EP3039026A1 - Procédé de métallation à sélectivité racémique - Google Patents

Procédé de métallation à sélectivité racémique

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Publication number
EP3039026A1
EP3039026A1 EP14840931.1A EP14840931A EP3039026A1 EP 3039026 A1 EP3039026 A1 EP 3039026A1 EP 14840931 A EP14840931 A EP 14840931A EP 3039026 A1 EP3039026 A1 EP 3039026A1
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EP
European Patent Office
Prior art keywords
indenyl
independently
hydrocarbyl
radical
elements
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EP14840931.1A
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German (de)
English (en)
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EP3039026A4 (fr
Inventor
Glen E. Alliger
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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Priority to EP14840931.1A priority Critical patent/EP3039026A4/fr
Publication of EP3039026A1 publication Critical patent/EP3039026A1/fr
Publication of EP3039026A4 publication Critical patent/EP3039026A4/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • 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 racemic bis(indenyl) metallocene transition metal compounds, preparation and uses thereof.
  • bridged bis(indenyl) metallocenes can be challenging.
  • Deprotonation of the pro-ligand followed by introduction of a metal halide, typically, a group 4 metal tetrachloride generally forms two isomers of the product, racemic (rac) and meso.
  • the meso form is often found to be undesirable because its polymerization activity relative to the rac isomer can be greatly reduced.
  • rac-dimethylsilyl-bridged bis(indenyl) metallocenes are of significant interest due to their ability to catalyze the formation of isotactic polypropylene.
  • repeated crystallizations may be required to isolate the pure rac product, leading to lengthy purification processes and diminished yields.
  • Directing metallation reagents are available, but can be difficult or expensive to scale, or can be found to be ineffective. Thus, the need for scalable, effective rac- directing metallation reagents still exists.
  • Nifant'ev et al. have used tert-butylamide as a directing agent for substituted bis indenyl and indacenyl compounds, however the effect with such was inconsistent, especially for 2- methyl, 4 phenyl substituted indenes, see Nifant'ev, I. E. et al., Organometallics, 2012, 31, 4340).
  • the instant disclosure is directed to racemic bis(indenyl) metallocene transition metal compounds, racemic directing metallation reagents, processes to produce racemic rich catalyst compounds, catalyst systems comprising such compounds, and processes for the polymerization of olefins using such catalyst compounds and systems.
  • a process comprises reacting a deprotonated bis(cyclopentadienyl) compound with a racemic directing (rac-directing) metallation reagent to form a product mixture having an increased concentration of the rac-isomer of a metallocene transition metal compound relative to the amount, if any, of the meso isomer formed.
  • a deprotonated bridged bis(indenyl) compound is reacted with a rac-directing metallation reagent to form a product mixture enriched in a racemic isomer of the corresponding bridged bis(indenyl)metallocene transition metal compound relative to any meso isomer formed.
  • a compound comprises greater than 50 mol% of a racemic isomer of a bridged bis(indenyl)metallocene transition metal compound based on the total amount of the compound present.
  • a process comprises contacting one or more olefins with a catalyst system comprising an activator and a racemic bridged bis(indenyl)metallocene transition metal compound at polymerization conditions to produce a polyolefin.
  • a process comprises contacting a deprotonated bridged bis(indenyl) compound with a rac-directing metallation reagent to form a product mixture enriched in a racemic isomer of a bridged bis(indenyl)metallocene transition metal compound relative to any meso isomer formed, contacting the bridged bis(indenyl)metallocene transition metal compound with an activator to form a catalyst system; and contacting one or more olefins with the catalyst system at polymerization conditions to produce a polyolefin.
  • a solid line indicates a bond
  • each dashed line represents a bond having varying degrees of covalency and a varying degree of coordination.
  • hydrocarbyl radical is defined to be Ci to C 7 o radicals, or Ci to C20 radicals, or Ci to Cio radicals, or C to C70 radicals, or C 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 and/or one or more functional groups comprising elements from groups 13, 14, 15, 16, or 17 of the periodic table of the elements.
  • 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 and/or a carbon atom in the base structure has been replaced with a hydrocarbyl radical, and/or a functional group, and/or a heteroatom or a heteroatom containing group.
  • hydrocarbyl radical includes heteroatom containing groups.
  • a heteroatom is defined as any atom other than carbon and hydrogen.
  • methyl cyclopentadiene is a Cp group, which is the base structure, substituted with a methyl radical, which may also be referred to as a methyl functional group
  • ethyl alcohol is an ethyl group, which is the base structure, substituted with an - OH functional group
  • pyridine is a phenyl group having a carbon in the base structure of the benzene ring substituted with a nitrogen atom.
  • a hydrocarbyl radical may be independently selected from substituted or unsubstituted 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, oc
  • hydrocarbyl radicals may also include isomers of saturated, partially unsaturated and aromatic cyclic structures wherein the radical may additionally be subjected to the types of substitutions described above.
  • aryl refers to aromatic cyclic structures, which may be substituted with hydrocarbyl radicals and/or functional groups as defined herein.
  • aryl radicals include: acenaphthenyl, acenaphthylenyl, acridinyl, anthracenyl, benzanthracenyls, benzimidazolyl, benzisoxazolyl, benzofluoranthenyls, benzofuranyl, benzoperylenyls, benzopyrenyls, benzothiazolyl, benzothiophenyls, benzoxazolyl, benzyl, carbazolyl, carbolinyl, chrysenyl, cinnolinyl, coronenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, dibenzoanthracen
  • Alkyl, alkenyl, and alkynyl radicals listed include all isomers including where appropriate cyclic isomers, for example, butyl includes «-butyl, 2- methylpropyl, 1 -methylpropyl, tert-butyl, and cyclobutyl (and analogous substituted cyclopropyls); pentyl includes n-pentyl, cyclopentyl, 1 -methylbutyl, 2-methylbutyl, 3- methylbutyl, 1-ethylpropyl, and nevopentyl (and analogous substituted cyclobutyls and cyclopropyls); butenyl includes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl, 1 -methyl- 1-
  • Cyclic compounds having substitutions include all isomer forms, for example, methylphenyl would include ortho-methylphenyl, meta-methylphenyl and para-methylphenyl; dimethylphenyl would include 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5- dimethylphenyl, 2,6-diphenylmethyl, 3,4-dimethylphenyl, and 3,5-dimethylphenyl.
  • a triflate is represented by the formula:
  • a functional group may include both organic and inorganic radicals or moieties comprising elements from groups 13, 14, 15, 16, 17 of the periodic table of elements.
  • Suitable functional groups may include hydrocarbyl radicals, e.g., alkyl radicals, alkene radicals, aryl radicals, and/or halogen (CI, Br, I, F), O, S, Se, Te, NR* X , OR*, SeR*, TeR*, PR* X , AsR* x , SbR* x , SR*, BR* X , SiR* x , GeR* x , SnR* x , PbR* x , and/or the like, wherein each R* is independently a hydrogen, a halogen, a Ci to C 20 hydrocarbyl as defined above and wherein x is the appropriate integer to provide an electron neutral moiety.
  • hydrocarbyl radicals e.g., alkyl radicals, alkene radicals, aryl radicals, and/or halogen (CI, Br, I, F)
  • O S, Se, Te, NR* X
  • Suitable functional groups include those typically referred to as amines, imides, amides, ethers, alcohols (hydroxides), sulfides, sulfates, phosphides, halides, phosphonates, alkoxides, esters, carboxylates, aldehydes, and the like.
  • direct bonds For purposes herein "direct bonds,” “direct covalent bonds” or “directly bridged” are used interchangeably to refer to covalent bonds directly between atoms that do not have any intervening atoms.
  • an "olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound comprising carbon and hydrogen having at least one double bond.
  • alkene is a linear, branched, or cyclic compound comprising carbon and hydrogen having at least one double bond.
  • the olefin present in such polymer or copolymer is the polymerized form of the olefin.
  • a copolymer when a copolymer is said to have a "propylene" content of 35 wt% to 55 wt%, it is understood that the mer unit in the copolymer is derived from propylene 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 an 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 mole% 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-C22 olefins.
  • 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, norbornene, 4- methylnorbornene, 2-methylcyclopentene, 4-methylcyclopentene, vinylcyclohexane, norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, vinylcyclohexene, 5-vinyl-2- norbornene, 1,3-divinylcyclopentane, 1 ,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4- divinylcyclohexane, 1 ,5-divinylcyclooctane, 1 -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, or a transition metal 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 a combination of at least one catalyst compound, at least one activator, an optional co-activator, and an optional 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 gPgcat ⁇ 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 labile ligand is a moiety which is bonded to the metal of a metallocene catalyst precursor, but which is removed upon activation of the catalyst precursor into a catalyst.
  • 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
  • mol% is mole percent.
  • Molecular weight distribution (MWD) also referred to as polydispersity, is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units, e.g., Mw, Mn, Mz, are g/mol.
  • the term "pseudohalogen" is defined to be any compound that is an azide, an isocyanate, a thiocyanate, an isothiocyanate or a cyanide.
  • 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 refers to secondary butyl
  • tert-butyl t-butyl
  • tert-Bu or t-Bu refers to tertiary butyl
  • n-butyl is normal butyl
  • pMe is para-methyl
  • Bz is benzyl
  • THF is tetrahydroiuran
  • (thf) is a tetrahydrofuranyl radical
  • Mes is mesityl, also known as 1,3,5-trimethylphenyl
  • Tol is toluene
  • tolyl is a toluene radical
  • TMS is trimethylsilyl
  • TIBAL is triis
  • 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 consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.
  • T room temperature, which is defined as 25 °C unless otherwise specified. All percentages are weight percent (wt%) unless otherwise specified.
  • Polypropylene microstructure is determined by ⁇ C-NM spectroscopy, including the concentration of isotactic and syndiotactic dyads ([m] and [r]), triads ([mm] and [rr]), and pentads ([mmmm] and [rrrr]).
  • concentration of isotactic and syndiotactic dyads [m] and [r]
  • triads [mm] and [rr]
  • pentads [mmmm] and [rrrr]
  • a bulky ligand substitution is defined as a C3 to C20 hydrocarbyl radical; -OR a -SR a , -NR3 ⁇ 4 and P(R a )(Rb), where each R a is independently a C3 to C20 hydrocarbyl having a molecular volume greater than or equal to an isopropyl substitution or a C3 to C20 hydrocarbyl substituted organometalloid having a molecular volume greater than or equal to an isopropyl substitution, and R ⁇ is hydrogen, a halogen, a Ci to C20 substituted or unsubstituted hydrocarbyl, or Rb is, independently, as defined for R a .
  • the molecular volume of a substituent is used herein as an approximation of spatial steric bulk. 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.
  • Vs 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 Vs is decreased by 7.5% per fused ring.
  • suitable bulky substituents include t-butyl, benzyl, adamantyl, halo substituted and unsubstituted aryl functional groups, and the like.
  • a metallocene compound is an organometallic coordination compound in which one, two or three cyclopentadienyl rings (with or without substituents) are bonded to a central transition metal atom.
  • indene and fluorine are considered cyclopentadienyl rings.
  • a "bridged bis(indenyl) compound” is a compound where two indenyl groups (with or without substituents) are bound together via a bridging group (such as those defined as A herein).
  • a racemic bridged bis(indenyl) catalyst compound also referred to as a racemic bridged bis(indenyl) transition metal compound or a racemic bridged bis(indenyl) metallocene catalyst precursor refers to a metallocene transition metal compound r
  • M is a Group 4, 5, or 6 metal of the periodic table of the elements
  • A is a bridging group, typically a divalent radical comprising a C 1 -C20 hydrocarbyl radical, a functional group comprising elements from groups 13, 14, 15, 16 or 17 of the periodic table of the elements, or combinations thereof;
  • each of and Y 2 is, independently, a halogen, a monovalent radical comprising a molecular volume greater than or equal to the molecular volume of an isopropyl substitution, or a combination thereof, the monovalent radical comprising a C3-C20 hydrocarbyl radical, a functional group comprising elements from groups 13, 14, 15, 16 or 17 of the periodic table of the elements, or a combination thereof (preferably each of and Y 2 is, independently, -O a - SR a , -NR a 2 and -P(R a )(R ⁇ ), where each R a is independently a C3 to C20 hydrocarbyl having a molecular volume greater than or equal to an isopropyl substitution or a C3 to C20 hydrocarbyl substituted organometalloid having a molecular volume greater than or equal to an isopropyl substitution, and R ⁇ is hydrogen, a halogen, a C
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 1 1 , and R 12 is, independently, hydrogen, halogen, a -C20 hydrocarbyl radical, a functional group comprising elements from groups 13, 14, 15, 16 or 17 of the periodic table of the elements, or combinations thereof.
  • metallation of a deprotonated bridged bis(cyclopentadiene) compound includes contacting the deprotonated compound with a metallation reagent to produce the metallocene transition metal compound which may then be contacted with an activator and thus, activated to produce a metallocene catalyst.
  • a metallocene transition metal compound may be reacted with a labile group replacement reagent to replace the labile groups of the compound with more readily substituted or removed labile groups prior to activation.
  • metallation of a deprotonated bridged bis(cyclopentadiene) compound (A) has the ability to produce two isomers of the corresponding metallocene; a racemic pair (B), referred to herein as the "rac" isomer, and a meso isomer (C) as foll
  • a rac-directing metallation reagent forms a product mixture having an increased concentration of the racemic mixture, referred to herein as a "rac-rich" or a racemic enriched product mixture, relative to any meso isomer, if any, formed.
  • a racemic enriched product mixture, compound, or product comprises at least 51 mol% of the racemic isomer based on the total amount of the racemic isomer and the meso isomer present.
  • the rac-directing metallation reagent produces a racemic enriched product mixture, product or compound, and in a further embodiment, without subsequent purification being required to remove any meso isomer formed.
  • a process comprises:
  • each Y is, independently, -O a -SR a , -NR a 2 and -P(R a )(Rb), where each R a is independently a C3 to C20 hydrocarbyl having a molecular volume greater than or equal to an isopropyl substitution or a C3 to C20 hydrocarbyl substituted organometalloid having a molecular volume greater than or equal to an isopropyl substitution, and R ⁇ is hydrogen, a halogen, a Ci to C20 substituted or unsubstituted hydrocarbyl, or Rb is, independently, as defined for R a ,
  • bridged bis(indenyl)metallocene transition metal compound is represented by the formula:
  • M is a Group 4, 5, or 6 metal of the periodic table of the elements, preferably group 4, preferably Hf, Ti or Zr;
  • A is a bridging group, preferably a divalent radical comprising a C1 -C20 hydrocarbyl radical, a functional group comprising elements from Groups 13, 14, 15, 16 or 17 of the periodic table of the elements, or a combination thereof;
  • each X is a halogen (preferably CI, Br, F or I), a triflate or a pseudohalogen;
  • each of Y 1 and Y 2 is independently, -O a , -SR a , -N(R a )2, or -P(R a )(R b ), where each R a is independently a C3 to C20 hydrocarbyl having a molecular volume greater than or equal to an isopropyl substitution or a C3 to C20 hydrocarbyl substituted organometalloid having a molecular volume greater than or equal to an isopropyl substitution, and Rb is hydrogen, a halogen, a C
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 1 1 , and R 12 is, independently, hydrogen, halogen, a C1 -C20 hydrocarbyl radical, a functional group comprising an element from Groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof (preferably H, CI, Br, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, phenyl, benzyl and isomers and substituted variations thereof); and wherein each Z is, independently, a leaving group, comprising a monovalent C2-C20 hydrocarbyl radical, a monovalent functional group comprising an element from Groups 13, 14, 15, 16 or 17 of the periodic table of the elements, or a
  • each of ⁇ and Y 2 are independently monovalent and as such, ⁇ and
  • each of R a and R b are independently monovalent and as such, R a and R b are not bound to each other to produce a single divalent radical.
  • each of the R a groups are independently monovalent and as such are not bound to each other to produce a single divalent radical.
  • the racemic enriched product mixture formed comprises greater than 55 mol% of the racemic isomer, or greater than 60 mol% of the racemic isomer, or greater than 65 mol% of the racemic isomer, or greater than 70 mol% of the racemic isomer, or greater than 75 mol% of the racemic isomer, or greater than 80 mol% of the racemic isomer, or greater than 85 mol% of the racemic isomer, or greater than 90 mol% of the racemic isomer, or greater than 92 mol% of the racemic isomer, or greater than 95 mol% of the racemic isomer, or greater than 98 mol% of the racemic isomer, based on the total amount of the racemic and meso isomer, if any, formed.
  • the racemic enriched product mixture formed comprises greater than 90 mol% of the racemic isomer, or greater than 95 mol% of the racemic isomer, or greater than 99 mol% of the racemic isomer, based on the total amount of the racemic and meso isomer, if any, formed.
  • the racemic enriched product mixture formed comprises greater than 90 mol% of the racemic isomer, or greater than 95 mol%, or greater than 99 mol% of the racemic isomer, based on the total amount of the racemic and meso isomer, if any, formed without subsequent purification to remove meso isomer present in the product mixture.
  • the bridged bis(indenyl)metallocene transition metal compound formed consists essentially of the racemic isomer.
  • Amounts of rac and meso isomers are determined by proton NMR. NMR data are collected at 120°C in a 5 mm probe using a 400 MHz Bruker spectrometer with deuterated chloroform. Data is recorded using a maximum pulse width of 45°, 8 seconds between pulses and signal averaging 16 transients. The spectrum is normalized to protonated chloroform in the deuterated chloroform, which is expected to show a peak at 7.27 ppm.
  • A is dimethylsilyl.
  • A is dimethylsilyl
  • X is CI
  • each Y is-O-iPr or -O-tBu
  • Z comprises a tetrahydrofuranyl radical.
  • A is represented by the formula R2 C J, where J is C, Si, or Ge, and each R c is, independently, hydrogen, halogen, to C20 hydrocarbyl or a Cj to C20 substituted hydrocarbyl, and two R c can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system.
  • A is represented by the formula, (R*2G)g, where each G is C, Si, or Ge, g is 1 or 2, and each R* is, independently, hydrogen, halogen, to C20 hydrocarbyl or a to C20 substituted hydrocarbyl, and two or more R* can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system.
  • A is CH2, CH2CH2, C(CH3)2, SiMe2, SiPh 2 , Si(Me3SiPh) 2 , SiMePh, Si(CH 2 )3, Si(CH 2 )4, or Si(CH 2 )5.
  • Y 2 are, independently,
  • one or both ⁇ and Y 2 may, independently, be M 4 -trialkylsilyl, M ⁇ -(trialkylsilyl)2, M 4 -triphenylsilyl, or M ⁇ -(triphenylsilyl)2, where each alkyl is, independently, methyl, ethyl, propyl, butyl, etc, preferably trimethylsilyl), M 4 is O or S, is N or P; and each phenyl is, independently, a substituted or unsubstituted phenyl, (preferably triphenylsilyl, tri(trimethylphenyl)silyl).
  • each ⁇ and Y 2 independently is -O-iPr, -O-tBu, or -0-SiMe 3 .
  • d is 4, 5 or 6, preferably 4.
  • e is 2, 3, 4 or 5, preferably 2 or 3, preferably 2; and f is 1, 2 or 3, preferably 2 and g is 0, 1 or 2, preferably 1 or 2, preferably 2.
  • the bridged bis(indenyl) compound is represented by the formu
  • each of 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 1 1 , R 12 , R 13 , and R 14 is independently, a hydrogen, a halogen, a -C20 hydrocarbyl radical, a functional group comprising elements from groups 13, 14, 15, 16 or 17 of the periodic table of the elements, or a combination thereof.
  • Rl3 and R14 are independently a C ⁇ -C ⁇ Q hydrocarbyl radical.
  • R 1 and R 14 are independently methyl or ethyl.
  • R 3 and RI O each comprise a phenyl group or a substituted phenyl group (preferably the substituted phenyl is substituted with 1, 2, 3, 4 or 5 C to C20 substituted or unsubstituted hydrocarbyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof, preferably the phenyl is substituted at the meta or para positions, preferably the 3 and/or 5 positions, preferably with a C4 to C ⁇ 2 alkyl group.
  • the substituted phenyl is substituted with 1, 2, 3, 4 or 5 C to C20 substituted or unsubstituted hydrocarbyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octy
  • the phenyl may be substituted at the 2 position, but is preferably not substituted in the 2 and 6 positions, e.g., in a preferred embodiment if the invention when the 2 position of the phenyl is substituted, the 6 position is H).
  • R1 and each comprise a C ⁇ -C ⁇ Q hydrocarbyl radical (preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl).
  • a C ⁇ -C ⁇ Q hydrocarbyl radical preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl.
  • R1 and each comprise a C ⁇ -C ⁇ Q hydrocarbyl radical (preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl) and R and R10 each comprise a phenyl group or a substituted phenyl group (preferably the substituted phenyl is substituted with 1, 2, 3, 4 or 5 Cj to C20 substituted or unsubstituted hydrocarbyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof, preferably the phenyl is substituted at the meta or para positions, preferably the 3 and/or 5 positions, preferably with a C4 to C ⁇ 2 alkyl group
  • the phenyl may be substituted at the 2 position, but is preferably not substituted in the 2 and 6 positions, e.g. in a preferred embodiment if the invention when the 2 position of the phenyl is substituted, the 6 position is H.
  • the bridged bis(indenyl) compound is a bridged bis(4-(phenyl or substituted phenyl)-2-alkylindene), where the alkyl may be a C ⁇ to C30 alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof; and the substituted phenyl is substituted with 1, 2, 3, 4 or 5 C i to C20 substituted or unsubstituted hydrocarbyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof, preferably the phenyl is substituted
  • the phenyl may be substituted at the 2 position, but is preferably not substituted in the 2 and 6 positions, e.g. in a preferred embodiment if the invention when the 2 position of the phenyl is substituted, the 6 position is H.
  • the bridged bis(indenyl) compound is one or more of dimethylsilyl bis(4-(o-tolyl)-2-methylindene), dimethylsilyl bis(4-phenyl-2- methylindene), dimethylsilyl bis(4-(3',5'-di-t-butylphenyl)-2-methylindene).
  • the rac-directing metallation reagent is represented by the formula:
  • M d X e Y f Zg preferably M*X 2 Y2Z2
  • M is a Group 4, 5, or 6 metal of the periodic table of the elements;
  • M* is a group 4 metal, preferably Zr, Ti or Hf;
  • each X is a halogen (preferably CI, Br, F or I), a triflate or a pseudohalogen;
  • each Y is, independently, -O a -SR a , -NR3 ⁇ 4 and -P(R a )(R b ), where each R a is independently a C3 to C20 hydrocarbyl having a molecular volume greater than or equal to an isopropyl substitution or a C3 to C20 hydrocarbyl substituted organometalloid having a molecular volume greater than or equal to an isopropyl substitution, and Rb is hydrogen, a halogen, a Cj to C20 substituted or unsubstituted hydrocarbyl, or R ⁇ is, independently, as defined for R a ; and each Z is, independently, a leaving group comprising a monovalent C2-C20 hydrocarbyl radical, a monovalent functional group comprising an element from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof.
  • M is Ti, Zr, or Hf.
  • each X is CI or Br.
  • each Y is independently -O-iPr or -O-tBu.
  • M is Ti, Zr, or Hf, each X is CI or Br, and each Y is independently OR a , where R a is a monovalent C3 to C20 hydrocarbyl radical comprising a molecular volume greater than or equal to the molecular volume of an isopropyl substitution.
  • each Y is, independently, -O-iPr, - O-t-Bu, -O-iBu, -O-n-Bu, -O-secBu, -0-(2-methyl-butene), -0-(3-methyl-butene), -O-isopentyl, - O-n-pentyl, -O-n-hexyl, -O-isohexyl, -O-methylpentene, -O-dimethylbutene, -O-cyclopentyl, -O- cyclohexyl, -O-octyl, N-iPr2, - ⁇ - ⁇ - ⁇ 3 ⁇ 4, - ⁇ - ⁇ 3 ⁇ 4, - ⁇ - ⁇ - ⁇ 3 ⁇ 4, -N-secBu2, -N-(2-methyl-butene)2, -N-(3-methyl-butene)2, -N-isopentyl2, -
  • Y groups may, independently, be M ⁇ - trialkylsilyl, M ⁇ -(trialkylsilyl)2, M ⁇ -triphenylsilyl, or M ⁇ -(triphenylsilyl)2, where each alkyl is, independently, methyl, ethyl, propyl, butyl, etc, (preferably trimethylsilyl), is O or S, is N or P; and each phenyl is, independently, a substituted or unsubstituted phenyl, (preferably triphenylsilyl, tri(trimethylphenyl)silyl).
  • Y is -O-iPr , -O-tBu, or -OSiMe3.
  • R a may be -O-iPr, -O-t-Bu, -O-iBu, -O-n-Bu, -O-secBu, -0-(2-methyl-butene), -0-(3-methyl-butene), -O-isopentyl, -O-n-pentyl, -O- n-hexyl, -O-isohexyl, -O-methylpentene, -O-dimethylbutene, -O-cyclopentyl, -O-cyclohexyl, -O- octyl, N-iPr, -N-t-Bu, -N-iBu, -N-n-Bu, -N-secBu, -N-(2-methyl-butene), -N-(3-methyl-butene), - N-isopentyl, -N-n-pentyl,
  • any embodiment of any formula described herein may be H, CI, Br, or a to C20 hydrocarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof or any of the specific embodiments listed for R a above.
  • each Z is, independently, a leaving group comprising a monovalent C2-C20 hydrocarbyl radical, a monovalent functional group comprising an element from Groups 13, 14, 15, 16 or 17 of the periodic table of the elements, or a combination thereof.
  • each Z is a monovalent C2-C20 cyclic hydrocarbyl, saturated or unsaturated, comprising an element from Group 15 or 16 of the periodic table of the elements.
  • Z comprises an oxirenyl radical, an azirinyl radical, a thiirenyl radical, a diazirinyl radical, an oxaziridinyl radical, a dioxiranyl radical, an azetidinyl radical, an azetyl radical, an oxetanyl radical, an oxetyl radical, a thietanyl radical, a thietyl radical, a diazetidinyl radical, a dioxetanyl radical, a dioxetyl radical, a dithietanyl radical, a dithietyl radical, a pyrrolidinyl radical, a pyrrolyl radical, a tetrahydrofuranyl radical, a furanyl radical, a thiolanyl radical, a thiophenyl radical, an imidazolidinyl radical, a pyrazo
  • Z comprises a tetrahydrofuranyl radical.
  • X is CI
  • Y is -O-iPr or -O-tBu
  • Z comprises a tetrahydrofuranyl radical.
  • the rac-directing metallation reagent is MCl2(0-R a )2(thf)2 or MBr2(0-R a )2(thf)2,wherein M is Zr or Hf and R a is a monovalent C3 to C20 hydrocarbyl radical comprising a molecular volume greater than or equal to the molecular volume of an isopropyl substitution.
  • the rac-directing metallation reagent is ZrCi2(0-tBu)2(thf)2, HfCi2(0-tBu)2(thf)2, ZrCl2(0-SiMe 3 )2(thf)2, HfCl2(0-SiMe 3 )2(thf), ZrCl 2 (0-iPr)2(thf)2, HfCl 2 (0-iPr) 2 (thf).
  • a compound comprises greater than 50 mol% of a racemic isomer of a bridged bis(indenyl)metallocene transition metal compound, based on the
  • M is a Group 4, 5, or 6 metal of the periodic table of the elements
  • A is a divalent radical comprising a C 1 -C20 hydrocarbyl radical, a functional group comprising elements from groups 13, 14, 15, 16 or 17 of the periodic table of the elements, or combinations thereof;
  • each of Y 1 and Y 2 is independently, -OR a , -SR a , -N(R a )2, or -P(R a )(Rb), where each R a is independently a C3 to C20 hydrocarbyl having a molecular volume greater than or equal to an isopropyl substitution or a C3 to C20 hydrocarbyl substituted organometalloid having a molecular volume greater than or equal to an isopropyl substitution, and Rb is hydrogen, a halogen, a C
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 1 1 , and R 12 is, independently, hydrogen, halogen, a Ci -C20 hydrocarbyl radical, a functional group comprising elements from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or combinations thereof.
  • the compound comprises greater than 90 mol% of the racemic isomer, based on the total amount of the compound present.
  • M is Zr
  • A is a dimethyl silyl
  • Rl2 are methyl
  • the racemic bridged bis(indenyl)metallocene transition metal compound is bridgedbis[4-(o-tolyl)-2-methylindenyl]Zr(Ot-Bu)2 comprising greater than 90 mol% racemic isomer, bridgedbis[4-(phenyl)-2-methylindenyl]Zr(Ot-Bu)2 comprising greater than 90 mol% racemic isomer, or bridgedbis[4-(3',5'-dimethyl-phenyl)-2- methylindenyl]Zr(Ot-Bu)2 comprising greater than 90 mol% racemic isomer, preferably the racemic bridged bis(indenyl)metallocene transition metal compound is dimethylsilylbis[4-(o- tolyl)-2-methylindenyl]Zr(Ot-Bu)2 comprising greater than 90 mol% racemic isomer, bridgedbis[4-(phenyl)-2-methylindeny
  • the bridged bis(indenyl) compound is a bridged bis(4-(phenyl or substituted phenyl)-2-alkylindene), where the alkyl may be a to C30 alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof; and the substituted phenyl is substituted with 1, 2, 3, 4, or 5 C i to C20 substituted or unsubstituted hydrocarbyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof, preferably the phenyl is substituted at the alkyl group, such as
  • the phenyl may be substituted at the 2 position, but is preferably not substituted in the 2 and 6 positions, e.g., in a preferred embodiment if the invention when the 2 position of the phenyl is substituted, the 6 position is H.
  • the bridged bis(indenyl) transition metal compound is a bridged bis(4-(phenyl or substituted phenyl)-2-alkylindene)MY2, where M is Hf, Zr or Ti, Y is as defined above, the alkyl may be a C ⁇ to C30 alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof; and the substituted phenyl is substituted with 1, 2, 3, 4 or 5 C ⁇ to C20 substituted or unsubstituted hydrocarbyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an iso
  • a catalyst precursor comprises the reaction product of a bridged bis(indenyl) compound according to any embodiment disclosed herein, reacted with a with a rac- directing metallation reagent represented by the formula M d X e YfZ g (preferably M*X 2 Y2Z2, where M* is a group 4 metal, both as defined above) according to any one or more embodiments disclosed herein.
  • the reaction product comprises greater than 90 mol% of the racemic isomer of the catalyst precursor, based on the total amount of the catalyst precursor present.
  • the process of preparing the catalyst compound may optionally comprise contacting the bridged bis(indenyl)metallocene transition metal compound with a labile group replacement reagent to replace labile groups (such as ⁇ and Y 2 in the formulae above) with a labile group less tightly bound and thus more facile as compared to iso- propoxy, t-butoxy, or the like.
  • a labile group replacement reagent to replace labile groups (such as ⁇ and Y 2 in the formulae above) with a labile group less tightly bound and thus more facile as compared to iso- propoxy, t-butoxy, or the like.
  • the bridged bis(indenyl)metallocene transition metal compound may be contacted or reacted with a labile group replacement reagent to replace ⁇ and Y ⁇ in the formulae above with a labile group selected from the group consisting of halogen, benzyl, phenyl, or a combination thereof.
  • the labile group replacement reagent is a halo-trialkyl silane, e.g., chlorotrimethylsilane; a mineral acid, e.g., HC1, HBr, or HI; and/or a halogenating compound e.g., SOCI2, and/or a combination thereof.
  • one racemic bridged bis(indenyl) transition metal compound is used in a polymerization herein, however when desired two or more racemic bridged bis(indenyl) transition metal compound catalysts may be used.
  • two or more different catalyst compounds preferably two or more racemic bridged bis(indenyl) transition metal compounds, are present in the catalyst system used herein.
  • two or more different catalyst compounds are present in the reaction zone where the process(es) described herein occur.
  • the two transition metal compound based catalysts are used in one reactor as a mixed catalyst system, the two transition metal compounds are chosen such that the two are compatible.
  • Compatible catalysts are those catalysts having similar kinetics of termination and insertion of monomer and comonomer(s) and/or do not detrimentally interact with each other.
  • the term “incompatible catalysts” refers to and means catalysts that satisfy one or more of the following:
  • those catalysts that under the same reactive conditions produce polymers such that one of the polymers has a molecular weight that is more than twice the molecular weight of the other polymer; and 3) those catalysts that differ in comonomer incorporation or reactivity ratio under the same conditions by more than about 30%.
  • a simple screening method such as by or NMR, known to those of ordinary skill in the art, can be used to determine which transition metal compounds are compatible.
  • the catalyst systems use the same activator for the catalyst compounds.
  • two or more different activators such as a non- coordinating anion activator and an alumoxane, can be used in combination.
  • one or more catalyst compounds contain an X 1 or X2 li gand which is not a hydride, or a hydrocarbyl, then in an embodiment the alumoxane is contacted with the catalyst compounds prior to addition of the non-coordinating anion activator.
  • transition metal compounds when two transition metal compounds are utilized, they may be used in any ratio.
  • a molar ratio of a first transition metal compound (A) to a second transition metal compound (B) will fall within the range of (A:B) 1 : 1000 to 1000:1, or 1 :100 to 500:1, or 1 : 10 to 200:1, or 1 :1 to 100: 1, or 1 :1 to 75:1, or 5:1 to 50:1.
  • the particular ratio chosen will depend on the exact pre-catalysts chosen, the method of activation, and the end product desired.
  • useful mole percents are 10:90 to 0.1 :99, or 25:75 to 99: 1, or 50:50 to 99.5:0.5, or 50:50 to 99: 1, or 75:25 to 99: 1, or 90: 10 to 99: 1.
  • 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, referred to herein as a labile ligand, making the metal complex cationic and providing a charge-balancing noncoordinating or weakly coordinating anion.
  • a process according to any one or combination of embodiments disclosed herein further includes contacting the bridged bis(indenyl)metallocene catalyst precursor with an activator to form a catalyst system.
  • the activator comprises alumoxane, a non-coordinating anion activator, or a combination thereof.
  • the process may further comprise contacting the bridged bis(indenyl)metallocene catalyst precursor with a labile group replacement reagent to replace labile groups Y 1 and Y 2 with a labile group less tightly bound and thus more readily substituted or removed as compared to iso-propoxy, t-butoxy, or the like.
  • the modified bridged bis(indenyl)metallocene catalyst precursor may then be contacted with an activation agent to form a catalyst or a catalyst system. Accordingly, the modification of the labile groups Y may allow for various types of activators to be used.
  • the bridged bis(indenyl)metallocene catalyst precursor may be further reacted with a labile group replacement reagent to replace and Y 2 with a labile group selected from the group consisting of halogen, benzyl, phenyl, or a combination thereof.
  • the labile group replacement reagent is a halo-trialkyl silane, e.g., chlorotrimethylsilane; a mineral acid, e.g., HC1, HBr, or HI; and/or a halogenating compound e.g., SOCI2, and/or a combination thereof.
  • the activator comprises alumoxane, a non- coordinating anion activator, or a combination thereof.
  • an alumoxane is combined with the metallocene compound before or in combination with a non-coordinating anion activator.
  • an alumoxane is contacted with the metallocene compound, preferably such that at least one leaving group (e.g., -O-t-Bu) is removed, and thereafter a non-coordinating anion activator is combined with the metallocene compound.
  • the activator comprises alumoxane and the alumoxane is present at a ratio of 1 mole aluminum or more to mole of catalyst.
  • Alumoxanes are generally oligomeric compounds containing -A1(R1)-0- sub-units, where Rl is an alkyl radical.
  • 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. 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 U.S. Patent No. 5,041,584 and/or commercially available from Akzo Chemicals, Inc. under the trade designation Modified Methylalumoxane type 3A.
  • MMAO modified methyl alumoxane
  • 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 1000: 1, or 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.
  • non-coordinating anion refers to an anion which either does not coordinate to a cation, or which is only weakly coordinated to a cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base.
  • “Compatible” non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral transition metal compound and a neutral by-product from the anion.
  • Non- coordinating anions useful in accordance with this invention are those that are compatible with the polymerization or catalyst system, stabilize the transition metal cation in the sense of balancing its ionic charge at +1, and yet are sufficiently labile to permit displacement during polymerization.
  • an ionizing or stoichiometric activator may be used, which may be neutral or ionic, such as tri (n-butyl) ammonium boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Patent No. 5,942,459), or a combination thereof.
  • neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators may be used.
  • 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 European publications EP 0 570 982 A; EP 0 520 732 A; EP 0 495 375 A; EP 0 500 944 Bl ; EP 0 277 003 A; EP 0 277 004 A; U.S. Patent Nos. 5,153,157; 5,198,401 ; 5,066,741 ; 5,206,197; 5,241,025; 5,384,299; 5,502,124; and WO 1996/04319; all of which are herein fully incorporated 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 and (L- H) + is a Bronsted acid; Ad- 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) ( j + 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, N,N- dimethylaniline, methyldiphenylamine, pyridine, p-bromo ⁇ , ⁇ -dimethylaniline, p-nitro-N,N- dimethyl
  • Z is a reducible Lewis acid, it may be represented by the formula: (Ar3C + ), where
  • Ar is aryl or aryl substituted with a heteroatom, or a Ci to C40 hydrocarbyl
  • the reducible Lewis acid may be represented by the formula: (Ph3C + ), where Ph is phenyl or phenyl substituted with a heteroatom, and/or a Ci to C40 hydrocarbyl.
  • the reducible Lewis acid is triphenyl carbenium.
  • non-coordinating anion activator is represented by the formula:
  • Z is (L-H), or a reducible Lewis acid, L is a neutral Lewis base, H is hydrogen and (L-H) + is a Bronsted acid; Ad- is a non-coordinating anion having the charge d " ; and
  • d is an integer from 1 to 3, preferably Z is a reducible Lewis acid represented by the formula: (Ar3C + ), where Ar is aryl radical, an aryl radical substituted with a heteroatom, an aryl radical substituted with one or more C ⁇ to C40 hydrocarbyl radicals, an aryl radical substituted with one or more functional groups comprising elements from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof.
  • Ar is aryl radical, an aryl radical substituted with a heteroatom, an aryl radical substituted with one or more C ⁇ to C40 hydrocarbyl radicals, an aryl radical substituted with one or more functional groups comprising elements from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof.
  • 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 ⁇ - components also include diboron compounds as disclosed in U.S. Patent No. 5,447,895, which is fully incorporated herein by reference.
  • the activator is represented by the formula:
  • Z is (L-H), or a reducible Lewis acid, wherein L is a neutral Lewis base, H is hydrogen and (L-H) + is a Bronsted acid;
  • Ad- is a non-coordinating anion having the charge d ⁇ ;
  • d is an integer from 1 to 3.
  • the activator is represented by the formula:
  • Ad- is a non-coordinating anion having the charge d " ;
  • d is an integer from 1 to 3
  • Z is a reducible Lewis acid represented by the formula: (Ar3C + ), where Ar is aryl radical, an aryl radical substituted with a heteroatom, an aryl radical substituted with one or more Ci to C40 hydrocarbyl radicals, an aryl radical substituted with one or more functional groups comprising elements from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof.
  • This invention also relates to a method to polymerize olefins comprising contacting olefins (such as ethylene) with a bridged bis(indenyl)metallocene catalyst compound as described above and an NCA activator represented by the Formula (2):
  • R is a monoanionic ligand
  • M** is a Group 13 metal or metalloid
  • ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclic aromatic ring, or aromatic ring assembly in which two or more rings (or fused ring systems) are joined directly to one another or together
  • n is 0, 1 , 2, or 3.
  • the NCA comprising an anion of Formula 2 also comprises a suitable cation that is essentially non-interfering with the ionic catalyst complexes formed with the transition metal compounds, or the cation is as described above.
  • R is selected from the group consisting of to C30 hydrocarbyl radicals.
  • C to C30 hydrocarbyl radicals may be substituted with one or more C ⁇ to C20 hydrocarbyl radicals, halide, hydrocarbyl substituted organometalloid, dialkylamido, alkoxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido, arylphosphide, or other anionic substituent; fluoride; bulky alkoxides, where bulky means C4 to C20 hydrocarbyl radicals; — SR a ,— NR3 ⁇ 4, and— PR3 ⁇ 4, where each R a is independently a monovalent C4 to C20 hydrocarbyl radical comprising a molecular volume greater than or equal to the molecular volume of an isopropyl substitution or a C4 to C20 hydrocarby
  • the NCA also comprises cation comprising a reducible Lewis acid represented by the formula: (Ar3C + ), where Ar is aryl or aryl substituted with a heteroatom, and/or a C ⁇ to C40 hydrocarbyl, or the reducible Lewis acid represented by the formula: (Ph3C + ), where Ph is phenyl or phenyl substituted with one or more heteroatoms, and/or C ⁇ to C40 hydrocarbyls.
  • a reducible Lewis acid represented by the formula: (Ar3C + ) where Ar is aryl or aryl substituted with a heteroatom, and/or a C ⁇ to C40 hydrocarbyl
  • the reducible Lewis acid represented by the formula: (Ph3C + ) where Ph is phenyl or phenyl substituted with one or more heteroatoms, and/or C ⁇ to C40 hydrocarbyls.
  • the NCA may also comprise a cation represented by the formula, (L-H) ( j + , wherein L is an neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or 3, or (L-H) ( j + is a Bronsted acid selected from ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof.
  • a cation represented by the formula, (L-H) ( j + wherein L is an neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or 3, or (L-H) ( j + is a Bronsted acid selected from ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof.
  • useful activators include those disclosed in U.S. Patent Nos. 7,297,653 and 7,799,879, which are fully incorporated by reference herein.
  • an activator useful herein comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the Formula (3):
  • OX e+ is a cationic oxidizing agent having a charge of e+; e is 1, 2 or 3; d is 1, 2 or 3; and Ad- is a non-coordinating anion having the charge of d- (as further described above).
  • cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag + , or Pb + 2.
  • Suitable embodiments of A ⁇ - include tetrakis(pentafluorophenyl)borate.
  • bridged bis(indenyl)metallocene catalyst compounds, described herein can be used with bulky activators.
  • a “bulky activator” as used herein refers to anionic activators represented by the formula:
  • each Pvi is, independently, a halide, or a fluoride
  • each P2 is, independently, a halide, a Cg to C20 substituted aromatic hydrocarbyl radical or a siloxy group of the formula -0-Si-R a , where R a is a Ci to C20 hydrocarbyl or hydrocarbylsilyl radical (or R2 is a fluoride or a perfluorinated phenyl radical);
  • each R3 is a halide, Cg to C20 substituted aromatic hydrocarbyl radical or a siloxy group of the formula -0-Si-R a , where R a is a Ci to C20 hydrocarbyl radical or hydrocarbylsilyl group (or R3 is a fluoride or a C perfluorinated aromatic hydrocarbyl radical); wherein R2 and R3 can form one or more saturated or unsaturated, substituted or unsubstituted rings (or R2 and R3 form a perfluorinated phenyl ring);
  • L is an neutral Lewis base
  • (L-H) + is a Bronsted acid
  • d is 1, 2, or 3;
  • the anion has a molecular weight of greater than 1020 g/mol
  • molecular volume is used herein as an approximation of spatial steric bulk of an activator molecule in solution.
  • Exemplary bulky substituents of activators suitable herein and their respective scaled volumes and molecular volumes are shown in the table below.
  • the dashed bonds indicate binding to boron, as in the general formula above.
  • Exemplary bulky activators useful in catalyst systems herein include: trimethylammonium terrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium terrakis(perfluoronaphthyl)borate, ⁇ , ⁇ -diethylanilinium terrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, trimethylammonium terrakis(perfluorobiphenyl)borate, ⁇ , ⁇ -dimethylanilinium terrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, and the types disclosed in U.S. Patent No. 7,297,653, which is fully incorporated by reference herein.
  • Suitable activators include:
  • the activator comprises a triaryl carbonium (such as triphenylcarbenium tetraphenylborate,
  • triphenylcarbenium tetrakis(pentafluorophenyl)borate triphenylcarbenium tetrakis-(2,3,4,6- terrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium terrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5- bis(rrifluoromethyl)phenyl)borate).
  • any of the activators described herein may be mixed together before or after combination with the catalyst compound and/or CTA and/or NCA, or before being mixed with the catalyst compound and/or CTA, and/or NCA.
  • two NCA activators may be used in the polymerization and the molar ratio of the first NCA activator to the second NCA activator can be any ratio. In an embodiment, the molar ratio of the first NCA activator to the second NCA activator is 0.01 : 1 to 10,000:1, or
  • the NCA activator-to-catalyst ratio is a 1 : 1 molar ratio, or 0.1 :1 to
  • the NCA activator- to-catalyst ratio is 0.5:1 to 10:1, or 1 :1 to 5: 1.
  • the catalyst compounds can be combined with combinations of alumoxanes and NCA's (see for example, US 5,153,157, US 5,453,410, EP 0 573 120 Bl, WO 94/07928, and WO 95/14044 which discuss the use of an alumoxane in combination with an ionizing activator, all of which are incorporated by reference herein).
  • 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, alumoxane, and the like.
  • Other oxophilic species such as diethyl zinc may be used.
  • the catalyst system may comprise an inert support material.
  • the support material comprises a porous support material, for example, talc, and/or inorganic oxides.
  • suitable 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 catalyst systems 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, and/or alumina include magnesia, titania, zirconia, montmorillonite, phyllosilicate, and/or the like.
  • Other suitable support materials include finely divided functionalized polyolefins, such as finely divided polyethylene.
  • the support material may have a surface area in the range of from about 10 to about 700 m ⁇ /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 ⁇ , or the surface area of the support material is in the range of from about 50 to about 500 rn ⁇ /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 ⁇ .
  • a majority portion of the surface area of the support material is in the range of from about 100 to about 400 m ⁇ /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 is in the range of from 10 to 1000 A, or 50 to about 500 A, or 75 to about 350 A.
  • the support material is a high surface area, amorphous silica having a surface area greater than or equal to about 300 m ⁇ /gm, and/or a pore volume of 1.65 cm ⁇ /gm.
  • Suitable silicas are marketed under the tradenames of Davison 952 or Davison 955 by the Davison Chemical Division of W. . Grace and Company.
  • the support may comprise Davison 948.
  • the support material should be essentially dry, that is, essentially free of absorbed water. Drying of the support material can be effected by heating or calcining at about 100°C to about 1000°C, or at a temperature of at least about 400°C, or 500°C, or 600°C. When the support material is silica, it is heated to at least 200°C, or about 200°C to about 850°C, or at least 600°C for a time of about 1 minute to about 100 hours, or from about 12 hours to about 72 hours, or from about 24 hours to about 60 hours. In an embodiment, the calcined support material must have at least some reactive hydroxyl (OH) groups to produce supported catalyst systems according to the instant disclosure.
  • OH reactive hydroxyl
  • the calcined support material is contacted with at least one polymerization catalyst comprising at least one catalyst compound and an activator.
  • the support material having reactive surface groups, typically hydroxyl groups, is slurried in a non-polar solvent and the resulting slurry is contacted with a solution of a catalyst compound and an activator.
  • the slurry of the 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, or from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.
  • the solution of the catalyst compound is then contacted with the isolated support/activator.
  • the supported catalyst system is generated in situ.
  • the slurry of the 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, or from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.
  • the slurry of the supported catalyst compound is then contacted with the activator solution.
  • the mixture of the catalyst, activator and support is heated to about 0°C to about 70°C, or to about 23°C to about 60°C, or to 25°C (room temperature).
  • Contact times typically range from about 0.5 hours to about 24 hours, or from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.
  • 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.
  • Suitable non-polar solvents include 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.
  • a polymerization processes includes contacting monomers (such as ethylene and propylene), and optionally comonomers, with a catalyst system comprising an activator and at least one embodiment of a catalyst precursor compound according to the invention.
  • 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.
  • a process comprises:
  • the catalyst system comprising an activator and a racemic bridged bis(indenyl)metallocene transition metal compound represented by the formula:
  • a process comprises contacting one or more olefins with a catalyst system at polymerization conditions to produce a polyolefin, the catalyst system comprising an activator and a racemic bridged bis(indenyl)metallocene transition metal compound according to any one of the embodiments disclosed herein.
  • a process comprises contacting one or more olefins with a catalyst system at polymerization conditions to produce a polyolefin, the catalyst system comprising an activator, or combination of activators, and a racemic bridged bis(indenyl)metallocene transition metal compound represented by the formula:
  • M is a Group 4, 5, or 6 metal of the periodic table of the elements
  • A is a divalent radical comprising a C1 -C20 hydrocarbyl radical, a functional group comprising elements from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or combinations thereof;
  • each of Y 1 and Y 2 is, independently, -O a -SR a , -NR3 ⁇ 4 and -P(R a )(Rb), where each R a is independently a C3 to C20 hydrocarbyl having a molecular volume greater than or equal to an isopropyl substitution or a C3 to C20 hydrocarbyl substituted organometalloid having a molecular volume greater than or equal to an isopropyl substitution, and R ⁇ is hydrogen, a halogen or a C ⁇ to C20 substituted or unsubstituted hydrocarbyl, or R ⁇ is, independently, as defined for R a ; and wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 1 1 , and R 12 is, independently, hydrogen, halogen, a -C20 hydrocarbyl radical, a functional group comprising elements from groups 13,
  • the polymerization conditions comprise a temperature of from about 0°C to about 300°C, a pressure from about 0.35 MPa to about 10 MPa, and a time from about 0.1 minutes to about 24 hours.
  • one or more olefins comprise propylene.
  • the polyolefin comprises at least 50 mole% propylene.
  • the catalyst system, and/or the polyolefin produced comprises less than about 0.01 wt% of fluoride, chloride, bromide, iodide, or a combination thereof.
  • a process comprises:
  • M d X e YfZg (preferably M*X2Y2Z2, where M* is a group 4 metal);
  • M is a Group 4, 5 or 6 metal of the periodic table of the elements
  • A is a divalent radical comprising a C 1 -C20 hydrocarbyl radical, a functional group comprising elements from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof;
  • each X is a halogen, a triflate or a pseudohalogen
  • each Y is, independently, -O a -SR a , -NR3 ⁇ 4 and -P(R a )(Rb), where each R a is independently a C3 to C20 hydrocarbyl having a molecular volume greater than or equal to an isopropyl substitution or a C3 to C20 hydrocarbyl substituted organometalloid having a molecular volume greater than or equal to an isopropyl substitution, and R ⁇ is hydrogen, a halogen or a Ci to C20 substituted or unsubstituted hydrocarbyl, or R ⁇ is, independently, as defined for R a ; and wherein each of Y 1 and Y 2 is independently, -OR a -SR a , -NR3 ⁇ 4 and -P(R a )(Rb), where each R a is independently a C3 to C20 hydrocarbyl having a molecular volume greater than or equal to an isopropyl substitution or a C3 to C20 hydro
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 1 1 , and R 12 is, independently, hydrogen, halogen, a -C20 hydrocarbyl radical, a functional group comprising an element from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof; and
  • each Z is, independently, a leaving group comprising a monovalent C2-C20 hydrocarbyl radical, a monovalent functional group comprising an element from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof;
  • step (C) optionally supporting the catalyst compound and or activator before or after step (B), and D) contacting one or more olefins with the catalyst system at polymerization conditions to produce a polyolefin.
  • the deprotonated bridged bis(indenyl) compound may be contacted with the rac-directing metallation reagent in the presence of the activator, in the presence of one or more olefins, or a combination thereof.
  • the bridged bis(indenyl)metallocene catalyst precursor may be contacted with a labile group replacement reagent to replace each of and Y 2 with a labile group selected from the group consisting of halogen, benzyl, phenyl, or a combination thereof, prior to contacting the bridged bis(indenyl)metallocene catalyst precursor with an activator to form a catalyst system.
  • a labile group replacement reagent to replace each of and Y 2 with a labile group selected from the group consisting of halogen, benzyl, phenyl, or a combination thereof
  • the labile group replacement reagent is chlorotrimethylsilane, HC1,
  • the deprotonated bridged bis(indenyl) compound is contacted with the rac-directing metallation reagent in the presence of the activator, in the presence of the one or more olefins, (i.e., an in-situ generated catalyst) or a combination thereof.
  • Monomers useful herein include substituted or unsubstituted C2 to C40 alpha olefins, or
  • the monomer comprises propylene and an optional comonomers comprising one or more of ethylene or C4 to C40 olefins, or C4 to C20 olefins, or Cg to C ⁇ 2 olefins.
  • the C4 to C40 olefin monomers may be linear, branched, or cyclic.
  • the C4 to C40 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 C20 olefins, or Cg to C ⁇ 2 olefins.
  • the C3 to C40 olefin monomers may be linear, branched, or cyclic.
  • the C3 to C40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.
  • Exemplary C2 to C40 olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbomadiene, 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, 1 -hydroxy-4-cyclooctene, 1 -acetoxy-4-cyclooctene, 5-methylcyclopen
  • one or more dienes are present in the polymer produced herein at up to
  • % 10 weight %, or at 0.00001 to 1.0 weight %, or 0.002 to 0.5 weight %, or 0.003 to 0.2 weight %, 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
  • 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
  • Cyclic dienes include cyclopentadiene, vinylnorbomene, norbomadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene or higher ring containing diolefins with or without substituents at various ring positions.
  • the butene source may be a mixed butene stream comprising various isomers of butene.
  • the 1 -butene monomers are expected to be preferentially consumed by the polymerization process.
  • Use of such mixed butene streams will provide an economic benefit, as these mixed streams are often waste streams from refining processes, for example, C4 raffinate streams, and can therefore be substantially less expensive than pure 1 -butene.
  • Polymerization processes according to the instant disclosure may be carried out in any manner known in the art. Any suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization process known in the art can be used. Such processes can be run in a batch, semi- batch, or continuous mode. Homogeneous polymerization processes and slurry processes are suitable for use herein, wherein a homogeneous polymerization process is defined to be a process where at least 90 wt% of the product is soluble in the reaction media. A bulk homogeneous 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 volume % or more.
  • 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).
  • 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 C4 0 alkanes, chlorobenzene, and aromatic and alkyl substituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene.
  • straight and branched-chain hydrocarbons such as isobutane, but
  • 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-l- 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.
  • 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 about 20°C to about 200°C, or about 35°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 24 hours, or up to 16 hours, or in the range of from about 5 to 250 minutes, or from about 10 to 120 minutes.
  • 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% based upon the weight of
  • 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.
  • a process to polymerize olefins comprises contacting one or more olefins with a catalyst system according to any one or combination of embodiments disclosed herein at polymerization conditions to produce a polyolefin.
  • the polymerization conditions comprise a temperature of from about 0°C to about 300°C, a pressure from about 0.35 MPa to about 10 MPa, and a time from about 0.1 minutes to about 24 hours.
  • the one or more olefins comprise propylene.
  • the polyolefin comprises at least 50 mole% propylene.
  • compositions of matter produced by the methods described herein also relates to compositions of matter produced by the methods described herein.
  • the process described herein produces propylene homopolymers or propylene copolymers, such as propylene-ethylene and/or propylene-a-olefin (or C3 to C20) copolymers (such as propylene-hexene copolymers or propylene-octene copolymers) having a Mw/Mn of greater than 1 to 4 (or greater than 1 to 3).
  • propylene homopolymers or propylene copolymers such as propylene-ethylene and/or propylene-a-olefin (or C3 to C20) copolymers (such as propylene-hexene copolymers or propylene-octene copolymers) having a Mw/Mn of greater than 1 to 4 (or greater than 1 to 3).
  • the process of this invention produces olefin polymers, or polyethylene and polypropylene homopolymers and copolymers.
  • the polymers produced herein are homopolymers of ethylene or propylene, are copolymers of ethylene or having from 0 to 25 mole% (or from 0.5 to 20 mole%, or from 1 to 15 mole%, or from 3 to 10 mole%) of one or more C3 to C20 olefin comonomer (or C3 to C ⁇ 2 alpha-olefin, or propylene, butene, hexene, octene, decene, dodecene, or propylene, butene, hexene, octene), or are copolymers of propylene or having from 0 to 25 mole% (or from 0.5 to 20 mole%, or from 1 to 15 mole%, or from 3 to 10 mole%) of one or more of C2 or C4 to C20 o
  • the polymers produced herein have an Mw of 5,000 to 1,000,000 g/mol (e.g., 25,000 to 750,000 g/mol, or 50,000 to 500,000 g/mol), and/or an Mw/Mn of greater than 1 to 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 Chromatography (GPC).
  • GPC Gel Permeation Chromatography
  • 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).
  • Mw, Mn, MWD are determined by GPC as described in US 2006/0173123 pages 24-25, paragraphs [0334] to [0341].
  • the polyolefin has a concentration of isotactic pentads [mmmm] of greater than or equal to about 50 wt%, or 60 wt%, or 70 wt%, or 80 wt%, or 90 wt%, or greater than or equal to about 99 wt%, based on the total weight of the polymer.
  • the polyolefin comprises at least 50 mole% propylene and has a melting point T me it determined using differential scanning calorimetry from about 145°C to about 165°C. Within this range, in an embodiment, the polyolefin has a melting point T me it of greater than or equal to about 148°C, or greater than or equal to about 150°C, or greater than or equal to about 152°C, or greater than or equal to about 154°C, or greater than or equal to about 155°C, or greater than or equal to about 156°C, or greater than or equal to about 157°C, or greater than or equal to about 158°C, or greater than or equal to about 159°C, or greater than or equal to about 160°C.
  • a polyolefin according to any one or more embodiments disclosed herein comprises a polyolefin produced according to any one or combination of embodiments disclosed herein.
  • an article comprises a polyolefin produced according to any one or combination of embodiments disclosed herein.
  • a particular embodiment of the invention is a polyolefin produced according to a process comprising:
  • M is a Group 4, 5, or 6 metal of the periodic table of the elements
  • A is a divalent radical comprising a C1 -C20 hydrocarbyl radical, a functional group comprising elements from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof;
  • each X is a halogen, a triflate or a pseudohalogen
  • each Y is, independently, -O a -SR a , -NR3 ⁇ 4 and -P(R a )(Rb), where each R a is independently a C3 to C20 hydrocarbyl having a molecular volume greater than or equal to an isopropyl substitution or a C3 to C20 hydrocarbyl substituted organometalloid having a molecular volume greater than or equal to an isopropyl substitution, and Rb is hydrogen, a halogen or a Ci to C20 substituted or unsubstituted hydrocarbyl, or Rb is, independently, as defined for R a ;
  • each of ⁇ and Y 2 is independently, -OR a -SR a , -NR3 ⁇ 4 and -P(R a )(Rb), where each R a is independently a C3 to C20 hydrocarbyl having a molecular volume greater than or equal to an isopropyl substitution or a C3 to C20 hydrocarbyl substituted organometalloid having a molecular volume greater than or equal to an isopropyl substitution, and Rb is hydrogen, a halogen or a Ci to C20 substituted or unsubstituted hydrocarbyl, or Rb is, independently, as defined for R a ;
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 1 1 , and R 12 is, independently, hydrogen, halogen, a C1 -C20 hydrocarbyl radical, a functional group comprising an element from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof; and
  • each Z is, independently, a leaving group comprising a monovalent C2-C20 hydrocarbyl radical, a monovalent functional group comprising an element from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof;
  • step (C) optionally supporting the catalyst, activator and/or catalyst system before or after step (B); and D) contacting one or more olefins with the catalyst system at polymerization conditions to produce a polyolefin.
  • the polymer (for example, 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 (EP ), vulcanized EPR, EPDM, block copolymer, styrenic block copolymers
  • the polymer (or the polyethylene or polypropylene) 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 IPvGANOX 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; antistatic agents; pigments; colorants; dyes; waxes; silica; fillers; talc; and the like.
  • antioxidants e.g., hindered phenolics such as IPvGANOX 1010 or IRGANOX 1076 available from Ciba-Geigy
  • 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 process 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, pp. 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, spunbonding, 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 calendar 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.
  • rec-directing metallation reagent is represented by the formula:
  • M is a Group 4, 5, or 6 metal of the periodic table of the elements
  • A is a divalent radical comprising a C -C20 hydrocarbyl radical, a functional group comprising elements from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof;
  • each X is a halogen, a triflate or pseudohalogen
  • each Y is, independently, -O a -SR a , -NR3 ⁇ 4 and -P(R a )(Rb), where each R a is independently a C3 to C20 hydrocarbyl having a molecular volume greater than or equal to an isopropyl substitution or a C3 to C20 hydrocarbyl substituted organometalloid having a molecular volume greater than or equal to an isopropyl substitution, and is hydrogen, a halogen or a C ⁇ to C20 substituted or unsubstituted hydrocarbyl, or is, independently, as defined for R a ;
  • each of Y 1 and Y 2 is, independently, -OR a -SR a , -NR3 ⁇ 4 and -P(R a )(Rb), where each R a is independently a C3 to C20 hydrocarbyl having a molecular volume greater than or equal to an isopropyl substitution or a C3 to C20 hydrocarbyl substituted organometalloid having a molecular volume greater than or equal to an isopropyl substitution, and Rb is hydrogen, a halogen or a C ⁇ to C20 substituted or unsubstituted hydrocarbyl, or Rb is, independently, as defined for R a ;
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 1 1 , and R 12 is, independently, hydrogen, halogen, a -C20 hydrocarbyl radical, a functional group comprising an element from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof; and
  • each Z is, independently, a leaving group comprising a monovalent C2-C20 hydrocarbyl radical, a monovalent functional group comprising an element from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof.
  • A is dimethyl silyl
  • X is CI
  • each Y is -O-iPr, or -O-tBu
  • Z comprises a tetrahydrofuranyl radical.
  • each of R 1 , R 12 , R 13 , and R 14 is independently, a hydrogen, a halogen, a -C20 hydrocarbyl radical, a functional group comprising elements from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof.
  • Embodiment E8 The process according to Embodiment E8, wherein the labile group replacement reagent is chlorotrimethylsilane, HC1, HBr, HI, SOCI2, or a combination thereof.
  • M is a Group 4, 5, or 6 metal of the periodic table of the elements;
  • A is a divalent radical comprising a C 1 -C20 hydrocarbyl radical, a functional group comprising elements from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or combinations thereof;
  • each of Y 1 and Y 2 is, independently, -O a -SR a , -NR3 ⁇ 4 and -P(R a )(Rb), where each R a is independently a C3 to C20 hydrocarbyl having a molecular volume greater than or equal to an isopropyl substitution or a C3 to C20 hydrocarbyl substituted organometalloid having a molecular volume greater than or equal to an isopropyl substitution, and Rb is hydrogen, a halogen or a Ci to C20 substituted or unsubstituted hydrocarbyl, or Rb is, independently, as defined for R a ; and wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 1 1 , and R 12 is, independently, hydrogen, halogen, a Ci -C20 hydrocarbyl radical, a functional group comprising elements from groups 13,
  • Embodiment E15 The compound of Embodiment E13 or Embodiment El 4 comprising greater than 50 mol% of a racemic isomer of the bridged bis(indenyl)metallocene transition metal compound based on the total amount of the compound present.
  • Embodiment El 8 A process according to Embodiment El 8, wherein the polymerization conditions comprise a temperature of from about 0°C to about 300°C, a pressure from about 0.35 MPa to about 10 MPa, and a time from about 0.1 minutes to about 24 hours.
  • M is a Group 4, 5, or 6 metal of the periodic table of the elements
  • A is a divalent radical comprising a C -C20 hydrocarbyl radical, a functional group comprising elements from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof;
  • each X is a halogen, a triflate or pseudohalogen
  • each Y is, independently, -O a -SR a , -NR3 ⁇ 4 and -P(R a )(Rb), where each R a is independently a C3 to C20 hydrocarbyl having a molecular volume greater than or equal to an isopropyl substitution or a C3 to C20 hydrocarbyl substituted organometalloid having a molecular volume greater than or equal to an isopropyl substitution, and R ⁇ is hydrogen, a halogen or a C ⁇ to C20 substituted or unsubstituted hydrocarbyl, or R ⁇ is, independently, as defined for R a ;
  • each of Y 1 and Y 2 is, independently, -OR a -SR a , -NR3 ⁇ 4 and -P(R a )(Rb), where each R a is independently a C3 to C20 hydrocarbyl having a molecular volume greater than or equal to an isopropyl substitution or a C3 to C20 hydrocarbyl substituted organometalloid having a molecular volume greater than or equal to an isopropyl substitution, and R ⁇ is hydrogen, a halogen or a C ⁇ to C20 substituted or unsubstituted hydrocarbyl, or Rb is, independently, as defined for R a ;
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 1 1 , and R 12 is, independently, hydrogen, halogen, a -C20 hydrocarbyl radical, a functional group comprising an element from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof; and
  • each Z is, independently, a leaving group comprising a monovalent C2-C20 hydrocarbyl radical, a monovalent functional group comprising an element from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof;
  • step (C) optionally, supporting the catalyst compound, activator or catalyst system before or after step (B);
  • This invention also relates to:
  • a process comprising:
  • M is a Hf, Zr or Ti
  • A is a divalent radical comprising a C1 -C20 hydrocarbyl radical, a functional group comprising elements from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof;
  • each X is a halogen, a triflate or pseudohalogen
  • each Y is, independently, -O a -SR a , -NR3 ⁇ 4 and -P(R a )(Rb), where each R a is independently a C3 to C20 hydrocarbyl having a molecular volume greater than or equal to an isopropyl substitution or a C3 to C20 hydrocarbyl substituted organometalloid having a molecular volume greater than or equal to an isopropyl substitution, and R ⁇ is hydrogen, a halogen or a Ci to C20 substituted or unsubstituted hydrocarbyl, or R ⁇ is, independently, as defined for R a ;
  • each of ⁇ and Y 2 is, independently, -OR a -SR a , -NR3 ⁇ 4 and -P(R a )(R rj ), where each R a is independently a C3 to C20 hydrocarbyl having a molecular volume greater than or equal to an isopropyl substitution or a C3 to C20 hydrocarbyl substituted organometalloid having a molecular volume greater than or equal to an isopropyl substitution, and R ⁇ is hydrogen, a halogen or a Ci to C20 substituted or unsubstituted hydrocarbyl, or R ⁇ is, independently, as defined for R a ;
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 1 1 , and R 12 is, independently, hydrogen, halogen, a C1 -C20 hydrocarbyl radical, a functional group comprising an element from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof, provided that R1 and R i2 are, independently, a Ci to C ⁇ 2 alkyl group and R 3 and RIO are a substituted or unsubstituted phenyl group; and
  • each Z is, independently, a leaving group comprising a monovalent C2-C20 hydrocarbyl radical, a monovalent functional group comprising an element from groups 13, 14, 15, 16, or 17 of the periodic table of the elements, or a combination thereof;
  • NM was performed as follows: NMR data were collected at 25 °C in a 5 mm probe using a spectrometer (Bruker) with a frequency of 400 MHz using deuterated chloroform as solvent. Data was recorded using a maximum pulse width of 45°, 8 seconds between pulses and signal averaging 16 transients. The spectrum is normalized to protonated chloroform in the deuterated chloroform having a peak at 7.27 ppm.
  • the compound ZrCl2(0-t-Bu)2(thf)2 was utilized as a rac-directing metallation reagent according to an embodiment of the invention.
  • Deprotonation of a dimethylsilyl-bridged bis(indene) and introduction of this compound as a metallation reagent in the place of a metal tetrahalide results, in many instances, in clean isolation consisting essentially of the rac product without the need for repeated crystallizations or other purification schemes directed towards removal of any meso isomer formed.
  • the use of the rac-directing metallation reagent leads to increase rac content and less need for crystallization or other purification.
  • a dimethylsilyl bis[4-(phenyl)-2-methylindenyl]Zr(0-t-Bu)2 catalyst precursor was used to polymerize ethylene and hexene.
  • the precursor was prepared according the general procedure in Example 1 and obtained about 3:1 race meso isomer. Thereafter the precursor was purified with using an ether wash and then crystallized from a methylene chloride/pentane solvent mixture.
  • a 2 L reactor was charged with 15 mL of hexene and 0.1 mL tri( «-octyl)aluminum.
  • the reactor was filled with hydrogen to a pressure of 20.7 kPa (3.0 psi).
  • 800 mL of isobutene were added, and the reactor was heated to 85°C.
  • the reactor was saturated with 758 kPa (110 psi) of ethylene, and 63.1 mg of the silica-supported catalyst was subsequently injected.
  • the reaction was run for 40 minutes under these conditions, resulting in 16.582 g of polymer.
  • a 2 L reactor was charged with 1000 mL of propylene and 0.1 mL tri( «-octyl)aluminum and was heated to 70°C. Subsequently, 100.8 mg of the silica-supported catalyst from Example 2 was injected. The reaction was run for 60 minutes under these conditions, resulting in 5.054 g of polymer.
  • the process according to embodiments of the invention produces a racemic enriched catalyst precursor, suitable for the polymerization processes disclosed herein.

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Abstract

La présente invention concerne des composés de métaux de transition bis(indényl)métallocènes pontés racémiques, des réactifs de métallation à orientation rac et un procédé pour produire des composés de métaux de transition bis(indényl)métallocènes pontés racémiques au moyen des réactifs de métallation à orientation rac.
EP14840931.1A 2013-08-28 2014-08-04 Procédé de métallation à sélectivité racémique Withdrawn EP3039026A4 (fr)

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US6339135B1 (en) * 1995-03-30 2002-01-15 Idemitsu Kosan Co., Ltd. Transition metal compound, catalyst for olefin polymerization, process for preparing olefin polymer
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US6620953B1 (en) * 1998-11-25 2003-09-16 Bassell Polyolefine Gmbh Method for producing monoaryloxy-ansa-metallocenes
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