WO2017058388A1 - Catalyseurs supportés de type salan - Google Patents

Catalyseurs supportés de type salan Download PDF

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Publication number
WO2017058388A1
WO2017058388A1 PCT/US2016/047867 US2016047867W WO2017058388A1 WO 2017058388 A1 WO2017058388 A1 WO 2017058388A1 US 2016047867 W US2016047867 W US 2016047867W WO 2017058388 A1 WO2017058388 A1 WO 2017058388A1
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hydrocarbyl radical
independently
catalyst
formula
catalyst system
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PCT/US2016/047867
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English (en)
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Xuan YE
Crisita Carmen H. ATIENZA
Matthew W. Holtcamp
David F. SANDERS
Gregory S. DAY
Michelle E. TITONE
David A. Cano
Matthew S. Bedoya
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Exxonmobil Chemical Patents Inc.
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Publication of WO2017058388A1 publication Critical patent/WO2017058388A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/07—Catalyst support treated by an anion, e.g. Cl-, F-, SO42-
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer

Definitions

  • This invention relates to supported Salan catalysts, processes utilizing such catalysts, and polymers produced thereby.
  • Supported olefin polymerization catalysts are of great use in industry. Hence, there is interest in finding new supported catalyst systems that increase the commercial usefulness of the catalyst and allow the production of polymers having improved properties.
  • the instant disclosure is directed to supported catalyst compounds, supported activators, and catalyst systems comprising such compounds, processes for the preparation of the catalyst compounds and systems, and processes for the polymerization of olefins using such supported catalyst compounds and systems.
  • some embodiments of the invention relate to catalyst systems comprising the reaction product of fluorided support (such as fluorided silica) that preferably has not been calcined at a temperature of 400°C or more, an activator and a catalyst compound represented by Formula I:
  • each solid line represents a covalent bond and each dashed line represents a coordinative link; wherein M is a Group 3, 4, 5, or 6 transition metal;
  • N 1 and N 2 are nitrogen
  • O oxygen
  • each of X 1 and X 2 is, independently, a univalent Ci to C2 0 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, or X 1 and X 2 join together to form a C4 to Ce2 cyclic or poly cyclic ring structure, provided however when M is trivalent X 2 is not present;
  • each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 is, independently, hydrogen, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical (such as a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements), two or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 independently join together to form a C4 to Ce2 cyclic or poly cyclic ring structure, or a combination thereof;
  • R* 1 and R* 2 independently comprise a bulky functional group, an electron withdrawing group, or a combination thereof;
  • Y is a divalent Ci to C20 hydrocarbyl radical.
  • some embodiments of the invention relate to processes comprising: contacting one or more olefins with a catalyst system described herein at a temperature, a pressure, and for a period of time sufficient to produce a poly olefin.
  • some embodiments of the invention relate to polyolefins comprising ethylene, wherein the poly olefin is produced by a process comprising: contacting ethylene and, optionally one or more comonomers with a catalyst system described herein at a temperature, a pressure, and for a period of time sufficient to produce a poly olefin.
  • transition metal catalyst compound is used to describe molecules in which an ancillary ligand is coordinated to a central transition metal atom.
  • the ligand is bulky and stably bonded to the transition metal so as to maintain its influence during use of the catalyst, such as polymerization.
  • the ligand may be coordinated to the transition metal by covalent bond and/or electron donation coordination or intermediate bonds.
  • the catalyst compounds are generally subjected to activation to perform their polymerization or oligomerization function using an activator, which is believed to create a cation as a result of the removal of an anionic group, often referred to as a leaving group, from the transition metal.
  • hydrocarbyl radical As used herein, the numbering scheme for the Periodic Table groups is the new notation as set out in Chemical and Engineering News, 63(5), 27, (1985).
  • hydrocarbyl radical As used herein, the numbering scheme for the Periodic Table groups is the new notation as set out in Chemical and Engineering News, 63(5), 27, (1985).
  • hydrocarbyl radical is defined to be Ci to C70 radicals, or Ci to C2 0 radicals, or Ci to Cio radicals, or Ce to C70 radicals, or Ce to C20 radicals, or C7 to C20 radicals that may be linear, branched, or cyclic and aromatic or non-aromatic.
  • hydrocarbyl radical is defined to be Ci to C70 radicals, or Ci to C2 0 radicals, or Ci to Cio radicals, or Ce to C70 radicals, or Ce to C20 radicals, or C7 to C20 radicals that may be linear, branched, or cyclic where appropriate (aromatic or non-aromatic) and includes hydrocarbyl radicals substituted with other hydrocarbyl radicals.
  • two or more such hydrocarbyl radicals may together form a fused ring system, including partially or fully hydrogenated fused ring systems, which may include heterocyclic radicals.
  • substituted means that a hydrogen atom or a carbon atom of a hydrocarbyl radical has been replaced by a heteroatom or a heteroatom-containing group.
  • a heteroatom is defined as any atom other than carbon and hydrogen.
  • methyl cyclopentadiene is a Cp group wherein one hydrogen has been replaced with a methyl radical, which may also be referred to as a methyl functional group
  • ethyl alcohol is an ethyl group, wherein one of the H atoms has been replaced with the heteroatom-containing group -OH
  • pyridine is considered a substituted phenyl group wherein a carbon of the benzene ring has been replaced with a nitrogen atom.
  • Exemplary hydrocarbyl radicals include methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, but
  • aryl refers to aromatic cyclic structures.
  • An aralkyl group is defined to be an aryl group having at least one H atom replaced by an alkyl group, such as a Ci to C40 alkyl.
  • aryl and aralkyl radicals include, but are not limited to: acenaphthenyl, acenaphthylenyl, acridinyl, anthracenyl, benzanthracenyls, benzimidazolyl, benzisoxazolyl, benzofluoranthenyls, benzofuranyl, benzoperylenyls, benzopyrenyls, benzothiazolyl, benzothiophenyls, benzoxazolyl, benzyl, carbazolyl, carbolinyl, chrysenyl, cinnolinyl, coronenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, dibenzoanthracenyls, fluoranthenyl, fluorenyl, furanyl, imidazolyl, indazolyl, indenopyrenyls, in
  • a carbazole radical a hydrocarbyl radical
  • a hydrocarbyl radical is represented by the formula:
  • each R 1 through R 8 is, independently, a hydrogen, a Ci to C40 hydrocarbyl radical, a substituted Ci to C40 hydrocarbyl radical (such as a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements), or two or more of R 1 to R 8 may independently join together to form a C4 to Ce2 cyclic or poly cyclic ring structure, or a combination thereof.
  • a substituted carbazole is one where at least one of R 1 to R 8 is not H.
  • a fluorenyl radical, another hydrocarbyl radical, is represented by the formula:
  • each R 1 through R 8 is, independently, a hydrogen, a Ci to C40 hydrocarbyl radical, a substituted Ci to C40 hydrocarbyl radical (such as a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements), or two or more of R 1 to R 8 may independently join together to form a C4 to Ce2 cyclic or poly cyclic ring structure, or a combination thereof; and
  • R* is a hydrogen, a Ci to C40 hydrocarbyl radical, a substituted Ci to C40 hydrocarbyl radical (preferably R* is methyl, phenyl, tolyl, substituted phenyl, or substituted tolyl).
  • a substituted fluorenyl is one where at least one of R*, or R 1 to R 8 is not H.
  • an "olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound comprising carbon and hydrogen having at least one double bond.
  • olefin present in such polymer or copolymer is the polymerized form of the olefin.
  • a copolymer is said to have an "ethylene" content of 35 wt% to 55 wt%, it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer.
  • a "polymer” has two or more of the same or different “mer” units.
  • a “homopolymer” is a polymer having mer units that are the same.
  • a “copolymer” is a polymer having two or more mer units that are different from each other.
  • a “terpolymer” is a polymer having three mer units that are different from each other. "Different” in reference to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically. Accordingly, the definition of copolymer, as used herein, includes terpolymers and the like.
  • An oligomer is typically a polymer having a low molecular weight, such as Mn of less than 25,000 g/mol, or in an embodiment less than 2,500 g/mol, or a low number of mer units, such as 75 mer units or less.
  • An "ethylene polymer” or “ethylene copolymer” is a polymer or copolymer comprising at least 50 mol% ethylene derived units
  • a "propylene polymer” or “propylene copolymer” is a polymer or copolymer comprising at least 50 mole% propylene derived units, and so on.
  • a-olefin includes C2 to C22 olefins having a double bond at the alpha position.
  • Non-limiting examples of a-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1- heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1- tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacos
  • Non-limiting examples of cyclic olefins and diolefins include: cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, norbomene, 4-methylnorbornene, 2-methylcyclopentene, 4- methylcyclopentene, vinylcyclohexane, norbornadiene, dicyclopentadiene, 5-ethylidene-2- norbomene, vinylcyclohexene, 5-vinyl-2-norbornene, 1,3-divinylcyclopentane, 1,2- divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane, 1,5-divinylcyclooctane, l-allyl-4-vinylcyclohexane
  • catalyst is defined to mean a compound capable of initiating polymerization catalysis under the appropriate conditions.
  • the catalyst may be described as a catalyst precursor, a pre-catalyst compound, a transition metal compound, a Salan compound, a Salan catalyst, or a Salan catalyst compound, and these terms are used interchangeably.
  • a catalyst compound may be used by itself to initiate catalysis or may be used in combination with an activator to initiate catalysis. When the catalyst compound is combined with an activator to initiate catalysis, the catalyst compound is often referred to as a pre-catalyst or catalyst precursor.
  • a “catalyst system” is the combination of at least one catalyst compound, at least one activator, an optional co-activator, and a support material, where the system can polymerize monomers to polymer.
  • catalyst systems are described as comprising neutral stable forms of the components, it is well understood by one of ordinary skill in the art that the ionic form of the component is the form that reacts with the monomers to produce polymers.
  • catalyst productivity is a measure of how many grams of polymer (P) are produced using a polymerization catalyst comprising W g of catalyst (cat), over a period of time of T hours; and may be expressed by the following formula: P/(T x W) and expressed in units of gP*gcat "1 *hr "1 . Conversion is the amount of monomer that is converted to polymer product, and is reported as mol% and is calculated based on the polymer yield and the amount of monomer fed into the reactor. "Catalyst activity” is a measure of how active the catalyst is and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kg P/mol cat).
  • An "anionic ligand” is a negatively charged ligand which donates one or more pairs of electrons to a metal ion.
  • a "neutral donor ligand” is a neutrally charged ligand which donates one or more pairs of electrons to a metal ion.
  • a "scavenger” is a compound that is typically added to facilitate oligomerization or polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. A co-activator, that is not a scavenger, may also be used in conjunction with an activator in order to form an active catalyst. In an embodiment a co- activator can be pre-mixed with the catalyst compound to form an alkylated catalyst compound.
  • Mn is number average molecular weight
  • Mw is weight average molecular weight
  • Mz is z average molecular weight
  • wt% is weight percent
  • vol% is volume percent
  • mol% is mole percent.
  • Molecular weight distribution (MWD) is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units, e.g., Mw, Mn, Mz, are g/mol.
  • a bulky functional group is defined as a functional group having a molecular size greater than or equal to an isopropyl moiety. Accordingly, for purposes herein a bulky functional group includes substituted or unsubstituted bulky aliphatic radicals having three carbons or more, bulky alicyclic radicals having three carbons or more, and/or bulky aromatic radicals having five carbons or more, each having a molecular size greater than or equal to an isopropyl moiety.
  • Molecular volume is used herein as an approximation of spatial steric bulk of an activator molecule in solution. Comparison of substituents with differing molecular volumes allows the substituent with the smaller molecular volume to be considered “less bulky” in comparison to the substituent with the larger molecular volume. Conversely, a substituent with a larger molecular volume may be considered “more bulky” than a substituent with a smaller molecular volume.
  • Molecular volume may be calculated as reported in "A Simple 'Back of the Envelope' Method for Estimating the Densities and Molecular Volumes of Liquids and Solids," Journal of Chemical Education, Vol. 71, No. 11, November 1994, pp. 962-964.
  • V s is the sum of the relative volumes of the constituent atoms, and is calculated from the molecular formula of the substituent using the following table of relative volumes. For fused rings, the V s is decreased by 7.5% per fused ring.
  • Me is methyl
  • Ph is phenyl
  • Et is ethyl
  • Pr is propyl
  • iPr is isopropyl
  • n-Pr is normal propyl
  • Bu is butyl
  • iso-butyl is isobutyl
  • sec-butyl is secondary butyl
  • tert-butyl and t-butyl are tertiary butyl
  • n-butyl is normal butyl
  • pMe is para-methyl
  • Bz is benzyl
  • THF also referred to as thf
  • Mes is mesityl, also known as 1,3,5-trimethylbenzene
  • Tol is toluene
  • TMS is trimethylsilyl
  • TIBAL is triisobutylaluminum
  • TNOAL is triisobutyl n- octylaluminum
  • MAO is methylalumox
  • RT room temperature, which is defined as 25°C unless otherwise specified. All percentages are weight percent (wt%) unless otherwise specified.
  • continuous means a system that operates without interruption or cessation.
  • a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn.
  • the catalyst compound comprises a catalyst compound represented by Formula I:
  • each solid line represents a covalent bond and each dashed line represents a coordinative link;
  • M is a Group 3, 4, 5, or 6 transition metal;
  • N 1 and N 2 are nitrogen;
  • O is oxygen;
  • each of X 1 and X 2 is, independently, a univalent Ci to C2 0 hydrocarbyl radical, a Ci to C2 0 substituted hydrocarbyl radical (such as a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements), or X 1 and X 2 join together to form a C4 to Ce2 cyclic or poly cyclic ring structure, provided, however, when M is trivalent X 2 is not present; particularly, wherein at least one of X 1 and/or X 2 is selected from Ce to C15 aryl groups, e.g., benzyl;
  • each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 is, independently, hydrogen, a C1-C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical (such as, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements), two or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 independently join together to form a C4 to Ce2 cyclic or poly cyclic ring structure, or a combination thereof; wherein each of R* 1 and R* 2 independently comprises a bulky functional group, an electron withdrawing group, or a combination thereof (such as, but not limited, to a substituted or unsubstituted Ci to C40 hydrocarbyl radical); and
  • Y is a divalent Ci to C2 0 hydrocarbyl radical, particularly a Ci to C5 hydrocarbyl radical, e.g., -(CH 2 CH 2 )-.
  • At least one of R* 1 and R* 2 independently comprises a cyclopentadienyl radical having a structure according to Formula II:
  • R 7 is a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical (such as or a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements); and each of R 8 , R 9 , R 10 , R 11 is, independently, hydrogen, a Ci to C40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, two or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 independently join together to form a C4 to Ce2 cyclic or poly cyclic ring structure, or a combination thereof.
  • each of R* 1 and R* 2 is selected from the group consisting of substituted or unsubstituted radicals comprising any one of the following formulae:
  • C* is the attachment carbon of the radical and each of the possible substituents of the formulae are independently, hydrogen, a Ci to C40 hydrocarbyl radical, a functional group comprising elements from Group 13 to 17 of the periodic table of the elements, or a combination thereof.
  • each of R* 1 and R* 2 independently comprises identical radicals.
  • R* 1 is a substituted or unsubstituted fluorenyl group
  • R* 2 is also a substituted or unsubstituted fluorenyl group.
  • the catalyst compound is represented by Formula III:
  • each of R 7 and R 26 is, independently, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical (such as or a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements);
  • R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , and R 34 is, independently, hydrogen, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical (such as a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements), and
  • R 1 , R , R , R , and R iJ may independently join together to form a C4 to Ce2 cyclic or polycyclic ring structure, or a combination thereof, and M, O, N 1 , N 2 , Y, X 1 , X 2 , R ⁇ R 6 , and R -R are as defined in Formula I.
  • At least one of R 5 and/or R 16 of any of the compounds according to Formulas I-III is selected from the group consisting of Ci to C 10 alkyl, Ci to C 10 alkoxy, and Ce to C 15 aryl.
  • R 7 of the catalyst compound of Formula III or Formula IV is selected from the group consisting of Ci to C lo alkyl groups, Ci to C lo alkoxy groups, Ce to Ci5 aryl groups, and combinations thereof.
  • each of R 7 and/or R 26 of catalysts, according to Formula III is selected from the group consisting of Ci to C lo alkyl groups, Ci to Cio alkoxy groups, Ce to C15 aryl groups, and combinations thereof.
  • each of R 5 and R 16 of the catalysts according to any of Formulas I-III is independently selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl, t-butyl, methoxy, ethoxy, n-propoxy, i-propoxy, n- butoxy, sec-butoxy, i-butoxy, t-butoxy, phenyl, and Ci to C5 substituted phenyl groups.
  • R 7 is independently selected from the group consisting of ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl, t-butyl, phenyl and Ci to C5 substituted phenyl groups.
  • each of R 7 and R 26 , according to Formula IV is independently selected from the group consisting of ethyl, n- propyl, i-propyl, n-butyl, sec-butyl, i-butyl, t-butyl, phenyl, and Ci to C5 substituted phenyl groups;
  • the catalyst of Formulas I-III may have a formula wherein each of R 1 , R 2 , R 3 , R 4 , R 6 , R 12 , R 13 , R 14 , R 15 , R 17 , is independently selected from H and Ci to C5 alkyl groups.
  • the catalyst may follow Formula II wherein R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , and R 25 are each independently selected from H and Ci to C 5 alkyl groups.
  • the catalyst compounds are each independently selected from H and Ci to C5 alkyl groups; particularly, wherein Y is a divalent Ci to C5 hydrocarbyl radical, particularly, -(CH 2 CH 2 )-; and, optionally, wherein at least one of X 1 and/or X 2 is selected from Ce to Ci5 aryl groups, particularly benzyl.
  • At least one of R* 1 and R* 2 independently comprises a pyrrole radical having the structure according to Formula IV:
  • N* indicates an attachment carbon of the radical; and each of R 8 , R 9 , R 10 , R 11 is, independently, a hydrogen, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical (such as a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements), optionally two or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 independently join together to form a C 4 to C 62 cyclic or poly cyclic ring structure, or a combination thereof.
  • each of R* 1 and R* 2 independently comprises a pyrrole radical according to Formula IV.
  • N 3 and N 4 are nitrogen
  • each R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , and R 33 is, independently, a hydrogen, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical (such as a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements), or two or more of R 1 to R 33 may independently join together to form a C4 to Ce2 cyclic or poly cyclic ring structure, or a combination thereof, and M, O, N 1 , N 2 , Y, X 1 , X 2 , R ⁇ R 6 , and R 12"17 are as defined in Formula I.
  • R 5 and/or R 16 is selected from the group consisting of Ci to C1 0 alkyl, Ci to C1 0 alkoxy, and Ce to C 15 aryl.
  • each of R 5 and R 16 is independently selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i- butyl, t-butyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, i-butoxy, t- butoxy, phenyl, and Ci to C5 substituted phenyl groups.
  • the catalyst compounds according to Formula V may have a structure wherein each of R 1 , R 2 , R 3 , R 4 , R 6 ,
  • R 12 R 13 R 14 R 15 R 17 R 18 R 19 R 20 R 21 R 22 R 23 R 24 R 25 R 26 R 27 R 28 R 29 R 30 R 31 R 32 and R 33 are each independently selected from H and Ci to C5 alkyl groups.
  • Y is a divalent Ci to C5 hydrocarbyl radical, particularly -(CH 2 CH 2 )-.
  • Y is a C1-C40 divalent hydrocarbyl radical comprising O, S, S(O), S(0) 2 , Si(R') 2 , P(R'), N, N(R'), or a combination thereof, wherein each R' is independently a Ci to Cig hydrocarbyl radical.
  • some catalysts according to Formula V have a structure wherein at least one of X 1 and/or X 2 is selected from the group consisting of a halogen or a Ci to C 7 hydrocarbyl radical, and a Ce to Ci5 aryl group, particularly benzyl.
  • the catalyst according to Formula V, has a structure
  • M is Zr; X and X are benzyl radicals; R and R are methyl radicals; R , R R , R , R 6 , R 13 , R 14 R 15 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , and R 25 are hydrogen; R 16 is bromine; and Y is -CH 2 CH 2 -.
  • the catalyst according to Formula V, has a structure
  • M is Zr; X and X are benzyl radicals; R , R and R are methyl radicals; R , R , R
  • R rv 31 R 32 , and R 33 are hydrogen; and Y is -CH 2 CH 2 -.
  • the catalyst composition has a structure according to Formula
  • each R , R , R z , R Z1 , R zz , R , R , R , and R is, independently, a hydrogen, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical (such as a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements), or two or more of R 1 to R 33 may independently join together to form a C4 to ei cyclic or poly cyclic ring structure, or a combination thereof, and M, O, N 1 , N 2 , Y, X 1 , X 2 , R ⁇ R 6 , and R 12 -R 17 are as defined in Formula I.
  • Y is a divalent Ci to C5 hydrocarbyl radical, particularly -(CH 2 CH 2 )-; and wherein at least one of X 1 and/or X 2 is selected from the group consisting of a halogen or a Ci to C 7 hydrocarbyl radical, and a e to C 15 aryl group, particularly benzyl.
  • M is Hf, Ti, Zr, or mixtures thereof.
  • Hf is particularly useful.
  • Zr is particularly useful.
  • Ti may be particularly useful.
  • the catalyst according to Formula VI, has a structure wherein each of X 1 and X 2 is, independently, a halogen or a Ci to C 7 hydrocarbyl radical.
  • each of X 1 and X 2 is a benzyl radical.
  • catalysts according to Formula VI, have a structure wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 is, independently, hydrogen, a halogen, or a Ci to C30 hydrocarbyl radical, particularly a Ci to C1 0 hydrocarbyl radical.
  • one or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 is a methyl radical, a fluoride, or a combination thereof.
  • Y may be -CH 2 CH 2 - or 1,2- cyclohexylene. In other embodiments, Y may be -CH2CH2CH2-.
  • catalysts, according to Formula VI have a structure wherein Y is a Ci to C40 divalent hydrocarbyl radical comprising a linker backbone comprising from 1 to 18 carbon atoms bridging between nitrogen atoms N 1 and N 2 .
  • Y may be a Ci to C 40 divalent hydrocarbyl radical comprising O, S, S(O), S(0) 2 , Si(R') 2 , P(R'), N, N(R'), or a combination thereof, wherein each R' is independently a Ci to Cig hydrocarbyl radical.
  • M is Ti;
  • X 1 and X 2 are benzyl radicals;
  • R 1 and R 12 are methyl radicals;
  • R 2 , R 3 , R 4 , R 6 , R 13 , R 14 , R 15 , R 16 and R 17 are hydrogen;
  • R 5 , R 16 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 are fluorine;
  • Y is -CH 2 CH 2 -.
  • M is Ti
  • X and X are benzyl radicals
  • R , R , R and R are methyl radicals
  • R 2 , R 3 , R 4 , R 6 , R 13 , R 14 , R 15 , and R 17 are hydrogen
  • R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 are fluorine
  • Y is -CH 2 CH 2 -.
  • certain catalyst compounds according to Formula VI, have a structure wherein M is Zr; X 1 and X 2 are benzyl radicals; R 1 and R 12 are methyl radicals; R 2 , R 3 , R 4 , R 6 , R 13 , R 14 , R 15 , and R 17 are hydrogen; R 5 , R 16 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 are fluorine; and Y is -CH 2 CH 2 -.
  • certain catalyst compounds according to Formula VI, have a structure wherein M is Zr; X 1 and X 2 are benzyl radicals; R 1 , R 5 , R 16 and R 16 are methyl radicals; R 2 , R 3 , R 4 , R 6 , R 12 , R 14 , R 15 , and R 17 are hydrogen; R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 are fluorine; and Y is -CH 2 CH 2 -.
  • the invention relates to catalysts systems wherein the catalyst, according to Formula I, has a structure according to Formula VII:
  • M may be a Group 3, 4, 5, or 6 transition metal; N 1 , N 2 , N 3 , and N 4 are nitrogen; O is oxygen; each of X 1 and X 2 may be, independently, a univalent Ci to C2 0 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, or X 1 and X 2 join together to form a C4 to Ce2 cyclic or polycyclic ring structure, provided however when M is trivalent X 2 is not present; Y is a divalent hydrocarbyl radical covalently bonded to and bridging between both of the nitrogen atoms N 1 and N 2 ; and each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 ,
  • Particular embodiments may have one or more of the following features:
  • each of X 1 and X 2 is, independently, a halogen or a to C 7 hydrocarbyl radical.
  • each of X 1 and X 2 is a benzyl radical.
  • Y may have a certain structure.
  • Y may be -CH 2 CH 2 - or 1,2-cyclohexylene.
  • Y is -CH2CH2CH2-.
  • Y is a Ci to C40 divalent hydrocarbyl radical comprising a linker backbone comprising from 1 to 18 carbon atoms bridging between nitrogen atoms N 1 and N 2 .
  • Y is a Ci to C40 divalent hydrocarbyl radical comprising O, S, S(O), S(0) 2 , Si(R')2, P(R'), N, N(R'), or a combination thereof, wherein each R' is independently a Ci to C 18 hydrocarbyl radical.
  • Certain catalysts according to Formula VII, have a structure wherein each R 1 , R 2 ,
  • each R , R , R , R , R , R , and R 37 and is, independently, a hydrogen, a Ci to C40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, or a combination thereof.
  • catalyst compounds according to Formula VII, have a structure wherein each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , and R 37 is, independently, hydrogen, a halogen, or a Ci to C30 hydrocarbyl radical, more particularly a Ci to Cio hydrocarbyl radical.
  • the catalysts according to Formula XI have a structure wherein one or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , and R 37 is a methyl radical, a fluoride, or a combination thereof.
  • catalyst compounds according to Formula VII, have a structure wherein R 22 and R 27 j oin together to form a divalent Ci to C2 0 hydrocarbyl radical, a divalent functional group comprising elements from Groups 13 to 16 of the periodic table of the elements, or a combination thereof, and wherein R 32 and R 37 join together to form a divalent Ci to C2 0 hydrocarbyl radical, a divalent functional group comprising elements from Groups 13 to 16 of the periodic table of the elements, or a combination thereof.
  • catalyst compounds may have a structure wherein:
  • M is Zr
  • X 1 and X 2 are benzyl radicals
  • R 1 and R 12 are methyl radicals
  • catalyst compounds may have a structure wherein: M is Zr;
  • X 1 and X 2 are benzyl radicals
  • R 1 , R 5 , R 12 , and R 16 are methyl radicals
  • R 2 , R 3 , R 4 , R 6 , R 13 , R 14 , R 15 , R 17 to R 37 are hydrogen;
  • catalyst compounds according to Formula VII, have a structure according to Formula VIII:
  • O is oxygen
  • M may be a Group 3, 4, 5, or 6 transition metal
  • N 1 , N 2 , N 3 , and N 4 are nitrogen
  • each of X 1 and X 2 is, independently, a univalent Ci to C2 0 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical (such as, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements), or X 1 and X 2 join together to form a C4 to Ce2 cyclic or poly cyclic ring structure, provided, however, when M is trivalent X 2 is not present; and
  • Y is a divalent Ci to C20 hydrocarbyl radical
  • Y 2 and Y 3 are independently a divalent Ci to C2 0 hydrocarbyl radical, a Ci to C2 0 substituted hydrocarbyl radical (such as a divalent functional group comprising elements from Groups 13 to 16 of the periodic table of the elements), or a combination thereof
  • each R 1 to R 6 , R 12 to R 21 , R 23 to R 26 , R 28 to R 31 , and R 33 to R 36 is, independently, a hydrogen
  • a Ci to C40 hydrocarbyl radical is, a Ci to C40 substituted hydrocarbyl radical (such as a functional group comprising elements from Groups
  • R o , R e to R , and R" to R 30 may independently join together to form a C4 to Ce2 cyclic or polycyclic ring structure.
  • the symmetric transition metal compounds may be prepared by two general synthetic routes.
  • the parent Salan ligands are prepared by a one- step Mannich reaction from the parent phenol (Reaction A) or by a two-step imine- condensation/alkylation procedure if the salicylaldehyde is used (Reaction B).
  • the ligand is then converted into the metal dibenzyl catalyst precursor by reaction with the metal tetra-aryl starting material, (e.g., tetrabenzyl), to yield the finished complex (Reaction C).
  • the metal tetra-aryl starting material e.g., tetrabenzyl
  • Asymmetric transition metal compounds may be prepared by a step-wise synthetic route.
  • the parent Salan ligands are prepared by reaction of the salicylaldehyde with the diamine, followed by reduction with NaBH 4 .
  • the asymmetric ligand is then formed by an HBr elimination reaction with a bromomethylphenol (Reaction D).
  • the ligand is then converted into the metal dibenzyl catalyst precursor by reaction with the metal tetrabenzyl starting material to yield the finished complex (Reaction E).
  • Reaction D :
  • activators are used interchangeably to describe activators and are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral catalyst compound to a catalytically active catalyst compound cation.
  • Non-limiting activators include alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and conventional-type cocatalysts.
  • Activators may include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract a reactive, ⁇ -bound, metal ligand making the metal complex cationic and providing a charge-balancing non-coordinating or weakly coordinating anion.
  • alumoxane activators are utilized as an activator in the catalyst composition.
  • Alumoxanes are generally oligomeric compounds containing -A ⁇ R 1 )- O- sub-units, where R 1 is an alkyl radical.
  • Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane.
  • Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the catalyst precursor compound comprises an abstractable ligand which is an alkyl, halide, alkoxide, or amide.
  • alumoxanes Mixtures of different alumoxanes and modified alumoxanes may also be used.
  • visually clear methylalumoxane may be used.
  • a cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution.
  • a useful alumoxane is a modified methyl alumoxane (MMAO) described in US 5,041,584 and/or commercially available from Akzo Chemicals, Inc., under the trade designation Modified Methylalumoxane type 3 A.
  • Solid alumoxanes may also be used.
  • the activator is a TMA-depleted activator (where TMA is the abbreviation for trimethylaluminum).
  • TMA is the abbreviation for trimethylaluminum.
  • MAO methylalumoxane
  • TMA trimethylaluminum
  • TMA trimethylaluminum
  • TMA-depleted activator any methods known in the art to remove TMA may be used.
  • a solution of alumoxane (such as methylalumoxane), for example, 30 wt% in toluene may be diluted in toluene and the aluminum alkyl (such as TMA in the case of MAO) is removed from the solution, for example, by combination with trimethylphenol and filtration of the solid.
  • the TMA-depleted activator comprises from about 1 wt% to about 14 wt% trimethylaluminum, or less than 13 wt%, or less than 12 wt%, or less than 10 wt%, or less than 5 wt%, or 0 wt%, and/or, greater than 0 wt%, or greater than 1 wt%.
  • the maximum amount of activator is a 5000-fold molar excess Al/M over the catalyst compound (per metal catalytic site).
  • the minimum activator-to-catalyst- compound which is determined according to molar concentration of the transition metal M in an embodiment, is 1 mole aluminum or less to mole of transition metal M.
  • the activator comprises alumoxane and the alumoxane is present at a ratio of 1 mole aluminum or more to mole of catalyst compound.
  • the minimum activator-to-catalyst-compound molar ratio is a 1 : 1 molar ratio.
  • Other embodiments of A1:M ranges include from 1 : 1 to 500: 1, or from 1 : 1 to 200: 1, or from 1 : 1 to 100: 1, or from 1 : 1 to 50: 1.
  • NCA non-coordinating anion activator
  • the activator is an alumoxane (modified or unmodified)
  • the maximum amount of activator is a 5000-fold molar excess Al/M over the catalyst compound (per metal catalytic site).
  • the minimum activator-to-catalyst-compound, which is determined according to molar concentration of the transition metal M, in an embodiment is 1 mole aluminum or less to mole of transition metal M.
  • the activator comprises alumoxane and the alumoxane is present at a ratio of 1 mole aluminum or more to mole of catalyst compound.
  • the minimum activator-to-catalyst-compound molar ratio is a 1 : 1 molar ratio.
  • Other embodiments of A1:M ranges include from 1 : 1 to 500: 1, or from 1 : 1 to 200: 1, or from 1 : 1 to 100: 1, or from 1 : 1 to 50: 1.
  • alumoxane is present at 0.00 mol%, or the alumoxane is present at a molar ratio of aluminum to catalyst compound transition metal less than 500: 1, or less than 300: 1, or less than 100: 1, or less than 1 : 1.
  • Examples of neutral stoichiometric activators include tri-substituted boron, tellurium, aluminum, gallium, and indium, or mixtures thereof.
  • the three substituent groups or radicals can be the same or different and in an embodiment are each independently selected from substituted or unsubstituted alkyls, alkenyls, alkyns, aryls, alkoxy, and halogens.
  • the three groups are independently selected from halogen, mono or multicyclic (including halosubstituted) aryls, alkyls, and alkenyl compounds, and mixtures thereof; or independently selected from alkenyl radicals having 1 to 20 carbon atoms, alkyl radicals having 1 to 20 carbon atoms, alkoxy radicals having 1 to 20 carbon atoms and aryl or substituted aryl radicals having 3 to 20 carbon atoms.
  • the three substituent groups are alkyl radicals having 1 to 20 carbon atoms, phenyl, naphthyl, or mixtures thereof.
  • the three groups are halogenated aryl groups, e.g., fluorinated aryl groups.
  • the neutral stoichiometric activator is tris- perfluorophenyl boron or tris perfluoronaphthyl boron.
  • ionic stoichiometric activator compounds may include an active proton, or some other cation associated with, but not coordinated to, or only loosely coordinated to the remaining ion of the ionizing compound.
  • Suitable examples include compounds and the like described in EP 0 570 982 Al ; EP 0 520 732 Al ; EP 0 495 375 Al ; EP 0 500 944 Bl; EP 0 277 003 Al; EP 0 277 004 Al; US 5,153,157; US 5,198,401; US 5,066,741; US 5,206,197; US 5,241,025; US 5,384,299; US 5,502,124; and WO 1996/04319; all of which are fully incorporated herein by reference.
  • compounds useful as an activator comprise a cation, which is, for example, a Bronsted acid capable of donating a proton, and a compatible non- coordinating anion which anion is relatively large (bulky), capable of stabilizing the active catalyst species (the Group 4 cation, e.g.) which is formed when the two compounds are combined and said anion will be sufficiently labile to be displaced by olefinic, diolefinic, or acetylenically unsaturated substrates or other neutral Lewis bases, such as ethers, amines, and the like.
  • a cation which is, for example, a Bronsted acid capable of donating a proton
  • a compatible non- coordinating anion which anion is relatively large (bulky)
  • the active catalyst species the Group 4 cation, e.g.
  • EP 0 277 003 Al Two classes of useful compatible non-coordinating anions are disclosed in EP 0 277 003 Al, and EP 0 277 004 Al , which include anionic coordination complexes comprising a plurality of lipophilic radicals covalently coordinated to and shielding a central charge- bearing metal or metalloid core; and anions comprising a plurality of boron atoms such as carboranes, metallacarboranes, and boranes.
  • the stoichiometric activators include a cation and an anion component, and may be represented by the following formula (1):
  • Z is (L-H) or a reducible Lewis Acid, L is a neutral Lewis base; H is hydrogen; (L-H) + is a Bronsted acid; A d" is a non-coordinating anion having the charge d-; and d is an integer from 1 to 3.
  • the cation component may include Bronsted acids such as protonated Lewis bases capable of protonating a moiety, such as an alkyl or aryl, from the catalyst precursor, resulting in a cationic transition metal species, or the activating cation (L-H) ⁇ "1" is a Bronsted acid, capable of donating a proton to the catalyst precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof, or ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, ⁇ , ⁇ -dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N- dimethylaniline, p-nitro-N,N
  • Z is a reducible Lewis acid it may be represented by the formula: (Ar 3 C + ), where Ar is aryl or aryl substituted with a heteroatom, or a C j to C 40 hydrocarbyl
  • the reducible Lewis acid may be represented by the formula: (Ph 3 C + ), where Ph is phenyl or phenyl substituted with a heteroatom, and/or a to C 40 hydrocarbyl.
  • the reducible Lewis acid is triphenyl carbenium.
  • Each Q may be a fluorinated hydrocarbyl radical having 1 to 20 carbon atoms, or each Q is a fluorinated aryl radical, or each Q is a pentafluoryl aryl radical.
  • suitable A d" components also include diboron compounds as disclosed in US 5,447,895, which is fully incorporated herein by reference.
  • the catalyst system may further include scavengers and/or co- activators.
  • Suitable aluminum alkyl or organoaluminum compounds, which may be utilized as scavengers or co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and the like. Other oxophilic species such as diethyl zinc may be used.
  • the scavengers and/or co-activators are present at less than 14 wt%, or from 0.1 to 10 wt%, or from 0.5 to 7 wt%, by weight of the catalyst system.
  • fluorided support and “fluorided support composition” mean a support, desirably particulate and porous, which has been treated with at least one inorganic fluorine-containing compound.
  • the fluorided support composition can be a silicon dioxide support wherein a portion of the silica hydroxy 1 groups has been replaced with fluorine or fluorine-containing compounds.
  • support composition means a support, desirably particulate and porous, which has been treated with at least one fluorine-containing compound.
  • Suitable fluorine-containing compounds include, but are not limited to, inorganic fluorine-containing compounds and/or organic fluorine-containing compounds.
  • Supports suitable for use in this invention are generally porous materials and can include organic materials, inorganic materials, and inorganic oxides.
  • supports suitable for use in this invention include talc, clay, silica, alumina, magnesia, zirconia, iron oxides, boria, calcium oxide, zinc oxide, barium oxide, thona, aluminum phosphate gel, polyvinyl chloride and substituted polystyrene, and mixtures thereof.
  • Other useful support materials include zeolites, clays, organoclays, or any other organic or inorganic support material and the like, or mixtures thereof.
  • the support material is an inorganic oxide in a finely divided form.
  • Suitable inorganic oxide materials for use in the catalyst systems described herein include Groups 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof.
  • Other inorganic oxides that may be employed either alone or in combination with the silica, or alumina are magnesia, titania, zirconia, and the like.
  • Other suitable support materials can be employed, for example, finely divided functionalized polyolefins, such as finely divided polyethylene.
  • Particularly useful supports include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, and the like. Also, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica-titania, and the like.
  • Preferred support materials include A1 2 0 3 , Zr0 2 , Si0 2 , and combinations thereof, more preferably Si0 2 , A1 2 0 3 , or Si0 2 /Al 2 0 3. In a preferred embodiment of the invention, the support is silica.
  • the support material preferably an inorganic oxide, preferably silica
  • the support material has a surface area in the range of from about 10 to about 800 m 2 /g (alternately about 10 to about 700 m 2 /g), pore volume in the range of from about 0.1 to about 4.0 cc/g and average particle size in the range of from about 5 to about 500 ⁇ . More preferably, the surface area of the support material is in the range of from about 50 to about 500 m 2 /g, pore volume of from about 0.5 to about 3.5 cc/g and average particle size of from about 10 to about 200 ⁇ .
  • the surface area of the support material is in the range of from about 100 to about 400 m 2 /g, pore volume from about 0.8 to about 3.0 cc/g and average particle size is from about 5 to about 100 ⁇ .
  • the average pore size of the support material useful in the invention is in the range of from 10 to 1000 A, preferably 50 to about 500 A, and most preferably 75 to about 350 A.
  • Useful silicas are available under the trade names of DAVISONTM 952, DAVISONTM 948, or DAVISONTM 955 by the Davison Chemical Division of W.R.
  • Total surface area also referred to as “surface area” and total pore volume, also referred to as “pore volume,” and average pore diameter, also referred as average pore size
  • BET Brunauer-Emmett-Teller
  • Average particle size is determined using a MastersizerTM 3000 (range of 1 to 3500 ⁇ ) available from Malvern Instruments, Ltd., Worcestershire, England,
  • the support is silica, is desirably porous and has a surface area in the range of from about 10 to about 800 m ' Vg, a total pore volume in the range of from about 0.1 to about 4.0 cc/g and an average particle diameter in the range of from about 10 to about 500 ⁇ . More desirably, the surface area is in the range of from about 50 to about 500 rrr/g, the pore volume is in the range of from about 0.5 to about 3.5 cc/g and the average particle diameter is in the range of from about 15 to about 150 ⁇ .
  • the surface area is in the range of from about 100 to about 400 rrr/g
  • the pore volume is in the range of from about 0.8 to about 3.0 cc/g
  • the average particle diameter is in the range of from about 20 to about 100 ⁇
  • the average pore diameter of typical porous silicon dioxide support materials is in the range of from about 10 to about 1000 A.
  • the support material has an average pore diameter of from about 50 to about 500 A, and most desirably from about 75 to about 350 A.
  • the fluorine compounds suitable for providing fluorine for the support may be organic or inorganic fluorine compounds and are desirably inorganic fluorine-containing compounds.
  • Such inorganic fluorine-containing compounds may be any compound containing a fluorine atom as long as it does not contain a carbon atom.
  • Particularly desirable are inorganic fluorine containing compounds are selected from the group consisting of NH4BF4, (NH 4 ) 2 8iF 6 , NH 4 PF 6 , NH4F, (NH 4 ) 2 TaF 7 , NH 4 NbF 4 , (NH 4 ) 2 GeF 6 , (NH 4 ) 2 8mF 6 , (NH 4 ) 2 TiF 6 , (NH 4 ) 2 ZrF 6 , MoF 6 , ReF 6 , GaF 3 , S0 2 C1F, F 2 , SiF 4 , SF 6 , C1F 3 , C1F 5 , BrF 5 , IF 7 , NF3, HF, BF 3 , NHF2, and NH 4 HF 2 .
  • Ammonium hexafluorosilicate and ammonium tetrafluoroborate fluorine compounds are typically solid particulates as are the silicon dioxide supports.
  • the fluorided supports described herein are prepared by combining an aqueous solution of fluorinating agent (such as SiF 4 or (NH ) 2 SiF 6 ) with a slurry of support (such as a toluene slurry of silica), then drying until it is free flowing, and, optionally, calcining (typically at temperatures over 100°C for at least 1 hour).
  • the supports are then combined with activator(s) and catalyst compounds (separately or together).
  • a useful method of treating the support with the fluorine compound is to dry mix the two components by simply blending at a concentration of from 0.01 to 10.0 millimole F/g of support, desirably in the range of from 0.05 to 6.0 millimole F/g of support, and most desirably in the range of from 0.1 to 3.0 millimole F/g of support.
  • the fluorine compound can be dry mixed with the support either before or after charging to a vessel for dehydration or calcining the support. Accordingly, the fluorine concentration present on the support is preferably in the range of from 0.1 to 25 wt%, alternately 0.19 to 19 wt%, alternately from 0.6 to 3.5 wt %, based upon the weight of the support.
  • Another method of treating the support with the fluorine compound is to dissolve the fluorine compound in a solvent, such as water, and then contact the support (dry or combined with water or hydrocarbon solvent) with the fluorine compound containing solution.
  • a solvent such as water
  • silica is the support, it is desirable to use a quantity of water which is less than the total pore volume of the support.
  • a disadvantage of typical dry mix methods is that the density difference between fluorinating agent (such as ammonium hexafluorosilicate - density about 2.1 g/cm J ) and silica (e.g., such as DavisonTM 948 - density about 0.7 g/cn ) makes it difficult to evenly/homogeneously distribute the fluorinating agent in the silica support.
  • the density difference has also led to settling of ammonium hexafluorosilicate in fluorided silica derived from dry mix method. Over a period of two weeks, a vertical gradient of ammonium hexafluorosilicate concentrations in fluorided silica (made via dry mix method) stored in a bottle is observed.
  • the aqueous (wet-mixing) method employs a minimal amount of a polar solvent (e.g., water, methanol, ethanol, isopropanol, or any solvent capable of dissolving the fluoride compound (such as ammonium hexailuorosilieate) to dissolve the fluorinating agent (e.g., ammonium hexailuorosilieate)).
  • a polar solvent e.g., water, methanol, ethanol, isopropanol, or any solvent capable of dissolving the fluoride compound (such as ammonium hexailuorosilieate) to dissolve the fluorinating agent (e.g., ammonium hexailuorosilieate)
  • the fluoride compound solution (such as an ammonium hexailuorosilieate solution) is then added to a slurry of silica in a non-polar solvent (e.g., toluene, or benzene, chloroform, etc.), followed by vigorous stirring of the resulting mixture.
  • a non-polar solvent e.g., toluene, or benzene, chloroform, etc.
  • the polar/hydrophilic nature of the fluoride compound (such as ammonium hexailuorosilieate) leads to its absorption onto the hydrophiiic silica surface.
  • fluorinating agent such as ammonium hexafluorosilicate
  • This method reduces or eliminates non-homogeneous distribution of fluorinating agent in silica associated with other methods.
  • fluonded silica prepared via wet- mixing method gave excellent operability, whereas fluonded silica prepared via dry-mixing method often gave poor operability due to frequent plugging of catalyst feed line.
  • Dehydration or calcining of the silica is not necessary prior to reaction with the fluorine compound, but can be done if desired.
  • the reaction between the silica and fluorine compound is carried out at a temperature of from about 100°C to about 400°C, and more desirably from about 150°C to about 350°C for about two to eight hours.
  • the fluonded support composition may be genencaliy represented by the formula: Sup-F, where "Sup” is a support, and "F” is a fluorine atom bound to the support.
  • the fluorine atom may be bound, directly or indirectly, chemically or physically to the support.
  • An example of chemical or physical bonding would be covalent and ionic bonding, respectively.
  • the fluonded support composition is represented by the formula: Sup-LF n , where "Sup' " is a support, preferably selected from the group consisting of talc, clay, silica, alumina, magnesia, zirconia, iron oxides, boria, calcium oxide, zinc oxide, barium oxide, thoria, aluminum phosphate gel, polyvinyichloride, and substituted polystyrene; "L” is a first member selected from the group consisting of (i) bonding, sufficient to bound the F to the Sup; (li) B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, Al, or Zr bound to the Sup and to the F; and (iii) O bound to the Sup and bound to a second member selected from the group consisting of B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, Al, or Zr which is bound to the F
  • the fluorided support material is then typically slurried in a non-polar solvent and the resulting slurry is contacted with a solution of catalyst compounds and activator.
  • the slurry of the fluorided support material is first contacted with the activator for a period of time in the range of from about 0.5 hours to about 24 hours, from about 1 hour to about 16 hours, or from about 2 hours to about 8 hours.
  • the solution of the catalyst compound is then contacted with the isolated fluorided support/activator.
  • the supported catalyst system is generated in situ.
  • the slurry of the fluorided support material is first contacted with the catalyst compound for a period of time in the range of from about 0.5 hours to about 24 hours, from about 1 hour (or 2 hours) to about 16 hours, or from about 2 hours (or 4 hours) to about 8 hours.
  • the slurry of the supported catalyst compound is then contacted with the activator solution.
  • the mixture of the catalysts, activator and fluorided support may be heated to about 0°C to about 70°C, preferably to about 23°C to about 60°C, preferably at room temperature.
  • Contact times typically range from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.
  • the fluorided support material is slurried in a non-polar solvent and the resulting slurry is contacted with a solution of methylalumoxane (typically 30 wt% MAO in toluene).
  • a solution of methylalumoxane typically 30 wt% MAO in toluene.
  • the fluorided support/MAO mixture is then heated to elevated temperature (30°C to 120°C, preferably 80 to 100°C) with vigorous stirring for a period of time (0.1 to 24 hours, preferably 1 to 3 hours).
  • the support activator is isolated by filtration, rinsed with non-polar solvent (e.g., toluene, pentane, hexane, etc.), and dried.
  • non-polar solvent e.g., toluene, pentane, hexane, etc.
  • the isolated support/activator is then slurried in a non-polar solvent (e.g., toluene), and a solution of catalyst compound/compounds is then contacted with the support/activator slurry. Vigorous stirring may then be applied.
  • a non-polar solvent e.g., toluene
  • the fluorided support material is slowly added in solid form to a solution of MAO in non-polar solvent (e.g., toluene) (typically at room temperature) with vigorous stirring.
  • This addition sequence namely slow and portion-wise addition of fluorided silica to MAO solution, is referred to as "reversed addition.”
  • the fluorided support/MAO mixture is then heated to elevated temperature (30°C to 120°C, preferably 80 to 100°C) with vigorous stirring for a period of time (0.1 to 24 hours, preferably 1 to 3 hours).
  • the support/activator is isolated by filtration, rinsed with non-polar solvent (e.g., toluene, pentane, hexane, etc.), and dried.
  • non-polar solvent e.g., toluene, pentane, hexane, etc.
  • the isolated support/activator is then slurried in a non- polar solvent (e.g., toluene), and a solution of catalyst compound/compounds is then contacted with the support/activator slurry. Vigorous stirring may be applied.
  • Suitable “non-polar solvents” are materials in which all of the reactants used herein, i.e., the activator, and the catalyst compound, are at least partially soluble and which are liquid at reaction temperatures.
  • Preferred non-polar solvents are alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, although a variety of other materials including cycloalkanes, such as cyclohexane, aromatics, such as benzene, toluene, and ethylbenzene, may also be employed.
  • alkanes such as isopentane, hexane, n-heptane, octane, nonane, and decane
  • cycloalkanes such as cyclohexane
  • aromatics such as benzene, toluene, and ethylbenzene
  • the fluorided supports described herein are prepared by combining an aqueous solution of fluorinating agent (such as (NH ⁇ SiFe) with a slurry of support (such as a toluene slurry of silica), drying until free flowing, optionally, calcining (typically at temperatures from 100°C to 400°C for at least 1 hour), then combining with activators and catalyst compounds (the activators and catalyst compounds may be added to the support separately or together).
  • fluorinating agent such as (NH ⁇ SiFe)
  • a slurry of support such as a toluene slurry of silica
  • the water to solvent ratio (by weight) is between 1 : 10 to 1 : 1000, preferably between 1 :20 to 1 :50.
  • the fluorided silica support can immobilize greater than 5.0 mmol "Al” per gram silica, and preferably greater than 6.0 mmol "Al'Vgram silica.
  • the amount of "Al” (from alkylalumoxane, such as MAO) that can be immobilized on 1 gram of fluorided silica is determined by an aluminum titration experiment. The titration is done at 100°C at ambient pressure allowing the alumoxane (15 mmol Al) and the 1 gram of fluorided silica to react for 3 hours.
  • silica is washed with toluene (10ml, 3 times) and then washed with pentane (10 ml, 3 times). The solid is then collected and dried under vacuum for 8 hours until solvent is removed. Then the sample is weighed and the difference in weight is divided by the Mw of the aluminum compound (Mw as reported in the CHEMICAL AND ENGINEERING NEWS, 63(5), pg. 27, (1985)). Methyl alumoxane is defined to be Me-Al-O.
  • the "Al" uptake for silica- 1 in the examples below is about 5.5 mmol Al/gram, whereas the "Al" uptake for silica-2 is about 6.8 mmol/gram.
  • the catalyst system comprising the fluorided silica support immobilizes greater than 5.0 mmol "Al" per gram of silica, and preferably greater than 6.0 mmol "Al" per gram of silica.
  • the fluorided silica support preferably contains less than 0.05 mmol/gram fluorinating agent (such as (NH 4 ) 2 SiF 6 ), preferably less than 0.02 mmol/gram fluorinating agent, as measured by X H NMR.
  • l H NMR data of non-polymeric compounds is collected at room temperature in a 5 mm probe using either a Bruker or Varian NMR spectrometer operating with a l frequency of 500 MHz. Data is recorded using a 30° flip angle RF pulse, 8 scans, with a delay of 5 seconds between pulses. Samples are prepared using approximately 5-10 mg of compound dissolved in approximately 1 mL of an appropriate deuterated solvent.
  • NMR spectroscopic data of polymers is recorded in a 5 mm probe on a Varian NMR spectrometer at 120°C using a d2-l,l,2,2-tetrachloroethane solution prepared from approximately 20 mg of polymer and 1 mL of solvent using a 30° flip angle RF pulse, 120 scans, with a delay of 5 seconds between pulses.
  • the surface area of the fluorided silica support is greater than 200 m 2 /g, preferably greater than 250 m 2 /g, as determined by BET.
  • the surface area of combined fluorided silica support and activator is greater than 250 m 2 /g, preferably greater than 350 m 2 /g, as determined by BET.
  • the combination immediately after combination of the alkylalumoxane with the fluorided support the combination preferably contains less than 0.04 mmoles per gram of silica (preferably less than 0.02 mmoles, preferably less than 0.01 mmoles) of tetraalkylsilane per gram of support as determined by X H NMR (where the alkyl is derived from the alkylalumoxane).
  • the ratio of mmol of fluorine per gram of silica in the fluorided support is between 0.1 and 1.5, preferably between 0.2 and 1.2, preferably between 0.4 and 1.0.
  • the amount of residual (NH ) 2 SiF 6 in the silica should be equal or less than 0.04 mmol (NH ) 2 SiF 6 /g silica, preferably equal or less than 0.02 mmol (NH ) 2 SiF 6 /g silica, more preferably equal or less than 0.01 mmol (NH 4 ) 2 SiF 6 /g silica.
  • polymerization processes include contacting monomers (such as ethylene and propylene), and optionally comonomers, with a catalyst system comprising an activator and at least one catalyst compound, as described above.
  • a catalyst system comprising an activator and at least one catalyst compound, as described above.
  • the catalyst compound and activator may be combined in any order, and may be combined prior to contacting with the monomer.
  • the catalyst compound and/or the activator are combined after contacting with the monomer.
  • Monomers useful herein include substituted or unsubstituted C 2 to C 4 o alpha olefins, or C 2 to C 2 o alpha olefins, or C 2 to C 12 alpha olefins, or ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof.
  • the monomer comprises propylene and optional comonomers comprising one or more ethylene or C 4 to C 40 olefins, or C 4 to C 2 o olefins, or C 6 to C 12 olefins.
  • the C 4 to C 40 olefin monomers may be linear, branched, or cyclic.
  • the C 4 to C 40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.
  • the monomer comprises ethylene or ethylene and a comonomer comprising one or more C3 to C40 olefins, or C4 to C 2Q olefins, or Cg to C 12 olefins.
  • the C3 to C40 olefin monomers may be linear, branched, or cyclic.
  • the C 3 to C 40 cyclic olefins may be strained or unstrained, monocyclic or poly cyclic, and may optionally include heteroatoms and/or one or more functional groups.
  • Exemplary C 2 to C 40 olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, or hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, l-hydroxy-4-cyclooctene, l-acetoxy-4- cyclooctene,
  • one or more dienes are present in the polymer produced herein at up to 10 wt%, or at 0.00001 to 1.0 wt%, or 0.002 to 0.5 wt%, or 0.003 to 0.2 wt%, based upon the total weight of the composition.
  • 500 ppm or less of diene is added to the polymerization, or 400 ppm or less, or 300 ppm or less.
  • at least 50 ppm of diene is added to the polymerization, or 100 ppm or more, or 150 ppm or more.
  • Diolefin monomers useful in this invention include any hydrocarbon structure, or C4 to C30, having at least two unsaturated bonds, wherein at least two of the unsaturated bonds are readily incorporated into a polymer by either a stereospecific or a non- stereospecific catalyst(s).
  • the diolefin monomers may be selected from alpha, omega-diene monomers (i.e., di-vinyl monomers).
  • the diolefin monomers are linear di-vinyl monomers, most or those containing from 4 to 30 carbon atoms.
  • dienes examples include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undeca
  • Cyclic dienes include cyclopentadiene, vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene or higher ring containing diolefins with or without substituents at various ring positions.
  • Polymerization processes according to the instant disclosure may be carried out in any manner known in the art. Any supported polymerization process known in the art (such as gas phase, slurry phase or bulk phase) can be used. Such processes can be run in a batch, semi-batch, or continuous mode.
  • a bulk process is suitable for use herein, wherein a bulk process is defined to be a process where monomer concentration in all feeds to the reactor is 70 vol% or more.
  • no solvent or diluent is present or added in the reaction medium, (except for the small amounts used as the carrier for the catalyst system or other additives, or amounts typically found with the monomer; e.g., propane in propylene).
  • the process is a slurry process.
  • slurry polymerization process means a polymerization process where a supported catalyst is employed and monomers are polymerized on the supported catalyst particles. At least 95 wt% of polymer products derived from the supported catalyst are in granular form as solid particles (not dissolved in the diluent).
  • the polymerization is not a homogeneous process, where a homogeneous polymerization process is defined to be a process where at least 90 wt% of the product is soluble in the reaction media.
  • the polymerization is not a solution process where a solution polymerization process is defined to be a process where the catalyst and the product are soluble in the reaction media.
  • Suitable diluents/solvents for polymerization include non-coordinating, inert liquids.
  • examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (IsoparTM); perhalogenated hydrocarbons, such as perfluorinated C 4 .
  • straight and branched-chain hydrocarbons such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and
  • alkanes such as benzene, toluene, mesitylene, and xylene.
  • Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3 -methyl- 1-pentene, 4-methyl- 1-pentene, 1-octene, 1-decene, and mixtures thereof.
  • aliphatic hydrocarbon solvents are used as the solvent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof.
  • the solvent is not aromatic, or aromatics are present in the solvent at less than 1 wt%, or less than 0.5 wt%, or less than 0.0 wt%, based upon the weight of the solvents.
  • the feed concentration of the monomers and comonomers for the polymerization is 60 vol% solvent or less, or 40 vol% or less, or 20 vol% or less, based on the total volume of the feedstream. Or the polymerization is run in a bulk process.
  • Polymerizations can be run at any temperature and/or pressure suitable to obtain the desired ethylene polymers.
  • Suitable temperatures and/or pressures include a temperature in the range of from about 0°C to about 300°C, or from about 20°C to about 200°C, or from about 35°C to about 150°C, or from about 50°C to about 150°C, or from about 40°C to about 120°C, or from about 45 °C to about 80°C; and at a pressure in the range of from about 0.35 MPa to about 10 MPa, or from about 0.45 MPa to about 6 MPa, or from about 0.5 MPa to about 4 MPa.
  • the run time of the reaction is from about 0.1 minutes to about
  • hydrogen is present in the polymerization reactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa), or from 0.01 to 25 psig (0.07 to 172 kPa), or 0.1 to 10 psig (0.7 to 70 kPa).
  • the activity of the catalyst is at least 50 g/mmol/hour, or 500 or more g/mmol/hour, or 5000 or more g/mmol/hr, or 50,000 or more g/mmol/hr.
  • the conversion of olefin monomer is at least 10%, based upon polymer yield and the weight of the monomer entering the reaction zone, or 20% or more, or 30% or more, or 50% or more, or 80% or more.
  • the polymerization conditions include one or more of the following: 1) temperatures of 0 to 300°C (or 25 to 150°C, or 40 to 120°C, or 45 to 80°C); 2) a pressure of atmospheric pressure to 10 MPa (or 0.35 to 10 MPa, or from 0.45 to 6 MPa, or from 0.5 to 4 MPa); 3) the presence of an aliphatic hydrocarbon solvent (such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as, cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; or where aromatics are or present in the solvent at less than 1 wt%, or less than 0.5 wt%, or at 0 wt%
  • the catalyst system used in the polymerization comprises no more than one catalyst compound.
  • a “reaction zone” also referred to as a "polymerization zone,” is a vessel where polymerization takes place, for example, a batch reactor. When multiple reactors are used in either series or parallel configuration, each reactor is considered as a separate polymerization zone. For a multi-stage polymerization in both a batch reactor and a continuous reactor, each polymerization stage is considered as a separate polymerization zone. In an embodiment, the polymerization occurs in one reaction zone.
  • the temperature is from about 0°C to about 300°C
  • the pressure is from about 0.35 MPa to about 10 MPa
  • the time is from about 0.1 minutes to about 24 hours, or a combination thereof.
  • the processes may be characterized by a temperature of from about 50°C to about 150°C.
  • the instant disclosure also relates to processes for using the catalyst systems described herein in olefin polymerization.
  • the invention relates in part to processes for producing olefin polymers, e.g., polyethylene and polypropylene homopolymers and copolymers, particularly alpha-olefin copolymers.
  • the polymers produced herein are homopolymers of ethylene or propylene, are copolymers of ethylene having from 0 to 25 mol% (or from 0.5 to 20 mol%, or from 1 to 15 mol%, or from 3 to 10 mol%) of one or more C3 to C20 olefin comonomer (or C3 to C 12 alpha-olefin, or propylene, butene, hexene, octene, decene, dodecene, or propylene, butene, hexene, octene), or are copolymers of propylene having from 0 to 25 mol% (or from 0.5 to 20 mol%, or from 1 to 15 mol%, or from 3 to 10 mol%) of one or more of C2 or C4 to C20 olefin comonomer (or ethylene or C4 to C 12 alpha-olefin, or ethylene, butene, hexen
  • the monomer is ethylene and the comonomer is hexene, or from 1 to 15 mol% hexene, or 1 to 10 mol% hexene.
  • Polymers produced by the catalyst systems described herein typically have a Mw > about 5,000 g/mol, e.g., > about 10,000 g/mol, > about 25,000 g/mol, > about 50,000 g/mol, > about 75,000 g/mol, > about 100,000 g/mol, > about 125,000 g/mol, > about 150,000 g/mol, > about 200,000 g/mol, > about 225,000 g/mol, > about 250,000 g/mol, > about 300,000 g/mol, > about 325,000 g/mol, > about 350,000 g/mol, > about 500,000 g/mol, > about 750,000 g/mol, > about 1,000,000 g/mol, > about 1,250,000 g/mol, > about 1,500,000 g/mol, > about 1,750,000 g/mol, > about 2,000,000 g/mol, or > about 2,225,000 g/mol.
  • the molecular weight may be ⁇ about 2,500,000 g/mol, e.g., ⁇ about 2,225,000 g/mol, ⁇ about 2,000,000 g/mol, ⁇ about 1,750,000 g/mol, ⁇ about 1,500,000 g/mol, ⁇ about 1,250,000 g/mol, ⁇ about 1,000,000 g/mol, ⁇ about 750,000 g/mol, ⁇ about 500,000 g/mol, ⁇ about 350,000 g/mol, ⁇ about 325,000 g/mol, ⁇ about 300,000 g/mol, ⁇ about 250,000 g/mol, ⁇ about 250,000 g/mol, ⁇ about 225,000 g/mol, ⁇ about 200,000 g/mol, ⁇ about 150,000 g/mol, ⁇ about 125,000 g/mol, ⁇ about 100,000 g/mol, ⁇ about 75,000 g/mol, ⁇ about 50,000 g/mol, ⁇ about 25,000 g/mol, or ⁇ about 10,000 g/mol.
  • the molecular weight may be in a range formed by any of the above-enumerated values, e.g., about 5,000 to about 2,500,000 g/mol, about 10,000 to about 2,250,000 g/mol, about 25,000 to about 2,000,000 g/mol, about 50,000 to about 1,750,000 g/mol, about 75,000 to about 1,500,000 g/mol, about 100,000 to about 1,250,000 g/mol, etc. Additionally or alternatively, some polymers made with the catalyst systems described herein may have an Mw/Mn of greater than 1 to about 40, or 1.2 to 20, or 1.3 to 10, or 1.4 to 5, or 1.5 to 4, or 1.5 to 3.
  • the polymer produced herein has a unimodal or multimodal molecular weight distribution as determined by Gel Permeation Chromotography (GPC).
  • GPC Gel Permeation Chromotography
  • unimodal is meant that the GPC trace has one peak or inflection point.
  • multimodal is meant that the GPC trace has at least two peaks or inflection points.
  • An inflection point is that point where the second derivative of the curve changes in sign (e.g., from negative to positive or vice versa).
  • the polymers may be linear in character, which may be determined by elution fractionation, wherein non-linear polymers have a CDBI of less than 45%, whereas linear polyethylene types refer to polyethylene having a CDBI of greater than 50%, the CDBI being determined as described in WO 93/03093 (US 5,206,075).
  • the polymer produced herein has a composition distribution breadth index (CDBI) of 50% or more, or 60% or more, or 70% or more.
  • CDBI is a measure of the composition distribution of monomer within the polymer chains and is measured by the procedure described in WO 93/03093, published February 18, 1993, specifically columns 7 and 8, as well as in Wild et al, J. Poly. Sci., Poly. Phys. Ed., Vol. 20, p. 441, (1982) and US 5,008,204, including that fractions having a weight average molecular weight (Mw) below 15,000 are ignored when determining CDBI.
  • Mw weight average molecular weight
  • Polymers with an Mw/Mn of 4.5 or less may include a significant level of long chain branching.
  • the long chain branching is understood to be the result of the incorporation of terminally unsaturated polymer chains (formed by the specific termination reaction mechanism encountered with single site catalysts) into other polymer chains in a manner analogous to monomer incorporation.
  • the branches are hence believed to be linear in structure and may be present at a level where no peaks can be specifically attributed to such long chain branches in the 1 C NMR spectrum.
  • the polymers produced, according to the instant disclosure comprise a significant amount of long chain branching, defined as having a ratio of long chain branching of at least 7 carbons per 1000 carbon atoms as determined according to the 1 C NMR spectrum of greater than 0.5.
  • the ratio of long chain branching with branches having at least 7 carbons, per 1000 carbon atoms as determined according to the 1 C NMR spectrum is greater than 1, or greater than 1.5, or greater than 2.
  • Polymers described herein may have one or more of the following features:
  • a Tm as determined by DSC, of 100°C or more, or 110°C or more, or 120°C or more;
  • the polymer comprises at least 50 mol% ethylene, or at least 60 mol%, or at least 70 mol%, or at least 75 mol%, or at least 80 mol%, or at least 85 mol%, or at least 90 mol%, or at least 95 mol%, or essentially 100 mol% ethylene; and/or
  • polymer produced herein has less than 1400 ppm aluminum, or less than 1200 ppm, or less than 1000 ppm, or less than 500 ppm, or less than 100 ppm as determined by ICPES (Inductively Coupled Plasma Emission Spectrometry), which is described in J. W. Olesik, "Inductively Coupled Plasma-Optical Emission Spectroscopy," in the Encyclopedia of Materials Characterization, C. R. Brundle, C. A. Evans, Jr. and S. Wilson, eds., Butterworth-Heinemann, Boston, Mass., 1992, pp.
  • ICPES Inductively Coupled Plasma Emission Spectrometry
  • the polymer has less than 1400 ppm of the Group 3, 4, 5, or 6 transition metal, or of the Group 4 transition metal, or of Ti, Zr, and/or Hf, or less than 1200 ppm, or less than 1000 ppm, or less than 500 ppm, or less than 100 ppm, as determined by ICPES as discussed above.
  • an ethylene polymer has less than 1400 ppm hafnium, or less than 1200 ppm, or less than 1000 ppm, or less than 500 ppm, or less than 100 ppm as determined by ICPES.
  • an ethylene polymer has less than 1400 ppm zirconium, or less than 1200 ppm, or less than 1000 ppm, or less than 500 ppm, or less than 100 ppm as determined by ICPES.
  • the polymer produced herein which may be an ethylene polymer, has a density of greater than 0.95 g/cc, or greater than 0.955 g/cc, or greater than 0.96 g/cc.
  • 1 C NMR data is collected at 120°C in a 10 mm probe using a Varian spectrometer with a hydrogen frequency of at least 400 MHz.
  • a 90 degree pulse, an acquisition time adjusted to give a digital resolution between 0.1 and 0.12 Hz, at least a 10 second pulse acquisition delay time with continuous broadband proton decoupling using swept square wave modulation without gating is employed during the entire acquisition period.
  • the spectra are acquired using time averaging to provide a signal to noise level adequate to measure the signals of interest.
  • Samples are dissolved in tetrachloroethane-d2 at concentrations between 10 to 15 wt% prior to being inserted into the spectrometer magnet.
  • Crystallization temperature (T c ), melting temperature (or melting point, T m ), glass transition temperature (T g ) and heat of fusion (H f ) are measured using Differential Scanning Calorimetry (DSC) on a commercially available instrument (e.g., TA Instruments 2920 DSC).
  • DSC Differential Scanning Calorimetry
  • 6 to 10 mg of molded polymer or plasticized polymer are sealed in an aluminum pan and loaded into the instrument at room temperature. Data are acquired by heating the sample to at least 30°C above its melting temperature, typically 220°C for polypropylene, at a heating rate of 10°C/min. The sample is held for at least 5 minutes at this temperature to destroy its thermal history.
  • the sample is cooled from the melt to at least 50°C below the crystallization temperature, typically -100°C for polypropylene, at a cooling rate of 20°C/min.
  • the sample is held at this temperature for at least 5 minutes, and finally heated at 10°C/min to acquire additional melting data (second heat).
  • the endothermic melting transition (first and second heat) and exothermic crystallization transition are analyzed according to standard procedures.
  • the melting temperatures (Tm) reported are the peak melting temperatures from the second heat unless otherwise specified.
  • the melting temperature is defined to be the peak melting temperature from the melting trace associated with the largest endothermic calorimetric response (as opposed to the peak occurring at the highest temperature).
  • the crystallization temperature is defined to be the peak crystallization temperature from the crystallization trace associated with the largest exothermic calorimetric response (as opposed to the peak occurring at the highest temperature).
  • H° H°(polypropylene).
  • Hm Heat of melting
  • the polymer (e.g., the polyethylene or polypropylene) produced herein is combined with one or more additional polymers prior to being formed into a film, molded part, or other article.
  • additional polymers include polyethylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene, and/or butene, and/or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene- 1, isotactic polybutene, ABS resins, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer, styrene, polyviny
  • the polymer e.g., the polyethylene or polypropylene
  • the polymer is present in the above blends, at from 10 to 99 wt%, based upon the weight of the polymers in the blend, or 20 to 95 wt%, or at least 30 to 90 wt%, or at least 40 to 90 wt%, or at least 50 to 90 wt%, or at least 60 to 90 wt%, or at least 70 to 90 wt%.
  • the blends described above may be produced by mixing the polymers of the invention with one or more polymers (as described above), by connecting reactors together in series to make reactor blends or by using more than one catalyst in the same reactor to produce multiple species of polymer.
  • the polymers can be mixed together prior to being put into the extruder or may be mixed in an extruder.
  • the blends may be formed using conventional equipment and methods, such as by dry blending the individual components and subsequently melt mixing in a mixer, or by mixing the components together directly in a mixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin-screw extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization process, which may include blending powders or pellets of the resins at the hopper of the film extruder. Additionally, additives may be included in the blend, in one or more components of the blend, and/or in a product formed from the blend, such as a film, as desired.
  • a mixer such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin-screw extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization
  • additives are well known in the art, and can include, for example: fillers; antioxidants (e.g., hindered phenolics such as IRGANOX 1010 or IRGANOX 1076 available from Ciba-Geigy); phosphites (e.g., IRGAFOS 168 available from Ciba-Geigy); anti-cling additives; tackifiers, such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosins; UV stabilizers; heat stabilizers; anti-blocking agents; release agents; anti-static agents; pigments; colorants; dyes; waxes; silica; fillers; talc; and the like.
  • antioxidants e.g., hindered phenolics such as IRGANOX 1010 or IRGANOX 1076 available from Ciba-Geigy
  • the invention relates to polyolefins comprising ethylene, wherein the polyolefin is produced by a process comprising: contacting one or more olefins with a supported catalyst system as described herein at a temperature, a pressure, and for a period of time sufficient to produce a polyolefin.
  • the polyolefin comprises at least 50 mol%, e.g., at least 75 mol%, at least 99.9 mol% ethylene, of polymer units derived from ethylene.
  • any of the foregoing polymers such as the foregoing polypropylenes or blends thereof, may be used in a variety of end-use applications.
  • Applications include, for example, mono- or multi-layer blown, extruded, and/or shrink films. These films may be formed by any number of well-known extrusion or coextrusion techniques, such as a blown bubble film processing technique, wherein the composition can be extruded in a molten state through an annular die and then expanded to form a uni-axial or biaxial orientation melt prior to being cooled to form a tubular, blown film, which can then be axially slit and unfolded to form a flat film.
  • Films may be subsequently unoriented, uniaxially oriented, or biaxially oriented to the same or different extents.
  • One or more of the layers of the film may be oriented in the transverse and/or longitudinal directions to the same or different extents.
  • the uniaxial orientation can be accomplished using typical cold drawing or hot drawing methods.
  • Biaxial orientation can be accomplished using tenter frame equipment or a double bubble processes and may occur before or after the individual layers are brought together.
  • a polyethylene layer can be extrusion coated or laminated onto an oriented polypropylene layer or the polyethylene and polypropylene can be coextruded together into a film then oriented.
  • oriented polypropylene could be laminated to oriented polyethylene or oriented polyethylene could be coated onto polypropylene then optionally the combination could be oriented even further.
  • the films are oriented in the machine direction (MD) at a ratio of up to 15, or between 5 and 7, and in the transverse direction (TD) at a ratio of up to 15, or 7 to 9.
  • MD machine direction
  • TD transverse direction
  • the film is oriented to the same extent in both the MD and TD directions.
  • the films may vary in thickness depending on the intended application; however, films of a thickness from 1 to 50 ⁇ are usually suitable. Films intended for packaging are usually from 10 to 50 ⁇ thick.
  • the thickness of the sealing layer is typically 0.2 to 50 ⁇ .
  • one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwave.
  • one or both of the surface layers is modified by corona treatment.
  • compositions described herein may also be used to prepare molded products in any molding process, including but not limited to, injection molding, gas-assisted injection molding, extrusion blow molding, injection blow molding, injection stretch blow molding, compression molding, rotational molding, foam molding, thermoforming, sheet extrusion, and profile extrusion.
  • injection molding gas-assisted injection molding
  • extrusion blow molding injection blow molding
  • injection stretch blow molding injection stretch blow molding
  • compression molding rotational molding
  • foam molding thermoforming, sheet extrusion, and profile extrusion.
  • compositions described herein may be shaped into desirable end use articles by any suitable means known in the art. Thermoforming, vacuum forming, blow molding, rotational molding, slush molding, transfer molding, wet lay-up or contact molding, cast molding, cold forming matched-die molding, injection molding, spray techniques, profile co-extrusion, or combinations thereof are typically used methods.
  • Thermoforming is a process of forming at least one pliable plastic sheet into a desired shape.
  • an extrudate film of the composition of this invention (and any other layers or materials) is placed on a shuttle rack to hold it during heating.
  • the shuttle rack indexes into the oven which pre-heats the film before forming. Once the film is heated, the shuttle rack indexes back to the forming tool.
  • the film is then vacuumed onto the forming tool to hold it in place and the forming tool is closed. The tool stays closed to cool the film and the tool is then opened.
  • the shaped laminate is then removed from the tool.
  • thermoforming is accomplished by vacuum, positive air pressure, plug-assisted vacuum forming, or combinations and variations of these, once the sheet of material reaches thermoforming temperatures, typically of from 140°C to 185°C or higher.
  • thermoforming temperatures typically of from 140°C to 185°C or higher.
  • a pre-stretched bubble step is used, especially on large parts, to improve material distribution.
  • Blow molding is another suitable forming means for use with the compositions of this invention, which includes injection blow molding, multi-layer blow molding, extrusion blow molding, and stretch blow molding, and is especially suitable for substantially closed or hollow objects, such as, for example, gas tanks and other fluid containers.
  • Blow molding is described in more detail in, for example, CONCISE ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING 90-92 (Jacqueline I. Kroschwitz, ed., John Wiley & Sons 1990).
  • molded articles may be fabricated by injecting molten polymer into a mold that shapes and solidifies the molten polymer into desirable geometry and thickness of molded articles.
  • Sheets may be made either by extruding a substantially flat profile from a die, onto a chill roll, or by calendaring. Sheets are generally considered to have a thickness of from 254 ⁇ to 2540 ⁇ (10 mils to 100 mils), although any given sheet may be substantially thicker.
  • the polyolefin compositions described above may also be used to prepare nonwoven fabrics and fibers of this invention in any nonwoven fabric and fiber making process, including but not limited to, melt blowing, spinbonding, film aperturing, and staple fiber carding.
  • a continuous filament process may also be used.
  • a spunbonding process is used.
  • the spunbonding process is well known in the art. Generally it involves the extrusion of fibers through a spinneret. These fibers are then drawn using high velocity air and laid on an endless belt. A calender roll is generally then used to heat the web and bond the fibers to one another although other techniques may be used such as sonic bonding and adhesive bonding.
  • a catalyst system comprising the result of the combination of and/or the reaction product of a fluorided support, an alumoxane activator, and a catalyst compound of Formula I:
  • each solid line represents a covalent bond and each dashed line represents a coordinative link; wherein M is a Group 3, 4, 5, or 6 transition metal;
  • N 1 and N 2 are nitrogen
  • O oxygen
  • each of X 1 and X 2 is, independently, a univalent Ci to C2 0 hydrocarbyl radical, a univalent Ci to C2 0 substituted hydrocarbyl radical (such as a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements), or X 1 and X 2 join together to form a C4 to C62 cyclic or polycyclic ring structure, provided, however, when M is trivalent X 2 is not present;
  • each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 is, independently, hydrogen, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical (such as a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements), two or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 independently join together to form a C4 to Ce2 cyclic or polycyclic ring structure, or a combination thereof; wherein each of R* 1 and R* 2 independently comprises a bulky functional group, an electron withdrawing group, or a combination thereof; and
  • Y is a divalent Ci to C2 0 hydrocarbyl radical.
  • C* indicates an attachment carbon of the radical
  • R 7 is a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical (such as a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements); and
  • each of R 8 , R 9 , R 10 , R 11 is, independently, hydrogen, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical (such as a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements), two or more of R X , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 independently join together to form a C 4 to Ce2 cyclic or poly cyclic ring structure, or a combination thereof.
  • each of R 7 and R 26 is, independently, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical (such as a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements);
  • each of R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , and R 34 is, independently, hydrogen, a Ci to C40 hydrocarbyl radical is, a Ci to C40 substituted hydrocarbyl radical (such as a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements), and
  • R 1 , R , R , R , and R iJ may independently join together to form a C4 to Ce2 cyclic or poly cyclic ring structure, or a combination thereof.
  • each of R 7 and/or R 26 is selected from the group consisting of Ci to C lo alkyl groups, Ci to C lo alkoxy groups, Ce to C15 aryl groups, and combinations thereof.
  • each of R 5 and R 16 is independently selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i- butyl, t-butyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, i-butoxy, t- butoxy, phenyl and Ci to C5 substituted phenyl groups;
  • each of R 7 and R 26 is independently selected from the group consisting of ethyl, n- propyl, i-propyl, n-butyl, sec-butyl, i-butyl, t-butyl, phenyl, and Ci to C5 substituted phenyl groups;
  • R 1 , R 2 , R 3 , R 4 , R 6 , R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , and R 34 are each independently selected from H and Ci to C5 alkyl groups;
  • Y is a divalent Ci to C5 hydrocarbyl radical, particularly -(CH 2 CH 2 )-; and wherein at least one of X 1 and/or X 2 is selected from Ce to C 15 aryl groups, particularly benzyl.
  • each of R* 1 and R* 2 independently comprises a pyrrole radical having the structure according to Formula IV:
  • N* indicates an attachment carbon of the radical; and each of R 8 , R 9 , R 10 , R 11 is, independently, hydrogen, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical (such as a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements), two or more of R X , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 independently join together to form a C 4 to Ce2 cyclic or poly cyclic ring structure, or a combination thereof;
  • each of R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 3 1 , R 32 , and R 33 is, independently, a hydrogen, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical (such as a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements), or two or more of R 1 to R 33 may independently join together to form a C4 to ei cyclic or poly cyclic ring structure, or a combination thereof.
  • 1 The catalyst system of Embodiment 10, wherein at least one of R 5 and/or R 16 is selected from the group consisting of Ci to C 10 alkyl, Ci to C 10 alkoxy, and Ce to C15 aryl.
  • each of R 5 and R 16 is independently selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i- butyl, t-butyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, i-butoxy, t- butoxy, phenyl, and C1-C5 substituted phenyl groups;
  • R 1 , R 2 , R 3 , R 4 , R 6 , R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , and R 33 are each independently selected from H and Ci to C5 alkyl groups;
  • Y is a divalent Ci to C5 hydrocarbyl radical, particularly -(CH 2 CH 2 )-; and wherein at least one of X 1 and/or X 2 is selected from the group consisting of a halogen or a Ci to C7 hydrocarbyl radical, and a Ce to C 15 aryl group, particularly benzyl.
  • Y is a C1-C40 divalent hydrocarbyl radical comprising O, S, S(O), S(0) 2 , Si(R') 2 , P(R'), N, N(R'), or a combination thereof, wherein each R' is independently a Ci-Cig hydrocarbyl radical.
  • M is Zr
  • X 1 and X 2 are benzyl radicals
  • R 1 and R 12 are methyl radicals
  • R 2 , R 3 R 4 , R 5 , R 6 , R 13 , R 14 R 15 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , and R 25 are hydrogen;
  • R 16 is bromine;
  • M is Zr
  • X 1 and X 2 are benzyl radicals
  • R 1 , R 12 and R 16 are methyl radicals
  • R 30 , R 31 R 32 , and R 33 are hydrogen
  • each of R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 is, independently, a hydrogen, a Ci to C40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, or two or more of R 1 to R 33 may independently join together to form a C4 to Ce2 cyclic or poly cyclic ring structure, or a combination thereof.
  • Y is a divalent Ci to C5 hydrocarbyl radical, particularly -(CH 2 CH 2 )-; and wherein at least one of X 1 and/or X 2 is selected from the group consisting of a halogen or a Ci to C7 hydrocarbyl radical, and a Ce to C15 aryl group, particularly benzyl.
  • each of X 1 and X 2 is, independently, a halogen or a Ci to C7 hydrocarbyl radical.
  • each of X 1 and X 2 is a benzyl radical.
  • M is Ti
  • X 1 and X 2 are benzyl radicals
  • R 1 and R 12 are methyl radicals
  • R 2 , R 3 , R 4 , R 6 , R 13 , R 14 , R 15 , R 16 and R 17 are hydrogen;
  • R 5 , R 16 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 are fluorine;
  • Y is -CH 2 CH 2 -.
  • M is Ti
  • X 1 and X 2 are benzyl radicals
  • R 1 , R 5 , R 12 , and R 16 are methyl radicals
  • R 2 , R 3 , R 4 , R 6 , R 13 , R 14 , R 15 , and R 17 are hydrogen;
  • R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 are fluorine;
  • Y is -CH 2 CH 2 -.
  • M is Zr
  • X 1 and X 2 are benzyl radicals
  • R 1 and R 12 are methyl radicals
  • R 2 , R 3 , R 4 , R 6 , R 13 , R 14 , R 15 , and R 17 are hydrogen;
  • R 5 , R 16 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 are fluorine;
  • M is Zr
  • X 1 and X 2 are benzyl radicals
  • R 1 , R 5 , R 12 , and R 16 are methyl radicals
  • R 2 , R 3 , R 4 , R 6 , R 12 , R 14 , R 15 , and R 17 are hydrogen;
  • R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 are fluorine;
  • each solid line represents a covalent bond and each dashed line represents a coordinative link
  • M is a Group 3, 4, 5, or 6 transition metal
  • N 1 , N 2 , N 3 , and N 4 are nitrogen
  • O oxygen
  • each of X 1 and X 2 is, independently, a univalent Ci to C2 0 hydrocarbyl radical, a univalent substituted Ci to C2 0 hydrocarbyl radical (such as a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, or X 1 and X 2 join together to form a C4 to C62 cyclic or polycyclic ring structure, provided, however, when M is trivalent X 2 is not present;
  • Y is a divalent hydrocarbyl radical covalently bonded to and bridging between both of the nitrogen atoms N 1 and N 2 ;
  • Y is a Ci to C40 divalent hydrocarbyl radical comprising O, S, S(O), S(0) 2 , Si(R') 2 , P(R'), N, N(R'), or a combination thereof, wherein each R' is independently a Ci to C 18 hydrocarbyl radical.
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 12 , 20 R 13 , R 14 , R 15 , R 16 , R 17 , R 19 , R 20 , R 21 , R 24 , R 25 , R 26 , R 29 , R 30 , R 31 , R 34 , R 35 , and R 36 is, independently, a hydrogen, a Ci to C40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, or two or more of R 1 , ⁇ 2 R 3 R 4 R 5 R 6 R 12 R 13 R 14 R 15 R 16 R 17 R 19 R 20 R 21 R 24 R 25 R 26 R 29 R 30 R 31 R 34 rv .
  • R 35 , and R 36 may independently join together to form a C4 to Ce2 cyclic or poly cyclic ring 25 structure, or a combination thereof; and each R 18 , R 22 , R 23 , R 27 , R 28 , R 32 , R 33 , and R 37 and is, independently, a hydrogen, a Ci to C40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, or a combination thereof.
  • R , R , R , R , and R is, independently, hydrogen, a halogen, or a Ci to C30 hydrocarbyl radical.
  • R 35 R 33 , R 34 , R 35 , R 36 , and R 37 is, independently, hydrogen, a halogen, or a Ci to Cio hydrocarbyl radical.
  • R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 R 21 R 22 R 23 R 24 R 25 R 26 R 27 R 28 R 29 R 30 R 31 rv . rv . rv . rv . rv . rv . rv . rv . rv . rv . rv . rv . rv . rv . rv . rv . rv . rv . rv . rv . rv . rv . rv . rv . rv . rv . rv , R , R , and R is a methyl radical, a fluoride, or a combination thereof.
  • M is Zr
  • X 1 and X 2 are benzyl radicals
  • R 1 and R 12 are methyl radicals
  • R 29 , R 30 , R 1 , R 32 , R 33 , R 34 , R 35 , R 36 , and R 37 are hydrogen;
  • M is Zr
  • X 1 and X 2 are benzyl radicals
  • R 1 , R 5 , R 12 , and R 16 are methyl radicals
  • R 2 , R 3 , R 4 , R 6 , R 13 , R 14 , R 15 , R 17 , to R 37 are hydrogen;
  • Y is -CH 2 CH 2 -.
  • each solid line represents a covalent bond and each dashed line represents a coordinative link
  • M is a Group 3, 4, 5, or 6 transition metal
  • N 1 , N 2 , N 3 , and N 4 are nitrogen;
  • each of X 1 and X 2 is, independently, a univalent Ci to C2 0 hydrocarbyl radical, a Ci to C2 0 substituted hydrocarbyl radical (such as a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements), or X 1 and X 2 join together to form a C4 to Ce2 cyclic or poly cyclic ring structure, provided however when M is trivalent X 2 is not present; Y is a divalent Ci to C2 0 hydrocarbyl radical;
  • Y 2 and Y 3 are independently a divalent Ci to C2 0 hydrocarbyl radical, a Ci to C2 0 substituted hydrocarbyl radical (such as a divalent functional group comprising elements from Groups 13 to 16 of the periodic table of the elements), or a combination thereof; and
  • each R 1 to R 6 , R 12 to R 21 , R 23 to R 26 , R 28 to R 31 , and R 33 to R 36 is, independently, a hydrogen, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical (such as a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements), or two or more of R 1 to R 6 , R 12 to R 21 , R 23 to R 26 , R 28 to R 31 , and R 33 to R 36 may independently join together to form a C4 to Ce2 cyclic or poly cyclic ring structure.
  • a process comprising:
  • Embodiment 49 The process of Embodiment 48, wherein the temperature is from about 0°C to about 300°C, the pressure is from about 0.35 MPa to about 10 MPa, the time is from about 0.1 minutes to about 24 hours, or a combination thereof.
  • the polyolefin of Embodiment 51 wherein the polyolefin comprises at least 50 mol% of polymer units derived from ethylene.
  • the polyolefin of Embodiment 51 wherein the polyolefin comprises at least 75 mol% of polymer units derived from ethylene.
  • the polyolefin of Embodiment 51 wherein the polyolefin has an Mn of 250 g/mol to 2,500,000 g/mol.
  • MI Melt index
  • High load melt index also referred to as I 21 , reported in g/10 min, is determined according to ASTM D1238, 190°C, 21.6 kg load.
  • Melt index ratio is MI divided by HLMI as determined by ASTM D1238.
  • Density is determined according to ASTM D1505.
  • Mw, Mn, and Mz may be determined by Rapid GPC and percent of 1-hexene incorporation may be determined by FT-IR to determine various molecular weight related values by GPC, high temperature size exclusion chromatography is performed using an automated "Rapid GPC" system as generally described in US 6,491,816; US 6,491,823; US 6,475,391; US 6,461,515; US 6,436,292; US 6,406,632; US 6,175,409; US 6,454,947; US 6,260,407; and US 6,294,388; each of which is incorporated herein by reference for US purposes.
  • This apparatus has a series of three 30 cm*7.5 mm linear columns, each containing PLgel 10 ⁇ , Mix B.
  • the GPC system is calibrated using polystyrene standards ranging from 580 - 3,390,000 g/mol.
  • the system is operated at an eluent flow rate of 2.0 mL/minutes and an oven temperature of 165°C. 1 ,2,4-trichlorobenzene was used as the eluent.
  • the polymer samples are dissolved in 1,2,4-trichlorobenzene at a concentration of 0.1-0.9 mg/mL. 250 uL of a polymer solution is injected into the system.
  • the concentration of the polymer in the eluent is monitored using an evaporative light scattering detector.
  • the molecular weights presented are relative to linear polystyrene standards and are uncorrected.
  • Illustrative catalyst compounds each according to one or more embodiments described, are synthesized and some are used to polymerize olefins. All reactions are carried out under a purified nitrogen atmosphere using standard glovebox, high vacuum, or Schlenk techniques, unless otherwise noted. All solvents used are anhydrous, de- oxygenated, and purified according to known procedures. All starting materials are either purchased from Aldrich and purified prior to use or prepared according to procedures known to those skilled in the art. ynthesis of Compound A
  • the ligand (3) is dissolved in toluene in a scintillation vial.
  • 1 equivalent of zirconium tetrabenzyl is also dissolved in toluene.
  • the solution of ligand 3 is stirred and the tetrabenzyl solution is added dropwise. After stirring for one hour, the solution is filtered with a syringe adapted with a 0.2 micron filter tip. The toluene is then removed under nitrogen and the resulting residue is slurried in pentane. Solids are collected using a frit, dried under vacuum and analyzed by ⁇ ⁇ NMR spectroscopy.
  • Compound B is prepared as described above for Compound A using Hf(Bn) 4 in place of Zr(Bn) 4 .
  • Compound D is prepared as described above for Compound C using Hf(Bn) 4 in place of Zr(Bn) 4 .
  • E-3 In a hood, E-2 (8.63g, 43.98mmol) in dichloromethane (250mL) is added drop-wise (over about 20min) with an addition funnel to a solution of 4-methoxyphenol (10.919g, 87.96mmol) and sulfuric acid (3.0mL, 46.18mmol) in dichloromethane (250mL) at 0°C. The solution is stirred at room temperature for lh. The reaction mixture is poured into water (200mL) and brought to a pH>7 (2M sodium hydroxide). Organic layer is washed with brine (4x250mL), dried with magnesium sulfate, filtered, and concentrated in vacuo.
  • F In a dry-box, at room temperature, paraformaldehyde (0.892g, 29.69mmol) then ⁇ , ⁇ '-dimethylethylenediamine (1.31g, 1.6mL, 14.845mmol) are added to F-3 (9.75g, 29.69mmol) in ethanol (33mL). The reaction solution is stirred for 3 days at 80°C. The reaction solution is cooled to room temperature and the solvent is removed in vacuo yielding desired product, F (10.12g, 14.116mmol, 95.09% yield).
  • the ligand F is dissolved in toluene in a scintillation vial.
  • 1 equivalent of zirconium tetrabenzyl is also dissolved in toluene.
  • the solution of ligand 3 is stirred and the tetrabenzyl solution is added dropwise. After stirring for one hour, the solution is filtered with a syringe adapted with a 0.2 micron filter tip. The toluene is then removed under nitrogen and the resulting residue is slurried in pentane. Solids are collected using a frit, dried under vacuum, and analyzed by ⁇ ⁇ NMR spectroscopy.
  • Compound F is prepared as described above for Compound E using Hf(Bn) 4 in place of Zr(Bn) 4 .
  • G-2 In the glove-box at 0°C, G-l, fluorenone, (30.00g, 166.5mmol) in tetrahydrofuran (70mL) is added to methylmagnesium bromide (66.5mL, 199.5mmol) in diethyl ether (500mL). The reaction solution is stirred at r.t. overnight. The reaction solution is cooled to 0°C and 200mL of water is added. The solution is brought to a pH of 9 with 2M NaOH. The organic fraction is washed with brine (3x200mL), dried with magnesium sulfate, filtered and concentrated in vacuo yielding the yellow oil, G-2 (29.10g, 148.28mmol, 89.06% yield).
  • G-3 In the hood, G-2 (229. lOg, 148.28mmol) in dichloromethane (400mL) is added drop-wise (over about 20min) with an addition funnel to a solution of 4-tert- butylphenol (22.28g, 148.28mmol) and sulfuric acid (8.65mL, 155.69mmol) in dichloromethane (300mL) at 0°C The solution is stirred at room temperature for lh. The reaction mixture is poured into water (300mL) and brought to a pH of 9 (2M sodium hydroxide). Organic layer is washed with brine (4x250mL), dried with magnesium sulfate, filtered, and concentrated in vacuo. This gave compound G-3 (44.23g, 134.66mmol, 90.82% yield) as a white solid.
  • G In the dry-box, at room temperature, paraformaldehyde (5.6g, 186.0mmol) then ⁇ , ⁇ '-dimethylethylenediamine (8.20g, lO.OmL, 93.1mmol) are added to G-3 (61.09g, 186.0mmol) in ethanol (550mL). Note: multiple batches of G-3 are combined to synthesize G. The reaction solution is stirred 3 days at 80°C. The reaction solution is cooled to room temperature and the solvent is removed in vacuo yielding desired product, G (60.044g, 8 l.Ommol, 87.00% yield)
  • hafnium tetrabenzyl (11.8443g, 21.812mmol) is added as a solid to ligand G (16.7754g, 21.813mmol) in toluene (250mL). This is stirred at room temperature for 2h 45min. Solvent is removed under a stream of nitrogen then placed under vacuum overnight, yielding a white solid (24.5863g, 21.80mmol, 99.95%).
  • Compound H may be prepared by a procedure analogous to Compound G except that the step for preparing the methyl substituted fluorene precursor is modified to provide the 4-methyl phenyl substituted fluorene precursor.
  • Silica Support Silica (D948, 40.7 g) is calcined at 600°C then slurried in 200mL of toluene. MAO (71.4 g of a 30 wt% toluene solution, 351.1mmol of Al) is added slowly to the slurry. The slurry is then heated to 80°C and stirred for lhr. The slurry is filtered, washed three times with 70mL of toluene and once with pentane. The solid is dried under vacuum overnight to give a 60.7 g amount of free flowing white solid.
  • Fluorided Silica Support 1.18 g (NH 4 ) 2 SiF 6 is dissolved in 7.00 g water in a 20 ml glass vial. 50 g silica (Grace D948 ) and 200 g of toluene are combined. Under vigorous stirring, the aqueous solution of (NH 4 ) 2 SiF6 is added via a syringe to the toluene slurry. The mixture is allowed to stir at room temperature for 2.5 h.
  • the milky slurry is filtered through a 500 ml Optichem disposable polyethylene frit (40 micron), rinsed with 200 g pentane for three times, then dried in air overnight to yield a white, free-flowing solid.
  • the solid is transferred into a tube furnace, and is heated to 200°C under constant nitrogen flow (temperature program: 25°C/h ramped to 150°C; held at 150°C for 4 hours; 50°C/h ramped to 200°C; held at 200°C for 4 hours; cooled down to room temperature).
  • MAO (37.6 g of 30%wt in toluene) is added to a 250 ml celstir along with lOOmL of toluene. 29.9 g fluorided silica prepared in the previous step is added to the slurry in 5 g increments. The reaction stirred for 10 minutes at room temperature and is then heated to 100°C for 3 hours. The solid is filtered, washed twice with 80mL of toluene, washed twice with pentane, and dried under vacuum overnight. 39.6g of free flowing white solid is collected.
  • N2 inert atmosphere
  • the autoclaves are prepared by purging with dry nitrogen prior to use.
  • Ethylene is allowed to enter (through the use of computer controlled solenoid valves) the autoclaves during polymerization to maintain reactor gauge pressure (+/- 2 psig). Reactor temperature is monitored and typically maintained within +/- 1°C. Polymerizations are halted by addition of approximately 50 psi 0 2 /Ar (5 mol% 02) gas mixture to the autoclaves for approximately 30 seconds. The polymerizations are quenched after a predetermined cumulative amount of ethylene had been added or for a maximum of 45 minutes polymerization time. In addition to the quench time for each run, the reactors are cooled and vented. The polymer is isolated after the solvent is removed in-vacuo. Yields reported include total weight of polymer and residual catalyst. Catalyst activity is reported as kilograms of polymer per mmol transition metal compound per hour of reaction time (kg/mmol » hr).
  • the supported catalysts are evaluated by high throughput polymerizations in slurry ethylene/1 -hexene polymerization tests to determine the effect of hydrogen pressure on molecular weight of resulting polyethylene polymer. For experiments with 0 ppm added hydrogen, ethylene gas is used as the feed. For experiments with 300 ppm added hydrogen, pre-mixed custom gas that contains 300 ppm H 2 in ethylene is used as feed. Results for these experiments are recorded in Table 2. These catalyst compositions show a wide range of responses to hydrogen concentration and are typically less sensitive to hydrogen concentration than conventional supported catalysts. Table 2
  • Run condition isohexane as solvent, 85°C, 130 psi ethylene pressure, 30 ⁇ (6 mol% in feed) 1 -hexene.
  • Example 25 48.8 g of F-sMAO (3.2.1b) is slurried in 180 mL of toluene. 2.20 g complex Compound G (1.95mmol) is added as a solid to the slurry and washed down with 20 mL of toluene. The slurry is stirred for 1 hour and is then filtered and washed three times with 50 mL of toluene and twice with pentane. The solid is dried under vacuum overnight to give 50.0 grams of off- white powder.
  • Example 25 The polymerization with the supported catalyst form Example 25 is performed in a gas-phase fluidized bed reactor with a 6" body and a 10" expanded section. Cycle and feed gases are fed into the reactor body through a perforated distributor plate, and the reactor is controlled at 300 psi and 70 mol% ethylene. Reactor temperature is maintained by heating the cycle gas. Supported catalyst is fed as a 10 wt% slurry in Sono Jell ® from Sonneborn (Parsippany, NJ). The slurry is thinned and delivered to the reactor by nitrogen and isopentane feeds in the cat probe. Products are collected from the reactor, as necessary, to maintain the desired bed weight.
  • Average process conditions are: Temperature: 85°C, Pressure: 300 psi, ethylene concentration: 70.0 mol%, hydrogen concentration: 949 ppm, hexene concentration: 0.30 mol%, bed wt : 2000 g, Residence time: 4.6 hours, Cycle gas velocity: 1.48 ft/s, production rate: 436 g/hour, Activity: 1508 g(polymer)/g(supported catalyst), Catalyst Slurry Feed rate: 3.3 cc/hour, N 2 Catalyst Probe feed rate: 6000 cc/min; isopentane probe feed rate: 1 g/min.
  • the resulting polymer had a melt index, h, of 0.96 g/10 min., a high load melt index (I 2 i) of 23.84 g/10 min., a density of 0.9188 g/cm 3 , a bulk density of 0.4854 g/cm 3 .
  • I 2 i high load melt index
  • Reaction is carried out in an 18" diameter fluidized bed gas phase reactor with a tapered expanded section with a maximum diameter of 50.”
  • the body of the reactor is 10 feet tall, and the expanded section is 8.5 feet tall.
  • Product is removed from the reactor to maintain a constant bed fluidization level at the top of the reactor body.
  • Catalyst is fed as a 20 wt% slurry in mineral oil. Conditions from the run are shown in Table 3.
  • the catalysts in an embodiment provide improvement in catalyst activity, produce polymers with improved properties, or both.
  • crystallographic techniques indicate that the appended ring system or systems (e.g., the carbazole ring systems) are oriented transversely, e.g., perpendicular, to the phenol rings.
  • these catalysts have a structure to provide a broad corridor for the polymeryl moiety to reside and for the monomer to insert during the polymerization process.
  • catalysts according to one embodiment of the instant disclosure provide for an ability to control one or more characteristics of polymerization, tacticity, comonomer insertion, and the like.
  • compositions, an element or a group of elements are preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements, and vice versa.

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Abstract

La présente invention concerne un système catalyseur comprenant le produit réactionnel d'un support fluoré, d'un activateur et d'au moins un premier composé catalyseur à base de métal de transition ; des procédés de fabrication de ces systèmes catalyseurs, des procédés de polymérisation utilisant de tels systèmes catalyseurs, et les polymères fabriqués à partir de ceux-ci.
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CN111448226A (zh) * 2017-11-15 2020-07-24 埃克森美孚化学专利公司 聚合方法
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Publication number Priority date Publication date Assignee Title
CN111356705A (zh) * 2017-11-15 2020-06-30 埃克森美孚化学专利公司 聚合方法
CN111448226A (zh) * 2017-11-15 2020-07-24 埃克森美孚化学专利公司 聚合方法
CN111448226B (zh) * 2017-11-15 2023-08-25 埃克森美孚化学专利公司 聚合方法
WO2019156968A1 (fr) 2018-02-07 2019-08-15 Exxonmobil Chemical Patents Inc. Systèmes de catalyseur et procédés de polymérisation pour leur utilisation
CN112351987A (zh) * 2018-04-26 2021-02-09 埃克森美孚化学专利公司 含有具有大烷基基团的阳离子的非配位阴离子型活化剂
CN112351987B (zh) * 2018-04-26 2024-02-02 埃克森美孚化学专利公司 含有具有大烷基基团的阳离子的非配位阴离子型活化剂

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