic monomer if desired, not necessarily the olefin monomer to be polymerized, and an organoaluminum compound for a first period of time prior to contacting this precontacted mixture with an activator-support.
  • the first period of time for contact, the precontact time, between the hybrid metallocene compound or compounds, the olefmic monomer, and the organoaluminum compound typically ranges from 0.1 hour to 24 hours, for example, from 0.1 to 1 hour. Precontact times from 10 minutes to 30 minutes are also employed.
  • a hybrid metallocene compound in another aspect of the invention, can be precontacted with an olefinic monomer and an activator-support for a first period of time prior to contacting this precontacted mixture with an organoaluminum compound.
  • the first period of time for contact, the precontact time, between the hybrid metallocene compound or compounds, the olefinic monomer, and the activator-support typically ranges from 0.1 hour to 24 hours, for example, from 0.1 to 2 hours. Precontact times from 10 minutes to 60 minutes are also employed.
  • the precontacting process is carried out in multiple steps, rather than a single step, in which multiple mixtures are prepared, each comprising a different set of catalyst components. For example, at least two catalyst components are contacted forming a first mixture, followed by contacting the first mixture with another 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 is fed into a first precontacting vessel for precontacting with another catalyst component, while the remainder of that same catalyst component is fed into a second precontacting vessel for precontacting with another catalyst component, or is 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 flask, a vessel of any type, or combinations of these apparatus.
  • the various catalyst components are 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 prior to entering the reaction zone.
  • This precontacting step can be continuous, in which the precontacted product is fed continuously to the reactor, or it can be a stepwise or batchwise process in which a batch of precontacted product is 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 generally lasts from 1 second to 1 hour.
  • the continuous precontacting step lasts from 10 seconds to 45 minutes, or from 1 minute to 30 minutes.
  • this composition (with the addition of the activator-support) is termed the "postcontacted mixture.”
  • the postcontacted mixture optionally remains in contact for a second period of time, the postcontact time, prior to initiating the polymerization process.
  • Postcontact times between the precontacted mixture and the activator- support generally range from 0.1 hour to 24 hours. In a further aspect, the postcontact time is in a range from 0.1 hour to 1 hour.
  • the precontacting step, the postcontacting step, or both, can increase the productivity of the polymer as compared to the same catalyst composition that is prepared without precontacting or postcontacting.
  • the postcontacted mixture can be heated at a temperature and for a time period sufficient to allow adsorption, impregnation, or interaction of precontacted mixture and the activator-support, such that a portion of the components of the precontacted mixture is immobilized, adsorbed, or deposited thereon.
  • the postcontacted mixture generally is heated to a temperature of from 0 0 F to 150 0 F, or from 40 0 F to 95 0 F.
  • the molar ratio of the moles of hybrid metallocene compound to the moles of organoaluminum compound in a catalyst composition generally is in a range from 1 : 1 to 1 : 10,000. In another aspect, the molar ratio is in a range from 1 : 1 to 1 : 1,000. Yet, in another aspect, the molar ratio of the moles of unbridged hybrid metallocene compound to the moles of organoaluminum compound is in a range from 1 : 1 to 1 : 100. These molar ratios reflect the ratio of total moles of metallocene compound or compounds to the total amount of organoaluminum compound (or compounds) in both the precontacted. mixture and the postcontacted mixture combined, if precontacting and/or postcontacting steps are employed.
  • the molar ratio of the total moles of olefin monomer to total moles of hybrid metallocene compound in the precontacted mixture is typically in a range from 1 : 10 to 100,000: 1. Total moles of each component are used in this ratio to account for aspects of this invention where more than one olefin monomer and/or more than metallocene compound is employed. Further, this molar ratio can be in a range from 10: 1 to 1,000: 1 in another aspect of the invention.
  • the weight ratio of organoaluminum compound to activator-support is in a range from 10: 1 to 1 : 1000. If more than one organoaluminum compound and/or more than one activator-support is employed, this ratio is based on the total weight of each respective component. In another aspect, the weight ratio of the organoaluminum compound to the activator-support is in a range from 3: 1 to 1 : 100, or
  • the weight ratio of hybrid metallocene to activator-support is in a range from 1 : 1 to 1 : 1 ,000,000. If more than one unbridged hybrid metallocene and/or more than one activator-support is employed, this ratio is based on the total weight of each respective component. In another aspect, this weight ratio is in a range from 1 :5 to 1 :100,000, or from 1 : 10 to 1 : 10,000. Yet, in another aspect, the weight ratio of the unbridged hybrid metallocene compound to the activator-support is in a range from 1 :20 to 1 : 1000.
  • Aluminoxane compounds are not required to form the catalyst composition.
  • the polymerization can proceed in the absence of aluminoxanes.
  • the present invention can use, for example, organoaluminum compounds and an activator-support in the absence of aluminoxanes.
  • organoboron and organoborate compounds are not required to form a catalyst composition of this invention. Nonetheless, aluminoxanes, organoboron or organoborate compounds, ionizing ionic compounds, or combinations thereof, can be used in other catalyst compositions contemplated by and encompassed within the present invention. Hence, aluminoxanes, organoboron or organoborate compounds, ionizing ionic compounds, or combinations thereof, can be employed with the hybrid metallocene compound, for example, either in the presence or in the absence of an organoaluminum compound.
  • Catalyst compositions of the present invention generally have a catalyst activity greater than 100 grams of polyethylene per gram of activator-support per hour (abbreviated gP/(gAS hr)). In another aspect, the catalyst activity is greater than 150, greater than 200, or greater than 250 gP/(gAS hr). In still another aspect, catalyst compositions of this invention are characterized by having a catalyst activity greater than 500, greater than 1000, or greater than 1500 gP/(gAS-hr). Yet, in another aspect, the catalyst activity is greater than 2000 gP/(gAS hr).
  • This activity is measured under slurry polymerization conditions using isobutane as the diluent, at a polymerization temperature of 90 0 C and an ethylene pressure of 450 psig.
  • any combination of the hybrid metallocene compound, the activator-support, the organoaluminum compound, and the olefin monomer can be precontacted in some aspects of this invention.
  • any precontacting occurs with an olefinic monomer, it is not necessary that the olefin monomer used in the precontacting step be the same as the olefin to be polymerized.
  • this precontacted mixture can be used in a subsequent postcontacting step between any other combination of catalyst components for a second period of time.
  • the hybrid metallocene compound, the organoaluminum compound, and 1-hexene can be used in a precontacting step for a first period of time, and this precontacted mixture then can be contacted with the activator-support to form a postcontacted mixture that is contacted for a second period of time prior to initiating the polymerization reaction.
  • the first period of time for contact, the precontact time, between any combination of the hybrid metallocene compound, the olef ⁇ nic monomer, the activator-support, and the organoaluminum compound can be from 0.1 hour to 24 hours, from 0.1 to 1 hour, or from 10 minutes to 30 minutes.
  • the postcontacted mixture optionally is allowed to remain in contact for a second period of time, the postcontact time, prior to initiating the polymerization process.
  • postcontact times between the precontacted mixture and any remaining catalyst components is from 0.1 hour to 24 hours, or from 0.1 hour to 1 hour.
  • Catalyst compositions of the present invention can be used to polymerize olefins to form homopolymers or copolymers.
  • One such process for polymerizing olefins in the presence of a catalyst composition of the present invention comprises contacting the catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce a polymer or copolymer, wherein the catalyst composition comprises a contact product of a hybrid metallocene compound and an activator.
  • the hybrid metallocene compound has the following formula:
  • M is Zr, Hf, or Ti
  • X 1 and X 2 independently are a halide or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;
  • X 3 is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X 3 independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;
  • R A is an aryl group substituted with an alkenyl substituent, any substituents on R A other than the alkenyl substituent independently are a hydrogen atom or a substituted or unsubstituted alkyl, alkenyl, or alkoxy group; and
  • R B and R c independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof.
  • the polymerization process can employ a catalyst composition which comprises a contact product of a hybrid metallocene compound and an activator, wherein the hybrid metallocene compound is:
  • the catalyst compositions of the present invention are intended for any olefin polymerization method using various types of polymerization reactors.
  • polymerization reactor includes any polymerization reactor capable of polymerizing olefin monomers to produce homopolymers or copolymers.
  • 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 phase reactors, a combination of loop and gas phase reactors, multiple high pressure reactors, or a combination of high pressure with loop and/or gas phase reactors.
  • the multiple reactors may be operated in series or in parallel.
  • the polymerization reactor system may comprise one or more loop slurry reactors comprising 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.
  • Slurry polymerization processes (also known as the particle form process) are disclosed, for example, in 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.
  • Suitable diluents used in slurry polymerization 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.
  • the polymerization reactor may comprise at least one gas phase reactor.
  • Such systems 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, 4,588,790 and 5,436,304.
  • a high pressure polymerization reactor may comprise a tubular reactor or an autoclave reactor.
  • 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 are utilized for dissipating the exothermic heat of polymerization.
  • Homopolymers and copolymers of ethylene produced in accordance with this invention generally have a melt index from 0.01 to 100 g/ 10 min.
  • a melt index in the range from 0.1 to 50 g/10 min, or from 0.5 to 25 g/10 min, are contemplated in some aspects of this invention.
  • the density of ethylene-based polymers produced using one or more hybrid metallocene compounds of the present invention typically falls within the range from 0.88 to 0.97 g/cc.
  • the polymer density is in a range from 0.90 to 0.95 g/cc.
  • the density is generally in a range from 0.91 to 0.94 g/cc.
  • the resultant polymer produced in accordance with the present invention is, for example, a polymer or copolymer of ethylene
  • articles include, but are not limited to, molded products, household containers, utensils, film or sheet products, drums, fuel tanks, pipes, geomembranes, liners, and the like.
  • Various processes can be employed to form these articles. Non-limiting examples of these processes include injection molding, blow molding, film extrusion, sheet extrusion, profile extrusion, and the like. Additionally, additives and modifiers are often added to these polymers in order to provide beneficial polymer processing or end-use product attributes.
  • MI Melt index
  • HLMI High load melt index
  • Polymer density was determined in grams per cubic centimeter (g/cc) on a compression molded sample, cooled at 15 0 C per hour, and conditioned for 40 hours at room temperature in accordance with ASTM Dl 505 and ASTM Dl 928, procedure C.
  • ⁇ * ⁇ ) I magnitude of complex shear viscosity
  • ⁇ o zero shear viscosity
  • ⁇ ⁇ viscous relaxation time
  • a "breadth” parameter
  • n fixes the final power law slope, fixed at 2/1 1
  • co angular frequency of oscillatory shearing deformation.
  • Dissolution of the sample in stabilized TCB was carried out by heating at 150 0 C for 5 hours with occasional, gentle agitation.
  • the columns used were three PLgel Mixed A LS columns (7.8x300mm) and were calibrated with a broad linear polyethylene standard (Phillips Marlex BHB 5003) for which the molecular weight had been determined.
  • Mn is the number- average molecular weight
  • Mw is the weight-average molecular weight
  • PDI is the polydispersity index, determined by the ratio Mw/Mn, a measure of molecular weight distribution.
  • Ethylene was polymerization grade ethylene obtained from Union Carbide
  • ethylene was then further purified through a column of ' ⁇ -inch beads of Alcoa A201 alumina, activated at 250 0 C in nitrogen.
  • Isobutane was polymerization grade obtained from Chevron Phillips Chemical Company LP, which was further purified by distillation and then also passed through a column of ' ⁇ -inch beads of Alcoa A201 alumina, activated at 250 0 C in nitrogen.
  • the 1-hexene was polymerization grade obtained from Chevron Corporation, which was further purified by nitrogen purging and storage over 13X molecular sieve activated at 250 0 C.
  • Triethylaluminum (TEA) was obtained from Akzo Corporation as a one molar solution in heptane.
  • Ethylene was then added to the reactor and fed on demand to maintain a constant total pressure of 450 psig.
  • the reactor was maintained and controlled at 90 0 C throughout the 60-minute run time of the polymerization.
  • the isobutane and ethylene were vented from the reactor, the reactor was opened, and the polymer product was collected and dried.
  • a silica-alumina was obtained from W. R. Grace Company containing 13% alumina by weight and having a surface area of 400 m 2 /g and a pore volume of 1.2 mL/g. This material was obtained as a powder having an average particle size of 70 microns. Approximately 100 grams of this material were impregnated with a solution containing 200 mL of water and 10 grams of ammonium hydrogen fluoride, resulting in a damp powder having the consistency of wet sand. This mixture was then placed in a flat pan and allowed to dry under vacuum at approximately 1 10 0 C for 16 hours. To calcine the support, 10 grams of this powdered mixture were placed in a
  • Bohemite was obtained from W. R. Grace Company under the designation "Alumina A” and having a surface area of 300 m 2 /g and a pore volume of 1.3 mL/g.
  • This material was obtained as a powder having an average particle size of 100 microns. This material was impregnated to incipient wetness with an aqueous solution of ammonium sulfate to equal 15% sulfate. This mixture was then placed in a flat pan and allowed to dry under vacuum at approximately 110 0 C for 16 hours.
  • the hybrid metallocene compound used in Example 3, abbreviated "MET 1,” has the following structure:
  • the MET 1 hybrid metallocene compound of Example 3 can be prepared in accordance with any suitable method.
  • One such synthesis technique reacts cyclopentadienyl titanium trichloride with three equivalents of benzyl magnesium chloride followed by reaction with one equivalent of n-butanol. These reactions are generally conducted at low temperature.
  • Example 3 the reactor was charged with 3.5 mg of MET 1 (hybrid metallocene), 100 mg of A-Sl (fluorided silica-alumina), 48 mL of 1-hexene, and 2 liters of isobutane. Triethylaluminum (TEA) was not employed in Example 3. After one hour of polymerization at 90 0 C and 450 psig ethylene pressure, the reaction was stopped and 309 g of polymer were removed from the reactor.
  • MET 1 hybrid metallocene
  • A-Sl fluorided silica-alumina
  • Example 3 Table I summarizes the polymer resin properties of Example 3. Properties of Example 4 are provided for comparison. Comparative Example 4 was a sample of a LLDPE copolymer resin commercially available from Chevron Phillips Chemical Company, which was produced using a chromium-based catalyst system. As shown in Table I, the polymer properties of Example 3 and Example 4 are very similar.
  • FIG. 1 compares the molecular weight distribution of the polymer of Example 3, produced using hybrid metallocene MET 1, with that of Example 4, a commercially available polymer produced using a chromium catalyst.
  • the molecular weight distribution profiles of Example 3 and Example 4 are very similar.
  • Example 3, however, has less of the low molecular weight fraction which can contribute to smoking during processing and to transport line wax build-up than the chromium- catalyzed polymer of Example 4.
  • the hybrid metallocene catalysts of the present invention allow the production of a polymer with properties similar to that of Example 4 without using a chromium- based catalyst system.
  • the MET 2 hybrid metallocene compound of Examples 5-6 can be prepared in accordance with any suitable method.
  • One such synthesis technique reacts cyclopentadienylzirconium trichloride with three equivalents of benzylmagnesium chloride, following by a reaction with one equivalent of 2,6-di-tert-butyl-4- methylphenol.
  • the reaction employing the Grignard reagent is generally conducted at a low temperature.
  • the tri-benzyl intermediate can be isolated at room temperature and stored at O 0 C for long periods of time without significant decomposition.
  • the tri-benzyl intermediate can be used in situ to prepare hybrid metallocene compounds (e.g., MET 2 and similar compounds) in a 1-pot reaction.
  • Example 5 the reactor was charged with 3.5 mg of MET 2 (hybrid metallocene), 100 mg of A-S2 (sulfated alumina), 0.5 mL of IM TEA (triethylaluminum), 40 mL of 1-hexene, and 2 liters of isobutane. After one hour of polymerization at 90 0 C and 450 psig ethylene pressure, the reaction was stopped and 213 g of polymer were removed from the reactor.
  • the polymer of Example 5 had a melt index of 0.35, a high load melt index of 32.2, a density of 0.9283, and a polydispersity of 15.
  • Example 6 was conducted in the same manner as Example 5, except that the hybrid metallocene (MET 2), the sulfated alumina activator-support (A-S2), and 1- hexene were precontacted prior to being introduced into the reactor.
  • MET 2 hybrid metallocene
  • A-S2 sulfated alumina activator-support
  • 1- hexene 1- hexene were precontacted prior to being introduced into the reactor.
  • MET 2 A-S2, and 1 -hexene were slurried in a vial containing 20 mL of n-heptane for 1 hour prior to being introduced to the reactor and subsequent contacting with ethylene and TEA co-catalyst.
  • 185 g of polymer were obtained from the polymerization of Example 6.
  • FIG. 2 compares the molecular weight distributions of the polymers of Examples 5-6, and illustrates the impact of precontacting (the hybrid metallocene, the activator-support, and an olefin) on molecular weight distribution.
  • Precontacting as in Example 6, resulted in a polymer with less of the low molecular weight fraction and more of the high molecular weight fraction.
  • the molecular weight distribution can be changed by varying the order in which the components of the catalyst system are combined together, and precontacting with an olefin.
  • FIG. 3 compares the rheological properties of the polymers of Examples 4-7.
  • Comparative Example 4 was a sample of a LLDPE copolymer resin produced using a chromium catalyst system. Examples 5-6 were produced using a hybrid metallocene of the present invention.
  • Comparative Example 7 was a sample of a LLDPE copolymer produced using a metallocene catalyst system, commercially available from Chevron Phillips Chemical Company. This LLDPE resin has a melt index of 1.4, a density of 0.916, and a PDI of 2.3. As illustrated in FIG. 3, the polymers of Examples 5-6 exhibited shear behavior similar to that of the chromium-derived resin of Comparative Example 4.
  • Examples 5-6 have high melt viscosity at low shear rates, and low melt viscosity at high shear rates.
  • FIG. 3 also demonstrates the difference in the rheological properties of the polymers of Example 5 and Example 6, due to the precontacting step discussed above.
  • hybrid metallocenes can be prepared in accordance with any suitable method.
  • One such synthesis technique reacts indenylzirconium trichloride with three equivalents of benzylmagnesium chloride, following by a reaction with one equivalent of an aryl alcohol or imine, respectively, depending on the example compound being prepared.
  • the reaction employing the Grignard reagent is generally conducted at a low temperature.
  • the tri-benzyl intermediate can be isolated at room temperature and stored at 0 0 C for long periods of time without significant decomposition.
  • the tri-benzyl intermediate can be used in situ to prepare hybrid metallocene compounds (e.g., compounds used in Examples 8-12 and similar compounds) in a 1 -pot reaction.
  • Example 8-12 For each of Examples 8-12, the reactor was charged with 3.5 mg of the respective hybrid metallocene, 100 mg of A-S2 (sulfated alumina), 0.5 mL of I M TEA, 40 mL of 1 -hexene, and 2 liters of isobutane. The polymerization runs were conducted for one hour at 90 °C and 450 psig ethylene pressure. For Examples 8-10, the respective hybrid metallocene, A-S2, and 1 -hexene were precontacted in the manner described in Example 6. Examples 1 1-12 did not utilize precontacting.
  • Table II summarizes the polymer properties of Examples 8-12.
  • the column heading "g PE” indicates the amount of copolymer produced, in grams, from the one- hour polymerization at 90 0 C and 450 psig ethylene pressure.
  • FIG. 4 compares the molecular weight distributions of the polymers of Examples 8-12, and illustrates the impact of precontacting (the hybrid metallocene, the activator-support, and an olefin) on molecular weight distribution. As demonstrated in Table II and in FIG. 4, the selection of the X 4 ligand does not, by itself, have a dramatic effect on the molecular weight distribution. Examples 1 1-12, without precontacting, produced fairly narrow molecular weight distributions.

Abstract

The present invention provides polymerization catalyst compositions employing half-metallocene compounds with a heteroatom-containing ligand bound to the transition metal. Methods for making these hybrid metallocene compounds and for using such compounds in catalyst compositions for the polymerization and copolymerization of olefins are also provided.

Description

HALF-METALLOCENE CATALYST COMPOSITIONS AND THEIR POLYMER PRODUCTS
BACKGROUND OF THE INVENTION The present invention relates generally to the field of olefin polymerization catalysis, catalyst compositions, methods for the polymerization and copolymerization of olefins, and polyolefins. More specifically, this invention relates to half- metallocene compounds with a heteroatom-containing ligand bound to the transition metal, and catalyst compositions employing such hybrid compounds. Polyolefins such as high density polyethylene (HDPE) homopolymer and linear low density polyethylene (LLDPE) copolymer can be produced using various combinations of catalyst systems and polymerization processes. One method that can be used to produce such polyolefins employs a chromium -based catalyst system. HDPE and LLDPE resins produced using a chromium-based catalyst system generally have a broad molecular weight distribution. For instance, resins having a polydispersity index (PDI) greater than 6 are not unusual. Polyolefin resins produced using a chromium catalyst also can have a low level of long chain branching. This combination of properties is difficult to duplicate with other commercially viable catalyst systems. Metallocene catalysts, for example, generally produce polyolefins with a much narrower molecular weight distribution and either have too little, or too much, long chain branching. Likewise, Ziegler-type catalyst systems produce polyolefin resins which are typically much narrower in molecular weight distribution and have substantially no long chain branching. Polyolefin resins produced using a ballard catalyst are generally too high in molecular weight, too broad in molecular weight distribution, and contain too much long chain branching.
It would be beneficial to have a non-chromium catalyst system that could produce a polyolefin homopolymer or copolymer having the desired combination of a relatively broad molecular weight distribution and a relatively low level of long chain branching. Accordingly, it is to this end that the present invention is directed.
SUMMARY OF THE INVENTION
The present invention generally relates to new catalyst compositions, methods for preparing catalyst compositions, methods for using the catalyst compositions to polymerize olefins, the polymer resins produced using such catalyst compositions, and articles produced using these polymer resins. In particular, the present invention relates to half-metallocene compounds with a heteroatom-containing ligand bound to the transition metal, and catalyst compositions employing such hybrid metallocene compounds. Catalyst compositions of the present invention which contain these hybrid metallocene compounds can be used to produce, for example, ethylene-based homopolymers and copolymers.
The present invention discloses novel hybrid metallocene compounds having a metallocene moiety and a heteroatom-containing ligand. According to one aspect of the present invention, these unbridged hybrid metallocene compounds have the formula:
Figure imgf000003_0001
wherein:
M is Zr, Hf, or Ti;
X1 and X2 independently are a halide or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;
X3 is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X3 independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof; X4 is -O-RA, -NH-RA, -PH-RA, -S-RA, or -CRB=NRC, wherein:
RA is an aryl group substituted with alkenyl substituent, any substituents on RA other than the alkenyl substituent independently are a hydrogen atom or a substituted or unsubstituted alkyl, alkenyl, or alkoxy group; and
RB and Rc independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof. Catalyst compositions containing these unbridged hybrid metallocene compounds are also provided by the present invention. In one aspect, a catalyst composition is disclosed which comprises a contact product of a hybrid metallocene compound and an activator. This catalyst composition can further comprise an organoaluminum compound. The activator can be an activator-support, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or combinations thereof.
In another aspect, a catalyst composition comprising a contact product of a hybrid metallocene compound and an activator is provided. In this aspect, the hybrid metallocene compound is:
Figure imgf000004_0001
Indenyl(X4)Zr(CH2Ph)2; wherein X4 is
Figure imgf000004_0002
or
Figure imgf000005_0001
and Ph is an abbreviation for phenyl.
This catalyst composition can further comprise an organoaluminum compound, and the activator can be an activator-support, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or combinations thereof.
The present invention also contemplates a process for polymerizing olefins in the presence of a catalyst composition, the process comprising contacting the catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce a polymer or copolymer. The catalyst composition can comprise a contact product of a hybrid metallocene compound and an activator. Optionally, organoaluminum compounds can be employed in this process. The activator can be an activator-support, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or a combination thereof.
Polymers produced from the polymerization of olefins, resulting in either homopolymers or copolymers, can be used to produce various articles of manufacture.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 presents a plot of the molecular weight distributions of the polymers of Example 3 and Example 4. FIG. 2 presents a plot of the molecular weight distributions of the polymers of
Example 5 and Example 6.
FIG. 3 presents a dynamic melt viscosity versus frequency plot, measured at 190 0C, for the polymers of Examples 4-7.
FIG. 4 presents a plot of the molecular weight distributions of the polymers of Examples 8-12. DEFINITIONS
To define more clearly the terms used herein, the following definitions are provided.
The term "polymer" means homopolymers comprising ethylene and copolymers of ethylene and a comonomer. "Polymer" also means homopolymers and copolymers of any olefin monomer disclosed herein (e.g., propylene).
The term "co-catalyst" generally refers to organoaluminum compounds that can constitute one component of a catalyst composition. Additionally, "co-catalyst" can refer to other components of a catalyst composition including, but not limited to, aluminoxanes, organoboron or organoborate compounds, ionizing ionic compounds, as disclosed herein. The term "co-catalyst" is used regardless of the actual function of the compound or any chemical mechanism by which the compound may operate. In one aspect of this invention, the term "co-catalyst" is used to distinguish that component of the catalyst composition from the hybrid metallocene compound. The term "fluoroorgano boron compound" is used with its ordinary meaning to refer to neutral compounds of the form BY3. The term "fluoroorgano borate compound" also has its usual meaning to refer to the monoanionic salts of a fluoroorgano boron compound of the form [cation]+[BY4]~, where Y represents a fluorinated organic group. Materials of these types are generally and collectively referred to as "organoboron or organoborate compounds."
The term "contact product" describes compositions wherein the components are contacted together in any order, in any manner, and for any length of time. For example, the components can be contacted by blending or mixing. Further, contacting of any component can occur in the presence or absence of any other component of the compositions described herein. Combining additional materials or components can be done by any suitable method. Further, the term "contact product" includes mixtures, blends, solutions, slurries, reaction products, and the like, or combinations thereof. Although "contact product" can include reaction products, it is not required for the respective components to react with one another. The term "precontacted" mixture is used 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. Often, the precontacted mixture describes a mixture of metallocene compound (or compounds), olefin monomer, and organoaluminum compound (or compounds), before this mixture is contacted with an activator-support and optional additional organoaluminum compound. Thus, 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. For example, according to this description, it is possible for 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. In this case, the precontacted organoaluminum compound or component is described as comprising an organoaluminum compound that was used to prepare the precontacted mixture.
Alternatively, the precontacted mixture can describe a mixture of metallocene compound, olefin monomer, and activator-support, before this mixture is contacted with an organoaluminum co-catalyst.
Similarly, the term "postcontacted" mixture is used 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. Typically, the term "postcontacted" mixture is used herein to describe the mixture of metallocene compound, olefin monomer, organoaluminum compound, and activator-support (e.g., chemically-treated solid oxide), formed from contacting the precontacted mixture of a portion of these components with any additional components added to make up the postcontacted mixture. For instance, the additional component added to make up the postcontacted mixture can be a chemically-treated solid oxide, and, optionally, can include an organoaluminum compound which is the same as 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 "hybrid metallocene," describes an unbridged half-metallocene compound with a heteroatom-containing ligand bound to the transition metal. The hybrid metallocenes of this invention contain one η3 to η5-cyclopentadienyl-type moiety, wherein η3 to η5-cycloalkadienyl moieties include cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, and the like, including partially saturated or substituted derivatives or analogs of any of these. Possible substituents on these ligands include hydrogen, therefore the description "substituted derivatives thereof in this invention comprises partially saturated ligands such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, substituted partially saturated indenyl, substituted partially saturated fluorenyl, and the like. In some contexts, the hybrid metallocene is referred to simply as the "catalyst," in much the same way the term "co-catalyst" is used herein to refer to, for example, an organoaluminum compound. Unless otherwise specified, the following abbreviations are used: Cp for cyclopentadienyl; Ind for indenyl; and Flu for fluorenyl.
The terms "catalyst composition," "catalyst mixture," "catalyst system," and the like, do not depend upon the actual product resulting from the contact or reaction of the components of the mixtures, the nature of the active catalytic site, or the fate of the co-catalyst, the hybrid metallocene compound, any olefin monomer used to prepare a precontacted mixture, or the activator-support, after combining these components. Therefore, the terms "catalyst composition," "catalyst mixture," "catalyst system," and the like, can include both heterogeneous compositions and homogenous compositions.
The term "hydrocarbyl" specifies 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 terms "chemically-treated solid oxide," "solid oxide activator-support,"
"treated solid oxide compound," and the like, indicate a solid, inorganic oxide of relatively high porosity, which exhibits Lewis acidic or Brønsted 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. Thus, the chemically-treated solid oxide compound comprises a calcined contact product of solid oxide compound with electron-withdrawing anion source compound. Typically, the chemically-treated solid oxide comprises ionizing, acidic solid oxide compound. The terms "support" and "activator-support" are not used to imply these components are inert, and such components should not be construed as an inert component of the catalyst composition. The activator-support of the present invention can be a chemically- treated solid oxide.
For any particular compound disclosed herein, any structure presented also encompasses all conformational isomers, regioisomers, and stereoisomers that may arise from a particular set of substituents. The structure also encompasses all enantiomers, diastereomers, and other optical isomers whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as would be recognized by a skilled artisan.
Applicants disclose several types of ranges in the present invention. These include, but are not limited to, a range of number of atoms, a range of integers, a range of weight ratios, a range of molar ratios, a range of temperatures, and so forth. When Applicants disclose or claim a range of any type, Applicants' intent is to disclose or claim individually each possible number that such a range could reasonably encompass, including end points of the range as well as any sub-ranges and combinations of sub-ranges encompassed therein. For example, when the Applicants disclose or claim a chemical moiety having a certain number of carbon atoms, Applicants' intent is to disclose or claim individually every possible number that such a range could encompass, consistent with the disclosure herein. For example, the disclosure that a moiety is an aliphatic group having from 1 to 20 carbon atoms, as used herein, refers to a moiety that can be selected independently from an aliphatic group having 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms, as well as any range between these two numbers (for example, an aliphatic group having 3 to 6 carbon atoms), and also including any combination of ranges between these two numbers (for example, an aliphatic group having 2 to 4 carbon atoms and an aliphatic group having 8 to 12 carbon atoms).
Similarly, another representative example follows for the weight ratio of organoaluminum to activator-support in a catalyst composition provided in one aspect of this invention. By a disclosure that the weight ratio of organoaluminum compound to activator-support is in a range from about 10:1 to about 1:1000, Applicants intend to recite that the weight ratio can be selected from about 10:1, about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1:1, about 1:5, about 1:10, about 1:25, about 1:50, about 1:75, about 1:100, about 1:150, about 1:200, about 1:250, about 1:300, about 1:350, about 1:400, about 1:450, about 1:500, about 1:550, about 1:600, about 1:650, about 1:700, about 1:750, about 1:800, about 1:850, about 1:900, about 1:950, or about 1:1000. Additionally, the weight ratio can be within any range from about 10:1 to about 1:1000 (for example, the weight ratio is in a range from about 3:1 to about 1:100), and this also includes any combination of ranges between about 10:1 to about 1:1000. Likewise, all other ranges disclosed herein should be interpreted in a manner similar to these two examples.
Applicants reserve the right to proviso out or exclude any individual members of any such group, including any sub-ranges or combinations of sub-ranges within the group, that can be claimed according to a range or in any similar manner, if for any reason Applicants choose to claim less than the full measure of the disclosure, for example, to account for a reference that Applicants may be unaware of at the time of the filing of the application. Further, Applicants reserve the right to proviso out or exclude any individual substituents, analogs, compounds, ligands, structures, or groups thereof, or any members of a claimed group, if for any reason Applicants choose to claim less than the full measure of the disclosure, for example, to account for a reference that Applicants may be unaware of at the time of the filing of the application.
The use of broader terms such as "comprising", "includes", "having" should be understood to provide support for the narrower terms "consisting essentially of or "consisting of or "comprised substantially of Use of the term "optionally" with respect to any element of a claim is intended to mean that the subject element is required, or alternatively, is not required. DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed generally to new catalyst compositions, methods for preparing catalyst compositions, methods for using the catalyst compositions to polymerize olefins, the polymer resins produced using such catalyst compositions, and articles produced using these polymer resins. In particular, the present invention relates to half-metallocene compounds with a heteroatom- containing ligand bound to the transition metal, and catalyst compositions employing such hybrid metallocene compounds.
HYBRID METALLOCENE COMPOUNDS
The present invention discloses novel hybrid metallocene compounds having a metallocene moiety and a heteroatom-containing ligand, and methods of making these compounds. For convenience, these compounds will be referred to herein as hybrid metallocene compounds. In one aspect of this, invention, the unbridged hybrid metallocene compounds have the formula:
Figure imgf000011_0001
wherein: M is Zr, Hf, or Ti;
X1 and X2 independently are a halide or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;
X3 is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X3 independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof; X4 is -O-RA, -NH-RA, -PH-RA, -S-RA, or -CRB=NRc, wherein:
RA is an aryl group substituted with an alkenyl substituent, any substituents on RA other than the alkenyl substituent independently are a hydrogen atom or a substituted or unsubstituted alkyl, alkenyl, or alkoxy group; and
RB and Rc independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof. Formula (I) above is not designed to show stereochemistry or isomeric positioning of the different moieties (e.g., this formula is not intended to display cis or trans isomers, or R or S diastereoisomers), although such compounds are contemplated and encompassed by this formula.
The metal in formula (I), M, is selected from Zr, Hf, or Ti. In one aspect of the present invention, M is either Zr or Ti.
In formula (I), X1 and X2 independently can be a halide, such as a fluorine, chlorine, bromine, or iodine atom. As used herein, an aliphatic group includes linear or branched alkyl and alkenyl groups. Generally, the aliphatic group contains from 1 to 20 carbon atoms. Unless otherwise specified, alkyl and alkenyl groups described herein are intended to include all structural isomers, linear or branched, of a given moiety; for example, all enantiomers and all diastereomers are included within this definition. As an example, unless otherwise specified, the term propyl is meant to include n-propyl and iso-propyl, while the term butyl is meant to include n-butyl, iso- butyl, t-butyl, sec-butyl, and so forth. For instance, non-limiting examples of octyl isomers include 2-ethyl hexyl and neooctyl. Examples of suitable alkyl groups which can be employed in the present invention include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl, and the like. Examples of alkenyl groups within the scope of the present invention include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, and the like.
Aromatic groups and combinations with aliphatic groups include aryl and arylalkyl groups, and these include, but are not limited to, phenyl, alkyl-substituted phenyl, naphthyl, alkyl-substituted naphthyl, phenyl-substituted alkyl, naphthyl- substituted alkyl, and the like. Generally, such groups and combinations of groups contain less than 20 carbon atoms. Hence, non-limiting examples of such moieties that can be used in the present invention include phenyl, tolyl, benzyl, dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl, propyl-2- phenylethyl, and the like. Cyclic groups include cycloalkyl and cycloalkenyl moieties and such moieties can include, but are not limited to, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, and the like. One example of a combination including a cyclic group is a cyclohexylphenyl group. Unless otherwise specified, any substituted aromatic or cyclic moiety used herein is meant to include all regioisomers; for example, the term tolyl is meant to include any possible substituent position, that is, ortho, meta, or para.
In one aspect of the present invention, X1 and X2 independently are a substituted or unsubstituted aliphatic group having from 1 to 20 carbon atoms. In another aspect, X1 and X2 independently are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl. In still another aspect, either X1 or X2, or both, are trimethylsilylmethyl. In yet another aspect, X1 and X2 independently are ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl. X1 and X2 independently are a substituted or unsubstituted aromatic group, for example, having up to 20 carbon atoms, in another aspect of the present invention.
In a different aspect, X1 and X2 are both chlorine atoms. X1 and X2 independently can be selected from phenyl, naphthyl, tolyl, benzyl, dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl, propyl-2-phenylethyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, or cyclohexylphenyl in other aspects of this invention. Yet, in another aspect, X1 and X independently are methyl, phenyl, benzyl, or a halide. Further, X1 and X2 independently can be methyl, phenyl, benzyl, or a chlorine atom in another aspect of the present invention.
In formula (I), X is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group. In one aspect of the present invention, X3 is a substituted or unsubstituted cyclopentadienyl group. In another aspect, X3 is a substituted or unsubstituted indenyl group.
X can be an unsubstituted cyclopentadienyl, indenyl, or fluorenyl group. Alternatively, X3 can have one or more substituents. Any substituents on X3 independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof. Hydrogen is included, therefore the notion of a substituted indenyl and substituted fluorenyl includes partially saturated indenyls and fluorenyls including, but not limited to, tetrahydroindenyls, tetrahydrofluorenyls, and octahydrofluorenyls. Exemplary aliphatics which can be employed in the present invention include alkyls and alkenyls, examples of which include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl, and the like. Illustrative aromatic groups and combinations with aliphatic groups, as discussed above, can include phenyl, tolyl, benzyl, and the like. Cyclic substituents are also contemplated herein, and non-limiting examples were also provided above, including moieties such as cyclopentyl and cyclohexyl.
In one aspect of this invention, each substituent on X independently is a hydrogen atom, or a methyl, ethyl, propyl, n-butyl, t-butyl, or hexyl group. In another aspect, substituents on X3 are selected independently from a hydrogen atom, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl.
X4 in formula (I) is -O-RA, -NH-RA, -PH-RA, -S-RA, or -CRB=NRC. In the - O-RA, -NH-RA, -PH-RA, and -S-RA moieties, RA is an aryl group substituted with an alkenyl substituent. Examples of suitable alkenyl group substituents include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, and the like. According to one aspect of the present invention, the alkenyl substituent on RA is an ethenyl, a propenyl, or a butenyl.
In some aspects of this invention, RA contains no further substitutions. In other aspects, RA can be further substituted with a hydrogen atom or a substituted or unsubstituted alkyl, alkenyl, or alkoxy group. For example, suitable alkyls that can be substituents on RA include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl, and the like. In addition to the alkenyl substituent, RA can have additional alkenyl substituents selected from, for example, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, and a decenyl group, and the like. Alkoxy substituents generally have between 1 and 20 carbons atoms and include, but are not limited to, methoxy, ethoxy, propoxy, or butoxy, and the like. In one aspect of the present invention, each substituent on RA other than the alkenyl substituent independently is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. In formula (I), X4 can be -O-RA. Non-limiting examples of X4 in this aspect of the invention include the following moieties:
Figure imgf000015_0001
and the like.
X4 in formula (I) can be -CRB=NRC, where RB and Rc independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof. Exemplary aliphatics which can be employed as RB and/or Rc include the alkyl and alkenyl selections discussed above. These include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl, and the like. Illustrate aromatic groups and combinations with aliphatic groups, also discussed above, can include phenyl, benzyl, tolyl, xylyl, and the like. Similarly, cyclic substituents can also be employed, and as discussed above, non-limiting examples include cyclopentyl, cyclohexyl, and the like.
In one aspect of this invention, RB and Rc in the -CRB=NRC moiety independently are a hydrogen atom, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a phenyl group, a benzyl group, a tolyl group, or a xylyl group. In formula (I), X4 can be -CRB=NRC. A non-limiting example of X4 in this aspect of the invention is the following moiety:
Figure imgf000015_0002
In formula (I), substituted aliphatic, aromatic, or cyclic groups, and combinations thereof, are disclosed, as well as substituted alkyl, alkenyl, or alkoxy groups. Such groups described herein are intended to include substituted analogs with substitutions at any position on these groups that conform to the normal rules of chemical valence. Thus, groups substituted with one or more than one substituent are contemplated.
Such substituents, when present, are independently selected from an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, a germanium group, a tin group, a lead group, a boron group, an aluminum group, an inorganic group, an organometallic group, or a substituted derivative thereof, any of which having from 1 to 20 carbon atoms; a halide; or hydrogen; as long as these groups do not terminate the activity of the catalyst composition. Examples of each of these substituent groups include, but are not limited to, the following groups. Examples of halide substituents, in each occurrence, include fluoride, chloride, bromide, and iodide.
In each occurrence, oxygen groups are oxygen-containing groups, examples of which include, but are not limited to, alkoxy or aryloxy groups (-ORX), -OSiR5S, - OPRX 2, -OA1RX 2, and the like, including substituted derivatives thereof, wherein Rx in each occurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to 20 carbon atoms. Examples of alkoxy or aryloxy groups (-ORX) groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, phenoxy, substituted phenoxy, and the like.
In each occurrence, sulfur groups are sulfur-containing groups, examples of which include, but are not limited to, -SRX and the like, including substituted derivatives thereof, wherein Rx in each occurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to 20 carbon atoms.
In each occurrence, nitrogen groups are nitrogen-containing groups, which include, but are not limited to, -NRX 2 and the like, including substituted derivatives thereof, wherein Rx in each occurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to 20 carbon atoms.
In each occurrence, phosphorus groups are phosphorus-containing groups, which include, but are not limited to, -PRX 2, -P(ORX)2, and the like, including substituted derivatives thereof, wherein Rx in each occurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to 20 carbon atoms.
In each occurrence, arsenic groups are arsenic-containing groups, which include, but are not limited to, -AsR 2, -As(0Rx)2, and the like, including substituted derivatives thereof, wherein Rx in each occurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to 20 carbon atoms.
In each occurrence, 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 20 carbon atoms, aralkyl groups with 1 to 20 carbon atoms, -
C(NRX)H, -C(NRX)RX, -C(NRX)ORX, and the like, including substituted derivatives thereof, wherein Rx in each occurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to 20 carbon atoms. In each occurrence, silicon groups are silicon-containing groups, which include, but are not limited to, silyl groups such as alkylsilyl groups, arylsilyl groups, arylalkylsilyl groups, siloxy groups, and the like, which in each occurrence have from
1 to 20 carbon atoms. For example, silicon group substituents include trimethylsilyl and phenyloctylsilyl groups. In each occurrence, germanium groups are germanium-containing groups, which include, but are not limited to, germyl groups such as alkylgermyl groups, arylgermyl groups, arylalkylgermyl groups, germyloxy groups, and the like, which in each occurrence have from 1 to 20 carbon atoms.
In each occurrence, tin groups are tin-containing groups, which include, but are not limited to, stannyl groups such as alkylstannyl groups, arylstannyl groups, arylalkylstannyl groups, stannoxy (or "stannyloxy") groups, and the like, which in each occurrence have from 1 to 20 carbon atoms. Thus, tin groups include, but are not limited to, stannoxy groups.
In each occurrence, lead groups are lead-containing groups, which include, but are not limited to, alkyllead groups, aryllead groups, arylalkyllead groups, and the like, which in each occurrence, have from 1 to 20 carbon atoms.
In each occurrence, boron groups are boron-containing groups, which include, but are not limited to, -BRX 2, -BX2, -BRXX, and the like, wherein X is a monoanionic group such as hydride, alkoxide, alkyl thiolate, and the like, and wherein Rx in each occurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to 20 carbon atoms.
In each occurrence, aluminum groups are aluminum-containing groups, which include, but are not limited to, -A1RX, -AlX2, -A1RXX, wherein X is a monoanionic group such as hydride, alkoxide, alkyl thiolate, and the like, and wherein Rx in each occurrence can be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having from 1 to 20 carbon atoms.
Examples of inorganic groups that may be used as substituents, in each occurrence include, but are not limited to, -OAlX2, -OSiX3, -OPX2, -SX, -AsX2, -PX2, and the like, wherein X is a monoanionic group such as hydride, amide, alkoxide, alkyl thiolate, and the like, and wherein any alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl group or substituent on these ligands has from 1 to 20 carbon atoms.
Examples of organometallic groups that may be used as substituents, in each occurrence, include, but are not limited to, organoboron groups, organoaluminum groups, organogallium groups, organosilicon groups, organogermanium groups, organotin groups, organolead groups, organo-transition metal groups, and the like, having from 1 to 20 carbon atoms.
According to one aspect of the present invention, M is Zr or Ti in formula (I), and both X1 and X2 are methyl groups, phenyl groups, or benzyl groups. In this aspect, X3 is an unsubstituted cyclopentadienyl or indenyl group, and X4 is -O-RA. In these and other aspects, RA is an aryl group substituted with one alkenyl substituent, such as propenyl or butenyl. Further, RA can be additionally substituted with, for example, a methyl or methoxy group. In accordance with another aspect of the present invention, M is Zr or Ti in formula (I), and both X1 and X2 are methyl groups, phenyl groups, or benzyl groups. In this aspect, X3 is an unsubstituted cyclopentadienyl or indenyl group, and X4 is - CRB=NRC. In these and other aspects, RB and Rc independently are a phenyl group, a benzyl group, a tolyl group, or a xylyl group.
Illustrative and non-limiting examples of hybrid metallocene compounds of the present invention include (Ind)(X )Zr(CH2Ph)2, wherein Ind is an abbreviation for indenyl, Ph is an abbreviation for phenyl, and X4 is one of the following moieties:
Figure imgf000019_0001
; and the like.
Other hybrid metallocene compounds are contemplated as being suitable for use in the present invention, but which do not fall within the scope of formula (I). These include, but are not limited to, the following compounds:
Figure imgf000020_0001
and the like. Additional hybrid metallocene compounds can be used in accordance with the present invention. Therefore, the scope of the present invention is not limited to the hybrid metallocene species provided above.
Methods of making the hybrid metallocene compounds of the present invention are also provided. One such method for synthesizing a hybrid metallocene compound of the present invention involves first the synthesis of, for example, half- metallocene compounds CpZr(CH2Ph)3 or IndZr(CH2Ph)3. These half-metallocene compounds can be synthesized in accordance with the procedures described in Scholz et al., "Benzyl compounds of electron-deficient transition metals. The molecular structure of Cp2Ti(CH2Ph)2 and CpZr(CH2Ph)3," is disclosed in Journal of Organometallic Chemistry (1993), 443(1), 93-9. This procedure employs initial reactant materials which are commercially available, for instance, benzylmagnesium chloride (PhCH2MgCl), cyclopentadienylzirconium trichloride (CpZrCl3), and indenylzirconium trichloride (IndZrCl3).
Synthesis of a hybrid metallocene compound of the present invention from CpZr(CH2Ph)3 or IndZr(CH2Ph)3 can be accomplished using a representative procedure described in Thorn et al., "Synthesis, structure and molecular dynamics of η2-iminoacyl compounds [Cp(ArO)Zr(η ^Bu1NCCH2Ph)(CH2Ph)] and
[Cp(ArO)Zr(η2-ButNCCH2Ph)2]," Journal of the Chemical Society, Dalton Transactions (2002), 17, 3398-3405. CATALYST COMPOSITIONS
The present invention also relates to catalyst compositions employing these half-metallocene compounds having a heteroatom-containing ligand. According to one aspect of the present invention, a catalyst composition is provided which comprises a contact product of a hybrid metallocene compound and an activator. This catalyst composition can further comprise an organoaluminum compound. The activator can be an activator-support, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or a combination thereof.
These catalyst compositions can be used to produce polyolefins, both homopolymers and copolymers, for a variety of end-use applications. The hybrid metallocene compound in these catalyst compositions has the formula:
Figure imgf000021_0001
wherein:
M is Zr, Hf, or Ti; X1 and X independently are a halide or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;
X3 is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X3 independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof; X4 is -O-RA, -NH-RA, -PH-RA, -S-RA, or -CRB=NRC, wherein:
RA is an aryl group substituted with an alkenyl substituent, any substituents on RA other than the alkenyl substituent independently are a hydrogen atom or a substituted or unsubstituted alkyl, alkenyl, or alkoxy group; and
RB and Rc independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof. In accordance with this and other aspects of the present invention, it is contemplated that the catalyst compositions disclosed herein can contain additional bridged or unbridged metallocene compounds as well as more than one activator. Additionally, more than one organoaluminum compound is also contemplated.
In another aspect of the present invention, a catalyst composition is provided which comprises a contact product of a hybrid metallocene compound, an activator- support, and an organoaluminum compound, wherein this catalyst composition is substantially free of aluminoxanes, organoboron or organoborate compounds, and ionizing ionic compounds. In this aspect, the catalyst composition has catalyst activity, to be discussed below, in the absence of these additional materials.
However, in other aspects of this invention, these compounds can be employed as activators. For example, a catalyst composition comprising a hybrid metallocene compound and an activator is contemplated, and in this aspect, the activator is an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof. More than one activator or co-catalyst can be present in the catalyst composition.
In a different aspect, a catalyst composition is provided which comprises a contact product of a hybrid metallocene compound and an activator, wherein the hybrid metallocene compound is:
Figure imgf000022_0001
and the like, or a combination thereof. Optionally, this catalyst composition can further comprise an organoaluminum compound. ACTIVATOR-SUPPORT
The present invention encompasses various catalyst compositions containing an activator, which can be an activator-support. In one aspect, the activator-support comprises a chemically-treated solid oxide. Alternatively, 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. Generally, the activator-support contains Brønsted acid groups.
The chemically-treated solid oxide exhibits enhanced acidity as compared to the corresponding untreated solid oxide compound. The chemically-treated solid oxide also functions as a catalyst activator as compared to the corresponding untreated solid oxide. While the chemically-treated solid oxide activates the metallocene in the absence of co-catalysts, it is not necessary to eliminate co-catalysts from the catalyst composition. The activation function of the activator-support is evident in the enhanced activity of catalyst composition as a whole, as compared to a catalyst composition containing the corresponding untreated solid oxide. However, it is believed that the chemically-treated solid oxide can function as an activator, even in the absence of an organoaluminum compound, aluminoxanes, organoboron compounds, ionizing ionic compounds, and the like. The chemically-treated solid oxide can comprise solid oxide treated with electron-withdrawing anion. While not intending to be bound by the following statement, it is believed that treatment of the solid oxide with an electron-withdrawing component augments or enhances the acidity of the oxide. Thus, either the activator- support exhibits Lewis or Brønsted acidity that is typically greater than the Lewis or Brønsted acid strength of the untreated solid oxide, or the activator-support has a greater number of acid sites than the untreated solid oxide, or both. 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. Chemically-treated solid oxides of this invention are formed generally from an inorganic solid oxide that exhibits Lewis acidic or Brønsted acidic behavior and has a relatively high porosity. The solid oxide is chemically-treated with an electron- withdrawing component, typically an electron-withdrawing anion, to form an activator-support.
According to one aspect of the present invention, the solid oxide used to prepare the chemically-treated solid oxide has a pore volume greater than 0.1 cc/g. According to another aspect of the present invention, the solid oxide has a pore volume greater than 0.5 cc/g. According to yet another aspect of the present invention, the solid oxide has a pore volume greater than 1.0 cc/g.
In another aspect, the solid oxide has a surface area of from 100 to 1000 m2/g. In yet another aspect, the solid oxide has a surface area of from 200 to 800 m2/g. In still another aspect of the present invention, the solid oxide has a surface area of from 250 to 600 m2/g.
The chemically-treated solid oxide can comprise a solid inorganic oxide comprising oxygen and an element selected from Group 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, or 15 of the periodic table, or comprising oxygen and an element selected from the lanthanide or actinide elements. (See: Hawley's Condensed Chemical Dictionary, 1 1th Ed., John Wiley & Sons; 1995; Cotton, F.A.; Wilkinson, G.; Murillo; C. A.; and Bochmann; M. Advanced Inorganic Chemistry, 6th Ed., Wiley- Interscience, 1999.) For example, the inorganic oxide can comprise oxygen and an 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 to form the chemically-treated solid oxide include, but are not limited to, AI2O3, B2O3, BeO, Bi2O3, CdO, Co3O4, Cr2O3, CuO, Fe2O3, Ga2O3, La2O3, Mn2O3, MoO3, NiO, P2O5, Sb2O5, SiO2, SnO2, SrO, ThO2, TiO2, V2O5, WO3, Y2O3, ZnO, ZrO2, and the like, including mixed oxides thereof, and combinations thereof. For example, the solid oxide can be silica, alumina, silica-alumina, aluminum phosphate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof.
The solid oxide of this invention encompasses oxide materials such as alumina, "mixed oxide" compounds thereof such as silica-alumina, and combinations and mixtures thereof. The mixed oxide compounds such as silica-alumina can be single or multiple chemical phases with more than one metal combined with oxygen to form a solid oxide compound. Examples of mixed oxides that can be used in the activator-support of the present invention include, but are not limited to, silica- alumina, silica-titania, silica-zirconia, zeolites, various clay minerals, alumina-titania, alumina-zirconia, zinc-aluminate, and the like. The electron-withdrawing component used to treat the solid oxide can be any component that increases the Lewis or Brønsted acidity of the solid oxide upon treatment (as compared to the solid oxide that is not treated with an electron- withdrawing anion). According to one aspect of the present invention, the electron- withdrawing component is an electron-withdrawing anion derived from a salt, an acid, or other compound, such as a volatile organic compound, that serves as a source or precursor for that anion. Examples of electron-withdrawing anions include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, trifluoroacetate, triflate, and the like, including mixtures and combinations thereof. In addition, other ionic or non-ionic compounds that serve as sources for these electron-withdrawing anions also can be employed in the present invention.
Thus, for example, the chemically-treated solid oxide used in the catalyst compositions of the present can be fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, and the like, or combinations thereof.
When the electron-withdrawing component comprises a salt of an electron- withdrawing anion, the counterion or cation of that salt can be selected from 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(OEt2^]+, 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 in any order that affords the desired chemically-treated solid oxide 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. Thus, one example of such a process by which a chemically-treated solid oxide is prepared is 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 calcined and then contacted with a second electron-withdrawing anion source compound to form a second mixture; the second mixture is then calcined to form a treated solid oxide compound. In such a process, the first and second electron-withdrawing anion source compounds can be either the same or different compounds.
According to another aspect of the present invention, the chemically-treated solid oxide 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 a metal source, including metal salts, metal ions, or other metal-containing compounds. Non-limiting examples of the metal or metal ion include zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, and the like, or combinations thereof. Examples of chemically-treated solid oxides that contain a metal or metal ion include, but are not limited to, zinc-impregnated chlorided alumina, titanium-impregnated fluorided alumina, zinc-impregnated fluorided alumina, zinc-impregnated chlorided silica- alumina, zinc-impregnated fluorided silica-alumina, zinc-impregnated sulfated alumina, chlorided zinc aluminate, fluorided zinc aluminate, sulfated zinc aluminate, and the like, or any combination thereof.
Any method capable 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, can include, but is not limited to, gelling, co- gelling, impregnation of one compound onto another, and the like. If desired, the metal-containing compound is added to or impregnated into the solid oxide in solution form, and subsequently converted into the supported metal upon calcining. Accordingly, the solid inorganic oxide can further comprise a metal selected from zinc, titanium, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, and the like, or combinations of these metals. For example, zinc is often used to impregnate the solid oxide because it can provide improved catalyst activity at a 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. Following any contacting method, the contacted mixture of oxide compound, electron-withdrawing anion, and the metal ion is typically calcined. Alternatively, a solid oxide material, an electron-withdrawing anion source, and the metal salt or metal-containing compound are contacted and calcined simultaneously.
Various processes are used to form the chemically-treated solid oxide useful in the present invention. The chemically-treated solid oxide can comprise the contact product of a solid oxide compound and an electron-withdrawing anion source. It is not required that the solid oxide compound be calcined prior to contacting the electron-withdrawing anion source. The contact product typically is 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. Various processes to prepare solid oxide activator-supports that can be employed in this invention have been reported. For example, such methods are described in U.S. Patent Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271 , 6,316,553, 6,355,594, 6,376,415, 6,388,017, 6,391 ,816, 6,395,666, 6,524,987, 6,548,441 , 6,548,442, 6,576,583, 6,613,712, 6,632,894, 6,667,274, and 6,750,302.
According to one aspect of the present invention, the solid oxide material is chemically-treated by contacting it with an electron-withdrawing component, typically an electron-withdrawing anion source. Further, the solid oxide material optionally is chemically treated with a metal ion, and then calcined to form a metal- containing or metal-impregnated chemically-treated solid oxide. According to another aspect of the present invention, the solid oxide material and electron- withdrawing anion source are contacted and calcined simultaneously.
The method by which the oxide is contacted with the electron-withdrawing component, typically a salt or an acid of an electron-withdrawing anion, can include, but is not limited to, gelling, co-gelling, impregnation of one compound onto another, and the like. Thus, following any contacting method, the contacted mixture of the solid oxide, electron-withdrawing anion, and optional metal ion, is calcined.
The solid oxide activator-support (i.e., chemically-treated solid oxide) thus can be produced by a process comprising: 1) contacting a solid oxide compound with an electron-withdrawing anion source compound to form a first mixture; and
2) calcining the first mixture to form the solid oxide activator-support. According to another aspect of the present invention, the solid oxide activator- support (chemically-treated solid oxide) is produced by a process comprising: 1) contacting a solid oxide compound with a first electron- withdrawing anion source compound to form a first mixture;
2) calcining the first mixture to produce a calcined first mixture;
3) contacting the calcined first mixture with a second electron- withdrawing anion source compound to form a second mixture; and 4) calcining the second mixture to form the solid oxide activator-support.
According to yet another aspect of the present invention, the chemically- treated solid oxide is produced or formed by contacting the solid oxide with the electron-withdrawing anion source compound, where the solid oxide compound is calcined before, during, or after contacting the electron-withdrawing anion source, and where there is a substantial absence of aluminoxanes, organoboron or organoborate compounds, and ionizing ionic compounds.
Calcining of the treated solid oxide generally is conducted in an ambient atmosphere, typically in a dry ambient atmosphere, at a temperature from 200 0C to 900 0C, and for a time from 1 minute to 100 hours. Calcining can be conducted at a temperature of from 300 0C to 800 0C, or alternatively, at a temperature from 400 0C to 700 0C. Calcining can be conducted for 1 hour to 50 hours, or for 3 hours to 20 hours. Thus, for example, calcining can be carried out for 1 to 10 hours at a temperature of from 350 0C to 550 0C. Any suitable ambient atmosphere can be employed during calcining. Generally, calcining is conducted in an oxidizing atmosphere, such as air. Alternatively, an inert atmosphere, such as nitrogen or argon, or a reducing atmosphere, such as hydrogen or carbon monoxide, can be used. According to one aspect of the present invention, the solid oxide material is treated with a source of halide ion, sulfate ion, or a combination of anions, optionally treated with a metal ion, and then calcined to provide the chemically-treated solid oxide in the form of a particulate solid. For example, 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; 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 of the above. Further, any of these activator-supports optionally can be treated with a metal ion. The chemically-treated solid oxide can comprise a fluorided solid oxide in the form of a particulate solid. The fluorided solid oxide can be formed by contacting a solid oxide with a fluoriding agent. The 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 not limited to, the one to three carbon alcohols because of their volatility and low surface tension. Examples of suitable fluoriding agents include, but are not limited to, hydrofluoric acid (HF), ammonium fluoride (NH4F), ammonium bifluoride (NH4HF2), ammonium tetrafluoroborate (NH4BF4), ammonium silicofluoride (hexafluorosilicate) ((NH4^SiF6), ammonium hexafluorophosphate (NH4PF6), analogs thereof, and combinations thereof. For example, ammonium bifluoride NH4HF2 can be used as the fluoriding agent, due to its ease of use and availability.
If desired, the solid oxide is treated with a fluoriding agent during the calcining step. Any fluoriding agent capable of thoroughly contacting the solid oxide during the calcining step can be used. For example, in addition to those fluoriding agents described previously, volatile organic fluoriding agents can be used. Examples of volatile organic fluoriding agents useful in this aspect of the invention include, but are not limited to, freons, perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, an the like, and combinations thereof. Gaseous hydrogen fluoride or fluorine itself also can be used with the solid oxide if fluorided while 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. Similarly, in another aspect of this invention, the chemically-treated solid oxide comprises a chlorided solid oxide in the form of a particulate solid. The chlorided solid oxide is formed by contacting a solid oxide 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. Examples of suitable volatile organic chloriding agents include, but are not limited to, certain freons, perchlorobenzene, chloromethane, dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, and the like, or any combination thereof. Gaseous hydrogen chloride or chlorine itself also can 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 while calcination.
The amount of fluoride or chloride ion present before calcining the solid oxide generally is from 2 to 50% by weight, where the weight percent is based on the weight of the solid oxide, for example, silica-alumina, before calcining. According to another aspect of this invention, the amount of fluoride or chloride ion present before calcining the solid oxide is from 3 to 25% by weight, and according to another aspect of this invention, from 4 to 20% by weight. Once impregnated with halide, the halided oxide can be dried by any suitable method 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 typically has a pore volume greater than 0.5 cc/g. According to one aspect of the present invention, the pore volume is greater than 0.8 cc/g, and according to another aspect of the present invention, greater than 1.0 cc/g. Further, the silica-alumina generally has a surface area greater than 100 m2/g. According to another aspect of this invention, the surface area is greater than 250 m /g. Yet, in another aspect, the surface area is greater than 350 m /g. The silica-alumina utilized in the present invention typically has an alumina content from 5 to 95% by weight. According to one aspect of this invention, the alumina content of the silica-alumina is from 5 to 50%, or from 8% to 30%, alumina by weight. In another aspect, high alumina content silica-alumina compounds can be employed, in which the alumina content of these silica-alumina compounds typically ranges from 60% to 90%, or from 65% to 80%, alumina by weight. According to yet another aspect of this invention, the solid oxide component comprises alumina without silica, and according to another aspect of this invention, the solid oxide component comprises silica without alumina.
The sulfated solid oxide comprises sulfate and a solid oxide component, such as alumina or silica-alumina, in the form of a particulate solid. Optionally, the sulfated oxide is treated further with a metal ion such that the calcined sulfated oxide comprises a metal. According to one aspect of the present invention, the sulfated solid oxide comprises sulfate and alumina. In some instances, the sulfated alumina is formed by a process wherein the alumina is treated with a sulfate source, for example, sulfuric acid or a sulfate salt such as ammonium sulfate. This process is generally 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. According to one aspect of this invention, the amount of sulfate ion present before calcining is from 0.5 parts by weight to 100 parts by weight sulfate ion to 100 parts by weight solid oxide. According to another aspect of this invention, the amount of sulfate ion present before calcining is from 1 part by weight to 50 parts by weight sulfate ion to 100 parts by weight solid oxide, and according to still another aspect of this invention, from 5 parts by weight to 30 parts by weight sulfate ion to 100 parts by weight solid oxide. These weight ratios are based on the weight of the solid oxide before calcining. Once impregnated with sulfate, the sulfated oxide can be dried by any suitable method 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.
According to another aspect of the present invention, the activator-support used in preparing the catalyst compositions of this invention comprises an ion- exchangeable activator-support, including but not limited to silicate and aluminosilicate compounds or minerals, either with layered or non-layered structures, and combinations thereof. In another aspect of this invention, ion-exchangeable, layered aluminosilicates such as pillared clays are used as activator-supports. When the acidic activator-support comprises an ion-exchangeable activator-support, it can optionally be treated with anelectron-withdrawing anion such as those disclosed herein, though typically the ion-exchangeable activator-support is not treated with an electron-withdrawing anion.
According to another aspect of the present invention, the activator-support of this invention comprises 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. Although the term "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 unbridged metallocene component.
According to another aspect of the present invention, 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. Typically, the clay material activator-support of this invention comprises clays that have been ion exchanged with large cations, including polynuclear, highly charged metal complex cations. However, 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.
According to another aspect of the present invention, the activator-support comprises a pillared clay. The term "pillared clay" 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. Thus, the term 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. These polymeric cations are then immobilized within the interlayers of the clay and when calcined are converted to metal oxide "pillars," effectively supporting the clay layers as column-like structures. Thus, once the clay is dried and calcined to produce the supporting pillars between clay layers, the expanded lattice structure is maintained and the porosity is enhanced. The resulting pores can vary in shape and size as a function of the pillaring material and the parent clay material used. Examples of 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. 5,376,61 1; and U.S. Patent No. 4,060,480.
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 montmorillonites (bentonites), nontronites, hectorites, or laponites; halloysites; vermiculites; micas; fluoromicas; chlorites; mixed-layer clays; the fibrous clays including but not limited to sepiolites, attapulgites, and palygorskites; a serpentine clay; illite; laponite; saponite; and any combination thereof. In one aspect, the pillared clay activator-support comprises bentonite or montmorillonite. The principal component of bentonite is montmorillonite. The pillared clay can be pretreated if desired. For example, a pillared bentonite is pretreated by drying at 300 0C under an inert atmosphere, typically dry nitrogen, for 3 hours, before being added to the polymerization reactor. Although an exemplary pretreatment is described herein, it should be understood that the preheating can be carried out at many other temperatures and times, including any combination of temperature and time steps, all of which are encompassed by this invention.
The activator-support used to prepare the catalyst compositions of the present invention can be combined with other inorganic support materials, including, but not limited to, zeolites, inorganic oxides, phosphated inorganic oxides, and the like. In one aspect, typical support materials that are used include, but are not limited to, silica, silica-alumina, alumina, titania, zirconia, magnesia, boria, thoria, aluminophosphate, aluminum phosphate, silica-titania, coprecipitated silica/titania, mixtures thereof, or any combination thereof. According to another aspect of the present invention, one or more of the hybrid metallocene compounds can be precontacted with an olefin monomer and an organoaluminum compound for a first period of time prior to contacting this mixture with the activator-support. Once the precontacted mixture of the metallocene compound(s), olefin monomer, and organoaluminum compound is contacted with the activator-support, the composition further comprising the activator-support is termed a "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.
According to yet another aspect of the present invention, one or more of the hybrid metallocene compounds can be precontacted with an olefin monomer and an activator-support for a first period of time prior to contacting this mixture with the organoaluminum compound. Once the precontacted mixture of the metallocene compound(s), olefin monomer, and activator-support is contacted with the organoaluminum compound, the composition further comprising the organoaluminum is termed a "postcontacted" mixture. The postcontacted mixture can be allowed to remain in further contact for a second period of time prior to being introduced into the polymerization reactor. A non-limiting example of precontacting in accordance with this aspect of the invention is illustrated in Example 6 that follows.
ORGANOALUMINUM COMPOUNDS In one aspect, organoaluminum compounds that can be used with the present invention include, but are not limited to, compounds having the formula:
(R2)3A1; where R is an aliphatic group having from 2 to 6 carbon atoms. For example, R can be ethyl, propyl, butyl, hexyl, or isobutyl. Other organoaluminum compounds which can be used in accordance with the present invention include, but are not limited to, compounds having the formula:
Al(X5)m(X6)3-m, where X5 is a hydrocarbyl; X6 is an alkoxide or an aryloxide, a halide, or a hydride; and m is from 1 to 3, inclusive. In one aspect, X is a hydrocarbyl having from 1 to 20 carbon atoms. In another aspect of the present invention, X5 is an alkyl having from 1 to 10 carbon atoms. For example, X5 can be ethyl, propyl, n-butyl, sec-butyl, isobutyl, or hexyl, and the like, in yet another aspect of the present invention.
According to one aspect of the present invention, X is an alkoxide or an aryloxide, any one of which has from 1 to 20 carbon atoms, a halide, or a hydride. In another aspect of the present invention, X6 is selected independently from fluorine or chlorine. Yet, in another aspect, X is chlorine.
In the formula, Al(X5)m(X6)3-m, m is a number from 1 to 3, inclusive, and typically, m is 3. The value of m is not restricted to be an integer; therefore, this formula includes sesquihalide compounds or other organoaluminum cluster compounds.
Examples of organoaluminum compounds suitable for use in accordance with the present invention include, but are not limited to, trialkylaluminum compounds, dialkylaluminum halide compounds, dialkylaluminum alkoxide compounds, dialkylaluminum hydride compounds, and combinations thereof. Specific non- limiting examples of suitable organoaluminum compounds include trimethylaluminum (TMA), triethylaluminum (TEA), tripropylaluminum, diethylaluminum ethoxide, tributylaluminum, diisobutylaluminum hydride, triisobutylaluminum, diethylaluminum chloride, and the like, or combinations thereof.
The present invention contemplates a method of precontacting an unbridged hybrid metallocene compound with an organoaluminum compound and an olefin monomer to form a precontacted mixture, prior to contacting this precontacted mixture with the activator-support to form a catalyst composition. When 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- support. However, the entire organoaluminum compound can be used to prepare the catalyst composition in either the precontacting or postcontacting step. Alternatively, all the catalyst components are contacted in a single step.
Further, more than one organoaluminum compound can be used in either the precontacting or the postcontacting step. When an organoaluminum compound is added in multiple steps, 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 or more than one organoaluminum compound is used.
ALUMINOXANE COMPOUNDS
The present invention provides a catalyst composition which contains an activator, and in some aspects of the invention, the activator comprises an aluminoxane compound. As used herein, the term "aluminoxane" refers to aluminoxane compounds, compositions, mixtures, or discrete species, regardless of how such aluminoxanes are prepared, formed or otherwise provided. For example, a catalyst composition comprising an aluminoxane compound can be prepared in which aluminoxane is provided as the poly(hydrocarbyl aluminum oxide), or in which aluminoxane is provided as the combination of an aluminum alkyl compound and a source of active protons such as water. Aluminoxanes are also referred to as poly(hydrocarbyl aluminum oxides) or organoaluminoxanes.
The other catalyst components typically are contacted with the aluminoxane in a saturated hydrocarbon compound solvent, though any solvent that is substantially inert to the reactants, intermediates, and products of the activation step can be used. The catalyst composition formed in this manner is collected by any suitable method, for example, by filtration. Alternatively, the catalyst composition is introduced into the polymerization reactor without being isolated.
The aluminoxane compound of this invention can be an oligomeric aluminum compound comprising linear structures, cyclic structures, or cage structures, or mixtures of all three. Cyclic aluminoxane compounds having the formula:
Figure imgf000037_0001
wherein R is a linear or branched alkyl having from 1 to 10 carbon atoms, and p is an integer from 3 to 20, are encompassed by this invention. The AlRO moiety shown here also constitutes the repeating unit in a linear aluminoxane. Thus, linear aluminoxanes having the formula:
Figure imgf000037_0002
wherein R is a linear or branched alkyl having from 1 to 10 carbon atoms, and q is an integer from 1 to 50, are also encompassed by this invention. Further, aluminoxanes can have cage structures of the formula R'5r+αRb r. αAl4rθ3r, wherein R' is a terminal linear or branched alkyl group having from 1 to 10 carbon atoms; Rb is a bridging linear or branched alkyl group having from 1 to 10 carbon atoms; r is 3 or 4; and α is equal to «AI(3) - «o(2) + «O(4)> wherein «Ai(3) is the number of three coordinate aluminum atoms, /io(2) is the number of two coordinate oxygen atoms, and «o(4) is the number of 4 coordinate oxygen atoms.
Thus, aluminoxanes which can be employed in the catalyst compositions of the present invention are represented generally by formulas such as (R-A1-O)P, R(R- Al-O)qAlR2, and the like. In these formulas, the R group is typically a linear or branched Ci-C6 alkyl, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. Examples of aluminoxane compounds that can be used in accordance with the present invention include, but are not limited to, methylaluminoxane, ethylaluminoxane, n- propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, t-butyl- aluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, 1 -pentylaluminoxane, 2- pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, and the like, or any combination thereof. Methylaluminoxane, ethylaluminoxane, and iso-butylaluminoxane are prepared from trimethylaluminum, triethylaluminum, or triisobutylaluminum, respectively, and sometimes are referred to as poly(methyl aluminum oxide), poly(ethyl aluminum oxide), and poly(isobutyl aluminum oxide), respectively. It is also within the scope of the invention to use an aluminoxane in combination with a trialkylaluminum, such as that disclosed in U.S. Patent No. 4,794,096.
The present invention contemplates many values of p and q in the aluminoxane formulas (R-Al-O)p and R(R-Al-O)qAlR2, respectively. Is some aspects, p and q are at least 3. However, depending upon how the organoaluminoxane is prepared, stored, and used, the value of p and q can vary within a single sample of aluminoxane, and such combinations of organoaluminoxanes are contemplated herein.
In preparing a catalyst composition containing an aluminoxane, the molar ratio of the total moles of aluminum in the aluminoxane (or aluminoxanes) to the total moles of hybrid metallocene compound (or compounds) in the composition is generally between 1 : 10 and 100,000: 1. In another aspect, the molar ratio is in a range from 5: 1 to 15,000: 1. Optionally, aluminoxane can be added to a polymerization zone in ranges from 0.01 mg/L to 1000 mg/L, from 0.1 mg/L to 100 mg/L, or from 1 mg/L to 50 mg/L.
Organoaluminoxanes can be prepared by various procedures. Examples of organoaluminoxane preparations are disclosed in U.S. Patent Nos. 3,242,099 and 4,808,561. For example, water in an inert organic solvent can be reacted with an aluminum alkyl compound, such as (R2^Al, to form the desired organoaluminoxane compound. While not intending to be bound by this statement, it is believed that this synthetic method can afford a mixture of both linear and cyclic R-Al-O aluminoxane species, both of which are encompassed by this invention. Alternatively, organoaluminoxanes can be prepared by reacting an aluminum alkyl compound, such as (R2)3A1 with a hydrated salt, such as hydrated copper sulfate, in an inert organic solvent.
ORGANOBORON/ORGANOBORATE COMPOUNDS
According to another aspect of the present invention, the catalyst composition can comprise an organoboron or organoborate activator. Organoboron or organoborate compounds include neutral boron compounds, borate salts, and the like, or combinations thereof. For example, fluoroorgano boron compounds and fluoroorgano borate compounds are contemplated.
Any suitable fluoroorgano boron or fluoroorgano borate compound can be utilized with the present invention. Examples of fluoroorgano borate compounds that can be used in the present invention include, but are not limited to, fluorinated aryl borates such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis- (pentafiuorophenyl)borate, N,N-dimethylanilinium tetrakis[3 ,5-bis(trifluoro- methyl)phenyl]borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)- phenyl]borate, and the like, or mixtures thereof. Examples of fluoroorgano boron compounds that can be used as optional co-catalysts in the present invention include, but are not limited to, tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)- phenyljboron, and the like, or mixtures thereof. Although not intending to be bound by the following theory, these examples of fluoroorgano borate and fluoroorgano boron compounds, and related compounds, are thought to form "weakly- coordinating" anions when combined with organometal or metallocene compounds, as disclosed in U.S. Patent 5,919,983. Applicants also contemplate the use of diboron, or bis-boron, compounds or other bifunctional compounds containing two or more boron atoms in the chemical structure, such as disclosed in J. Am. Chem. Soc, 2005, 127, pp. 14756-14768.
Generally, any amount of organoboron compound can be used. According to one aspect of this invention, the molar ratio of the total moles of organoboron or organoborate compound (or compounds) to the total moles of hybrid metallocene compound (or compounds) in the catalyst composition is in a range from 0.1 : 1 to 15: 1. Typically, the amount of the fluoroorgano boron or fluoroorgano borate compound used as a co-catalyst for the hybrid metallocene is from 0.5 moles to 10 moles of boron/borate compound per mole of unbridged hybrid metallocene compound. According to another aspect of this invention, the amount of fluoroorgano boron or fluoroorgano borate compound is from 0.8 moles to 5 moles of boron/borate compound per mole of hybrid metallocene compound.
IONIZING IONIC COMPOUNDS
The present invention further provides a catalyst composition which can comprise an ionizing ionic compound. An ionizing ionic compound is an ionic compound that can function as an activator or co-catalyst to enhance the activity of the catalyst composition. While not intending to be bound by theory, it is believed that the ionizing ionic compound is capable of reacting with a metallocene compound and converting the metallocene into one or more cationic metallocene compounds, or incipient cationic metallocene compounds. 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- alkadienyl ligand such as X1 or X2, from the hybrid metallocene. However, the ionizing ionic compound is an activator regardless of whether it ionizes the hybrid metallocene, abstracts an X or X ligand in a fashion as to form an ion pair, weakens the metal-X1 or metal-X2 bond in the hybrid metallocene, simply coordinates to an X1 or X2 ligand, or activates the hybrid metallocene compound by some other mechanism.
Further, it is not necessary that the ionizing ionic compound activate the hybrid metallocene compound only. The activation function of the ionizing ionic compound can be evident in the enhanced activity of catalyst composition as a whole, as compared to a catalyst composition that does not contain an ionizing ionic compound.
Examples of ionizing ionic compounds include, but are not limited to, the following compounds: tri(n-butyl)ammonium tetrakis(p-tolyl)borate, tri(n-butyl) ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammonium 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-tolyl)borate, N5N- dimethylanilinium tetrakis(2,4-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoro- methyl)phenyl]borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m- tolyl)borate, triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate, triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropylium tetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropylium tetrakis(2,4-dimethylphenyl)borate, tropylium tetrakis(3,5-dimethylphenyl)borate, tropylium tetrakis[3,5-bis(trifluoro- methyl)phenyl]borate, tropylium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithium tetrakis(p- tolyl)borate, lithium tetrakis(m-tolyl)borate, lithium tetrakis(2,4- dimethylphenyl)borate, lithium tetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodium tetrakis(pentafluorophenyl)borate, sodium tetraphenylborate, sodium tetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodium tetrakis(2,4-dimethylphenyl)borate, sodium tetrakis(3,5- dimethylphenyl)borate, sodium tetrafluoroborate, potassium tetrakis- (pentafluorophenyl)borate, potassium tetraphenylborate, potassium tetrakis(p- tolyl)borate, potassium tetrakis(m-tolyl)borate, potassium tetrakis(2,4-dimethyl- phenyl)borate, potassium tetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoro- borate, lithium tetrakis(pentafluorophenyl)aluminate, lithium tetraphenylaluminate, lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate, lithium tetrakis(2,4-dimethylphenyl)aluminate, lithium tetrakis(3,5- dimethylphenyl)aluminate, lithium tetrafluoroaluminate, sodium tetrakis(pentafluoro- phenyl)aluminate, sodium tetraphenylaluminate, sodium tetrakis(p-tolyl)aluminate, sodium tetrakis(m-tolyl)aluminate, sodium tetrakis(2,4-dimethylphenyl)aluminate, sodium tetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate, potassium tetrakis(pentafluorophenyl)aluminate, potassium tetraphenylaluminate, potassium tetrakis(p-tolyl)aluminate, potassium tetrakis(m-tolyl)aluminate, potassium tetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis (3,5- dimethylphenyl)aluminate, potassium tetrafluoroaluminate, and the like, or combinations thereof. Ionizing ionic compounds useful in this invention are not limited to these; other examples of ionizing ionic compounds are disclosed in U.S. Patent Nos. 5,576,259 and 5,807,938.
OLEFIN MONOMERS
Unsaturated reactants that can be employed with catalyst compositions and polymerization processes of this invention typically include olefin compounds having from 2 to 30 carbon atoms per molecule and having an olefϊnic double bond. This invention encompasses homopolymerization processes using a single olefin such as ethylene or propylene, as well as copolymerization reactions with a different olefϊnic compound. The resulting copolymers generally contain a major amount of ethylene (>50 mole percent) and a minor amount of comonomer (<50 mole percent), though this is not a requirement. The comonomers that can be copolymerized with ethylene often have from 3 to 20 carbon atoms in their molecular chain.
Acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched, substituted, unsubstituted, functionalized, and non-functionalized olefins can be employed in this invention. For example, typical unsaturated compounds that can be polymerized with the catalyst compositions of this invention include, but are not limited to, ethylene, propylene, 1-butene, 2-butene, 3-methyl-l-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-heptene, 3-heptene, the four normal octenes, the four normal nonenes, the five normal decenes, and the like, or mixtures of two or more of these compounds. Cyclic and bicyclic olefins, including but not limited to, cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like, can also be polymerized as described above. Styrene can also be employed as a monomer in the present invention. When a copolymer is desired, the monomer can be, for example, ethylene or propylene, which is copolymerized with a comonomer. Examples of olefin comonomers include, but are not limited to, 1-butene, 2-butene, 3-methyl-l-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-l-pentene, 4-methyl-l-pentene, 1 - hexene, 2-hexene, 3-ethyl-l-hexene, 1-heptene, 2-heptene, 3-heptene, 1 -octene, and the like. According to one aspect of the present invention, the comonomer is selected from 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, and styrene, or any combination thereof.
Generally, the amount of comonomer introduced into a reactor zone to produce the copolymer is from 0.01 to 50 weight percent of the comonomer based on the total weight of the monomer and comonomer. According to another aspect of the present invention, the amount of comonomer introduced into a reactor zone is from 0.01 to 40 weight percent comonomer based on the total weight of the monomer and comonomer. In still another aspect, the amount of comonomer introduced into a reactor zone is from 0.1 to 35 weight percent comonomer based on the total weight of the monomer and comonomer. Yet, in another aspect, the amount of comonomer introduced into a reactor zone is from 0.5 to 20 weight percent comonomer based on the total weight of the monomer and comonomer.
While not intending to be bound by this theory, where branched, substituted, or functionalized olefins are used as reactants, it is believed that a 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. According to one aspect of the present invention, a monomer/reactant is ethylene, so the polymerizations are either a homopolymerization involving only ethylene, or copolymerizations with a different acyclic, cyclic, terminal, internal, linear, branched, substituted, or unsubstituted olefin. In addition, the catalyst compositions of this invention can be used in the polymerization of diolefϊn compounds including, but not limited to, 1 ,3-butadiene, isoprene, 1 ,4-pentadiene, and 1,5-hexadiene.
PREPARATION OF THE CATALYST COMPOSITION In one aspect, the present invention encompasses a catalyst composition comprising a contact product of an unbridged hybrid metallocene compound and an activator. Such a composition can further comprise an organoaluminum compound. Suitable activators include, but are not limited to, activator-supports, aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, and the like, or combinations thereof.
This invention further encompasses methods of making these catalyst compositions, such as, for example, contacting the respective catalyst components in any order or sequence.
In one aspect of the invention, a hybrid metallocene compound can be precontacted with an olefϊnic monomer if desired, not necessarily the olefin monomer to be polymerized, and an organoaluminum compound for a first period of time prior to contacting this precontacted mixture with an activator-support. The first period of time for contact, the precontact time, between the hybrid metallocene compound or compounds, the olefmic monomer, and the organoaluminum compound typically ranges from 0.1 hour to 24 hours, for example, from 0.1 to 1 hour. Precontact times from 10 minutes to 30 minutes are also employed. In another aspect of the invention, a hybrid metallocene compound can be precontacted with an olefinic monomer and an activator-support for a first period of time prior to contacting this precontacted mixture with an organoaluminum compound. The first period of time for contact, the precontact time, between the hybrid metallocene compound or compounds, the olefinic monomer, and the activator-support typically ranges from 0.1 hour to 24 hours, for example, from 0.1 to 2 hours. Precontact times from 10 minutes to 60 minutes are also employed.
Alternatively, the precontacting process is carried out in multiple steps, rather than a single step, in which multiple mixtures are prepared, each comprising a different set of catalyst components. For example, at least two catalyst components are contacted forming a first mixture, followed by contacting the first mixture with another catalyst component forming a second mixture, and so forth.
Multiple 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. For example, 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. In another aspect, one or more of the catalyst components can be split and used in different precontacting treatments. For example, part of a catalyst component is fed into a first precontacting vessel for precontacting with another catalyst component, while the remainder of that same catalyst component is fed into a second precontacting vessel for precontacting with another catalyst component, or is 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 flask, a vessel of any type, or combinations of these apparatus.
In another aspect of this invention, the various catalyst components (for example, unbridged hybrid metallocene, activator-support, organoaluminum co- catalyst, and optionally an unsaturated hydrocarbon) are contacted in the polymerization reactor simultaneously while the polymerization reaction is proceeding. Alternatively, any two or more of these catalyst components can be precontacted in a vessel prior to entering the reaction zone. This precontacting step can be continuous, in which the precontacted product is fed continuously to the reactor, or it can be a stepwise or batchwise process in which a batch of precontacted product is 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. In this aspect, the continuous precontacting step generally lasts from 1 second to 1 hour. In another aspect, the continuous precontacting step lasts from 10 seconds to 45 minutes, or from 1 minute to 30 minutes.
Once the precontacted mixture of the hybrid metallocene compound, olefin monomer, and organoaluminum co-catalyst is contacted with the activator-support, this composition (with the addition of the activator-support) is termed the "postcontacted mixture." The postcontacted mixture optionally remains in contact for a second period of time, the postcontact time, prior to initiating the polymerization process. Postcontact times between the precontacted mixture and the activator- support generally range from 0.1 hour to 24 hours. In a further aspect, the postcontact time is in a range from 0.1 hour to 1 hour. The precontacting step, the postcontacting step, or both, can increase the productivity of the polymer as compared to the same catalyst composition that is prepared without precontacting or postcontacting. However, neither a precontacting step nor a postcontacting step is required. The postcontacted mixture can be heated at a temperature and for a time period sufficient to allow adsorption, impregnation, or interaction of precontacted mixture and the activator-support, such that a portion of the components of the precontacted mixture is immobilized, adsorbed, or deposited thereon. Where heating is employed, the postcontacted mixture generally is heated to a temperature of from 0 0F to 150 0F, or from 40 0F to 95 0F.
According to one aspect of this invention, the molar ratio of the moles of hybrid metallocene compound to the moles of organoaluminum compound in a catalyst composition generally is in a range from 1 : 1 to 1 : 10,000. In another aspect, the molar ratio is in a range from 1 : 1 to 1 : 1,000. Yet, in another aspect, the molar ratio of the moles of unbridged hybrid metallocene compound to the moles of organoaluminum compound is in a range from 1 : 1 to 1 : 100. These molar ratios reflect the ratio of total moles of metallocene compound or compounds to the total amount of organoaluminum compound (or compounds) in both the precontacted. mixture and the postcontacted mixture combined, if precontacting and/or postcontacting steps are employed.
When a precontacting step is used, the molar ratio of the total moles of olefin monomer to total moles of hybrid metallocene compound in the precontacted mixture is typically in a range from 1 : 10 to 100,000: 1. Total moles of each component are used in this ratio to account for aspects of this invention where more than one olefin monomer and/or more than metallocene compound is employed. Further, this molar ratio can be in a range from 10: 1 to 1,000: 1 in another aspect of the invention.
Generally, the weight ratio of organoaluminum compound to activator-support is in a range from 10: 1 to 1 : 1000. If more than one organoaluminum compound and/or more than one activator-support is employed, this ratio is based on the total weight of each respective component. In another aspect, the weight ratio of the organoaluminum compound to the activator-support is in a range from 3: 1 to 1 : 100, or
Figure imgf000046_0001
In some aspects of this invention, the weight ratio of hybrid metallocene to activator-support is in a range from 1 : 1 to 1 : 1 ,000,000. If more than one unbridged hybrid metallocene and/or more than one activator-support is employed, this ratio is based on the total weight of each respective component. In another aspect, this weight ratio is in a range from 1 :5 to 1 :100,000, or from 1 : 10 to 1 : 10,000. Yet, in another aspect, the weight ratio of the unbridged hybrid metallocene compound to the activator-support is in a range from 1 :20 to 1 : 1000.
Aluminoxane compounds are not required to form the catalyst composition. Thus, the polymerization can proceed in the absence of aluminoxanes. Accordingly, the present invention can use, for example, organoaluminum compounds and an activator-support in the absence of aluminoxanes.
Additionally, organoboron and organoborate compounds are not required to form a catalyst composition of this invention. Nonetheless, aluminoxanes, organoboron or organoborate compounds, ionizing ionic compounds, or combinations thereof, can be used in other catalyst compositions contemplated by and encompassed within the present invention. Hence, aluminoxanes, organoboron or organoborate compounds, ionizing ionic compounds, or combinations thereof, can be employed with the hybrid metallocene compound, for example, either in the presence or in the absence of an organoaluminum compound.
Catalyst compositions of the present invention generally have a catalyst activity greater than 100 grams of polyethylene per gram of activator-support per hour (abbreviated gP/(gAS hr)). In another aspect, the catalyst activity is greater than 150, greater than 200, or greater than 250 gP/(gAS hr). In still another aspect, catalyst compositions of this invention are characterized by having a catalyst activity greater than 500, greater than 1000, or greater than 1500 gP/(gAS-hr). Yet, in another aspect, the catalyst activity is greater than 2000 gP/(gAS hr). This activity is measured under slurry polymerization conditions using isobutane as the diluent, at a polymerization temperature of 90 0C and an ethylene pressure of 450 psig. As discussed above, any combination of the hybrid metallocene compound, the activator-support, the organoaluminum compound, and the olefin monomer, can be precontacted in some aspects of this invention. When any precontacting occurs with an olefinic monomer, it is not necessary that the olefin monomer used in the precontacting step be the same as the olefin to be polymerized. Further, when a precontacting step among any combination of the catalyst components is employed for a first period of time, this precontacted mixture can be used in a subsequent postcontacting step between any other combination of catalyst components for a second period of time. For example, the hybrid metallocene compound, the organoaluminum compound, and 1-hexene can be used in a precontacting step for a first period of time, and this precontacted mixture then can be contacted with the activator-support to form a postcontacted mixture that is contacted for a second period of time prior to initiating the polymerization reaction. For example, the first period of time for contact, the precontact time, between any combination of the hybrid metallocene compound, the olefϊnic monomer, the activator-support, and the organoaluminum compound can be from 0.1 hour to 24 hours, from 0.1 to 1 hour, or from 10 minutes to 30 minutes. The postcontacted mixture optionally is allowed to remain in contact for a second period of time, the postcontact time, prior to initiating the polymerization process. According to one aspect of this invention, postcontact times between the precontacted mixture and any remaining catalyst components is from 0.1 hour to 24 hours, or from 0.1 hour to 1 hour.
POLYMERIZATION PROCESS
Catalyst compositions of the present invention can be used to polymerize olefins to form homopolymers or copolymers. One such process for polymerizing olefins in the presence of a catalyst composition of the present invention comprises contacting the catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce a polymer or copolymer, wherein the catalyst composition comprises a contact product of a hybrid metallocene compound and an activator. In this aspect, the hybrid metallocene compound has the following formula:
Figure imgf000048_0001
wherein:
M is Zr, Hf, or Ti;
X1 and X2 independently are a halide or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof; X3 is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X3 independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;
X4 is -O-RA, -NH-RA, -PH-RA, -S-RA, or -CRB=NRC, wherein:
RA is an aryl group substituted with an alkenyl substituent, any substituents on RA other than the alkenyl substituent independently are a hydrogen atom or a substituted or unsubstituted alkyl, alkenyl, or alkoxy group; and
RB and Rc independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof.
In a different aspect, the polymerization process can employ a catalyst composition which comprises a contact product of a hybrid metallocene compound and an activator, wherein the hybrid metallocene compound is:
Figure imgf000049_0001
or a combination thereof.
The catalyst compositions of the present invention are intended for any olefin polymerization method using various types of polymerization reactors. As used herein, "polymerization reactor" includes any polymerization reactor capable of polymerizing olefin monomers to produce homopolymers or copolymers. 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. Alternatively, 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 phase reactors, a combination of loop and gas phase reactors, multiple high pressure reactors, or a combination of high pressure with loop and/or gas phase reactors. The multiple reactors may be operated in series or in parallel. According to one aspect of the invention, the polymerization reactor system may comprise one or more loop slurry reactors comprising vertical or horizontal loops. Monomer, diluent, catalyst and optionally any comonomer may be continuously fed to a loop reactor where polymerization occurs. Generally, 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. Slurry polymerization processes (also known as the particle form process) are disclosed, for example, in 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.
Suitable diluents used in slurry polymerization include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquids under reaction conditions. Examples of 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. According to yet another aspect of this invention, the polymerization reactor may comprise at least one gas phase reactor. Such systems 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. Simultaneously, 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, 4,588,790 and 5,436,304.
According to still another aspect of the invention, a high pressure polymerization reactor may comprise a tubular reactor or an autoclave reactor. 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.
According to yet another aspect of the invention, 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. If desired, 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 are utilized for dissipating the exothermic heat of polymerization. Homopolymers and copolymers of ethylene produced in accordance with this invention generally have a melt index from 0.01 to 100 g/ 10 min. For example, a melt index in the range from 0.1 to 50 g/10 min, or from 0.5 to 25 g/10 min, are contemplated in some aspects of this invention.
The density of ethylene-based polymers produced using one or more hybrid metallocene compounds of the present invention typically falls within the range from 0.88 to 0.97 g/cc. In one aspect of this invention, the polymer density is in a range from 0.90 to 0.95 g/cc. Yet, in another aspect, the density is generally in a range from 0.91 to 0.94 g/cc.
If the resultant polymer produced in accordance with the present invention is, for example, a polymer or copolymer of ethylene, it can be formed into various articles of manufacture. Such articles include, but are not limited to, molded products, household containers, utensils, film or sheet products, drums, fuel tanks, pipes, geomembranes, liners, and the like. Various processes can be employed to form these articles. Non-limiting examples of these processes include injection molding, blow molding, film extrusion, sheet extrusion, profile extrusion, and the like. Additionally, additives and modifiers are often added to these polymers in order to provide beneficial polymer processing or end-use product attributes.
EXAMPLES The invention is further illustrated by the following examples, which are not to be construed in any way as imposing limitations to the scope of this invention. Also contemplated are various other aspects, embodiments, modifications, and equivalents that may suggest themselves to one of ordinary skill in the art.
Melt index (MI, g/10 min) was determined in accordance with ASTM D1238 at 190 0C with a 2,160 gram weight. High load melt index (HLMI, g/10 min) was determined in accordance with
ASTM D1238 at 190 0C with a 21,600 gram weight.
Polymer density was determined in grams per cubic centimeter (g/cc) on a compression molded sample, cooled at 15 0C per hour, and conditioned for 40 hours at room temperature in accordance with ASTM Dl 505 and ASTM Dl 928, procedure C.
Melt rheological characterizations were performed as follows. Small-strain (10%) oscillatory shear measurements were performed on a Rheometrics Scientific, Inc. ARES rheometer using parallel-plate geometry. All rheological tests were performed at 190 0C. The complex viscosity \η*\ versus frequency (ω) data were then curve fitted using the modified three parameter Carreau-Yasuda (CY) empirical model to obtain the zero shear viscosity - ηo, characteristic viscous relaxation time - τη, and the breadth parameter — a. The simplified Carreau-Yasuda (CY) empirical model is as follows.
Figure imgf000053_0001
wherein: \η*{ώ) I = magnitude of complex shear viscosity; ηo = zero shear viscosity; τη = viscous relaxation time; a = "breadth" parameter; n = fixes the final power law slope, fixed at 2/1 1 ; and co = angular frequency of oscillatory shearing deformation.
Details of the significance and interpretation of the CY model and derived parameters may be found in: C. A. Hieber and H. H. Chiang, Rheol. Acta, 28, 321
(1989); CA. Hieber and H.H. Chiang, Polym. Eng. ScL, 32, 931 (1992); and R. B.
Bird, R. C. Armstrong and O. Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition, John Wiley & Sons (1987). Molecular weights and molecular weight distributions were obtained using a PL 220 SEC high temperature chromatography unit (Polymer Laboratories) with trichlorobenzene (TCB) as the solvent, with a flow rate of 1 mL/minute at a temperature of 145 0C. BHT (2,6-di-tert-butyl-4-methylphenol) at a concentration of 0.5 g/L was used as a stabilizer in the TCB. An injection volume of 200 μL was used with a nominal polymer concentration of 1.5 mg/mL. Dissolution of the sample in stabilized TCB was carried out by heating at 1500C for 5 hours with occasional, gentle agitation. The columns used were three PLgel Mixed A LS columns (7.8x300mm) and were calibrated with a broad linear polyethylene standard (Phillips Marlex BHB 5003) for which the molecular weight had been determined. The following abbreviations are used in the Examples that follow: Mn is the number- average molecular weight; Mw is the weight-average molecular weight; and PDI is the polydispersity index, determined by the ratio Mw/Mn, a measure of molecular weight distribution. Ethylene was polymerization grade ethylene obtained from Union Carbide
Corporation. This ethylene was then further purified through a column of 'Λ-inch beads of Alcoa A201 alumina, activated at 250 0C in nitrogen. Isobutane was polymerization grade obtained from Chevron Phillips Chemical Company LP, which was further purified by distillation and then also passed through a column of 'Λ-inch beads of Alcoa A201 alumina, activated at 250 0C in nitrogen. The 1-hexene was polymerization grade obtained from Chevron Corporation, which was further purified by nitrogen purging and storage over 13X molecular sieve activated at 250 0C. Triethylaluminum (TEA) was obtained from Akzo Corporation as a one molar solution in heptane. All polymerizations were conducted in a one-gallon stirred reactor. First, the reactor was purged with nitrogen and heated to 120 0C. After cooling to below 40 0C and purging with isobutane vapor, 3.5 mg of the hybrid metallocene compound were charged to the reactor under nitrogen. Approximately 100 mg of the activator-support (A-S) were then added to the reactor, followed by 0.5 mL of IM triethylaluminum (TEA) co-catalyst. The reactor was then closed, 1-hexene comonomer and two liters of isobutane were added, and the reactor was subsequently heated to 90 0C. The reactor contents were mixed at 700 rpm. Ethylene was then added to the reactor and fed on demand to maintain a constant total pressure of 450 psig. The reactor was maintained and controlled at 90 0C throughout the 60-minute run time of the polymerization. Upon completion, the isobutane and ethylene were vented from the reactor, the reactor was opened, and the polymer product was collected and dried.
EXAMPLE 1 Synthesis of a fluorided silica-alumina activator-support
A silica-alumina was obtained from W. R. Grace Company containing 13% alumina by weight and having a surface area of 400 m2/g and a pore volume of 1.2 mL/g. This material was obtained as a powder having an average particle size of 70 microns. Approximately 100 grams of this material were impregnated with a solution containing 200 mL of water and 10 grams of ammonium hydrogen fluoride, resulting in a damp powder having the consistency of wet sand. This mixture was then placed in a flat pan and allowed to dry under vacuum at approximately 1 10 0C for 16 hours. To calcine the support, 10 grams of this powdered mixture were placed in a
1.75-inch quartz tube fitted with a sintered quartz disk at the bottom. While the powder was supported on the disk, air (nitrogen can be substituted) dried by passing through a 13X molecular sieve column, was blown upward through the disk at the linear rate of 1.6 to 1.8 standard cubic feet per hour. An electric furnace around the quartz tube was then turned on and the temperature was raised at the rate of 400 0C per hour to the desired calcining temperature of 450 0C. At this temperature, the powder was allowed to fluidize for three hours in the dry air. Afterward, the fluorided silica-alumina was collected and stored under dry nitrogen, and was used without exposure to the atmosphere. The fluorided silica-alumina activator-support of Example 1 is abbreviated A-Sl .
EXAMPLE 2 Synthesis of a sulfated alumina activator-support
Bohemite was obtained from W. R. Grace Company under the designation "Alumina A" and having a surface area of 300 m2/g and a pore volume of 1.3 mL/g.
This material was obtained as a powder having an average particle size of 100 microns. This material was impregnated to incipient wetness with an aqueous solution of ammonium sulfate to equal 15% sulfate. This mixture was then placed in a flat pan and allowed to dry under vacuum at approximately 110 0C for 16 hours.
To calcine the support, 10 grams of this powdered mixture were placed in a 1.75-inch quartz tube fitted with a sintered quartz disk at the bottom. While the powder was supported on the disk, air (nitrogen can be substituted) dried by passing through a 13X molecular sieve column, was blown upward through the disk at the linear rate of 1.6 to 1.8 standard cubic feet per hour. An electric furnace around the quartz tube was then turned on and the temperature was raised at the rate of 400 0C per hour to the desired calcining temperature of 600 0C. At this temperature, the powder was allowed to fluidize for three hours in the dry air. Afterward, the sulfated alumina was collected and stored under dry nitrogen, and was used without exposure to the atmosphere. The sulfated alumina activator-support of Example 2 is abbreviated A-S2.
EXAMPLES 3-4
Comparison of polymer made using hybrid metallocene MET 1 and A-Sl to a commercial LLDPE copolymer produced using a chromium-based catalyst system
The hybrid metallocene compound used in Example 3, abbreviated "MET 1," has the following structure:
Figure imgf000056_0001
The MET 1 hybrid metallocene compound of Example 3 can be prepared in accordance with any suitable method. One such synthesis technique reacts cyclopentadienyl titanium trichloride with three equivalents of benzyl magnesium chloride followed by reaction with one equivalent of n-butanol. These reactions are generally conducted at low temperature.
In Example 3, the reactor was charged with 3.5 mg of MET 1 (hybrid metallocene), 100 mg of A-Sl (fluorided silica-alumina), 48 mL of 1-hexene, and 2 liters of isobutane. Triethylaluminum (TEA) was not employed in Example 3. After one hour of polymerization at 90 0C and 450 psig ethylene pressure, the reaction was stopped and 309 g of polymer were removed from the reactor.
Table I summarizes the polymer resin properties of Example 3. Properties of Example 4 are provided for comparison. Comparative Example 4 was a sample of a LLDPE copolymer resin commercially available from Chevron Phillips Chemical Company, which was produced using a chromium-based catalyst system. As shown in Table I, the polymer properties of Example 3 and Example 4 are very similar.
Table I. Polymer property comparison for Examples 3-4.
Figure imgf000057_0001
FIG. 1 compares the molecular weight distribution of the polymer of Example 3, produced using hybrid metallocene MET 1, with that of Example 4, a commercially available polymer produced using a chromium catalyst. The molecular weight distribution profiles of Example 3 and Example 4 are very similar. Example 3, however, has less of the low molecular weight fraction which can contribute to smoking during processing and to transport line wax build-up than the chromium- catalyzed polymer of Example 4.
The hybrid metallocene catalysts of the present invention allow the production of a polymer with properties similar to that of Example 4 without using a chromium- based catalyst system. EXAMPLES 5-7
Comparison of polymers made using hybrid metallocene MET 2 and A-S2, with and without precontacting, to commercial LLDPE copolymers The hybrid metallocene compound used in Examples 5-6, abbreviated "MET
2," has the following structure:
Figure imgf000058_0001
The MET 2 hybrid metallocene compound of Examples 5-6 can be prepared in accordance with any suitable method. One such synthesis technique reacts cyclopentadienylzirconium trichloride with three equivalents of benzylmagnesium chloride, following by a reaction with one equivalent of 2,6-di-tert-butyl-4- methylphenol. The reaction employing the Grignard reagent is generally conducted at a low temperature. The tri-benzyl intermediate can be isolated at room temperature and stored at O0C for long periods of time without significant decomposition. Alternatively, the tri-benzyl intermediate can be used in situ to prepare hybrid metallocene compounds (e.g., MET 2 and similar compounds) in a 1-pot reaction.
In Example 5, the reactor was charged with 3.5 mg of MET 2 (hybrid metallocene), 100 mg of A-S2 (sulfated alumina), 0.5 mL of IM TEA (triethylaluminum), 40 mL of 1-hexene, and 2 liters of isobutane. After one hour of polymerization at 90 0C and 450 psig ethylene pressure, the reaction was stopped and 213 g of polymer were removed from the reactor. The polymer of Example 5 had a melt index of 0.35, a high load melt index of 32.2, a density of 0.9283, and a polydispersity of 15.
Example 6 was conducted in the same manner as Example 5, except that the hybrid metallocene (MET 2), the sulfated alumina activator-support (A-S2), and 1- hexene were precontacted prior to being introduced into the reactor. For Example 6, MET 2, A-S2, and 1 -hexene were slurried in a vial containing 20 mL of n-heptane for 1 hour prior to being introduced to the reactor and subsequent contacting with ethylene and TEA co-catalyst. 185 g of polymer were obtained from the polymerization of Example 6.
FIG. 2 compares the molecular weight distributions of the polymers of Examples 5-6, and illustrates the impact of precontacting (the hybrid metallocene, the activator-support, and an olefin) on molecular weight distribution. Precontacting, as in Example 6, resulted in a polymer with less of the low molecular weight fraction and more of the high molecular weight fraction. Hence, the molecular weight distribution can be changed by varying the order in which the components of the catalyst system are combined together, and precontacting with an olefin.
FIG. 3 compares the rheological properties of the polymers of Examples 4-7. Comparative Example 4 was a sample of a LLDPE copolymer resin produced using a chromium catalyst system. Examples 5-6 were produced using a hybrid metallocene of the present invention. Comparative Example 7 was a sample of a LLDPE copolymer produced using a metallocene catalyst system, commercially available from Chevron Phillips Chemical Company. This LLDPE resin has a melt index of 1.4, a density of 0.916, and a PDI of 2.3. As illustrated in FIG. 3, the polymers of Examples 5-6 exhibited shear behavior similar to that of the chromium-derived resin of Comparative Example 4. That is, Examples 5-6 have high melt viscosity at low shear rates, and low melt viscosity at high shear rates. FIG. 3 also demonstrates the difference in the rheological properties of the polymers of Example 5 and Example 6, due to the precontacting step discussed above.
EXAMPLES 8-12
Comparison of polymers made using hybrid metallocenes having formula (I) and A- S2, and the effect of precontacting The hybrid metallocenes used in Examples 8-12 had the formula (I):
Figure imgf000060_0001
wherein M was Zr, X and X2 were both benzyl, X was an unsubstituted indenyl, and X4 was:
Figure imgf000060_0002
for Examples 8 and 1 1 ;
Figure imgf000060_0003
for Example 9; and
Figure imgf000060_0004
for Examples 10 and 12. These hybrid metallocenes can be prepared in accordance with any suitable method. One such synthesis technique reacts indenylzirconium trichloride with three equivalents of benzylmagnesium chloride, following by a reaction with one equivalent of an aryl alcohol or imine, respectively, depending on the example compound being prepared. The reaction employing the Grignard reagent is generally conducted at a low temperature. The tri-benzyl intermediate can be isolated at room temperature and stored at 0 0C for long periods of time without significant decomposition. Alternatively, the tri-benzyl intermediate can be used in situ to prepare hybrid metallocene compounds (e.g., compounds used in Examples 8-12 and similar compounds) in a 1 -pot reaction.
For each of Examples 8-12, the reactor was charged with 3.5 mg of the respective hybrid metallocene, 100 mg of A-S2 (sulfated alumina), 0.5 mL of I M TEA, 40 mL of 1 -hexene, and 2 liters of isobutane. The polymerization runs were conducted for one hour at 90 °C and 450 psig ethylene pressure. For Examples 8-10, the respective hybrid metallocene, A-S2, and 1 -hexene were precontacted in the manner described in Example 6. Examples 1 1-12 did not utilize precontacting.
Table II summarizes the polymer properties of Examples 8-12. The column heading "g PE" indicates the amount of copolymer produced, in grams, from the one- hour polymerization at 90 0C and 450 psig ethylene pressure. FIG. 4 compares the molecular weight distributions of the polymers of Examples 8-12, and illustrates the impact of precontacting (the hybrid metallocene, the activator-support, and an olefin) on molecular weight distribution. As demonstrated in Table II and in FIG. 4, the selection of the X4 ligand does not, by itself, have a dramatic effect on the molecular weight distribution. Examples 1 1-12, without precontacting, produced fairly narrow molecular weight distributions. While not wishing to be bound by theory, it is believed that this may be the result of using an indenyl group instead of a cyclopentadienyl group in the hybrid metallocene compound. Precontacting, as in Examples 8-10, produced broader molecular weight distributions than Examples 1 1- 12, in which the catalyst components were not precontacted.
Table II. Polymer property comparison for Examples 8-12.
Figure imgf000061_0001
The scope of protection is not limited by the description set forth above, but is only limited by the Claims which follow, that scope including all equivalents of the subject matter of the Claims.

Claims

1. A catalyst composition comprising a contact product of a hybrid metallocene compound and an activator, wherein the hybrid metallocene compound has the formula:
Figure imgf000063_0001
wherein:
M is Zr, Hf, or Ti;
X and X independently are a halide or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;
X3 is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyL group, any substituents on X3 independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;
X4 is -O-RA, -NH-RA, -PH-RA, -S-RA, or -CRB=NRC, wherein:
RA is an aryl group substituted with an alkenyl substituent, any substituents on RA other than the alkenyl substituent independently are a hydrogen atom or a substituted or unsubstituted alkyl, alkenyl, or alkoxy group; and RB and Rc independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof.
2. The catalyst composition of claim 1 , wherein X1 and X2 independently are a methyl group, a phenyl group, a benzyl group, or a halide.
3. The catalyst composition of claim 1, wherein each substituent on X3 independently is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, or a hexyl group.
4. The catalyst composition of claim 1, wherein the alkenyl substituent on RA is an ethenyl, a propenyl, or a butenyl.
5. The catalyst composition of claim 1, wherein each substituent on RΛ other than the alkenyl substituent independently is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group.
6. The catalyst composition of claim 1, wherein X4 is -O-RΛ.
7. The catalyst composition of claim 1, wherein RB and Rc independently are a hydrogen atom, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t- butyl group, a phenyl group, a benzyl group, a tolyl group, or a xylyl group
8. The catalyst composition of claim 1, wherein the activator is an activator- support comprising a solid oxide treated with an electron-withdrawing anion, wherein: the solid oxide is silica, alumina, silica-alumina, aluminum phosphate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, any mixed oxides thereof, or any mixture thereof; and the electron-withdrawing anion is fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, or any combination thereof.
9. The catalyst composition of claim 8, wherein the activator-support further comprises a metal or metal ion, and wherein the metal or metal ion is zinc, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, or any combination thereof.
10. The catalyst composition of claim 1, wherein the activator is an activator- support comprising 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.
1 1. The catalyst composition of claim 1, further comprising an organoaluminum compound having the formula:
Al(X5)m(X6)3.m; wherein:
X5 is a hydrocarbyl;
X6 is an alkoxide or an aryloxide, a halide, or a hydride; and m is from 1 to 3, inclusive.
12. The catalyst composition of claim 11, wherein the organoaluminum compound is trimethylaluminum, triethylaluminum, tri-n-propylaluminum, diethylaluminum ethoxide, tri-n-butylaluminum, diisobutylaluminum hydride, triisobutylaluminum, diethylaluminum chloride, or any combination thereof.
13. The catalyst composition of claim 1, wherein the activator is an activator- support, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.
14. A catalyst composition of any of claims 1 - 13, wherein the hybrid metallocene compound is:
Figure imgf000065_0001
or Indenyl(X4)Zr(CH2Phenyl)2; wherein X4 is
Figure imgf000066_0001
15. An olefin polymerization process comprising contacting the catalyst composition of any of claims 1 -14 with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce a polymer or copolymer.
16. The process of claim 15, wherein the catalyst composition and the olefin monomer are contacted in a gas phase reactor, a loop slurry reactor, or a stirred tank reactor.
17. The process of claim 15, wherein the olefin monomer comprises ethylene, propylene, or styrene.
18. The process of claim 15, wherein the olefin comonomer is 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-ethyl-l-hexene, 1-heptene, 2-heptene, 3-heptene, 1- octene, or styrene.
19. A compound having the formula:
Indenyl(X4)Zr(CH2Phenyl)2; wherein X4 is
Figure imgf000067_0001
or
Figure imgf000067_0002
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