WO2004074333A2 - Process for homo- or copolymerizationof conjugated olefines - Google Patents

Process for homo- or copolymerizationof conjugated olefines Download PDF

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WO2004074333A2
WO2004074333A2 PCT/US2004/004637 US2004004637W WO2004074333A2 WO 2004074333 A2 WO2004074333 A2 WO 2004074333A2 US 2004004637 W US2004004637 W US 2004004637W WO 2004074333 A2 WO2004074333 A2 WO 2004074333A2
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bis
ethylidene
pyridine
hydrocarbyl
occurrence
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PCT/US2004/004637
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French (fr)
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WO2004074333A3 (en
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Sven K.-H. Thiele
David R. Wilson
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Dow Global Technologies Inc.
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/54—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 other compounds thereof
    • 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic System without C-Metal linkages
    • 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
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/06—Butadiene

Definitions

  • This invention relates to metal complex compositions, their preparation and their use as catalysts to produce polymers through (homo)polymerization of ethylenically unsaturated addition polymerizable monomers or through copolymerization of ethylenically unsaturated addition polymerizable monomers with at least one different type of ethylenically unsaturated addition polymerizable monomer.
  • the used metal complex compositions are yttrium, group 4 metal, lanthanide and actinide compounds, preferably yttrium, group 4, and lanthanide compounds, more preferably neodymium compounds in combination with activator compound(s) and optionally a catalyst support.
  • This invention relates to metal complex compositions, their preparation and their use as catalysts to produce polymers of conjugated dienes through polymerization of conjugated ethylenically unsaturated addition polymerizable monomers or through copolymerization of conjugated ethylenically unsaturated addition polymerizable monomers with at least one different type of ethylenically unsaturated addition polymerizable monomer.
  • the used metal complex compositions are yttrium, group 4, lanthanide and actinide compounds, preferably yttrium group 4, and lanthanide compounds, more preferably neodymium compounds in combination with activator compound(s) and optionally a catalyst support.
  • the invention relates to metal complexes containing at least three metal - nitrogen and/or metal - phosphorus bonds and at least one metal halide or metal carbon bond. More particularly the three nitrogen or phosphorus atoms attached to the metal center are constituents of the same chelate ligand. Even more particularly the invention relates to metal complexes containing at least three metal - nitrogen bonds and at least one metal halide or metal carbon bond and to the preparation of the catalyst and the use of the prepared catalyst to produce homo- or copolymers of conjugated dienes, preferably through, but not limited to, through homopolymerization of 1 ,3-butadiene or copolymerization of 1 ,3-butadiene with styrene or isoprene. More preferably the polydiene or the polydiene sequences of the copolymer consist predominantly of cis units.
  • metal complexes corresponding to Formula 1 for the polymerization of one type of ethylenically unsaturated addition polymerizable monomer or the copolymerization of one type of ethylenically unsaturated addition polymerizable monomer with at least one different type of ethylenically unsaturated addition polymerizable monomer there are provided metal complexes corresponding to Formula 1
  • M is yttrium, a group 4 metal of the Periodic Table of the elements, a lanthanide or actinide metal;
  • M 1 is a group 1 or group 2 metal of the Periodic Table of the elements
  • T independently each occurrence is nitrogen or phosphorus
  • R c independently each occurrence is hydrogen or a group having from 1 to 80 atoms not counting hydrogen, which is halide, nitro, nitrile, hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy, oxygen-substituted hydrocarbyl, including hydrocarbyloxyhydrocarbyl, hydroxy-, keto- aldehyde-, and ester-substituted hydrocarbyl; amino, hydrocarbylamino, nitrogen-substituted hydrocarbyl, including amide, amino- or hydrocarbylamino-substituted hydrocarbyl; hydrocarbylsilyl, silicon-substituted hydrocarbyl, including siloxy, or hydrocarbylsilyl-substituted hydrocarbyl; or two R c groups are joined together forming a divalent ligand group;
  • R B independently each occurrence is a hydrogen or a group having from 1 to 80 atoms not counting hydrogen, which is hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl, hydrocarbyloxy, amino, hydrocarbylamino;
  • X independently each occurrence is an anionic ligand group having up to 60 atoms, provided however that in no occurrence is X a cyclic, delocalized, aromatic group that is ⁇ - bonded to M, and optionally two X groups together form a divalent ligand group;
  • D independently each occurrence is a neutral Lewis base ligand having up to 30 nonhydrogen atoms; x is the number 1 , 2 or 3; x' is the number 1 or 2; t is a number from 0 to 3;
  • V is a number from 0 to 3; r is the number 0 or 1 ; and o is the number 1 or 2.
  • M is yttrium, a group 4 metal of the Periodic Table of the elements, a lanthanide or actinide metal;
  • M 1 is a group 1 or group 2 metal of the Periodic Table of the elements
  • T independently each occurrence is nitrogen or phosphorus
  • R A and R D independently each occurrence are hydrogen or groups having from 1 to 80 atoms not counting hydrogen, which is halide, hydrocarbyl, hydrocarbylsilyl, halo- substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino- substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl, hydrocarbyloxy, amino, hydrocarbylamino;
  • R B independently each occurrence is a hydrogen or a group having from 1 to 80 atoms not counting hydrogen, which is hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl, hydrocarbyloxy, amino, hydrocarbylamino;
  • R c independently each occurrence is hydrogen or a group having from 1 to 80 atoms not counting hydrogen, which is halide, nitro, nitrile, hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy, oxygen-substituted hydrocarbyl, including hydrocarbyloxyhydrocarbyl, hydroxy-, keto- aldehyde-, and ester-substituted hydrocarbyl; amino, hydrocarbylamino, nitrogen-substituted hydrocarbyl, including amide, amino- or hydrocarbylamino-substituted hydrocarbyl; hydrocarbylsilyl, silicon-substituted hydrocarbyl, including siloxy, or hydrocarbylsilyl-substituted hydrocarbyl; or two R c groups are joined together forming a divalent ligand group;
  • X independently each occurrence is an anionic ligand group having up to 60 atoms, provided however that in no occurrence is X a cyclic, delocalized, aromatic group that is ⁇ - bonded to M, and optionally two X groups together form a divalent ligand group;
  • D independently each occurrence is a neutral Lewis base ligand having up to 30 nonhydrogen atoms; x is the number 1 , 2 or 3; x' is the number 1 or 2; t is a number from 0 to 3; t' is a number from 0 to 3; r is the number 0 or 1 ; and o is the number 1 or 2.
  • the formula weight of the metal complex preferably is lower than 2000 g/mol, more preferably lower than 1000 g/mol.
  • X" is chloro, bromo or iodo
  • R E independently each occurrence is hydrogen or a group having from 1 to 80 atoms not counting hydrogen, which is hydrocarbyl, including methyl, ethyl, propyl, isopropyl, t-butyl, n-butyl, pentyl, hexyl, allyl, benzyl, tolyl, phenyl, neopentyl; oxygen- substituted hydrocarbyl; including methoxyethyl; nitrogen-substituted hydrocarbyl, including N,N-dimethylaminoethyl, N,N-dimethylaminobenzyl, N,N-dimethylaminomethylphenyl; or hydrocarbylsilyl, including trimethylsilylmethyl, t-butyldimethylsilylmethyl, bis(trim et ylsilyl) methyl ; or NR2 wherein R independently each occurrence is hydrogen or
  • _ 25 hydrocarbyl including methyl, ethyl, propyl, isopropyl, t-butyl, n-butyl, pentyl, hexyl n is the number 1 or 2; and the sum of n and x'-1 is equal to the oxidation state of M'; and comprising: for complexes of Formula Ic, contacting in a solvent a pyridine or phosphabenzene compound according to the Formula IVb
  • M is yttrium, a group 4 metal of the periodic Table of the elements, a lanthanide or a actinide metal and X, m, t and D are as previously defined, and optionally, with between 1 and 4 equivalents of a metal compound corresponding to the Formula V
  • M 1 , x', X", R E and n are as previously defined.
  • catalysts for the polymerization of one type of ethylenically unsaturated addition polymerizable monomer or the copolymerization of one type of ethylenically unsaturated addition polymerizable monomer with at least one different type of ethylenically unsaturated addition polymerizable monomer comprising
  • the present invention also provides a process for preparing catalysts for the polymerization of one type of ethylenically unsaturated addition polymerizable monomer or copolymerization of one type of ethylenically unsaturated addition polymerizable monomer with at least one different type of ethylenically unsaturated addition polymerizable monomer comprising: contacting one or more of the above metal complexes with one or more activators and optionally a support or subjecting one or more of the above metal complexes and optionally a support to activating techniques.
  • the present invention also provides a polymerization process comprising contacting one or more ethylenically unsaturated addition polymerizable monomers optionally in the presence of an inert, aliphatic, alicyclic or cyclic or aromatic hydrocarbon, under polymerization conditions with a catalyst comprising
  • the polymerization may be performed under solution, suspension, slurry, or gas phase process conditions, and the catalyst or individual components thereof may be used in a heterogeneous, that is, a supported state, or in a homogeneous state as dictated by process conditions.
  • the catalyst can be used in combination with one or more additional catalysts of the same or different nature either simultaneously in the same reactor and/or sequentially in separate reactors.
  • the catalyst can be formed in situ in the presence of or prior to addition to a reaction mixture comprising one or more ethylenically unsaturated addition polymerizable monomers.
  • homopolymers comprising one ethylenically unsaturated addition polymerizable monomer, even more especially one conjugated ethylenically polyunsaturated addition polymerizable monomer.
  • copolymers comprising more than one ethylenically unsaturated addition polymerizable monomer, even more especially conjugated ethylenically polyunsaturated addition polymerizable monomers in combination with a second type of ethylenically unsaturated addition polymerizable monomer.
  • Catalysts for polymerization of ethylenically unsaturated addition polymerizable monomers preferably catalysts for polymerization of conjugated ethylenically polyunsaturated addition polymerizable monomers according to the invention possess improved catalytic properties and are especially useful in the polymerization of conjugated dienes.
  • the complexes are compatible with and may be used in combination with alkylaluminum compounds which may be employed to scavenge monomer impurities without detrimental effects to their catalytic properties.
  • neutral Lewis base ligand uncharged groups that are sufficiently nucleophilic to be capable of forming a coordination bond to a metal atom of the metal complex of the invention.
  • Preferred neutral Lewis base ligand groups, D are carbon monoxide, ethers, polyethers, thioethers, amines, polyamines, phosphines, phosphites, polyphosphines, alcohols, nitriles, esters, amides, olefins and conjugated dienes.
  • the metal complexes according to the present invention may be present as coordination complexes of neutral Lewis base ligands.
  • Preferred pyridine metal complexes according to the present invention correspond to the formulas la, lb and Ic:
  • M 1 is a metal of group 1 or group 2 of the Periodic Table of the Elements, preferably M 1 is lithium, sodium, potassium or magnesium, even more preferably lithium, sodium or potassium;
  • M is yttrium, a group 4 metal of the Periodic Table of the elements, a lanthanide metal or an actinide metal; preferably M is a group 4 metal of the Periodic Table of the elements or a lanthanide metal and more preferably M is lanthanum, cerium, praseodymium, neodymium, promethium, samarium, titanium or zirconium, even more preferably M is neodymium;
  • T independently each occurrence is nitrogen or phosphorus
  • R A and R D independently each occurrence are hydrogen or groups having from 1 to 80 atoms not counting hydrogen, which is halide, hydrocarbyl, hydrocarbylsilyl, halo- substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino- substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl, hydrocarbyloxy, amino, hydrocarbylamino;
  • R c independently each occurrence is hydrogen or a group having from 1 to 80 atoms not counting hydrogen, which is halide, nitro, nitrile, hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy, oxygen-substituted hydrocarbyl, including hydrocarbyloxyhydrocarbyl, hydroxy-, keto- aldehyde-, and ester-substituted hydrocarbyl; amino, hydrocarbylamino, nitrogen-substituted hydrocarbyl, including amide, amino- or hydrocarbylamino-substituted hydrocarbyl; hydrocarbylsilyl, silicon-substituted hydrocarbyl, including siloxy, or hydrocarbylsilyl-substituted hydrocarbyl; or two R c groups are joined together forming a divalent ligand group;
  • R A , R c and R D groups are hydrogen, halide, especially chloride or bromide, hydrocarbyl, hydrocarbylsilyl, amino, hydrocarbylamino, hydrocarbyloxy, hydrocarbylsiloxy, especially hydrogen, halide, alkyl, cyclic alkyl, aryl, acyl, alkyloxy, hydrocarbylsilyl, alkylsiloxy, alkaryl, amino and hydrocarbylamino, more especially hydrogen, chloride, bromide, methyl, ethyl, 1-methylethyl, 1 ,1-dimethylethyl, cyclohexyl, phenyl, benzyl, trimethylsilyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, methoxy, ethoxy, methylethyloxy, 1 ,1-dimethylethyloxy, trimethylsiloxy, 1 ,1-di
  • R B independently each occurrence is a hydrogen or a group having from 1 to 80 atoms not counting hydrogen, which is hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl, hydrocarbyloxy, amino, hydrocarbylamino;
  • R B groups are hydrocarbyl, especially alkyl, cyclic alkyl, aryl, alkaryl, more especially methyl, ethyl, 1-methylethyl, 1 ,1-dimethylethyl, cyclohexyl, phenyl, 2,6- dialkylphenyl, benzyl, trimethylsilyl; hydrocarbylsilyl and hydrocarbylamino, especially alkylamino, cyclic alkylamino, arylamino and alkaryl, more especially methylamino, dimethylamino, diethylamino, methylethylamino, methylphenylamino, phenylamino, cyclohexylamino, dipropylamino, dibutylamino, piperidino, morpholino, pyrrolidino.
  • X independently each occurrence is hydrogen or a group having from 1 to 60 atoms not counting hydrogen, which is hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl, hydrocarbyloxy, hydrocarbylcarboxylate, hydrocarbylsulfide, hydrocarbylsiloxy, hydrocarbylamido, cyanide, acetylacetonate, dithiocarbamate, dithiocarboxylate and halide, provided however that in no occurrence is X a cyclic, delocalized, aromatic group that is ⁇ -bonded to M;
  • Preferred X are hydrogen and groups which are halide, hydrocarbyl (including alkyl, alkenyl, aryl, alkaryl, aralkyl, cycloalkyl and cycloalkenyl) hydrocarbyloxide, hydrocarbylsulfide, N,N-dihydrocarbylamide, hydrocarbyleneamide, hydrocarbylcarboxylate, acetylacetonate, cyanide, dithiocarbamate, and dithiocarboxylate groups, said X groups having from 1 to 20 atoms other than hydrogen.
  • X are hydrogen and groups which are halide, hydrocarbyl, including alkyl, alkenyl, aryl, alkaryl, arylalkyl, cycloalkyl and cycloalkenyl, said X groups having from 1 to 20 atoms other than hydrogen, especially hydrogen, chloride, bromide, iodide, fluoride, methyl, ethyl, propyl, benzyl, neopentyl, trimethysilylmethyl, phenyl, tolyl, allyl, cyclohexenyl, methallyl.
  • D independently each occurrence is selected from carbon monoxide; phosphines,
  • 0 is the number 1 or 2;
  • Especially preferred pyridine metal complexes according to the present invention correspond to the formula la, lb, or Ic wherein R A , R B , R c , R D , X, D, x, t and are as previously defined; M is yttrium, a lanthanide metal or a group IV metal;
  • M 1 is lithium, sodium or potassium
  • T is nitrogen; and x' is the number 1 ; o is the number 1 ; and r is the number 1.
  • Especially preferred pyridine metal complexes according to the present invention correspond to the formulas lla, lib, and lie:
  • M is a lanthanide metal or a group IV metal, especially lanthanum, cerium, praseodymium, neodymium, promethium, samarium, titanium or zirconium, even more especially M is neodymium;
  • M 1 is lithium, sodium or potassium
  • N is nitrogen
  • R A or R D independently each occurrence is hydrogen or alkyl, most preferably methyl, ethyl, 1-methylethyl, t-butyl, cyclohexyl;
  • R c independently each occurrence is hydrogen, halide or C 1-6 alkyl, most preferably hydrogen, chloride, methyl, ethyl, 1-methylethyl, cyclohexyl;
  • X independently each occurrence is halide, hydrogen, C 1-10 hydrocarbyl, or C 1-10 hydrocarbylsilylhydrocarbyl, especially fluoride, chloride, bromide, iodide, methyl, ethyl, benzyl, neopentyl, trimethylsilylmethyl;
  • x is the 1 , 2 or 3;
  • x' is the number 1 t is the number zero, one or two;
  • D is THF, DME, TEA, TMEDA, Et 2 O; f is a number from zero to two; o is the number one and r is the number one.
  • pyridine metal complexes according to the present invention correspond to the Formula lla, ([2,6-bis-(1-(hydrocarbylamido)-2-R A -2-R D -ethylidene)-4- R c -)pyridine]MX x D t * (M'X x >) r D t ').
  • exemplary, but non-limiting metal complexes according to the invention include the following neodymium, zirconium, titanium (IV), and titanium (III) complexes:
  • yttrium lanthanide, actinide, and group IV analogs, including yttrium, samarium, cerium, neodymium, promethium, praesodymium, lanthanum, hafnium, and uranium.
  • alkaline earth metal salt adducts can be present either as a 1 :1 complex or as a 2:1 complex, that is, in Formulas la, lb, Ic, lla, lib, or lie, o is 1 and r is 1 or o is 2 and r is 1.
  • the complexes according to Formulas la, lb, Ic, lla, lib, and He can be prepared by contacting a pyridine or phosphabenzene compound corresponding to the formula Formula IVa or, optionally Formula IVb for complexes according to Formulas Ic and He, with a metal compound corresponding to Formula III and, optionally for the complexes according to Formulas Ic and lie, with a metal compound corresponding to Formula V
  • the molar ratio of the metal compound corresponding to Formula III to the compound corresponding to Formula IVa or Formula IVb being from 1 :0.5 to 1 :1.5, preferably from 1 :0.7 to 1 :1.3, more preferably from 1 :0.9 to 1 :1.1 ; and, for the complexes according to Formulas la, lb, lla, and lib, the molar ratio of the metal compound corresponding to Formula III to the metal compound corresponding to Formula V being from 1 :1 to 1 :4, preferably from 1 :1.5 to 1 :3.5, more preferably from 1 :1.9 to 1 :2.1 or from 1 :2.1 to 1 :3.1 , in a suitable noninterfering solvent or reaction medium at a temperature from -100°C to 300°C, preferably from -78°C to 150°C, most preferably from -50°C to 75°C.
  • Suitable reaction media for the formation of the complexes are aliphatic and aromatic hydrocarbons and halohydrocarbons, ethers, amines, alcohols, amides, nitriles and esters.
  • Examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, decane and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; chlorinated-, fluorinated- or chlorofluorinated hydrocarbons such as chloroform, dichloromethane, chlorobenzene, dichlorobenzene, and perfluorinated C4..-10 alkanes; aromatic and hydrocarbyl-substituted aromatic compounds such as benzene, toluene, xylene, and styrene; alkyl ethers having from 1 to 5 carbons in each alkyl group such as diethyl ether, THF and dioxane; C-
  • polyalkylene glycols such as DME
  • aromatic or aliphatic amines such as tetramethylethylenediamine (TMEDA) and triethylamine (TEA); dimethylformamide (DMF) and dimethylacetamide (DMA); nitriles, especially acetonitrile, propanenitrile, benzonitrile; esters, especially methyl acetate, ethyl acetate and butyl acetate.
  • TME tetramethylethylenediamine
  • TEA triethylamine
  • DMF dimethylformamide
  • DMA dimethylacetamide
  • nitriles especially acetonitrile, propanenitrile, benzonitrile
  • esters especially methyl acetate, ethyl acetate and butyl acetate. Mixtures of the foregoing are also suitable.
  • Preferred solvents include diethylether, toluene, DME and THF.
  • the recovery procedure usually involves a separation of the product from the reaction medium and/or any possible byproducts and/or unreacted starting materials.
  • the solvents and other volatile components are advantageously removed via devolatilization of the reaction medium. Extraction into a secondary solvent may be employed if desired. If extraction is employed, nonpolar aliphatic, aromatic or chlorinated solvents can be used such as but not limited to pentane, hexane, octane, cyclohexane, methylcyclohexane, cycloheptane, benzene, toluene, chloroform or dichloromethane and mixtures thereof. Alternatively, if the desired product is insoluble or only slightly soluble, filtration or other separation technique may be employed.
  • Exemplary, but non-limiting examples for the compound corresponding to Formula III, M(X) m Dt, according to the invention include the following neodymium compounds:
  • M' 'x'.-j R E n include the following compounds:
  • the catalyst compositions are formed by rendering the metal complexes catalytically active in a process comprising 1 ) contacting one or more of the above pyridine or phosphabenzene metal complexes with one or more activators and optionally a support or 2) by subjecting one or more of the above pyridine or phosphabenzene metal complexes to activating techniques optionally in the presence of a support.
  • the process for the activation of the metal complexes with an activator or cocatalyst or by an activating technique can be performed during a separate reaction step optionally including an isolation of the activated compound or preferably can be performed in situ in the polymerization reactor or just prior to it in an aging reactor, for example.
  • the activation is preferably performed in situ if, after the activation of the metal complex, separation and/or purification of the activated complex is not necessary.
  • the process for the activation of the metal complexes is carried out in a suitable noninterfering solvent or reaction medium at a temperature from -78°C to 250°C, preferably from -5°C to 160°C, more preferably from 10°C to 110°C.
  • Suitable reaction media for the formation of the catalyst compositions are aliphatic and aromatic hydrocarbons and halohydrocarbons.
  • Examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, decane and mixtures thereof, cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; chlorinated-, fluorinated- or chlorofluorinated hydrocarbons such as chloroform, dichloromethane, chlorobenzene, dichlorobenzene, and perfluorinated C4.-10 alkanes; aromatic and hydrocarbyl-substituted aromatic compounds such as benzene, toluene, xylene, and styrene.
  • the reaction medium used for the activation is the same reaction medium as is used in the subsequent polymerization, obviating the need to use a secondary solvent system.
  • this includes heptane or mineral oil fractions such as light or regular petrol, naphtha, kerosine or gas oil and other low-priced aliphatic hydrocarbons or mixtures thereof, as marketed by the petrochemical industry as solvent.
  • heptane or mineral oil fractions such as light or regular petrol, naphtha, kerosine or gas oil and other low-priced aliphatic hydrocarbons or mixtures thereof, as marketed by the petrochemical industry as solvent.
  • a further advantage of the invention is that the catalysts of the invention usually do not require a separate aging step (which is the case with all examples presented to demonstrate the invention) and if it is desirable to employ an optional aging step, it advantageously does not require long aging times. Therefore, it is possible to start the polymerization reaction just by adding the catalyst components in the desired order into the polymerization reactor.
  • the polymerization can be started for example either by addition of the metal complex as the last component (see for example Runs 1 , 5 and 8) or by the addition of the conjugated diene as the last component.
  • the aging time is short, such as less than 30 minutes, more preferably less than 10 minutes or even more preferably less than 5 minutes and can be performed in a broad temperature range, such as, but not limited to, 0°C to 150°C with high catalyst activity.
  • the temperature ranges of the catalyst preparation, catalyst aging and polymerization are independently selected and are between -50°C and +250°C, preferably between -5 and +160 °C, more preferably between 10°C and 110°C.
  • the catalyst activity of polymerization Run 1 (polymerization temperature 70°C), amounts to 0.74 kg of polybutadiene per mmol neodymium per hour([kg ⁇ polymerj/mmol ⁇ Nd ⁇ [hr]]). It is beneficial that the polymerization reaction can be induced without substantial waiting period (delay) upon addition of the last catalyst component into the polymerization reactor.
  • Suitable activating cocatalysts for use herein include:
  • (hydrocarbyl)aluminum- or (hydrocarbyl)boron compounds even more especially triaryl and trialkyl aluminum compounds, such as triethyl aluminum, triisobutyl aluminum, trioctylaluminum; alkyl aluminum hydrides, such as diisobutylaluminum hydride; alkylalkoxy aluminum compounds, such as dibutylethoxyaluminum; halogenated aluminum compounds, such as diethylaluminum chloride, ethylaluminum dichloride, diisobutylaluminum chloride, ethyl(octyl)aluminum chloride, ethylaluminum sesquichloride, ethyl(cyclohexyl)aluminum chloride, dicyclohexylaluminum chloride, dioctylaluminum chloride, and ii) organohalogenated (including perhalogenated) derivatives of organo Group 13 compounds,
  • Suitable activators for use herein include hydrocarbyl sodium, hydrocarbyl lithium, hydrocarbyl zinc, hydrocarbyl magnesium halide, dihydrocarbyl magnesium, especially alkyl sodium, alkyl lithium, alkyl zinc, alkyl magnesium halide, dialkyl magnesium, such as n-octylsodium, butyllithium, neopentyllithium, methyllithium, ethyllithium, phenyllithium, diethylzinc, dibutylzinc, butylmagnesium chloride, ethylmagnesium chloride, octylmagnesium chloride, dibutylmagnesium, dioctylmagnesium, butyl(octyl)magnesium.
  • Especially desirable activating cocatalysts for use herein are combinations of neutral optional Lewis acids, especially the combination of a trialkyl aluminum compound having from 1 to 4 carbons in each alkyl group with one or more G-t_3Q hydrocarbyl- substituted Group 13 Lewis acid compounds, especially halogenated tri(hydrocarbyl)boron or -aluminum compounds having from 1 to 20 carbons in each hydrocarbyl group, especially tris(pentafluorophenyl)borane or tris(pentafluorophenyl)alumane, further combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane ortris(pentafluorophenyl)alumane, with a polymeric or oligomeric alumoxane.
  • neutral optional Lewis acids especially the combination of a trialkyl aluminum compound having
  • a benefit according to the present invention is the discovery that the most efficient catalyst activation using such a combination of tris(pentafluorophenyl)borane/ alumoxane mixture occurs at reduced levels of alumoxane.
  • Preferred molar ratios of the metal complex:tris(pentafluorophenylborane:alumoxane are from 1 :1 :1 to 1 :5:5, more preferably from 1 :1 :1.5 to 1 :5:3.
  • Suitable ion-forming compounds useful as activators in one embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton, and a compatible, noncoordinating or poorly coordinating anion.
  • noncoordinating means an anion or substance which either does not coordinate to the metal containing precursor complex and the catalytic derivative derived therefrom, or which is only weakly coordinated to such complexes thereby remaining sufficiently labile to be displaced by a Lewis base such as olefin monomer in a manner such that the polymerization may proceed.
  • a noncoordinating anion specifically refers to an anion which when functioning as a charge-balancing anion in a cationic metal complex does not transfer an anionic substituent or fragment thereof to said cation thereby forming neutral complexes.
  • “Compatible anions” are anions which are not degraded to neutrality when the initially formed complex decomposes and are noninterfering with desired subsequent polymerization or other uses of the complex.
  • Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core which anion is capable of balancing the charge of the active catalyst species (the metal cation) which may be formed when the two components are combined.
  • said anion should be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nitriles.
  • Suitable metals include, but are not limited to, aluminum, gold and platinum.
  • Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon.
  • Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially.
  • activators may be represented by the following general formula: (L*-H) + d Ad- wherein:
  • L" is a neutral Lewis base
  • a ⁇ " is a noncoordinating, compatible anion having a charge of d-, and d is an integer from I to 3.
  • a 0 "- corresponds to the formula:
  • M* is boron or aluminum in the +3 formal oxidation state; and Q independently each occurrence is selected from hydride, dialkylamido, halide, hydrocarbyl, halohydrocarbyl, halocarbyl, hydrocarbyloxide, hydrocarbyloxy substituted- hydrocarbyl, organometal substituted- hydrocarbyl, organometalloid substituted- hydrocarbyl, halohydrocarbyloxy, halohydrocarbyloxy substituted hydrocarbyl, halocarbyl- substituted hydrocarbyl, and halo- substituted silylhydrocarbyl radicals (including perhalogenated hydrocarbyl-, perhalogenated hydrocarbyloxy- and perhalogenated silythydrocarbyl radicals), said Q having up to 20 carbon atoms with the proviso that in not more than one occurrence is Q halide.
  • suitable hydrocarbyloxide Q groups are disclosed in U.S. Pat. No. 5,296,
  • d is one, that is, the counter ion has a single negative charge and is A " .
  • Activating cocatalysts comprising boron which are particularly useful in the preparation of catalysts of this invention may be represented by the following general formula: (L * -H) + (BQ 4 )-; wherein:
  • B is boron in a formal oxidation state of 3
  • Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy-, or fluorinated silylhydrocarbyl- group of up to 20 nonhydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl.
  • Q is each occurrence a fluorinated aryl group, especially, a pentafluorophenyl or nonafluorobiphenyl group.
  • Preferred BQ4 " anions are methyltris(pentafluorophenyl)borate, tetrakis(pentafluorophenyl)borate or tetrakis(nonafluorobiphenyl)borate.
  • Such mixtures include protonated ammonium cations derived from amines comprising two G14, C-jg or G ⁇ g alkyl groups and one methyl group.
  • Such amines are available from Witco Corp., under the trade name KemamineTM T9701 , and from Akzo- Nobel under the trade name ArmeenTM M2HT.
  • catalyst activators herein include the foregoing trihydrocarbylammonium-, especially, methylbis(tetradecyl)ammonium- or methylbis(octadecyl)ammonium- salts of: bis(tris(pentafluorophenyl)borane)imidazolide, bis(tris(pentafluorophenyl)borane)-2- undecylimidazolide, bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolide, bis(tris(pentafluorophenyl )borane)-4,5-bis(undecyl)imidazolide, bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide, bis(tri s(pentafluorophenyl )borane)imidazo
  • Another suitable ammonium salt is formed upon reaction of an organometal compound, especially a tri(C-
  • the resulting compound is an organometaloxyaryltris(fluoroaryl)borate compound which is generally insoluble in aliphatic liquids.
  • suitable compounds include the reaction product of atri(C ⁇ _6 alkyl)aluminum compound with the ammonium salt of hydroxyaryltris(aryl)borate.
  • Suitable hydroxyaryltris(aryl)borates include the ammonium salts, especially the foregoing long chain alkyl ammonium salts of: (4-dimethylaluminumoxyphenyl)tris(pentafluorophenyl) borate, (4-dimethylaluminumoxy- 3,5-di(trimethylsilyl)phenyl) tris(pentafluorophenyl)borate, (4- dimethylaluminumoxy-3,5- di(t-butyl)phenyl) tris(pentafluorophenyl)borate, (4-dimethylaluminumoxybenzyl) tris(pentafluorophenyl) borate, (4-dimethylaluminumoxy-3-methylphenyl) tris(pentafluorophenyl)borate, (4-dimethylaluminumoxy-tetrafluorophenyl) tris(pentafluorophenyl)borate, (5-
  • ammonium compounds are methyldi(tetradecyl)ammonium (4- diethylaluminumoxyphenyl) tris(pentafluorophenyl)borate, methyldi(hexadecyl)ammonium (4-diethylaluminumoxyphenyl) tris(pentafluorophenyl)borate, methyldi(octadecyl)ammonium (4-diethylaluminumoxyphenyl) tris(pentafluorophenyl) borate, and mixtures thereof.
  • the foregoing complexes are disclosed in U.S. Pat. Nos. 5,834,393 and 5,783,512.
  • Another suitable ion-forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula:
  • Ox e+ is a cationic oxidizing agent having a charge of e+; d is an integer from 1 to 3; e is an integer from 1 to 3; and
  • Ad- is as previously defined.
  • cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Pb +2 or Ag + .
  • Preferred embodiments of A ⁇ - are those anions previously defined with respect to the Bronsted acid containing activating cocatalysts, especially tetrakis(pentafluorophenyl)borate.
  • Another suitable ion-forming, activating cocatalyst comprises a compound which is a salt of a carbenium ion and a noncoordinating, compatible anion represented by the formula
  • A" is a noncoordinating, compatible anion having a charge of -1.
  • a preferred carbenium ion is the trityl cation, especially triphenylmethylium.
  • Preferred carbenium salt activating cocatalysts are triphenylmethylium tetrakis(pentafluorophenyl)borate, triphenylmethylium tetrakis(nonafluorobiphenyl)borate, tritolylmethylium tetrakis(pentafluorophenyl)borate and ether substituted adducts thereof.
  • a further suitable ion-forming, activating cocatalyst comprises a compound which is a salt of a silylium ion and a noncoordinating, compatible anion represented by the formula R3Si + A " wherein:
  • R is C-i-10 hydrocarbyl
  • a " is as previously defined.
  • Preferred silylium salt activating cocatalysts are trimethylsilylium tetrakis(pentafluorophenyl)borate, trimethylsilylium tetrakis(nonafluorobiphenyl)borate, triethylsilylium tetrakis(pentafluorophenyl)borate and other substituted adducts thereof.
  • Silylium salts have been previously generically disclosed in J. Chem Soc. Chem. Comm., 1993, 383-384, as well as Lambert, J. B., et al., Organometallics, 1994, 13, 2430-2443. The use of the above silylium salts as activating cocatalysts for addition polymerization catalysts is claimed in U.S. Pat. No. 5,625,087.
  • the activating cocatalysts may also be used in combination.
  • An especially preferred combination is a mixture of a tri(hydrocarbyl)aluminum or tri(hydrocarbyl)borane compound having from 1 to 4 carbons in each hydrocarbyl group with an oligomeric or polymeric alumoxane compound.
  • the molar ratio of catalyst/activator employed preferably ranges from 1 :10,000 to 10:1 , more preferably from 1 :5000 to 10:1 , most preferably from 1 :2500 to 1 :1.
  • Alumoxane when used by itself as an activating cocatalyst, is preferably employed in large molar ratio, generally at least 50 times the quantity of metal complex on a molar basis.
  • Tris(pentafluorophenyl)borane, where used as an activating cocatalyst is preferably employed in a molar ratio to the metal complex of from 0.5:1 to 10:1 , more preferably from 1 :1 to 6:1 most preferably from 1 :1 to 5:1.
  • the remaining activating cocatalysts are generally preferably employed in approximately equimolar quantity with the metal complex.
  • the metal complex according to the invention is alkylated (that is, one of the X groups of the metal complex is an alkyl or aryl group).
  • Activators comprising boron are preferred.
  • activators comprising tetrakis(pentafluorophenyl)borate, tris(pentafluorophenyl)borane, tris(o-nonafluorobiphenyl)borane, tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, tris(pentafluorophenyl)alumane, tris(o- nonafluorobiphenyl)alumane.
  • the molar ratio of the activator relative to the metal center in the metal complex in the case an organometallic compound is selected as the activator usually is in a range of from 1 :10 to 10,000:1 , more preferably from 1 :10 to 5000:1 and most preferably in a range of from 1 :1 to 2,500:1. If a compound containing or yielding a non-coordinating or poorly coordinating anion is selected as activator, the molar ratio usually is in a range of from 1 :100 to 1 ,000:1 , and preferably is in range of from 1 :2 to 250:1.
  • Especially desirable activating cocatalysts for use herein are combinations of neutral optional Lewis acids, especially the combination of a trialkyl aluminum compound having from 1 to 4 carbons in each alkyl group with one or more C-j_3rj hydrocarbyl-substituted
  • Group 13 Lewis acid compounds especially halogenated tetrakis(hydrocarbyl)boron or- aluminum compounds having from 1 to 20 carbons in each hydrocarbyl group, especially tetrakis(pentafluorophenyl)borate, tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, further combinations of a single neutral Lewis acid, especially tetrakis(pentafluorophenyl)borate or tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, with a polymeric or oligomeric alumoxane.
  • a benefit according to the present invention is the discovery that the most efficient catalyst activation using such a combination of tetrakis(pentafluorophenyl)borane/ alumoxane mixture occurs at reduced levels of alumoxane.
  • Preferred molar ratios of the metal complex tetrakis(pentafluorophenylborane : alumoxane from 1 :1 :1 to 1 :5:1.000, more preferably from 1 :1 :1.5 to 1 :5:500.
  • the surprising efficient use of lower levels of alumoxane with the present invention allows for the production of diene polymers with high catalytic efficiencies using less of the expensive alumoxane activator. Additionally, polymers with lower levels of aluminum residue, and hence greater clarity, are obtained.
  • Preferred molar ratios of the metal complex:tetrakis(pentafluorophenylborane:neutral optional Lewis acids especially trialkyl aluminum or dialkyl aluminum hydride compounds are from 1 :1 :10 to 1 :10:1000, more preferably from 1 :1 :20 to 1 :5:500. Also in this case are polymers with lower levels of aluminum residue, and hence greater clarity, obtained.
  • Especially desirable activating cocatalysts for use herein are neutral optional Lewis acids, especially the combination of a trihydrocarbonyl aluminum compound, more especially trialkyl aluminum compound having from 1 to 5 carbons in each alkyl group with neutral Lewis acids containing at least one metal halide bond, especially perhalogenated metals or transition metals, especially boron trifluoride, boron trichloride, boron tribromide, aluminum trifluoride, aluminum trichloride, aluminum tribromide, scandium trifluoride, titanium tetrafluoride, further combinations of a single neutral Lewis acid, especially boron trifluoride, boron trichloride, boron tribromide, aluminum trifluoride, aluminum trichloride, aluminum tribromide, scandium trifluoride, titanium tetrafluoride, with a polymeric or oligomeric alumoxane in a molar ratio of the metal complex : metal fluoride : a
  • the catalyst composition can also contain a small amount of another organometallic compound that is used as a so-called scavenger agent.
  • the scavenger agent is added to react with or passivate activity-decreasing impurities in the reaction mixture. It may be added at any time, but normally is added to the reaction mixture before addition of the metal complex and the activator (cocatalyst).
  • organoaluminum compounds are used as scavenger agents.
  • Suitable scavengers are trioctylaluminum, triethylaluminum, diethylaluminum chloride, tri-isobutylaluminum, methylalumoxane or MMAO.
  • the metal complex as well as the activator can be present in the catalyst composition as a single component or as a mixture of several components. For instance, a mixture may be desired where there is a need to influence the molecular properties of the polymer, such as molecular weight distribution.
  • the reaction system optionally contains a solid material, which serves as carrier or support material for the activator component and/or the metal complex.
  • the carrier material can be chosen from one of the following materials: clay, silica, charcoal (activated carbon), graphite, expanded clay, expanded graphite, carbon black, layered silicates, and alumina.
  • Clays and layered silicates include, but are not limited to, magadiite, montmorillonite, hectorite, sepiolite, attapulgite, smectite, and laponite.
  • Supported catalyst systems of the invention may be prepared by several methods. The metal complex and optionally the activator can be combined before the addition of the support material.
  • the mixture may be prepared in conventional solution in a normally liquid alkane or aromatic solvent.
  • the solvent is preferably also suitable for use as a polymerization diluent for the liquid phase polymerization of an olefin monomer.
  • the activator can be placed on the support material followed by the addition of the metal complex or conversely, the metal complex may be applied to the support material followed by the addition of the activator.
  • the supported catalyst maybe prepolymerized.
  • third components can be added during any stage of the preparation of the supported catalyst.
  • Third components can be defined as compounds containing Lewis acidic or basic functionalities exemplified by, but not limited to, compounds such as N,N-dimethylaniline, tetraethoxysilane, phenyltriethoxysilane, and bis-tert-butylhydroxytoluene (BHT).
  • the catalyst can be supported onto the carrier material using techniques such as the solid-phase immobilization (SPI) technique described by H.C.L. Abbenhuis in Angew. Chem. Int. Ed. 37 (1998) 356-58 and by M. Buisio et al., in Microporous Mater., 5 (1995) 211 and by J.S. Beck et al., in J. Am. Chem.
  • SPI solid-phase immobilization
  • the isolation of the impregnated carrier can be done by filtration or by removing the volatile material present (that is, solvent) under reduced pressure or by heating.
  • the support if present, is preferably employed in an amount to provide a weight ratio of catalyst (based on metal) :support from 1 :100,000 to 1 :10, more preferably from 1 :50,000 to 1 :20, and most preferably from 1 :10,000 to 1 :30.
  • Suitable gas phase reactions may utilize condensation of the monomer or monomers employed in the reaction, or of an inert diluent to remove heat from the reactor.
  • the catalyst is used in a catalytically effective amount, that is, any amount that successfully results in the formation of polymer.
  • a catalytically effective amount that is, any amount that successfully results in the formation of polymer.
  • Such amounts may be readily determined by routine experimentation by the worker skilled in the art, but typically the molar ratio of catalyst:polymerizable compounds employed is from 10 " 12;1 to
  • the catalysts may be used to homopolymerize or copolymerize ethylenically unsaturated addition polymerizable monomers having from 2 to 100,000 carbon atoms either alone for homopolymers or in combination with a different type of ethylenically unsaturated addition polymerizable monomer for copolymers.
  • Preferred monomers include ⁇ -olefins selected from ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1- pentene,1-octene, styrene, alpha methylstyrene, divinyl benzene, acrylonitrile, acrylic acid ester, methyl meth acrylate, ethylmethacrylate and n-butylmethacrylate and conjugated dienes chosen from the group comprising internal conjugated olefins, cyclic conjugated olefins and non-cyclic conjugated olefins.
  • Preferred conjugated dienes are 1 ,3-butadiene, isoprene (2-methyl-1 ,3-butadiene), 2,3-dimethyl-1 ,3-butadiene, 1 ,3-pentadiene, 2,4- hexadiene, 1 ,3-hexadiene, 1 ,4-hexadiene, 1 ,3-heptadiene, 1 ,3-octadiene, 2-methyl-2,4- pentadiene, cyclopentadiene, 2,4-hexadiene, 1 ,3-cyclooctadiene. More preferably butadiene, isoprene and/or cyclopentadiene is used as conjugated diene and ethylene, propene and styrene is used as ⁇ -olefin.
  • Especially desirably formed polymers using the catalyst in the polymerization process of the invention are homo-, co- and terpolymers of conjugated ethylenically unsaturated addition polymerizable monomers, especially conjugated dienes, especially butadiene or isoprene, and random or block copolymers of at least one conjugated diene, especially butadiene, with at least one different type of conjugated diene, especially isoprene, or with an ⁇ -olefin, especially ethylene, propene and styrene.
  • homopolymerization of butadiene or isoprene and random or block copolymerization optionally terpolymerization, of at least one conjugated diene, especially butadiene with at least one different type of conjugated diene, especially isoprene, or with at least one ⁇ -olefin, especially styrene.
  • Highly preferred homopolymers comprise butadiene and highly preferred copolymers comprise conjugated dienes chosen from butadiene or isoprene or comprise butadiene and styrene.
  • the homopolymerization of the conjugated diene or the copolymerization of one type the conjugated diene monomers with a second type of monomer, an ⁇ -olefin or a conjugated diene monomer may be accomplished at conditions well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, such as temperatures from -50 - 250° C.
  • the polymerization or copolymerization can be effected at atmospheric pressure, at sub-atmospheric pressure, or at elevated pressures of up to, or even higher than 500 MPa, continuously or discontinuously.
  • the homo- or copolymerization is performed at pressures between 0.01 and 500 MPa, most preferably between 0.01 and 10 MPa, in particular between 0.1-2 MPa. Higher pressures can be applied. In such a high- pressure process the metal complex according to the present invention can also be used with good results. Slurry and solution polymerizations normally take place at lower pressures, preferably below 10 MPa.
  • the polymerization can be carried out in the gas phase as well as in a liquid reaction medium. The polymerization is generally conducted under batch, continuous or semicontinuous polymerization conditions.
  • the polymerization process can be conducted as a gas phase polymerization (for example, in a fluidized bed or stirred bed reactor), as a solution polymerization, wherein the homopolymer or copolymer formed is substantially soluble in the reaction mixture, a suspension/slurry polymerization, wherein the polymer formed is substantially insoluble in the reaction medium, as a solid phase powder polymerization or as a so-called bulk polymerization process, in which an excess of monomer to be polymerized is used as the reaction medium.
  • a gas phase polymerization for example, in a fluidized bed or stirred bed reactor
  • a solution polymerization wherein the homopolymer or copolymer formed is substantially soluble in the reaction mixture
  • a suspension/slurry polymerization wherein the polymer formed is substantially insoluble in the reaction medium
  • a solid phase powder polymerization or as a so-called bulk polymerization process, in which an excess of monomer to be polymerized is used as the reaction medium.
  • the catalysts may also be utilized in combination with at least one additional homogeneous or heterogeneous polymerization catalyst in the same or in separate reactors connected in series or in parallel to prepare polymer blends having desirable properties.
  • An example of such a process is disclosed in WO 94/00500, equivalent to U.S. Ser. No. 07/904,770, as well as U.S. Pat. No. 5,844,045.
  • the quantity of catalyst to be used generally is such that its concentration in the solvent or dispersion agent amounts to 10 "8 -10 "3 mol/L, preferably 10 "7 - 10 "4 mol/L.
  • Suitable solvents, dispersion agents or diluents for the polymerization or copolymerization process via a solution or slurry process are typically noninterfering, inert liquids and can be chosen from the group comprising, but not limited to, straight and branched-chain hydrocarbons such as propane, butane, isobutane, pentane, hexane, heptane, octane, cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, and xylene and isomers of the foregoing and mixtures thereof as well as pentamethyl heptane or mineral oil fractions such as light or regular petrol, naphtha, kerosine or gas oil.
  • Fluorinated hydrocarbon fluids such as perfluorinated C4-1 Q alkanes are also suitable.
  • Further suitable solvents include liquid olefins which may act as comonomers in the polymerization process including cyclopentadiene, butadiene isoprene, butene, pentene, hexene and cyclooctadiene, including isomers of the foregoing. Mixtures of the foregoing are also suitable.
  • Aromatic hydrocarbons for instance benzene and toluene, can also be used. Out of cost considerations it is preferred therefore to use low-priced aliphatic hydrocarbons or mixtures thereof in polymerization processes on a technical scale as marketed by the petrochemical industry as solvent.
  • the solvent may optionally contain minor quantities of aromatic hydrocarbon, for instance toluene.
  • toluene can be used as solvent for the MAO in order to supply the MAO in dissolved form to the polymerization reactor. Drying or purification of the solvents is desirable if such solvents are used; this can be done without problems by known methods by one skilled in the art.
  • the polymerization or copolymerization is conducted under batch, continuous or semicontinous solution or bulk polymerization conditions in hydrocarbons such as propylene, propane, butane, butene, pentane, hexane, heptane, cyclohexane, benzene, toluene, including isomers of the foregoing and mixtures thereof at temperatures from -10°C and 200°C, preferably from 0° to 130°C.
  • the polymerization may be conducted n one or more continuous stirred reactors or fluidized bed, gas phase reactors, connected n series or parallel. Monomer and/or solvent may be added to the reactor as is well known n the art.
  • the catalyst may also be supported and/or prepolymerized prior to use.
  • a continuous process is preferred, in which event advantageously the mixture of reaction components of catalyst, solvent and dienes is substantially supplied continuously or at frequent intervals into the reactor system and is continuously monitored so as to ensure an efficient reaction and the desired product which is continuously removed therefrom.
  • catalyst poisons such as water, oxygen, carbon oxides, acetylenic compounds and sulfur compounds. Introduction of such compounds may result in reactor upset and production of off-grade product.
  • computer control systems may be used to maintain process variables within acceptable limits, often by measuring variables such as temperature, viscosity, molecular weight, exotherm, flow rates or catalyst productivity. If the polymerization process is carried out under suspension or gas phase polymerization conditions, the temperatures typically are below 150°C.
  • high molecular weight polymers can be readily attained by use of the present catalysts, even at elevated reactor temperatures.
  • This result is highly desirable because the molecular weight of diene polymers can be readily reduced by the use of hydrogen, di- and trihydrocarbylaluminum compounds (such as but not limited to triisopropylaluminum, diisopropylaluminum hydride, triethylaluminum, trioctylaluminum, diethylaluminum chloride and diisopropylaluminum chloride), 1 ,5- cyclooctadiene or similar chain transfer agent.
  • high molecular weights can be reduced using aromatic monomers such as but not limited to styrene.
  • productivity is increased due to improved polymer solubility, decreased solution viscosity, and a higher polymer concentration.
  • catalysts of the present invention Utilizing the catalysts of the present invention, homopolymers and copolymers having different comonomer incorporation may be readily prepared.
  • polymers of the invention such as but not limited to polybutadiene, polyisoprene, polystyrene, polyethylene and polypropylene preferably polybutadiene, polyisoprene and polystyrene, even more preferably polybutadiene and polyisoprene can be prepared as completely amorphous polymers or as polymers comprising more or less expanded crystalline areas.
  • polybutadiene prepared with metal complex 2 and modified methylalumoxane had much more expanded crystalline areas when nonpolar solvents such as cyclohexane were used as polymerization solvents.
  • the use of more polar solvents such as toluene resulted in a much more amorphous polybutadiene.
  • the percentage of one type of monomers in the copolymer, preferably of one type of conjugated diene is higher than 0 and less than 100 percent.
  • the polybutadiene content of the polybutadiene homopolymer or of the butadiene copolymers preferably comprises high cis-1 ,4-polybutadiene.
  • the polymer resulting from the polymerization or copolymerization can be worked up by a method known per se.
  • the catalyst is deactivated at some point during the processing of the polymer in a manner known per se, for example, by means of water or an alcohol. Removal of the catalyst residues can mostly be omitted because the quantity of catalyst in the polymer or copolymer, in particular the content of halogen and metal, is very low owing to the use of the catalyst system according to the invention. If desired, however, the level of catalyst residues in the polymer can be reduced in a known manner, for example, by washing.
  • the deactivation step can be followed by a stripping step (removal of organic solvent(s) from the copolymer).
  • the polymerization or copolymerization can also be performed in several steps, in series as well as in parallel. If required, the catalyst composition, temperature, hydrogen concentration, pressure, residence time, etc., may be varied from step to step. In this way it is also possible to obtain products with a wide property distribution, for example, molecular weight distribution.
  • the catalysts of the present invention for the polymerization of olefins polymers may be obtained with molecular weights between 50,000 and 1 ,500,000 g/mol preferably between 100,000 and 1 ,000,000 g/mol and polydispersities (Mw/Mn) of 1.0 - 50, preferably polydispersities of 1.0 - 20.
  • the fraction of the residual olefinic double bonds in the polymer or copolymer resulting from the polymerization of the conjugated dienes that are Z or cis units ranges from 50 — 100 percent, even more preferably from 60 to 100 percent, yet still more preferably from 85 — 99 percent and yet still more preferably from 90 -99 percent of the total amount of residual olefinic double bonds resulting from the polymerization of the conjugated dienes.
  • the conjugated diene polymers having high cis-1 ,4- content also have a vinyl content (1 ,2-polybutadiene and/or 1 ,2- and 3,4- polyisoprene) between 0 and 30 percent, preferably between 0 and 20 percent, more preferably the 1 ,2-polybutadiene content of the polybutadiene fraction of the homo- or copolymer is between 0 and 10 percent, even more preferably between 0 and 5 percent.
  • the cis content of polybutadiene can be very high such as for example but not limited to 97.0 percent (see Runs 1 , 4 and 6).
  • Formed copolymerization products of one type of conjugated diene monomer with a second ethylenically unsaturated addition polymerizable monomer preferably can be chosen to be a random or block copolymer, even more preferably the copolymer comprises butadiene and styrene or butadiene and isoprene.
  • Such polymers of the invention are well-suited for use in the modification of plastics, particularly polystyrene in the preparation of HIPS (high impact polystyrene).
  • the polymerization process of the invention allows the production of tailor-made copolymers.
  • the choice of the activator and of the metal complex and also the manner of preparation of catalyst, as well as the solvent used for the polymerization reaction (nonaromatic or aromatic), the concentration of the diene monomers and the polymerization temperature enable an adjustment of the molecular weight of the resulting polymer, the molecular weight distribution and the polymerization activity of a given catalyst.
  • Non-limiting examples are the following:
  • the molecular weight distribution can vary over a wide range; in one example it was 2.31 , typical for a single site polymerization process (Run 2) while in another example it was 4.9 (see Run 5).
  • the cis content is generally very high regardless of the polarity of the polymerization solvent.
  • the cis content of polybutadiene amounted to 97.0 percent when complex 2 was combined with modified methylalumoxane (MMAO) in cyclohexane (see Run 1) and the cis content amounted to 95 percent when complex 2 was combined with modified methylalumoxane (MMAO) in toluene (see Run 2).
  • Another advantage of the invention for diene polymerization reactions is that the manner of preparation of the catalyst (for example, order of addition of the catalyst components and catalyst aging) can favorably influence the polymer properties such as the polymer microstructure and the molecular weight.
  • the polymers of the invention may be used in the production of many useful shapes, molded parts, films, foams, golf balls, tires, hoses, conveyor and other belts, gaskets, seals, shoes and in the modification of plastics, such as the manufacture of high impact polystyrene or impact-modified polypropylene.
  • the IR samples were prepared using CS 2 as swelling agent and using a two or fourfold dissolution.
  • DSC differential scanning calorimetry
  • Mn and Mw are molecular weights and were determined by universal calibration of SEC.
  • the ratio between the 1 ,4-cis-, 1 ,4-trans- and 1 ,2-polydiene content of the butadiene or isoprene polymers was determined by IR and 13 C NMR-spectroscopy.
  • the glass transition temperatures of the polymers were determined by DSC determination. 1. Synthesis of the transition metal complexes
  • NdCI 3 (THF) 3 (0.82 g, 1.8 mmol) was stirred with 1b (1.50 g, 1.8 mmol) in THF (60 mL) at room temperature overnight. After THF was evaporated, the residue was extracted with Et 2 O (80 mL) and centrifuged to remove LiCI. Et 2 O was again evaporated, and the residue was recrystallized from THF (10 mL)/ hexane (80 mL) to give orange crystals of Nd(C 33 H 4 ⁇ N 3 )(THF)( ⁇ -CI) 2 Li(THF) 2 (5) (1.69g, 1.8 mmol, >99 percent, as 0.5 hexane solvate).
  • YCI 3 3THF (2.87 g, 7.0 mmol) and neutral ligand 1 (3.35 g, 7.0 mmol) were mixed and stirred in 80 ml of THF at room temperature overnight.
  • the polymerizations were performed in a double wall 2 L steel reactor, which was purged with nitrogen before the addition of organic solvent, metal complex, activator(s), Lewis acids or other components.
  • the polymerization reactor was tempered to 50°C unless stated otherwise.
  • the following components were then added in the following order: organic solvent, the activator 1 , conjugated diene monomer(s) and the mixture was allowed to stir for one hour.
  • the following components were added in the following order into the 2 L steel reactor: optionally a second activator component and/or Lewis acid and subsequently the metal complex was added to start the polymerization.
  • the polymerization was performed at 50°C unless stated otherwise.
  • the polymerization time varied depending on the experiment.
  • the polymer solution was transferred into a separate double wall steel reactor containing 50 mL of methanol and Irganox 1520 as stabilizer for the polymer (1 L of methanol contains 2 g of Irganox). This mixture was stirred for 15 minutes. The recovered polymer was then stripped with steam for 1 hour to remove solvent and other volatiles and dried in an oven at 45°C for 24 hours.
  • the polymerizations were performed in a double wall 2 L steel reactor, which was purged with nitrogen before the addition of organic solvent, metal complex, activator(s), Lewis acids or other components.
  • the polymerization reactor was tempered to 50°C unless stated otherwise.
  • the following components were then added in the following order: organic solvent and the activator 1 and the mixture was allowed to stir for one hour.
  • the following components were added in the following order into the 2 L steel reactor: optionally a second activator component and/or Lewis acid and subsequently the metal complex was added and the reaction mixture was stirred for a short period. Afterwards the conjugated diene monomer(s) was added to start the polymerization.
  • the polymerization was performed at 50°C unless stated otherwise.
  • the polymerization time varied depending on the experiment.
  • the polymer solution was transferred into a separate double wall steel reactor containing 50 mL of methanol and Irganox 1520 as stabilizer for the polymer (1 L of methanol contains 2 g of Irganox). This mixture was stirred for 15 minutes. The recovered polymer was then stripped with steam for 1 hour to remove solvent and other volatiles and dried in an oven at 45°C for 24 hours.
  • the Mooney value amounted to 119.6 the melt enthalpy ( ⁇ H SL ) amounts to 38.8 J/g, the glass transition temperature amounted to -108.3°C and the melting points are at -74 and -8°C.
  • the experiment was carried out according to the general polymerization procedure described above (2.1).
  • the polymerization was carried out in 500 g of toluene solvent.
  • 500 g of toluene, 54.1 g (1.0 mol) of 1 ,3-butadiene monomer and MMAO (11.8 g of a heptane solution containing 30.3 mmol of MMAO) were added into the polymerization reactor and stirred for one hour and 27 minutes.
  • 90.3 mg (0.1 mmol) of neodymium complex 2 dissolved in 4.1 g toluene were added into the polymerization reactor to start the polymerization reaction.
  • the polymerization reaction was terminated as described above (see 2.1. ). At this point, the conversion level of the monomers into polybutadiene was 67.5 percent. 36.5 g of polybutadiene were recovered as result of the stripping process.
  • the polymer contained 95.0 percent cis-1 ,4-; 4.5 percent trans-1 ,4-, 0.5 percent 1 ,2- polybutadiene according to 13 C-NMR and IR determination.
  • the experiment was carried out according to the general polymerization procedure described above (2.2).
  • the polymerization was carried out in 3515 g of toluene solvent.
  • MMAO 82.5 g of a heptane solution containing 0.211 mol of MMAO
  • 0.62 g (0.686 mmol) of neodymium complex 2 dissolved in 10.3 g toluene were added into the polymerization reactor and stirred for four minutes.
  • 379.0 g (7.0 mol) of 1 ,3- butadiene monomer were added into the polymerization reactor to start the polymerization reaction.
  • the experiment was carried out according to the general polymerization procedure described above (2.1).
  • the polymerization was carried out in 500 g of cyclohexane solvent.
  • 500 g of cyclohexane, 53.9 g (1.0 mol) of 1 ,3-butadiene monomer and MMAO (11.8 g of a heptane solution containing 30.3 mmol of MMAO) were added into the polymerization reactor and stirred for two hours and 5 minutes.
  • 95.1 mg (0.1 mmol) of neodymium complex 3 dissolved in 8.1 g cyclohexane were added into the polymerization reactor to start the polymerization reaction.
  • the polymer contained 97.0 percent cis-1 ,4-; 2.2 percent trans-1 ,4-, 0.8 percent 1 ,2- polybutadiene according to IR determination.
  • the experiment was carried out according to the general polymerization procedure described above (2.1).
  • the polymerization was carried out in 500 g of cyclohexane solvent.
  • 500 g of cyclohexane, 54.2 g (1.0 mol) of 1 ,3-butadiene monomer and MMAO (11.8 g of a heptane solution containing 30.3 mmol of MMAO) were added into the polymerization reactor and stirred for two hours and 48 minutes. Afterwards 89.6 mg (0.1 mmol) of neodymium complex 4 dissolved in 6.6 g cyclohexane were added into the polymerization reactor to start the polymerization reaction.
  • the polymer contained 95.9 percent cis-1 ,4-; 3.3 percent trans-1 ,4-, 0.8 percent 1 ,2- polybutadiene according to IR determination.
  • the experiment was carried out according to the general polymerization procedure described above (2.1).
  • the polymerization was carried out in 503 g of cyclohexane solvent.
  • 503 g of cyclohexane, 54.1 g (1.0 mol) of 1 ,3-butadiene monomer and MMAO (11.8 g of a heptane solution containing 30.3 mmol of MMAO) were added into the polymerization reactor and stirred for one hour and 42 minutes.
  • 96.1 mg (0.1 mmol) of neodymium complex 5 dissolved in 3.6 g cyclohexane were added into the polymerization reactor to start the polymerization reaction.
  • the polymer contained 97.0 percent cis-1 ,4-; 2.3 percent trans-1 ,4-, 0.7 percent 1 ,2- polybutadiene according to IR determination.
  • the Mooney value amounted to 108.5.
  • the experiment was carried out according to the general polymerization procedure described above (2.1).
  • the polymerization was carried out in 500 g of cyclohexane solvent.
  • 499 g of cyclohexane, 54.2 g (1.0 mol) of 1 ,3-butadiene monomer and MMAO (11.8 g of a heptane solution containing 30.3 mmol of MMAO) were added into the polymerization reactor and stirred for one hour and 53 minutes.
  • 84.5 mg (0.1 mmol) of neodymium complex 6 dissolved in 5.9 g cyclohexane were added into the polymerization reactor to start the polymerization reaction.
  • the polymer contained 96.6 percent cis-1 ,4-; 2.7 percent trans-1 ,4-, 0.7 percent 1 ,2- polybutadiene according to IR determination.

Abstract

Metal complexes suitable for use in polymerization are described which correspond to Formula (1) in which M is yttrium, a group 4 metal, a lanthanide or an actinide metal; Ml is a group 1 or group 2 metal; T independently each occurrence is nitrogen or phosphorus; RB and RC independently each occurrence is hydrogen or is selected from certain groups and two RC groups may be joined together forming a divalent ligand group; X independently each occurrence is an anionic ligand group having up to 60 atoms, provided that X is not a cyclic, delocalized, aromatic group that is π-bonded to M, and two X groups together may form a divalent ligand group; D independently each occurrence is a neutral Lewis base ligand having up to 30 nonhydrogen atoms; x is the number 1, 2 or 3; x' is the number 1 or 2; t is a number from 0 to 3; t' is a number from 0 to 3; r is the number 0 or 1 and o is the number 1 or 2. These metal complexes may be combined with one or more activator compounds to make catalyst compositions which may be used to manufacture polymers having a high percentage of the fraction of residual olefinic double bonds that are Z or cis units and a, low 1,2 polybutadiene content. The polymers are useful for modification of plastics and for the manufacture of a wide range of products including tires, golf balls, hoses, belts, gaskets, seals, and shoes.

Description

PROCESS FOR HOMO- OR COPOLYMERIZATION OF CONJUGATED OLEF1NES
This invention relates to metal complex compositions, their preparation and their use as catalysts to produce polymers through (homo)polymerization of ethylenically unsaturated addition polymerizable monomers or through copolymerization of ethylenically unsaturated addition polymerizable monomers with at least one different type of ethylenically unsaturated addition polymerizable monomer. The used metal complex compositions are yttrium, group 4 metal, lanthanide and actinide compounds, preferably yttrium, group 4, and lanthanide compounds, more preferably neodymium compounds in combination with activator compound(s) and optionally a catalyst support.
Polymers from conjugated ethylenically unsaturated addition polymerizable monomers and metal complex catalysts for producing the same are known.
Though a few patents describe some characteristics of the polydiene obtained, little effort has been made to improve the polymerization activity and to change the molecular weight of the polymer while maintaining the interesting polymer cis selectivity.
It is noteworthy that different mixtures of the metal complex (precatalysi) with the co-catalyst can have a dominant effect on the molecular weight of the polymer and on the polymerization activity of the polymerization reaction.
It is desired to achieve a high cis selectivity of the polydiene regardless of the polarity of the polymerization solvent, which could be realized by selecting suitable precatalysts in combination with specific activators. On the other hand it is desirable to be able to tune the molecular weight of the polydienes and the polymerization activity of the polymerization reaction by selecting suitable types and amounts of co-catalysts. In addition, there is a need for catalyst precursors and catalysts which are stable in a dry state and in solution at room temperature and at higher temperatures so that these compounds may be more easily handled and stored. In addition, it would be desirable to have catalyst components that could be directly injected into the polymerization reactor without the need to "age" (stir, shake or store) the catalyst or catalyst components for a longer period of time. Especially for a solution polymerization process or a continuous polymerization process, liquid or dissolved catalyst or catalyst components are more suitable for a proper dosing into the polymerization vessel. Furthermore, it is highly desirably to have a highly active polymerization catalyst for conjugated dienes which is stable and efficient in a broad temperature range for a longer period without deactivation. It also would be beneficial if polydienes with high cis contents and high molecular weight could be produced efficiently. High molecular weight polybutadienes with a high fraction of cis-1 ,4-polybutadiene are interesting materials for the production of tire tread and side walls.
These and other problems are solved by the present invention.
This invention relates to metal complex compositions, their preparation and their use as catalysts to produce polymers of conjugated dienes through polymerization of conjugated ethylenically unsaturated addition polymerizable monomers or through copolymerization of conjugated ethylenically unsaturated addition polymerizable monomers with at least one different type of ethylenically unsaturated addition polymerizable monomer. The used metal complex compositions are yttrium, group 4, lanthanide and actinide compounds, preferably yttrium group 4, and lanthanide compounds, more preferably neodymium compounds in combination with activator compound(s) and optionally a catalyst support.
More particularly, the invention relates to metal complexes containing at least three metal - nitrogen and/or metal - phosphorus bonds and at least one metal halide or metal carbon bond. More particularly the three nitrogen or phosphorus atoms attached to the metal center are constituents of the same chelate ligand. Even more particularly the invention relates to metal complexes containing at least three metal - nitrogen bonds and at least one metal halide or metal carbon bond and to the preparation of the catalyst and the use of the prepared catalyst to produce homo- or copolymers of conjugated dienes, preferably through, but not limited to, through homopolymerization of 1 ,3-butadiene or copolymerization of 1 ,3-butadiene with styrene or isoprene. More preferably the polydiene or the polydiene sequences of the copolymer consist predominantly of cis units.
According to the present invention for the polymerization of one type of ethylenically unsaturated addition polymerizable monomer or the copolymerization of one type of ethylenically unsaturated addition polymerizable monomer with at least one different type of ethylenically unsaturated addition polymerizable monomer there are provided metal complexes corresponding to Formula 1
Figure imgf000003_0001
Formula 1 wherein
M is yttrium, a group 4 metal of the Periodic Table of the elements, a lanthanide or actinide metal;
M1 is a group 1 or group 2 metal of the Periodic Table of the elements;
T independently each occurrence is nitrogen or phosphorus;
Rc independently each occurrence is hydrogen or a group having from 1 to 80 atoms not counting hydrogen, which is halide, nitro, nitrile, hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy, oxygen-substituted hydrocarbyl, including hydrocarbyloxyhydrocarbyl, hydroxy-, keto- aldehyde-, and ester-substituted hydrocarbyl; amino, hydrocarbylamino, nitrogen-substituted hydrocarbyl, including amide, amino- or hydrocarbylamino-substituted hydrocarbyl; hydrocarbylsilyl, silicon-substituted hydrocarbyl, including siloxy, or hydrocarbylsilyl-substituted hydrocarbyl; or two Rc groups are joined together forming a divalent ligand group;
RB independently each occurrence is a hydrogen or a group having from 1 to 80 atoms not counting hydrogen, which is hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl, hydrocarbyloxy, amino, hydrocarbylamino;
X independently each occurrence is an anionic ligand group having up to 60 atoms, provided however that in no occurrence is X a cyclic, delocalized, aromatic group that is π- bonded to M, and optionally two X groups together form a divalent ligand group;
D independently each occurrence is a neutral Lewis base ligand having up to 30 nonhydrogen atoms; x is the number 1 , 2 or 3; x' is the number 1 or 2; t is a number from 0 to 3;
V is a number from 0 to 3; r is the number 0 or 1 ; and o is the number 1 or 2.
Further according to the present invention there are provided metal complexes corresponding to the Formulas la, lb, and Ic:
Figure imgf000005_0001
Formula la
Figure imgf000005_0002
Formula lb
Figure imgf000005_0003
Formula Ic
wherein:
M is yttrium, a group 4 metal of the Periodic Table of the elements, a lanthanide or actinide metal;
M1 is a group 1 or group 2 metal of the Periodic Table of the elements,
T independently each occurrence is nitrogen or phosphorus;
RA and RD independently each occurrence are hydrogen or groups having from 1 to 80 atoms not counting hydrogen, which is halide, hydrocarbyl, hydrocarbylsilyl, halo- substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino- substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl, hydrocarbyloxy, amino, hydrocarbylamino;
RB independently each occurrence is a hydrogen or a group having from 1 to 80 atoms not counting hydrogen, which is hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl, hydrocarbyloxy, amino, hydrocarbylamino;
Rc independently each occurrence is hydrogen or a group having from 1 to 80 atoms not counting hydrogen, which is halide, nitro, nitrile, hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy, oxygen-substituted hydrocarbyl, including hydrocarbyloxyhydrocarbyl, hydroxy-, keto- aldehyde-, and ester-substituted hydrocarbyl; amino, hydrocarbylamino, nitrogen-substituted hydrocarbyl, including amide, amino- or hydrocarbylamino-substituted hydrocarbyl; hydrocarbylsilyl, silicon-substituted hydrocarbyl, including siloxy, or hydrocarbylsilyl-substituted hydrocarbyl; or two Rc groups are joined together forming a divalent ligand group;
X independently each occurrence is an anionic ligand group having up to 60 atoms, provided however that in no occurrence is X a cyclic, delocalized, aromatic group that is π- bonded to M, and optionally two X groups together form a divalent ligand group;
D independently each occurrence is a neutral Lewis base ligand having up to 30 nonhydrogen atoms; x is the number 1 , 2 or 3; x' is the number 1 or 2; t is a number from 0 to 3; t' is a number from 0 to 3; r is the number 0 or 1 ; and o is the number 1 or 2.
The formula weight of the metal complex preferably is lower than 2000 g/mol, more preferably lower than 1000 g/mol.
Additionally, according to the present invention for polymerization of conjugated ethylenically unsaturated addition polymerizable monomers there is provided a process for preparing pyridine or phosphabenzene yttrium, group 4 metal, lanthanide or actinide metal complexes corresponding to the Formulas la, lb, and Ic: comprising: for complexes of Formulas la and lb, contacting in a solvent a pyridine or phosphabenzene compound according to the Formula IVa
Figure imgf000007_0001
Formula IVa wherein T, RA, RB, Rc, RD are as previously defined, with more than 0.5 and less than 1.5 equivalents of a metal compound corresponding to Formula III
M(X)mDt
Formula III, wherein m is the number 3 or 4; and M, X, t and D are as previously defined, and with between 1 and 4 equivalents of a metal compound corresponding to the Formula V:
M'XV-1 REn
Formula V wherein
M'and x' are as previously defined;
X" is chloro, bromo or iodo;
RE independently each occurrence is hydrogen or a group having from 1 to 80 atoms not counting hydrogen, which is hydrocarbyl, including methyl, ethyl, propyl, isopropyl, t-butyl, n-butyl, pentyl, hexyl, allyl, benzyl, tolyl, phenyl, neopentyl; oxygen- substituted hydrocarbyl; including methoxyethyl; nitrogen-substituted hydrocarbyl, including N,N-dimethylaminoethyl, N,N-dimethylaminobenzyl, N,N-dimethylaminomethylphenyl; or hydrocarbylsilyl, including trimethylsilylmethyl, t-butyldimethylsilylmethyl, bis(trim et ylsilyl) methyl ; or NR2 wherein R independently each occurrence is hydrogen or
C-| _ 25 hydrocarbyl, including methyl, ethyl, propyl, isopropyl, t-butyl, n-butyl, pentyl, hexyl n is the number 1 or 2; and the sum of n and x'-1 is equal to the oxidation state of M'; and comprising: for complexes of Formula Ic, contacting in a solvent a pyridine or phosphabenzene compound according to the Formula IVb
Figure imgf000008_0001
Formula IVb wherein T, RA, RB, Rc are as previously defined, with more than 0.5 and less than 1.5 equivalents of a metal compound corresponding to Formula III
M(X)mDt
Formula III, wherein m is the number 3 or 4;
M is yttrium, a group 4 metal of the periodic Table of the elements, a lanthanide or a actinide metal and X, m, t and D are as previously defined, and optionally, with between 1 and 4 equivalents of a metal compound corresponding to the Formula V
M'XV-i RE n
Formula V wherein
M1, x', X", RE and n are as previously defined.
Further according to the present invention there are provided catalysts for the polymerization of one type of ethylenically unsaturated addition polymerizable monomer or the copolymerization of one type of ethylenically unsaturated addition polymerizable monomer with at least one different type of ethylenically unsaturated addition polymerizable monomer comprising
1 ) a combination of one or more of the above metal complexes and one or more activators (cocatalysts) and optionally a support (carrier material) or
2) the reaction product formed by contacting one or more of the above metal complexes with one or more activators and optionally a support or
3) the product formed by subjecting one or more of the above metal complexes and optionally a support to activating techniques.
The present invention also provides a process for preparing catalysts for the polymerization of one type of ethylenically unsaturated addition polymerizable monomer or copolymerization of one type of ethylenically unsaturated addition polymerizable monomer with at least one different type of ethylenically unsaturated addition polymerizable monomer comprising: contacting one or more of the above metal complexes with one or more activators and optionally a support or subjecting one or more of the above metal complexes and optionally a support to activating techniques.
The present invention also provides a polymerization process comprising contacting one or more ethylenically unsaturated addition polymerizable monomers optionally in the presence of an inert, aliphatic, alicyclic or cyclic or aromatic hydrocarbon, under polymerization conditions with a catalyst comprising
1 ) a combination of one or more of the above metal complexes and one or more activators and optionally a support or
2) the reaction product formed by contacting one or more of the above metal complexes with one or more activators and optionally a support or
3) the product formed by subjecting one or more of the above metal complexes and optionally a support to activating techniques.
The polymerization may be performed under solution, suspension, slurry, or gas phase process conditions, and the catalyst or individual components thereof may be used in a heterogeneous, that is, a supported state, or in a homogeneous state as dictated by process conditions. The catalyst can be used in combination with one or more additional catalysts of the same or different nature either simultaneously in the same reactor and/or sequentially in separate reactors. The catalyst can be formed in situ in the presence of or prior to addition to a reaction mixture comprising one or more ethylenically unsaturated addition polymerizable monomers.
According to the present invention there are provided homopolymers comprising one ethylenically unsaturated addition polymerizable monomer, even more especially one conjugated ethylenically polyunsaturated addition polymerizable monomer. Further according to the present invention there are provided copolymers comprising more than one ethylenically unsaturated addition polymerizable monomer, even more especially conjugated ethylenically polyunsaturated addition polymerizable monomers in combination with a second type of ethylenically unsaturated addition polymerizable monomer.
Catalysts for polymerization of ethylenically unsaturated addition polymerizable monomers preferably catalysts for polymerization of conjugated ethylenically polyunsaturated addition polymerizable monomers according to the invention possess improved catalytic properties and are especially useful in the polymerization of conjugated dienes. In addition, the complexes are compatible with and may be used in combination with alkylaluminum compounds which may be employed to scavenge monomer impurities without detrimental effects to their catalytic properties.
All references to the Periodic Table of the Elements herein shall be to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1989. Also, any reference to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups.
By the term "neutral Lewis base ligand" is meant uncharged groups that are sufficiently nucleophilic to be capable of forming a coordination bond to a metal atom of the metal complex of the invention. Preferred neutral Lewis base ligand groups, D, are carbon monoxide, ethers, polyethers, thioethers, amines, polyamines, phosphines, phosphites, polyphosphines, alcohols, nitriles, esters, amides, olefins and conjugated dienes. The metal complexes according to the present invention may be present as coordination complexes of neutral Lewis base ligands.
Preferred pyridine metal complexes according to the present invention correspond to the formulas la, lb and Ic:
Figure imgf000010_0001
Formula la
Figure imgf000011_0001
Formula lb
Figure imgf000011_0002
Formula Ic wherein:
M1 is a metal of group 1 or group 2 of the Periodic Table of the Elements, preferably M1 is lithium, sodium, potassium or magnesium, even more preferably lithium, sodium or potassium;
M is yttrium, a group 4 metal of the Periodic Table of the elements, a lanthanide metal or an actinide metal; preferably M is a group 4 metal of the Periodic Table of the elements or a lanthanide metal and more preferably M is lanthanum, cerium, praseodymium, neodymium, promethium, samarium, titanium or zirconium, even more preferably M is neodymium;
T independently each occurrence is nitrogen or phosphorus;
RA and RD independently each occurrence are hydrogen or groups having from 1 to 80 atoms not counting hydrogen, which is halide, hydrocarbyl, hydrocarbylsilyl, halo- substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino- substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl, hydrocarbyloxy, amino, hydrocarbylamino;
Rc independently each occurrence is hydrogen or a group having from 1 to 80 atoms not counting hydrogen, which is halide, nitro, nitrile, hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy, oxygen-substituted hydrocarbyl, including hydrocarbyloxyhydrocarbyl, hydroxy-, keto- aldehyde-, and ester-substituted hydrocarbyl; amino, hydrocarbylamino, nitrogen-substituted hydrocarbyl, including amide, amino- or hydrocarbylamino-substituted hydrocarbyl; hydrocarbylsilyl, silicon-substituted hydrocarbyl, including siloxy, or hydrocarbylsilyl-substituted hydrocarbyl; or two Rc groups are joined together forming a divalent ligand group;
Preferred RA, Rc and RD groups are hydrogen, halide, especially chloride or bromide, hydrocarbyl, hydrocarbylsilyl, amino, hydrocarbylamino, hydrocarbyloxy, hydrocarbylsiloxy, especially hydrogen, halide, alkyl, cyclic alkyl, aryl, acyl, alkyloxy, hydrocarbylsilyl, alkylsiloxy, alkaryl, amino and hydrocarbylamino, more especially hydrogen, chloride, bromide, methyl, ethyl, 1-methylethyl, 1 ,1-dimethylethyl, cyclohexyl, phenyl, benzyl, trimethylsilyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, methoxy, ethoxy, methylethyloxy, 1 ,1-dimethylethyloxy, trimethylsiloxy, 1 ,1-dimethylethyl(dimethylsilyl)oxy, amino, methylamino, dimethylamino, diethylamino, methylethylamino, methylphenylamino, dipropylamino, dibutylamino, piperidino, morpholino, pyrrolidino, hexahydro-1 H-azepin-1-yl, hexahydro-1 (2H)-azocinyl, octahydro-1 H-azonin-1-yl or octahydro-1 (2H)-azecinyl.
RB independently each occurrence is a hydrogen or a group having from 1 to 80 atoms not counting hydrogen, which is hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl, hydrocarbyloxy, amino, hydrocarbylamino;
Preferred RB groups are hydrocarbyl, especially alkyl, cyclic alkyl, aryl, alkaryl, more especially methyl, ethyl, 1-methylethyl, 1 ,1-dimethylethyl, cyclohexyl, phenyl, 2,6- dialkylphenyl, benzyl, trimethylsilyl; hydrocarbylsilyl and hydrocarbylamino, especially alkylamino, cyclic alkylamino, arylamino and alkaryl, more especially methylamino, dimethylamino, diethylamino, methylethylamino, methylphenylamino, phenylamino, cyclohexylamino, dipropylamino, dibutylamino, piperidino, morpholino, pyrrolidino.
X independently each occurrence is hydrogen or a group having from 1 to 60 atoms not counting hydrogen, which is hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl, hydrocarbyloxy, hydrocarbylcarboxylate, hydrocarbylsulfide, hydrocarbylsiloxy, hydrocarbylamido, cyanide, acetylacetonate, dithiocarbamate, dithiocarboxylate and halide, provided however that in no occurrence is X a cyclic, delocalized, aromatic group that is π-bonded to M;
Preferred X are hydrogen and groups which are halide, hydrocarbyl (including alkyl, alkenyl, aryl, alkaryl, aralkyl, cycloalkyl and cycloalkenyl) hydrocarbyloxide, hydrocarbylsulfide, N,N-dihydrocarbylamide, hydrocarbyleneamide, hydrocarbylcarboxylate, acetylacetonate, cyanide, dithiocarbamate, and dithiocarboxylate groups, said X groups having from 1 to 20 atoms other than hydrogen.
Even more preferred X are hydrogen and groups which are halide, hydrocarbyl, including alkyl, alkenyl, aryl, alkaryl, arylalkyl, cycloalkyl and cycloalkenyl, said X groups having from 1 to 20 atoms other than hydrogen, especially hydrogen, chloride, bromide, iodide, fluoride, methyl, ethyl, propyl, benzyl, neopentyl, trimethysilylmethyl, phenyl, tolyl, allyl, cyclohexenyl, methallyl.
D independently each occurrence is selected from carbon monoxide; phosphines,
PR'3, and phosphites, P(OR')3, wherein R' independently each occurrence is hydrocarbyl or silyl, especially trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine and 1 ,2-bis(dimethylphosphino)ethane, 1 ,2- bis(diphenylphosphino)ethane, bis(diphenylphosphino)methane, 1 ,3- bis(diphenylphosphino)propane, trimethylphosphite, triethylphosphite, tributylphosphite, triphenylphosphite; thioethers, especially dimethylthioether, methylphenylthioether, diethylthioether; ethers and polyethers, especially tetrahydrofuran (THF), diethylether (Et2θ), dioxane, 1 ,2-dimethoxyethane (DME); amines and polyamines, especially pyridine, bipyridine, pyrrolidine, piperidine, tetramethylethylenediamine (TMEDA) and triethylamine (TEA); oiefins, especially ethylene, propylene, butene, hexene, octene, styrene, divinylbenzene; conjugated dienes having from 4 to 40 carbon atoms, especially butadiene, isoprene, 1 ,3-pentadiene, 2,4-hexadiene; alcohols, especially methanol, ethanol, propanol, butanol; nitriles, especially acetonitrile, acrylonitrile, propanenitrile, benzonitrile; esters, especially methyl acetate, ethyl acetate, butyl acetate, methyl acrylate, methyl methacrylate, methyl benzoate; for Formulas la and lb, r is the number 0 or 1 ; for Formula Ic, r is the number 1 ; x is the number 1 , 2 or 3; x' is the number 1 or 2; t is a number from 0 to 3; t' is a number from 0 to 3;
0 is the number 1 or 2;
Especially preferred pyridine metal complexes according to the present invention correspond to the formula la, lb, or Ic wherein RA, RB, Rc, RD, X, D, x, t and are as previously defined; M is yttrium, a lanthanide metal or a group IV metal;
M1 is lithium, sodium or potassium
T is nitrogen; and x' is the number 1 ; o is the number 1 ; and r is the number 1.
Especially preferred pyridine metal complexes according to the present invention correspond to the formulas lla, lib, and lie:
Figure imgf000014_0001
Formula lla
Figure imgf000014_0002
Formula lib
Figure imgf000015_0001
Formula lie wherein
M is a lanthanide metal or a group IV metal, especially lanthanum, cerium, praseodymium, neodymium, promethium, samarium, titanium or zirconium, even more especially M is neodymium;
M1 is lithium, sodium or potassium;
N is nitrogen;
RA or RD independently each occurrence is hydrogen or
Figure imgf000015_0002
alkyl, most preferably methyl, ethyl, 1-methylethyl, t-butyl, cyclohexyl;
Rc independently each occurrence is hydrogen, halide or C1-6 alkyl, most preferably hydrogen, chloride, methyl, ethyl, 1-methylethyl, cyclohexyl;
X independently each occurrence is halide, hydrogen, C1-10 hydrocarbyl, or C1-10 hydrocarbylsilylhydrocarbyl, especially fluoride, chloride, bromide, iodide, methyl, ethyl, benzyl, neopentyl, trimethylsilylmethyl; x is the 1 , 2 or 3; x' is the number 1 t is the number zero, one or two;
D is THF, DME, TEA, TMEDA, Et2O; f is a number from zero to two; o is the number one and r is the number one.
Most highly preferred pyridine metal complexes according to the present invention correspond to the Formula lla, ([2,6-bis-(1-(hydrocarbylamido)-2-RA-2-RD-ethylidene)-4- Rc-)pyridine]MXxDt * (M'Xx>)rDt'). Exemplary, but non-limiting metal complexes according to the invention include the following neodymium, zirconium, titanium (IV), and titanium (III) complexes:
[2,6-bis 2,6-diisopropylphenylamido) )ethylidene)pyrid nejneodymium fluoride
[2,6-bis 2,6-diisopropylphenylamido) )ethylidene)pyrid nejneodymium chloride
[2,6-bis 2,6-diisopropylphenylamido) )ethylidene)pyrid nejneodymium bromide
[2,6-bis 2,6-diisopropylphenylamido) )ethylidene)pyrid nejneodymium iodide
[2,6-bis 2,6-diisopropylphenylamido) )ethylidene)pyrid nejneodymium methyl
[2,6-bis 2,6-diisopropylphenylamido) )ethylidene)pyrid nejneodymium ethyl
[2,6-bis 2,6-diisopropylphenylamido) )ethylidene)pyrid nejneodymium propyl
[2,6-bis 2,6-diisopropylphenylamido) )ethylidene)pyrid nejneodymium butyl
[2,6-bis 2,6-diisopropylphenylamido) )ethylidene)pyrid nejneodymium benzyl
[2,6-bis 2,6-diisopropylphenylamido) )ethylidene)pyrid nejneodymium neopentyl
[2,6-bis 2,6-diisopropylphenylamido) )ethylidene)pyrid nejneodymium trimethylsilylmethyl
[2,6-bis 2,6-diisopropylphenylamido) )ethylidene)pyrid nejneodymium allyl
[2,6-bis 2,6-diisopropylphenylamido) )ethylidene)pyrid nejneodymium phenyl
[2,6-bis 2,6-diisopropylphenylamido) )ethylidene)pyrid nejneodymium tolyl
[2,6-bis 2,6-diisopropylphenylami do)ethylidene)pyrid nejneodymium methallyl
[2,6-bis 2,6-diisopropylphenylam! do)ethylidene)pyrid nejneodymium cyclohexyl
[2,6-bis(1 2,6-diisopropylphenylam do)ethylidene)pyrid nejneodymium methoxide
[2,6-bis(1 2,6-diisopropylphenylam do)ethylidene)pyrid nejneodymium ethoxide 2,6-bis(1 -(2,6-diisopropylphenylam do)ethylidene)pyrid nejneodymium hexanoate 2,6-bis(1 -(2,6-diisopropylphenylam do)ethylidene)pyrid nejneodymium neodecanoate 2,6-bis(1 -(2,6-diisopropylphenylam do)ethylidene)pyridi nejneodymium acetate 2,6-bis(1 -(2,6-diisopropylphenylam do)ethylidene)pyridi nejneodymium cyanide 2,6-bis(1 -(2,6-diisopropylphenylam do)ethylidene)pyrid: nejneodymium dimethylamide 2,6-bis(1 -(2,6-diisopropylphenylam do)ethylidene)pyrid nejneodymium diethylamide 2,6-bis(1 -(2,6-diisopropylphenylam do)ethylidene)pyrid nejneodymium acetylacetonate 2,6-bis(1 -(2,6-diisopropylphenylam do)ethylidene)pyrid nejneodymium hydride 2,6-bis(1 -(2,6-diisopropylphenylam do)ethylidene)pyrid! nejneodymium N,N-dimethylaminobenzyl
2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)pyridine]neodymium NjN-dimethylaminomethylphenyl
2,6-bis(1-(2!6-dimethylphenylamido)ethylidene)pyridine]neodymium fluoride 2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium chloride 2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium bromide 2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium iodide 2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium methyl [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridinejneodymium ethyl [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium propyl [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium butyl [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium benzyl [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridinejneodymium neopentyl [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium trimethylsilylmethyl [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridinejneodymium allyl [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium phenyl [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium tolyl [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium methallyl [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium cyclohexyl [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium methoxide [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium ethoxide [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium hexanoate [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium neodecanoate [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium acetate [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium cyanide [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium dimethylamide [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium diethylamide [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium acetylacetonate [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium hydride [2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium N,N-dimethylaminobenzyl
[2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]neodymium N,N-dimethylaminomethylphenyl
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]neodymium fluoride [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]neodymium chloride [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]neodymium bromide [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridinejneodymium iodide [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]neodymium methyl [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]neodymium ethyl [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]neodymium propyl [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]neodymium butyl [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]neodymium benzyl [2,6-bis(1-(2J6-diisopropyl-4-methylphenylamido)ethylidene)pyridinejneodymium neopentyl [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]neodymium trimethylsilylmethyl [2,6-bis(1 -(2,6-diisopropyl -4-methylphenylamido)ethylidene)pyridine]neodymium allyl [2,6-bis(1 -(2,6-diisopropy; -4-methylphenylamido)ethylidene)pyridine]neodymium phenyl [2,6-bis(1 -(2,6-diisopropy -4-methylphenylamido)ethylidene)pyridine]neodymium tolyl [2,6-bis(1 -(2,6-diisopropy -4-methylphenylamido)ethylidene)pyridinejneodymium methallyl [2,6-bis(1 -(2,6-diisopropy -4-methylphenylamido)ethylidene)pyridine]neodymium cyclohexyl [2,6-bis(1-(2,6-diisopropy -4-methylphenylamido)ethylidene)pyridine]neodymium methoxide [2,6-bis(1 -(2,6-diisopropy -4-methylphenylamido)ethylidene)pyridine]neodymium ethoxide [2,6-bis(1-(2,6-diisopropy -4-methylphenylamido)ethylidene)pyridine]neodymium hexanoate [2,6-bis(1 -(2,6-diisopropyl 4-methylphenylamido)ethylidene)pyridine]neodymium neodecanoate [2,6-bis(1 -(2,6-diisopropyl -4-methylphenylamido)ethyl dene)pyridine]neodymium acetate [2,6-bis(1 -(2,6-diisopropy 4-methylphenylamido)ethyl dene)pyridine]neodymium cyanide [2,6-bis(1 -(2,6-diisopropyl 4-methylphenylamido)ethyl dene)pyridine]neodymium dimethylamide [2,6-bis(1 -(2,6-diisopropy -4-methylphenylamido)ethylidene)pyridinejneodymium diethylamide [2,6-bis(1 -(2,6-diisopropyl -4-methylphenylamido)ethylidene)pyridine]neodymium acetylacetonate [2,6-bis(1 -(2,6-diisopropy -4-methylphenylamido)ethylidene)pyridine]neodymium hydride [2,6-bis(1 -(2,6-diisopropy -4-methylphenylamido)ethylidene)pyridine]neodymium N,N-dimethylaminobenzyl [2,6-bis(1 -(2,6-diisopropyl -4-methylphenylamido)ethylidene)pyridine]neodymium N,N-dimethylaminomethy! phenyl
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine]neodymium fluoride [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine]neodymium chloride [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine]neodymium bromide [2,6-bis(1-(2)6-t-butylamido)ethylidene)pyridine]neodymium iodide [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine]neodymium methyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine]neodymium ethyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine]neodymium propyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine]neodymium butyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine]neodymium benzyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine]neodymium neopentyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine]neodymium trimethylsilylmethyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine]neodymium allyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridinejneodymium phenyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine]neodymium tolyl [2,6-bis 1-(2,6-t- •butylamido)ethylidene)pyridine]neodymium methallyl [2,6-bis 1-(2,6-t- ■butylamido)ethylidene)pyridine]neodymium cyclohexyl [2,6-bis 1-(2,6-t- •butylamido)ethylidene)pyridine]neodymium methoxide [2,6-bis 1-(2,6-t- •butylamido)ethylidene)pyridine]neodymium ethoxide [2,6-bis 1-(2,6-t- ■butylamido)ethylidene)pyridine]neodymium hexanoate [2,6-bis 1-(2,6-t- ■butylamido)ethylidene)pyridine]neodymium neodecanoate [2,6-bis 1-(2,6-t- butylamido)ethylidene)pyr dinejneodymium acetate [2,6-bis 1-(2,6-t- butylamido)ethylidene)pyridinejneodymi urn cyanide [2,6-bis 1-(2,6-t :--butylamido)ethylidene)pyridine]neodymium dimethylamide [2,6-bis 1-(2,6 butylamido)ethylidene)pyridine]neodymium diethylamide [2,6-bis 1-(2,6-t- butylamido)ethylidene)pyridine]neodymium acetylacetonate [2,6-bis 1-(2,6-t- butylamido)ethylidene)pyridinejneodymium hydride [2,6-bis 1-(2,6-t :--butylamido)ethylidene)pyridine]neodymium N,N-dimethylaminobenzyl [2,6-bis 1-(2,6-t butylamido)ethylidene)pyridine]neodymium
N,N-dimethylam nomethylphenyl
[2,6-bis 1-(2,6-d sopropylphenylam do)ethylidene)-4-methylpyri nejneodymium fluoride [2,6-bis 1-(2,6-d! sopropylphenylam do)ethylidene)-4-methylpyri nejneodymium chloride [2,6-bis (1-(2,6-d: sopropylphenylam do)ethylidene)-4-methylpyri nejneodymium bromide [2,6-bis 1-(2,6-d sopropylphenylam do)ethylidene)-4-methylpyr nejneodymium iodide [2,6-bis 1-(2,6-d sopropylphenylam do)ethylidene)-4-methylpyr nejneodymium methyl [2,6-bis 1-(2,6-d: sopropylphenylam do)ethylidene)-4-methylpyr nejneodymium ethyl [2,6-bis 1-(2,6-d sopropylphenylam !do)ethylidene)-4-methylpyri nejneodymium propyl [2,6-bis (1-(2,6-d sopropylphenylam do)ethylidene)-4-methylpyri nejneodymium butyl [2,6-bis 1-(2,6-d sopropylphenylam do)ethylidene)-4-methylpyri nejneodymium benzyl [2,6-bis 1-(2,6-d sopropylphenylam !do)ethylidene)-4-methylpyri nejneodymium neopentyl [2,6-bis 1-(2,6-d sopropylphenylam do)ethylidene)-4-methylpyri nejneodymium trimethylsilylmethyl
[2,6-bis 1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]neodymium allyl [2,6-bis 1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridinejneodymium phenyl [2,6-bis 1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]neodymium tolyl [2,6-bis 1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]neodymium methallyl [2,6-bis 1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]neodymium cyclohexyl [2,6-bis 1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]neodymium methoxide [2,6-bis 1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]neodymium ethoxide [2,6-bis 1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridinejneodymium hexanoate [2,6-bis 1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]neodymium neodecanoate 2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]neodymium acetate 2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]neodymium cyanide 2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]neodymium dimethylamide
2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]neodymium diethylamide
2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]neodymium acetylacetonate
2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]neodymium hydride 2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]neodymium N,N-dimethylaminobenzyl
2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]neodymium N,N-dimethylaminomethylphenyl
2,6-bis(- I -(an do)ethylidene)pyrid nejneodymium fluoride
2,6-bis(" I -(an do)ethylidene)pyrid nejneodymium chloride
2,6-bis(" I -(an do)ethylidene)pyrid nejneodymium bromide
2,6-bis(" -(an do)ethylidene)pyrid nejneodymium iodide
2,6-bis(' -(an do)ethy!idene)pyrid nejneodymium methyl
2,6-bis(" -(an do)ethylidene)pyrid nejneodymium ethyl
2,6-bis(' I -(an do)ethylidene)pyrid nejneodymium propyl
2,6-bis(" I -(an do)ethylidene)pyrid nejneodymium butyl
2,6-bis(- I -(an do)ethylidene)pyrid nejneodymium benzyl
2,6-bis(' I -(an do)ethylidene)pyrid nejneodymium neopentyl
2,6-bis(' -(an do)ethylidene)pyrid nejneodymium trimethylsilylmethyl
2,6-bis(" I -(an do)ethylidene)pyrid nejneodymium allyl
2,6-bis(" I -(an do)ethylidene)pyrid nejneodymium phenyl
2,6-bis(' I -(an do)ethylidene)pyrid nejneodymium tolyl
2,6-bis(- I -(an do)ethylidene)pyrid nejneodymium methallyl
2,6-bis(- I -(an do)ethylidene)pyrid nejneodymium cyclohexyl
2,6-bis(" I -(an do)ethylidene)pyrid nejneodymium methoxide
2,6-bis(' I -(an do)ethylidene)pyrid nejneodymium ethoxide
2,6-bis(' I -(an do)ethylidene)pyrid nejneodymium hexanoate
2,6-bis(" I -(an do)ethylidene)pyrid nejneodymium neodecanoate
2,6-bis(" I -(an do)ethylidene)pyrid nejneodymium acetate
2,6-bis(' I -(an do)ethylidene)pyrid nejneodymium cyanide
2,6-bis(- I -(an do)ethylidene)pyrid nejneodymium dimethylamide
2,6-bis(" -(an do)ethylidene)pyrid nejneodymium diethylamide [2,6-bis( -(anilido)ethylidene)pyridinejneodymium acetylacetonate
[2,6-bis( -(anilido)ethylidene)pyridinejneodymium hydride
[2,6-bis( -(anilido)ethylidene)pyridine]neodymium N,N-dimethylaminobenzyl
[2,6-bis( -(anilido)ethylidene)pyridine]neodymium N,N-dimethylaminomethylphenyl
[2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine zirconium difluoride
[2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine zirconium dichloride
[2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine zirconium dibromide
[2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine zirconium diiodide
[2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine zirconium dimethyl
[2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine zirconium diethyl
[2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine zirconium dipropyl
[2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine^ zirconium dibutyl
[2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine; zirconium dibenzyl
[2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine; zirconium dineopentyl
[2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine; zirconium bis(tri methyl silylmethyl)
[2,6-bis( -(2,6-d sopropyl Ipheny lam do)ethyl dene)pyrid ne rconium d allyl
[2,6-bis( -(2,6-d isopropyl Ipheny lam do)ethy! dene)pyri ne'. rconium d phenyl
[2,6-bis( -(2,6-d sopropy Ipheny] lam do)ethyl dene)pyr! ne' rconium d tolyl
[2,6-bis( -(2,6-d sopropy Ipheny lam do)ethyl dene)pyri ne rconium d methallyl
[2,6-bis( -(2,6-d isopropyl Ipheny lam do)ethyl dene)pyri ne rconium di cyclohexyl
[2,6-bis( -(2,6-d sopropyl Ipheny lam do)ethyl dene)pyri ne rconium di methoxide
[2,6-bis( -(2,6-d sopropyl Ipheny lam !do) ethyl dene)pyri ne rconium d ethoxide
[2,6-bis( -(2,6-d sopropyl Ipheny lam do) ethyl idene)pyri ne rconium d hexanoate
[2,6-bis( -(2,6-di sopropyl Ipheny lam do)ethyl dene)pyri ne rconium d neodecanoate
[2,6-bis( -(2,6-d: sopropy Ipheny lam do) ethyl dene)pyr ne^ rconium d HCΘIcllθ
[2,6-bis( -(2,6-d sopropyl Ipheny lam do) ethyl idene)pyri ne' rconium d cyanide
[2,6-bis( -(2,6-di sopropyl Ipheny lam do) ethyl dene)pyri ne' rconium b s(dimethylamide)
[2,6-bis( -(2,6-di sopropyl Ipheny lam do)ethyl dene)pyr ne^ rconium b s(diethylamide)
[2,6-bis( -(2,6-d: sopropy Ipheny lam do)ethyl dene)pyri ne' rconium d acetylacetonate
[2,6-bis( -(2,6-d sopropy Iphenyl lam do) ethyl dene)pyr ne' rconium d hydride
[2,6-bis( -(2,6-d sopropy Ipheny lam do) ethyl dene)pyri ne rconium bis(N,N-l dimethylaminobenzyl)
[2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]zirconium bis(N,N dimethylaminomethylphenyl)
[2,6-bis( -(2,6-dimethylphenylamido)ethylidene)pyridine]zirconium difluoride
[2,6-bis( -(2,6-dimethylphenylamido)ethylidene)pyridine]zirconium dichloride [2,6-bis 1 -(2,6-dimethylphenylamido D)ethylidene)pyr dine zirconium dibromide
[2,6-bis 1 -(2,6-dimethylphenylamido ))ethylidene)pyri dine' zirconium diiodide
[2,6-bis 1 -(2,6-dimethylphenylamido D)ethylidene)pyri dine zirconium dimethyl
[2,6-bis 1 -(2,6-dimethylphenylamido D)ethylidene)pyri dine' zirconium diethyl
[2,6-bis 1 -(2,6-dimethylphenylamido ))ethylidene)pyri dine' zirconium dipropyl
[2,6-bis 1 -(2,6-dimethylphenylamido ))ethylidene)pyri dine zirconium dibutyl
[2,6-bis 1 -(2,6-dimethylphenylamido ))ethylidene)pyri dine zirconium dibenzyl
[2,6-bis 1 -(2,6-dimethylphenylamido D)ethylidene)pyr dine zirconium dineopentyl
[2,6-bis 1 -(2,6-dimethylphenylamido ))ethylidene)pyri dine' zirconium bis(trimethylsilylmethyl)
[2,6-bis 1 -(2,6-dimethylphenylamido D)ethylidene)pyr dine zirconium diallyl
[2,6-bis 1 -(2,6-dimethylphenylamido ))ethylidene)pyr dine' zirconium diphenyl
[2,6-bis 1 -(2,6-dimethylphenylamido ))ethylidene)pyri dine' zirconium ditolyl
[2,6-bis 1 -(2,6-dimethylphenylamido ))ethylidene)pyri dine zirconium dimethallyl
[2,6 bis(1 (2,6-dimethylphenylamido D')ethylidene)pyri dine' zirconium dicyclohexyl
[2,6-bis 1 -(2,6-dimethylphenylamido ))ethylidene)pyri dine zirconium dimethoxide
[2,6-bis 1 -(2,6-dimethylphenylamido ))ethylidene)pyri dine' zirconium diethoxide
[2,6 bis(1 (2,6-dimethylphenylamido)ethylidene)pyri din zirconium dihexanoate
[2,6-b 1-(2,6-dimethylphenylamido)ethylidene)pyr dine zirconium dineodecanoate [2,6-b 1-(2,6-dimethylphenylamido)ethylidene)pyridine]zirconium diacetate
[2,6-b 1-(2,6-dimethylphenylamido)ethylidene)pyridine zirconium dicyanide
[2,6-b 1-(2,6-dimethylphenylamido)ethylidene)pyridine' zirconium bis(dimethylamide)
[2,6 bis(1 -(2,6-dimethylphenylamido)ethylidene)pyridine' zirconium bis(diethylamide)
[2,6-bis 1-(2,6-dimethylphenylamido)ethylidene)pyridine zirconium diacetylacetonate
[2,6 bis(1 (2,6-dimethylphenylamido)ethylidene)pyridine zirconium dihydride
[2,6-bis 1-(2,6-dimethylphenylamido)ethylidene)pyridine zirconium bis(N,N dimethylaminobenzyl)
[2,6-bis 1-(2,6-dimethylphenylamido)ethylidene)pyridine]zirconium bis(N,N dimethylaminomethylphenyl)
[2,6-bis 1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine jzirconium difluoride
[2,6-bis 1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine ijzirconium dichloride
[2,6-bis 1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine i'jzirconium dibromide
[2,6-bis 1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine' jzirconium diiodide
[2,6-bis 1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine^ jzirconium dimethyl
[2,6-bis 1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine jzirconium diethyl
[2,6-bis 1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine (;jzirconium dipropyl
[2,6-bis 1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine; jzirconium dibutyl
[2,6-bis 1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine^ jzirconium dibenzyl [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]zirconium dineopentyl [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]zirconium bis(trimethylsilylmethyl)
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]zirconium diallyl [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]zirconium diphenyl [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]zirconium ditolyl [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]zirconium di ethallyl [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]zirconium dicyclohexyl [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]zirconium dimethoxide [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]zirconium diethoxide [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]zirconium dihexanoate [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]zirconium dineodecanoate
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylam do) ethyl dene)pyridine]z rconium diacetate
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylam do) ethyl dene)pyridine]z rconium dicyanide
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylam do) ethyl dene)pyri dinejz rconium bis(dimethylamide)
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]zirconium bis(diethylamide)
[2,6-bis(1-(2]6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]zirconium diacetylacetonate
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]zirconium dihydride
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]zirconium bis(N,N-dimethylaminobenzyl)
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]zirconium bis(N,N-dimethylaminomethylphenyl)
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine]zirconium difluoride
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine; zirconium dichloride [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine; zirconium dibromide [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine; zirconium diiodide [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine zirconium dimethyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine zirconium diethyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine zirconium dipropyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine zirconium dibutyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine zirconium dibenzyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine zirconium dineopentyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine zirconium bis(trimethylsilylmethyl) [2,6-bis(1 -(2,6-t-butylamido)ethylidene)pyridine jzirconium diallyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine jzirconium diphenyl [2,6-bis(1 -(2,6-t-butylamido)ethylidene)pyridine (j' zirconium ditolyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine jzirconium dimethallyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine (jzirconium dicyclohexyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine jzirconium dimethoxide [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine (jzirconium diethoxide [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine jzirconium dihexanoate [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine (jzirconium dineodecanoate [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine jzirconium diacetate [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine (jzirconium dicyanide [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine jzirconium bis(dimethylamide) [2,6-bis(1 -(2,6-t-butylamido)ethylidene)pyridine ^zirconium bis(diethylamide) [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine; jzirconium diacetylacetonate [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine jzirconium dihydride [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine; jzirconium bis(N,N-dimethylaminobenzyl) [2,6-bis(1 -(2,6-t-butylamido)ethylidene)pyridine' jzirconium bis(N,N-dimethylaminomethylphenyl)
[2,6-b s(1 -(2,6-d sopropylphenylam do)ethyl dene)-4-methylpyrid ne rconium d fluoride [2,6-bi s(1 -(2,6-d sopropylphenylam do)ethyl dene)-4-methylpyrid ne' rconium d chloride [2,6-bi s(1 -(2,6-d sopropylphenylam do)ethylι dene)-4-methylpyrid ne'. rconium d bromide
[2,6-bi s(1 -(2,6-d sopropylphenylam do)ethyl dene)-4-methylpyrid ne rconium d iodide [2,6-bi s(1 -(2,6-d sopropylphenylam do)ethyl dene)-4-methylpyrid ne' rconium d methyl [2,6-b s(1 -(2,6-d sopropylphenylam do)ethyl! dene)-4-methylpyrid nejzi rconium d ethyl [2,6-bi s(1 -(2,6-d sopropylphenylam do)ethyl dene)-4-methylpyrid ne rconium d propyl [2,6-bi s(1 -(2,6-d sopropylphenylam do)ethyl dene)-4-methylpyrid ne; rconium d butyl [2,6-bi s(1 -(2,6-d sopropylphenylam do)ethyl dene)-4-methylpyrid ne rconium d benzyl [2,6-bi s(1 -(2,6-d sopropylphenylam do)ethyl dene)-4-methylpyrid ne; rconium d neopentyl [2,6-bi s(1 -(2,6-d sopropylphenylam do)ethyl dene)-4-methylpyrid ne' rconium bis(trimethylsilylmethyl) [2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine; zirconium diallyl [2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine zirconium diphenyl [2,6-bis(1 -(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine zirconium ditolyl [2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine zirconium dimethallyl [2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine zirconium dicyclohexyl [2,6-bis(1 -(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine; zirconium dimethoxide [2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine; zirconium diethoxide [2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]zirconium dihexanoate
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]zirconium dineodecanoate
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]zirconium diacetate
[2,6-bis(1-(2J6-diisopropylphenylamido)ethylidene)-4-methylpyridinejzirconium dicyanide
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]zirconium bis(dimethylamide)
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]zirconium bis(diethylamide)
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]zirconium diacetylacetonate
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]zirconium dihydride
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]zirconium bis(N,N-dimethylaminobenzyl)
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]zirconium bis(N,N-dimethylaminomethylphenyl)
[2,6-bis(- I -(an do)ethylidene)pyridine rconium difluoride
[2,6-bis(' -(an do)ethylidene)pyridine rconium dichloride
[2,6-bis(' -(an do)ethylidene)pyridine rconium dibromide
[2,6-bis(- I -(an do)ethylidene)pyridinej rconium diiodide
[2,6-bis(' I -(an do)ethylidene)pyridine rconium dimethyl
[2,6-bis(- I -(an do)ethylidene)pyridine rconium diethyl
[2,6-bis(- I -(an do)ethylidene)pyridine rconium dipropyl
[2,6-bis(- I -(an do)ethylidene)pyridine rconium dibutyl
[2,6-bis(- I -(an do)ethylidene)pyridine rconium dibenzyl
[2,6-bis( I -(an do)ethylidene)pyridine rconium dineopentyl
[2,6-bis(- I -(an do)ethylidene)pyridine rconium bis(trimethylsilylmethyl)
[2,6-bis(" I -(an do)ethylidene)pyridine rconium diallyl
[2,6-bis( 1-(an do)ethylidene)pyridine rconium diphenyl
[2,6-bis( 1-(an do)ethylidene)pyridine rconium ditolyl
[2,6-bis( l-(an do)ethylidene)pyridine rconium dimethallyl
[2,6-bis( 1-(an do)ethylidene)pyridine rconium dicyclohexyl
[2,6-bis( 1-(an do)ethylidene)pyridine rconium dimethoxide
[2,6-bis( 1-(an do)ethylidene)pyridine rconium diethoxide
[2,6-bis( 1-(an do)ethylidene)pyridine rconium dihexanoate
[2,6-bis( l-(an do)ethylidene)pyridine rconium dineodecanoate
[2,6-bis( 1-(an do)ethylidene)pyridine rconium diacetate [2,6-bis( -(an lido)ethylidene)pyridine]zirconium dicyanide [2,6-bis( -(an lido)ethylidene)pyridine]zirconium bis(dimethylamide) [2,6-bis( -(an lido)ethylidene)pyridine]zirconium bis(diethylamide) [2,6-bis( -(an lido)ethylidene)pyridine]zirconium diacetylacetonate [2,6-bis( -(an lido)ethylidene)pyridine]zirconium dihydride [2,6-bis( -(an lido)ethylidene)pyridine]zirconium bis(N,N-dimethylaminobenzyl) [2,6-bis( -(an lido)ethylidene)pyridine]zirconium bis(N,N-dimethylaminomethylphenyl) [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]ti tanium difluoride [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]tϊ tanium dichloride [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]ti tanium dibromide [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridinejti tanium diiodide [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]ti tanium dimethyl [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]ti itanium diethyl [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]ti tanium dipropyl [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]ti itanium dibutyl [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridinejti tanium dibenzyl [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]ti itanium dineopentyl [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]ti itanium bis(trimethylsilylmethyl) [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]ti tanium diallyl [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]ti tanium diphenyl [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]t tanium ditolyl [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]ti tanium dimethallyl [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]ti tanium dicyclohexyl [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]ti tanium dimethoxide [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]ti tanium diethoxide [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridinejtitanium dihexanoate [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]titanium dineodecanoate [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]titanium diacetate [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridinejtitanium dicyanide [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]titanium bis(dimethylamide) [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]titanium bis(diethylamide) [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]titanium diacetylacetonate [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]titanium dihydride [2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)pyridine]titanium bis(N,N-dimethylaminobenzyl)
[2,6-bis(1 -(2,6-diisopropylphenylamido)ethylidene)pyridine]titanium bis(N,N-dimethylaminomethylphenyl) [2,6-bis( 1 -(2,6-di methylphenylamido)ethylidene)pyridine titanium difluoride
[2,6-bis( 1 -(2,6-di methylphenylamido)ethylidene)pyridine titanium dichloride
[2,6-bis( 1 -(2,6-d1 methylphenylamido)ethylidene)pyridine titanium dibromide
[2,6-bis( 1 -(2,6-d methylphenylamido)ethylidene)pyridine titanium diiodide
[2,6-bis( 1 -(2,6-d methylphenylamido)ethylidene)pyridine [titanium dimethyl
[2,6-bis( 1 -(2,6-d methylphenylamido)ethylidene)pyridine titanium diethyl
[2,6-bis( 1 -(2,6-d methylphenylamido)ethylidene)pyridine titanium dipropyl
[2,6-bis( 1 -(2,6-d methylphenylamido)ethylidene)pyridine titanium dibutyl
[2,6-bis 1 -(2,6-d methylphenylamido)ethylidene)pyridine titanium dibenzyl
[2,6-bis( 1 -(2,6-d methylphenylamido)ethylidene)pyridine titanium dineopentyl
[2,6-bis( 1 -(2,6-d methylphenylamido)ethylidene)pyridine titanium bis(trimethylsilylmethyl)
[2,6-bis 1 -(2,6-d methylphenylamido)ethylidene)pyridine titanium diallyl
[2,6-bis 1 -(2,6-d methylphenylamido)ethylidene)pyridine (titanium diphenyl
[2,6-bis [1 -(2,6-d methylphenylamido)ethylidene)pyridine titanium ditolyl
[2,6-bis 11 -(2,6-d methylphenylamido)ethylidene)pyridine itanium dimethallyl
[2,6-bis [1 -(2,6-d methylphenylamido)ethylidene)pyridine itanium dicyclohexyl
[2,6-bis [1 -(2,6-d methylphenylamido)ethylidene)pyridine] itanium dimethoxide
[2,6-bis [1 -(2,6-d methylphenylamido)ethylidene)pyridinejtitanium diethoxide
[2,6-bis [1 -(2,6-d methylphenylamido)ethylidene)pyridine] itanium dihexanoate
[2,6-bis [1 -(2,6-d methylphenylamido)ethylidene)pyridine] itanium dineodecanoate
[2,6-bis (1 -(2,6-d methylphenylamido)ethylidene)pyridine] itanium diacetate
[2,6-bis (1 -(2,6-d methylphenylamido)ethylidene)pyridine] itanium dicyanide
[2,6-bis (1 -(2,6-d methylphenylamido)ethylidene)pyridine] itanium bis(dimethylamide)
[2,6-bis (1 -(2,6-d methylphenylamido)ethylidene)pyridine] itanium bis(diethylamide)
[2,6-bis (1 -(2,6-d methylphenylamido)ethylidene)pyridine] itanium diacetylacetonate
[2,6-bis (1 -(2,6-d methylphenylamido)ethylidene)pyridine] itanium dihydride
[2,6-bis (1 -(2,6-d methylphenylamido)ethylidene)pyridine]t itanium bis(N,N-dimethylaminobenzyl)
[2,6-bis(1-(2,6-dimethylphenylamido)ethylidene)pyridine]titanium bis(N,N-dimethylaminomethylphenyl)
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]titanium difluoride [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]titanium dichloride [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridinejtitanium dibromide [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]titanium diiodide [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]titanium dimethyl [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]titanium diethyl [2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine titanium dipropyl
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine titanium dibutyl
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine titanium dibenzyl
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine; titanium dineopentyl
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine titanium bis(trimethylsilylmethyl)
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine titanium diallyl
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine titanium diphenyl
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine titanium ditolyl
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine titanium dimethallyl
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine titanium dicyclohexyl
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine titanium dimethoxide
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine titanium diethoxide
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine (titanium dihexanoate
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine titanium dineodecanoate
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]titanium diacetate
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridinejtitanium dicyanide
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]titanium bis(dimethylamide)
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]titanium bis(diethylamide)
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]titanium diacetylacetonate
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]titanium dihydride
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridinejtitanium bis(N,N-dimethylaminobenzyl)
[2,6-bis(1-(2,6-diisopropyl-4-methylphenylamido)ethylidene)pyridine]titanium bis(N,N-dimethylaminomethylphenyl)
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine j;titanium difluoride [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine; jtitanium dichloride [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine; jtitanium dibromide [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine; jtitanium diiodide [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine; jtitanium dimethyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine jtitanium diethyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine jtitanium dipropyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine ^titanium dibutyl [2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine' (titanium dibenzyl
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine titanium dineopentyl
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine titanium bis(trimethylsilylmethyl)
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine' titanium diallyl
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine titanium diphenyl
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine titanium ditolyl
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine (titanium dimethallyl
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine titanium dicyclohexyl
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine titanium dimethoxide
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine titanium diethoxide
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine titanium dihexanoate
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine titanium dineodecanoate
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine titanium diacetate
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine titanium dicyanide
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine titanium bis(dimethylamide)
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine titanium bis(diethylamide)
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine titanium diacetylacetonate
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridin titanium dihydride
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine' titanium bis(N,N-dimethylaminobenzyl)
[2,6-bis(1-(2,6-t-butylamido)ethylidene)pyridine titanium bis(N,N-dimethylaminomethylphenyl) opropyl Iphenylam ido)ethyl dene)-4-methylpyri ne] tanium d fluoride opropyl Iphenylam do) ethyl dene)-4-methylpyri ne] itanium d chloride opropyl Iphenylam do)ethyl dene)-4-methylpyri ne] tanium d bromide opropyi Iphenylam ido)ethyl dene)-4-methylpyri ne itanium d iodide opropyl Iphenylam do) ethyl dene)-4-methylpyr ne] tanium d methyl opropyl Iphenylam do)ethyl dene)-4-methylpyr ne] itanium d ethyl opropy Iphenylam do) ethyl dene)-4-methylpyri ne] tanium d propyl opropy Iphenylam do)ethyl dene)-4-methylpyri ne] tanium d butyl opropyl Iphenylam do)ethyl dene)-4-methylpyri ne] tanium d benzyl opropy Iphenylam do) ethyl dene)-4-methylpyri ne] tanium d neopentyl
Figure imgf000029_0001
opropy Iphenylam ιido)ethyli dι ene)-4-methylpyri ne] tanium bis(trimethylsilylmethyl)
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]titanium diallyl [2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]titanium diphenyl [2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]titanium ditolyl [2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]titanium dimethallyl [2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]titanium dicyclohexyl
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]titanium dimethoxide
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridinejtitanium diethoxide
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]titanium dihexanoate
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]titanium dineodecanoate
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]titanium diacetate
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]titanium dicyanide
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]titanium bis(dimethylamide)
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]titanium bis(diethylamide)
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]titanium diacetylacetonate
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]titanium dihydride
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridinejtitanium bis(N,N-dimethylaminobenzyl)
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]titanium bis(N,N-dimethylaminomethylphenyl)
[2,6-bis(1- (ani llido)ethylidene)pyridine]titanium difluoride
[2,6-bis(1-(ani llido)ethylidene)pyridine]titanium dichloride
[2,6-bis(1-(ani llido)ethylidene)pyridine]titanium dibromide
[2,6-bis(1-(ani llido)ethylidene)pyridine]titanium diiodide
[2,6-bis(1- (ani llido)ethylidene)pyridine]titanium dimethyl
[2,6-bis(1- (ani llido)ethylidene)pyridine]titanium diethyl
[2,6-bis(1- (ani llido)ethylidene)pyridine]titanium dipropyl
[2,6-bis(1- (ani llido)ethylidene)pyridine]titanium dibutyl
[2,6-bis(1- (ani llido)ethylidene)pyridine]titanium dibenzyl
[2,6-bis(1- (ani llido)ethylidene)pyridine]titanium dineopentyl
[2,6-bis(1- (ani llido)ethylidene)pyridine]titanium bis(trimethylsilylmethyl)
[2,6-bis(1- (ani llido)ethylidene)pyridine]titanium diallyl
[2,6-bis(1- (ani llido)ethylidene)pyridine]titanium diphenyl
[2,6-bis(1- (ani llido)ethylidene)pyridine]titanium ditolyl
[2,6-bis(1- (ani llido)ethylidene)pyridine]titanium dimethallyl
[2,6-bis(1- (ani llido)ethylidene)pyridine]titanium dicyclohexyl
[2,6-bis(1- (ani llido)ethylidene)pyridine]titanium dimethoxide
[2,6-bis(1- (ani llido)ethylidene)pyridine]titanium diethoxide [2,6-bis -(an lido)ethylidene)pyridine titanium dihexanoate
[2,6-bis -(an lido)ethylidene)pyridine titanium dineodecanoate
[2,6-bis -(an lido)ethylidene)pyridine titanium diacetate
[2,6-bis -(an lido)ethylidene)pyridine' titanium dicyanide
[2,6-bis -(an lido)ethylidene)pyridine' titanium bis(dimethylamide)
[2,6-bis -(an lido)ethylidene)pyridine titanium bis(diethylamide)
[2,6-bis -(an lido)ethylidene)pyridine; titanium diacetylacetonate
[2,6-bis -(an lido)ethylidene)pyridine' titanium dihydride
[2,6-bis -(an lido)ethylidene)pyridine' titanium bis(N,N-dimethylaminobenzyl)
[2,6-bis -(an lido)ethylidene)pyridine! titanium bis(N,N-dimethylaminomethylphenyl)
[2,6-bis -(2,6-d isopropyiphenylam do)ethyl dene) pyr ne]titanium benzyl
[2,6-bis -(2,6-d isopropylphenylam do) ethyl dene)pyr ne]titanium allyl
[2,6-bis -(2,6-d sopropylphenylam do)ethyl dene)pyr nejtitanium methallyl
[2,6-bis -(2,6-di isopropylphenylam do)ethyl idene)pyri nejtitanium
N,N-ddiimethylam nobenzyi
[2,6-bis -(2,6-d isopropylphenylamido)ethylidene)pyridine]titanium
N,N-dim ethyl am nomethylphenyl
[2,6-bis -(2,6-d methy lphenylamido)ethyl dene)pyridine]ti itanium benzyl
[2,6-bis -(2,6-d! methy iphenylamido)ethyi dene)pyridine]t tanium allyl
[2,6-bis -(2,6-d methy lphenyiamido)ethyl dene)pyridine]t tanium methallyl
[2,6-bis (1 -(2,6-d methy lphenylamido)ethyl dene)pyridine]ti tanium N,N-dimethylaminobenzyl
[2,6-bis( -(2,6-d methyl lphenylamido)ethylidene)pyri dine]ti itanium
N,N-dim ethylam nomethyl phenyl
[2,6-bis( -(2,6-d sopropyl -4-methylphenylarnido)ethyl dene)pyrid ne]t tan urn benzyl
[2,6-bis( -(2,6-d sopropy] -4-methylphenylamido)ethyl dene)pyrid nejt tan urn allyl
[2,6-bis( -(2,6-d sopropy -4-methylphenylamido)ethyl dene)pyrid nejt tan urn methallyl
[2,6-bis( -(2,6-d sopropyl -4-methylphenylamido)ethyl dene)pyrid ne]t tan urn
N,N dimethylam nobenzyi
[2,6-bis( (2,6-di iissoopprrooppyyll-4-methylphenylamido)ethylidene)pyridine]titanium
N,N dimethylaminomethylphenyl
[2,6-bis( -(2,6-t-butylamido)ethylidene)pyridine]titanium benzyl
[2,6-bis( -(2,6-t-butylamido)ethylidene)pyridinejtitanium allyl
[2,6-bis( -(2,6-t-butylamido)ethylidene)pyridine]titanium methallyl
[2,6-bis( -(2,6-t-butylamido)ethylidene)pyridine]titanium N,N-dimethylaminobenzyl
[2,6-bis( -(2,6-t-butylamido)ethylidene)pyridine]titanium N,N-dimethylaminomethylphenyl
[2,6-bis( -(2,6-diisopropylphenylamido)ethyiidene)-4-methylpyridine]titanium benzyl
[2,6-bis( -(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridinejtitanium allyl [2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]titanium methallyl
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]titanium
N,N-dimethylaminobenzyl
[2,6-bis(1-(2,6-diisopropylphenylamido)ethylidene)-4-methylpyridine]titanium
N,N-dimethylaminomethylphenyl
[2,6-bis(1 -(anilido)ethylidene)pyridine]titanium benzyl
[2,6-bis(1 -(anilido)ethylidene)pyridine]titanium allyl
[2,6-bis(1 -(anilido)ethylidene)pyridine]titanium methallyl
[2,6-bis(1-(anilido)ethylidene)pyridine]titanium N,N-dimethylaminobenzyl
[2,6-bis(1-(anilido)ethylidene)pyridine]titanium N,N-dimethylaminomethylphenyl
The skilled artisan will recognize that additional members of the foregoing list will include the corresponding yttrium, lanthanide, actinide, and group IV analogs, including yttrium, samarium, cerium, neodymium, promethium, praesodymium, lanthanum, hafnium, and uranium.
Further, the skilled artisan will recognize that additional members of the foregoing list will include the corresponding alkali metal salt or alkaline earth metal salt adducts thereof, as well as the corresponding Lewis base adducts thereof.
The skilled artisan will further recognize that the alkaline earth metal salt adducts can be present either as a 1 :1 complex or as a 2:1 complex, that is, in Formulas la, lb, Ic, lla, lib, or lie, o is 1 and r is 1 or o is 2 and r is 1.
In general, the complexes according to Formulas la, lb, Ic, lla, lib, and He can be prepared by contacting a pyridine or phosphabenzene compound corresponding to the formula Formula IVa or, optionally Formula IVb for complexes according to Formulas Ic and He, with a metal compound corresponding to Formula III and, optionally for the complexes according to Formulas Ic and lie, with a metal compound corresponding to Formula V
wherein for the complexes according to Formulas la, lb, Ic, lla, lib and lie, the molar ratio of the metal compound corresponding to Formula III to the compound corresponding to Formula IVa or Formula IVb being from 1 :0.5 to 1 :1.5, preferably from 1 :0.7 to 1 :1.3, more preferably from 1 :0.9 to 1 :1.1 ; and, for the complexes according to Formulas la, lb, lla, and lib, the molar ratio of the metal compound corresponding to Formula III to the metal compound corresponding to Formula V being from 1 :1 to 1 :4, preferably from 1 :1.5 to 1 :3.5, more preferably from 1 :1.9 to 1 :2.1 or from 1 :2.1 to 1 :3.1 , in a suitable noninterfering solvent or reaction medium at a temperature from -100°C to 300°C, preferably from -78°C to 150°C, most preferably from -50°C to 75°C. By noninterfering is meant that the solvent does not prevent formation of metal complex according to Formula la, lb, Ic, lla, lib, to He. Suitable reaction media for the formation of the complexes are aliphatic and aromatic hydrocarbons and halohydrocarbons, ethers, amines, alcohols, amides, nitriles and esters. Examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, decane and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; chlorinated-, fluorinated- or chlorofluorinated hydrocarbons such as chloroform, dichloromethane, chlorobenzene, dichlorobenzene, and perfluorinated C4..-10 alkanes; aromatic and hydrocarbyl-substituted aromatic compounds such as benzene, toluene, xylene, and styrene; alkyl ethers having from 1 to 5 carbons in each alkyl group such as diethyl ether, THF and dioxane; C-\ .4 dialkyl ether derivatives of
(poly)alkylene glycols, such as DME; aromatic or aliphatic amines such as tetramethylethylenediamine (TMEDA) and triethylamine (TEA); dimethylformamide (DMF) and dimethylacetamide (DMA); nitriles, especially acetonitrile, propanenitrile, benzonitrile; esters, especially methyl acetate, ethyl acetate and butyl acetate. Mixtures of the foregoing are also suitable. Preferred solvents include diethylether, toluene, DME and THF.
The recovery procedure usually involves a separation of the product from the reaction medium and/or any possible byproducts and/or unreacted starting materials. The solvents and other volatile components are advantageously removed via devolatilization of the reaction medium. Extraction into a secondary solvent may be employed if desired. If extraction is employed, nonpolar aliphatic, aromatic or chlorinated solvents can be used such as but not limited to pentane, hexane, octane, cyclohexane, methylcyclohexane, cycloheptane, benzene, toluene, chloroform or dichloromethane and mixtures thereof. Alternatively, if the desired product is insoluble or only slightly soluble, filtration or other separation technique may be employed.
Exemplary, but non-limiting examples for the compound corresponding to Formula III, M(X)mDt, according to the invention include the following neodymium compounds:
Neodymium bromide; neodymium chloride; neodymium iodide; neodymium fluoride, neodymium chloride dibromide; neodymium bromide dichloride; neodymium fluoride dibromide; neodymium bromide difluoride; neodymium fluoride dichloride; and neodymium chloride difluoride, neodymium acetate, neodymium hexanoate, neodymium neodecanoate, neodymium isopropoxide, neodymium acetylacetonate, neodymium cyanide.
The skilled artisan will recognize that additional members of the foregoing list will include the corresponding Lewis base adducts thereof, for example, the tetrahydrofuran adducts of neodymium chloride or neodymium bromide. Exemplary, but non-limiting examples for the compound corresponding to Formula IVa and Formula IVb according to the invention include the following compounds:
2,6-bis[1 -(2,6-diisopropylphenylimino)ethyl]pyridine, 2,6-bis[1 -(2,6- diisopropylphenylimino)ethyl]-4-methylpyridine, 2,6-bis[1-(2,6- dimethylphenylimino)ethyl]pyridine, 2,6-bis[1-(2,6-dimethylphenylimino)ethyl]-4- methylpyridine, 2,6-bis[1-(isopropylimino)ethyl]pyridine, 2,6-bis[1 -(t- butylimino)ethyl]pyridine, 2,6-bis[1 -(phenylimino)ethyl]pyridine, 2,6-bis[1 -(2,6-diisopropyl- 4-methylphenylimino)ethyl]pyridine, 2,6-bis[1-(2,4,6-trimethylphenylimino)ethyl]pyridine, 2,6-bis[1 -(2,4,6-trimethylphenylimino)ethyl]-4-methylpyridine, 2-[1 -(t-butylimino)ethyl]-6-[1 - (2,6-diisopropylphenylimino)ethyl]pyridine, 2-[1 -(phenylimino)ethyl]-6-[1 -(2,6- diisopropylphenyl imino)ethyl]pyridine, 2-[1 -(2,6-dimethylphenylimino)ethyl]-6-[1 -(2,6- diisopropylphenyl imino)ethyl]pyridine, 2-[1 -(t-butylimino)ethyl]-6-[1 -(2,6- dimethylphenylim ino)ethyl]pyridine, 2-[1 -(phenylimino)ethyl]-6-[1 -(2,6- dimethylphenylim ino)ethyl]pyridine, 2-[1 -(2,6-dimethylphenylimino)ethyl]-6-[1 - (phenylimino)ethyl]pyridine, 2-[1 -(t-butylimino)ethyl]-6-[1 -(2,6- diisopropylphenylimino)ethyl]-4-methylpyridine, 2-[1 -(phenylimino)ethyl]-6-[1 -(2,6- diisopropylphenylimino)ethyl]-4-methylpyridine, 2-[1 -(2,6-dimethylphenylimino)ethyl]-6-[1 - (2,6-diisopropylphenylimino)ethyl]-4-methylpyridine, 2-[1 -(t-butylimino)ethyl]-6-[1 -(2,6- dimethylphenylimino)ethyl]-4-methylpyridine, 2-[1 -(phenylimino)ethyl]-6-[1 -(2,6- dimethylphenylimino)βthyl]-4-methylpyridine, 2-[1 -(2,6-dimethylphenylimino)ethyl]-6-[1 - (phenylimino)ethyl]-4-methylpyridine, 2-[1 -(t-butylimino)ethyl]-6-[1 -(2,6-diisopropyl-4- methylphenylimino)ethyl]pyrid ne, 2-[1 -(phenylimino)ethyl]-6-[1 -(2,6-diisopropyl-4- methylphenylimino)ethyl]pyrid ne, 2-[1 -(2,6-dimethylphenylimino)ethyl]-6-[1 -(2,6- isopropyl-4-methylphenylimi no)ethyl]pyridine, 2-[1 -(t-butylimino)ethyl]-6-[1 -(2,4,6- methylphenylimino)ethyl]pyri dine, 2-[1 -(phenylimino)ethyl]-6-[1 -(2,4,6- methylphenylimino)ethyl]pyri dine, 2-[1 -(2,6-dimethylphenylimino)ethyl]-6-[1 -(4- methylphenylimino)ethyl]pyrid ne, 2,6-bis[1 -(2,6-diisopropylphenylimino)methyl]pyridine, 2,6-bis[1 -(2,6-diisopropylphenylimino)methyl]-4-methylpyridine, 2,6-bis[1 -(2,6- dimethylphenylimino)methyl]pyridine, 2,6-bis[1-(2,6-dimethylphenylimino)methyl]-4- methylpyridine, 2,6-bis[1 -(isopropylimino)methyl]pyridine, 2,6-bis[1 -(t- butylimino)methyl]pyridine, 2,6-bis[1 -(phenylimino)methyljpyridine, 2,6-bis[1 -(2,6- diisopropyl-4-methylphenylimino)methyl]pyridine, 2,6-bis[1 -(2,4,6- trimethylphenylimino)methyl]pyridine, 2,6-bis[1-(2,4,6-trimethylphenylimino)methylj-4- methylpyridine, 2-[1-(t-butylimino)methyl]-6-[1-(2,6-diisopropylphenylimino)methyl]pyridine, 2-[1 -(phenylimino)methyl]-6-[1 -(2,6-diisopropylphenylimino)methyl]pyridine, 2-[1 -(2,6- dimethylphenylimino)methyl]-6-[1 -(2,6-diisopropylphenylimino)methyl]pyridine, 2-[1 -(t- butylimino)methyl]-6-[1 -(2,6-dimethylphenylimino)methyl]pyridine, 2-[1 - (phenylimino)methyl]-6-[1 -(2,6-dimethylphenylimino)methyl]pyridine, 2-[1 -(2,6- dimethylphenylimino)methyl]-6-[1 -(phenylimino)methyljpyridine, 2-[1 -(t-butylimino)methylj- 6-[1 -(2,6-diisopropylphenylimino)methyl]-4-methylpyridine, 2-[1 -(phenylimino)methyl]-6-[1 - (2,6-diisopropylphenylimino)methyl]-4-methylpyridine, 2-[1-(2,6- dimethylphenylimino)methyl]-6-[1-(2,6-diisopropylphenylimino)methyl]-4-methylpyridine, 2- [1 -(t-butylimino)methyl]-6-[1 -(2,6-dimethylphenylimino)methyl]-4-methylpyridine, 2-[1 - (phenylimino)methyl]-6-[1 -(2,6-dimethylphenylimino)methyl]-4-methylpyridine, 2-[1 -(2,6- dimethylphenylimino)methyl]-6-[1 -(phenylimino)methyl]-4-methylpyridine, 2-[1 -(t- butylimino)methyl]-6-[1 -(2,6-diisopropyl-4-methylphenylimino)methyl]pyridine, 2-[1 - (phenylimino)methyl]-6-[1 -(2,6-diisopropyl-4-methylphenylimino)methyl]pyridine, 2-[1 -(2,6- dimethylphenylimino)methyl]-6-[1-(2,6-diisopropyl-4-methylphenylimino)methyl]pyridine, 2- [1 -(t-butylimino)methyl]-6-[1 -(2,4,6-trimethylphenylimino)methyl]pyridine, 2-[1 - (phenylimino)methyl]-6-[1 -(2,4,6-trimethylphenylimino)methyl]pyridine, 2-[1 -(2,6- dimethylphenylimino)methyl]-6-[1-(4-methylphenylimino)methyl]pyridine.
Exemplary, but non-limiting examples for the compound corresponding to Formula V,
M' 'x'.-j RE n, according to the invention include the following compounds:
Methyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, t-butyl lithium, n-butyl lithium, pentyl lithium, hexyl lithium, allyl lithium, benzyl lithium, tolyl lithium, phenyl lithium, neopentyl lithium, methoxyethyl lithium, N,N-dimethylaminoethyl lithium, N,N- dimethylaminobenzyl lithium, N,N-dimethylaminomethylphenyl lithium, trimethylsilylmethyl lithium, t-butyldimethylsilylmethyl lithium, bis(trimethylsilyl) methyl lithium, lithium dimethylamide, lithium diethylamide, lithium diisopropylamide, lithium pyrrolidinide, methyl magnesium chlori ide ethyl magnesium chloride, propyl magnesium chloride, isopropyl magnesium chlori ide t-butyl magnesium chloride, n-butyl magnesium chloride, pentyl magnesium chlori de, hexyl magnesium chloride, allyl magnesium chloride, benzyl magnesium chlori de, tolyl magnesium chloride, phenyl magnesium chloride, neopentyl magnesium chlori de, methoxyethyl magnesium chloride, N,N-dimethylaminoethyl magnesium chlori de, N,N-dimethylaminobenzyl magnesium chloride, N,N- dimethylaminomethylphenyl magnesium chloride, trimethylsilylmethyl magnesium chloride, t-butyldimethylsilylmethyl magnesium chloride, bis(trimethylsilyl)methyl magnesium chloride, dimethylamido magnesium chloride, diethylamido magnesium chloride, diisopropylamido magnesium chloride, pyrrolidinido magnesium chloride, methyl magnesium bromide, ethyl magnesium bromide, propyl magnesium bromide, isopropyl magnesium bromide, t-butyl magnesium bromide, n-butyl magnesium bromide, pentyl magnesium bromide, hexyl magnesium bromide, allyl magnesium bromide, benzyl magnesium bromide, tolyl magnesium bromide, phenyl magnesium bromide, neopentyl magnesium bromide, methoxyethyl magnesium bromide, N,N-dimethylaminoethyl magnesium bromide, N,N-dimethylaminobenzyl magnesium bromide, N,N- dimethylaminomethylphenyl magnesium bromide, trimethylsilylmethyl magnesium bromide, t-butyldimethylsilylmethyl magnesium bromide, bis(trimethylsilyl)methyl magnesium bromide, dimethylamido magnesium bromide, diethylamido magnesium bromide, dϋsopropylamido magnesium bromide, pyrrolidinido magnesium bromide, methyl magnesium iodide, ethyl magnesium iodide, propyl magnesium iodide, isopropyl magnesium iodide, t-butyl magnesium iodide, n-butyl magnesium iodide, pentyl magnesium iodide, hexyl magnesium iodide, allyl magnesium iodide, benzyl magnesium iodide, tolyl magnesium iodide, phenyl magnesium iodide, neopentyl magnesium iodide, methoxyethyl magnesium iodide, N,N-dimethylaminoethyl magnesium iodide, N,N- dimethylaminobenzyl magnesium iodide, N,N-dimethylaminomethylphenyl magnesium iodide, trimethylsilylmethyl magnesium iodide, t-butyldimethylsilylmethyl magnesium iodide, bis(trimethylsilyl)methy] magnesium iodide, dimethylamido magnesium iodide, diethylamido magnesium iodide, diisopropylamido magnesium iodide, pyrrolidinido magnesium iodide, dimethyl magnesium, diethyl magnesium, dipropyl magnesium, diisopropyl magnesium, di- t-butyl magnesium, di-n-butyl magnesium, dipentyl magnesium, dihexyl magnesium, diallyl magnesium, dibenzyl magnesium, ditolyl magnesium, diphenyl magnesium, dineopentyl magnesium, dimethoxyethyl magnesium, bis(N,N-dimethylaminoethyl) magnesium, bis(N,N-dimethylaminobenzyl) magnesium, bis(N,N-dimethylaminomethylphenyl) magnesium, bis(trimethylsilylmethyl) magnesium, bis(t-butyldimethylsilylmethyl) magnesium, bis(bis(trimethylsilyl)methyl) magnesium, bis(dimethylamido) magnesium, bis(diethylamido) magnesium, bis(diisopropylamido) magnesium, bis(pyrrolidinido) magnesium
The catalyst composit .iions which are useful in the polymerization of ethylenically unsaturated addition polymeri izable monomers or in the copolymerization of ethylenically unsaturated addition polymer iizable monomers with at least one different type of ethylenically unsaturated add lition polymerizable monomer, preferably catalyst compositions which are useful in the polymerization of conjugated ethylenically unsaturated addition polymerizable monomers or in the copolymerization of conjugated ethylenically unsaturated addition polymerizable monomers with at least one different type of ethylenically unsaturated addition polymerizable monomer, according to the invention comprise
1) a combination of one or more of the above pyridine or phosphabenzene metal complexes and one or more activators (cocatalyst) and optionally a support or
2) the reaction product formed by contacting one or more of the above pyridine or phosphabenzene metal complexes with one or more activators and optionally a support or 3) the product formed by subjecting one or more of the above mentioned pyridine or phosphabenzene metal complexes and optionally a support to activating techniques.
The catalyst compositions are formed by rendering the metal complexes catalytically active in a process comprising 1 ) contacting one or more of the above pyridine or phosphabenzene metal complexes with one or more activators and optionally a support or 2) by subjecting one or more of the above pyridine or phosphabenzene metal complexes to activating techniques optionally in the presence of a support.
The process for the activation of the metal complexes with an activator or cocatalyst or by an activating technique can be performed during a separate reaction step optionally including an isolation of the activated compound or preferably can be performed in situ in the polymerization reactor or just prior to it in an aging reactor, for example. The activation is preferably performed in situ if, after the activation of the metal complex, separation and/or purification of the activated complex is not necessary. The process for the activation of the metal complexes is carried out in a suitable noninterfering solvent or reaction medium at a temperature from -78°C to 250°C, preferably from -5°C to 160°C, more preferably from 10°C to 110°C. Suitable reaction media for the formation of the catalyst compositions are aliphatic and aromatic hydrocarbons and halohydrocarbons. Examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, decane and mixtures thereof, cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; chlorinated-, fluorinated- or chlorofluorinated hydrocarbons such as chloroform, dichloromethane, chlorobenzene, dichlorobenzene, and perfluorinated C4.-10 alkanes; aromatic and hydrocarbyl-substituted aromatic compounds such as benzene, toluene, xylene, and styrene. Advantageously, the reaction medium used for the activation is the same reaction medium as is used in the subsequent polymerization, obviating the need to use a secondary solvent system. In addition to the reaction media mentioned above, this includes heptane or mineral oil fractions such as light or regular petrol, naphtha, kerosine or gas oil and other low-priced aliphatic hydrocarbons or mixtures thereof, as marketed by the petrochemical industry as solvent. An advantage of the invention is that the metal complex catalyst precursors according to the invention can be stored at room temperature or even at elevated temperatures such as, for example, but not limited to, 50°C, in the solid state for extended periods of time. In addition, solutions of the catalyst in suitable solvents also can be stored at room temperature at least for hours. This greatly increases the flexibility of production in an industrial plant. A further advantage of the invention is that the catalysts of the invention usually do not require a separate aging step (which is the case with all examples presented to demonstrate the invention) and if it is desirable to employ an optional aging step, it advantageously does not require long aging times. Therefore, it is possible to start the polymerization reaction just by adding the catalyst components in the desired order into the polymerization reactor. The polymerization can be started for example either by addition of the metal complex as the last component (see for example Runs 1 , 5 and 8) or by the addition of the conjugated diene as the last component. If an optional aging step is incorporated into the catalyst preparation/polymerization procedure, the aging time is short, such as less than 30 minutes, more preferably less than 10 minutes or even more preferably less than 5 minutes and can be performed in a broad temperature range, such as, but not limited to, 0°C to 150°C with high catalyst activity. The temperature ranges of the catalyst preparation, catalyst aging and polymerization are independently selected and are between -50°C and +250°C, preferably between -5 and +160 °C, more preferably between 10°C and 110°C. For example, the catalyst activity of polymerization Run 1 (polymerization temperature 70°C), amounts to 0.74 kg of polybutadiene per mmol neodymium per hour([kg {polymerj/mmol {Nd}[hr]]). It is beneficial that the polymerization reaction can be induced without substantial waiting period (delay) upon addition of the last catalyst component into the polymerization reactor.
Suitable activating cocatalysts for use herein include:
1) neutral Lewis acids, especially a) organo Group 13 compounds, especially i) C^_3o organoboron or organoaluminum compounds more especially
(hydrocarbyl)aluminum- or (hydrocarbyl)boron compounds, even more especially triaryl and trialkyl aluminum compounds, such as triethyl aluminum, triisobutyl aluminum, trioctylaluminum; alkyl aluminum hydrides, such as diisobutylaluminum hydride; alkylalkoxy aluminum compounds, such as dibutylethoxyaluminum; halogenated aluminum compounds, such as diethylaluminum chloride, ethylaluminum dichloride, diisobutylaluminum chloride, ethyl(octyl)aluminum chloride, ethylaluminum sesquichloride, ethyl(cyclohexyl)aluminum chloride, dicyclohexylaluminum chloride, dioctylaluminum chloride, and ii) organohalogenated (including perhalogenated) derivatives of organo Group 13 compounds, especially halogenated C-J_3Q organoboron or organoaluminum compounds, more especially halogenated (hydrocarbyl)aluminum- or (hydrocarbyl)boron compounds, more especially fluorinated or perfluorinated tri (aryl) boron or -aluminum compounds, such as tris(pentafluorophenyl)boron, tris(pentafluorophenyl)aluminum, tris(o- nonafluorobiphenyl)boron, tris(o-nonafluorobiphenyl)aluminum, tris[3,5- bis(trifluoromethyl)phenyl]boron, tris[3,5-bis(trifluoromethyl)phenyl]aluminum; or b) polymeric or oligomeric alumoxanes, especially methylalumoxane (MAO), triisobutyl aluminum-modified methylalumoxane (MMAO), or isobutylalumoxane; or 2) nonpolymeric, compatible, noncoordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium-, phosphonium-, oxonium-, carbonium-, silylium-, sulfonium-, or ferrocenium- salts of compatible, noncoordinating anions; and combinations of the foregoing activating compounds. The foregoing activating cocatalysts have been previously taught with respect to different metal complexes in the following references: U.S. Pat. Nos. 5,132,380, 5,153,157, 5,064,802, 5,321 ,106, 5,721,185, 5,350,723, and WO-97/04234, equivalent to U.S. Ser. No. 08/818,530, filed Mar. 14, 1997.
Suitable activators for use herein include hydrocarbyl sodium, hydrocarbyl lithium, hydrocarbyl zinc, hydrocarbyl magnesium halide, dihydrocarbyl magnesium, especially alkyl sodium, alkyl lithium, alkyl zinc, alkyl magnesium halide, dialkyl magnesium, such as n-octylsodium, butyllithium, neopentyllithium, methyllithium, ethyllithium, phenyllithium, diethylzinc, dibutylzinc, butylmagnesium chloride, ethylmagnesium chloride, octylmagnesium chloride, dibutylmagnesium, dioctylmagnesium, butyl(octyl)magnesium.
Especially desirable activating cocatalysts for use herein are combinations of neutral optional Lewis acids, especially the combination of a trialkyl aluminum compound having from 1 to 4 carbons in each alkyl group with one or more G-t_3Q hydrocarbyl- substituted Group 13 Lewis acid compounds, especially halogenated tri(hydrocarbyl)boron or -aluminum compounds having from 1 to 20 carbons in each hydrocarbyl group, especially tris(pentafluorophenyl)borane or tris(pentafluorophenyl)alumane, further combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane ortris(pentafluorophenyl)alumane, with a polymeric or oligomeric alumoxane. A benefit according to the present invention is the discovery that the most efficient catalyst activation using such a combination of tris(pentafluorophenyl)borane/ alumoxane mixture occurs at reduced levels of alumoxane. Preferred molar ratios of the metal complex:tris(pentafluorophenylborane:alumoxane are from 1 :1 :1 to 1 :5:5, more preferably from 1 :1 :1.5 to 1 :5:3. The surprising efficient use of lower levels of alumoxane with the present invention allows for the production of diene polymers with high catalytic efficiencies using less of the expensive alumoxane activator. Additionally, polymers with lower levels of aluminum residue, and hence greater clarity, are obtained.
Suitable ion-forming compounds useful as activators in one embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton, and a compatible, noncoordinating or poorly coordinating anion. As used herein, the term "noncoordinating" means an anion or substance which either does not coordinate to the metal containing precursor complex and the catalytic derivative derived therefrom, or which is only weakly coordinated to such complexes thereby remaining sufficiently labile to be displaced by a Lewis base such as olefin monomer in a manner such that the polymerization may proceed. A noncoordinating anion specifically refers to an anion which when functioning as a charge-balancing anion in a cationic metal complex does not transfer an anionic substituent or fragment thereof to said cation thereby forming neutral complexes. "Compatible anions" are anions which are not degraded to neutrality when the initially formed complex decomposes and are noninterfering with desired subsequent polymerization or other uses of the complex.
Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core which anion is capable of balancing the charge of the active catalyst species (the metal cation) which may be formed when the two components are combined. Also, said anion should be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nitriles. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon. Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially.
Preferably such activators may be represented by the following general formula: (L*-H)+ dAd- wherein:
L" is a neutral Lewis base;
(L"-H)+ is a Bronsted acid;
A^" is a noncoordinating, compatible anion having a charge of d-, and d is an integer from I to 3.
More preferably A0"- corresponds to the formula:
[M*Q4]-; wherein:
M* is boron or aluminum in the +3 formal oxidation state; and Q independently each occurrence is selected from hydride, dialkylamido, halide, hydrocarbyl, halohydrocarbyl, halocarbyl, hydrocarbyloxide, hydrocarbyloxy substituted- hydrocarbyl, organometal substituted- hydrocarbyl, organometalloid substituted- hydrocarbyl, halohydrocarbyloxy, halohydrocarbyloxy substituted hydrocarbyl, halocarbyl- substituted hydrocarbyl, and halo- substituted silylhydrocarbyl radicals (including perhalogenated hydrocarbyl-, perhalogenated hydrocarbyloxy- and perhalogenated silythydrocarbyl radicals), said Q having up to 20 carbon atoms with the proviso that in not more than one occurrence is Q halide. Examples of suitable hydrocarbyloxide Q groups are disclosed in U.S. Pat. No. 5,296,433.
In a more preferred embodiment, d is one, that is, the counter ion has a single negative charge and is A". Activating cocatalysts comprising boron which are particularly useful in the preparation of catalysts of this invention may be represented by the following general formula: (L*-H)+ (BQ4)-; wherein:
(L*-H)+ is as previously defined;
B is boron in a formal oxidation state of 3; and
Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy-, or fluorinated silylhydrocarbyl- group of up to 20 nonhydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl. Most preferably, Q is each occurrence a fluorinated aryl group, especially, a pentafluorophenyl or nonafluorobiphenyl group. Preferred BQ4" anions are methyltris(pentafluorophenyl)borate, tetrakis(pentafluorophenyl)borate or tetrakis(nonafluorobiphenyl)borate.
Illustrative, but not limiting, examples of boron compounds which may be used as an activating cocatalyst in the preparation of the improved catalysts of this invention are trisubstituted ammonium salts such as: trimethylammonium tetraphenylborate, tri(n- butyl)ammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n- butyl)ammonium tetraphenylborate, methyltetradecyloctadecylammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N,-2,4,6-pentamethylanilinium) tetraphenylborate, N,N-dimethyl anilinium bis(7,8-dicarbundecaborate) cobaltate (III), trimethylammonium tetrakis(pentafluorophenyl)borate, methy!di(tetradecyl)ammonium tetrakis(pentafluorophenyl) borate, methyldi(octadecyl)ammonium tetrakis(pentafluorophenyl) borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyi)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N,2,4,6-pentamethylanilinium) tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(2,3,4,6- tetrafluorophenyl)borate, triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate, dimethyl(t-butyl) ammonium tetrakis(2,3,4,6- tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl) borate, N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl) borate, and N,N,2,4,6- pentamethylanilinium) tetrakis-(2,3,4,6- tetrafluorophenyl)borate; dialkyl ammonium salts such as: di(octadecyl)ammonium tetrakis(pentafluorophenyl)borate, di(tetradecyl)ammonium tetrakis(pentafluorophenyl)borate, and dicyclohexylammonium tetrakis(pentafluorophenyl)borate; trisubstituted phosphonium salts such as: triphenylphosphonium tetrakis(pentafluorophenyl)borate, methyldi(octadecyl)phosphonium tetrakis(pentafluorophenyl) borate, and tris(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.
Preferred are tetrakis(pentafluorophenyl)borate salts of long chain alkyl mono- di- and trisubstituted ammonium complexes, especially C14-C20 alkyl ammonium complexes, especially methyldi(octadecyl) ammonium tetrakis (pentafluorophenyl)borate and methyldi(tetradecyl)ammonium tetrakis(pentafluorophenyl)borate, or mixtures including the same. Such mixtures include protonated ammonium cations derived from amines comprising two G14, C-jg or G^g alkyl groups and one methyl group. Such amines are available from Witco Corp., under the trade name Kemamine™ T9701 , and from Akzo- Nobel under the trade name Armeen™ M2HT.
Examples of the most highly preferred catalyst activators herein include the foregoing trihydrocarbylammonium-, especially, methylbis(tetradecyl)ammonium- or methylbis(octadecyl)ammonium- salts of: bis(tris(pentafluorophenyl)borane)imidazolide, bis(tris(pentafluorophenyl)borane)-2- undecylimidazolide, bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolide, bis(tris(pentafluorophenyl )borane)-4,5-bis(undecyl)imidazolide, bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide, bis(tri s(pentafluorophenyl )borane)imidazolinide, bis(tri s(pentafluorophenyl )borane)-2-undecylimidazolinide, bis(tri s(pentafluorophenyl )borane)-2-heptadecylimidazolinide, bis(tr: s(pentafluoropheny' )borane)-4,5-bis(undecyl)imidazolinide, bis(tri s(pentafluoropheny )borane)-4,5-bis(heptadecyl)imidazolinide, bis(tri s(pentafluoropheny! )borane)-5,6-dimethylbenzimidazolide, bis(tri s(pentafluoropheny )borane)-5,6-bis(undecyl)benzimidazolide, bis(tri s(pentafluoropheny )alumane)imidazolide, bis(tri s(pentafluoropheny )alumane)-2-undecylimidazolide, bis(tri s(pentafluoropheny )alumane)-2-heptadecylimidazolide, bis(tri s(pentafluoropheny )alumane)-4,5-bis(undecyl)imidazolide, bis(tri s(pentafluoropheny )alumane)-4,5-bis(heptadecyl)imidazolide, bis(tris(pentafluorophenyl)alumane)imidazolinide, bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide, bis(tris(pentafluorophenyl)aiumane)-2-heptadecylimidazolinide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolinide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolinide, bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazolide, and bis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide. The foregoing activating cocatalysts have been previously taught with respect to different metal complexes in the following reference: EP 1 560 752 A1.
Another suitable ammonium salt, especially for use in heterogeneous catalyst systems, is formed upon reaction of an organometal compound, especially a tri(C-|_6 alkyl)aluminum compound with an ammonium salt of a hydroxyaryltris(fluoroaryl)borate compound. The resulting compound is an organometaloxyaryltris(fluoroaryl)borate compound which is generally insoluble in aliphatic liquids. Examples of suitable compounds include the reaction product of atri(C^_6 alkyl)aluminum compound with the ammonium salt of hydroxyaryltris(aryl)borate. Suitable hydroxyaryltris(aryl)borates include the ammonium salts, especially the foregoing long chain alkyl ammonium salts of: (4-dimethylaluminumoxyphenyl)tris(pentafluorophenyl) borate, (4-dimethylaluminumoxy- 3,5-di(trimethylsilyl)phenyl) tris(pentafluorophenyl)borate, (4- dimethylaluminumoxy-3,5- di(t-butyl)phenyl) tris(pentafluorophenyl)borate, (4-dimethylaluminumoxybenzyl) tris(pentafluorophenyl) borate, (4-dimethylaluminumoxy-3-methylphenyl) tris(pentafluorophenyl)borate, (4-dimethylaluminumoxy-tetrafluorophenyl) tris(pentafluorophenyl)borate, (5-dimethylaluminumoxy-2-naphthyl) tris(pentafluorophenyl)borate, 4-(4-dimethylaluminumoxyphenyl) phenyltris(pentafluorophenyl)borate, 4-(2-(4-(dimethylaluminumoxyphenyl)propane-2- yl)phenyloxy) tris(pentafluorophenyl)borate, (4 -diethylaluminumoxyphenyl) tris(pentafluorophenyl) borate, (4-diethylaluminumoxy-3,5-di(trimethylsilyl)phenyl) tris(pentafluorophenyl)borate, (4-diethylaluminumoxy-3,5-di(t-butyl)phenyl) tris(pentafluorophenyl)borate, (4-diethylaluminumoxybenzyl) tris(pentafluorophenyl)borate, (4-diethylaluminumoxy-3-methylphenyl) tris(pentafluorophenyl)borate, (4 - diethylaluminumoxy-tetrafluorophenyl) tris(pentafluorophenyl)borate, (5- diethylaluminumoxy-2-naphthyl) tris(pentafluorophenyl) borate, 4-(4- diethylaluminumoxyphenyl)phenyl tris(pentafluorophenyl)borate, 4-(2-(4- (diethylaluminumoxyphenyl)propane-2-yl)phenyloxy) tris(pentafluorophenyl)borate, (4- diisopropylaluminumoxyphenyl) tris(pentafluorophenyl)borate, (4-diisopropylaluminumoxy- 3,5-di(trimethylsilyl)phenyl)tris(pentafluorophenyl)borate, (4-diisopropylaluminumoxy-3,5- di(t-butyl)phenyl) tris(pentafluorophenyl)borate, (4-diisopropylaluminumoxybenzyl) tris(pentafluorophenyl)borate, (4-diisopropylaluminumoxy-3-methylphenyl) tris(pentafluorophenyl)borate, (4- diisopropylaluminumoxy-tetrafluorophenyl) tris(pentafluorophenyl)borate, (5-diisopropylaluminumoxy-2-naphthyl) tris(pentafluorophenyl)borate, 4-(4-diisopropylaluminumoxyphenyl)phenyl tris(pentafluorophenyl)borate, and 4-(2-(4-(diisopropylaluminumoxyphenyl)propane-2- yl)phenyloxy) tris(pentafluorophenyl)borate.
Especially preferred ammonium compounds are methyldi(tetradecyl)ammonium (4- diethylaluminumoxyphenyl) tris(pentafluorophenyl)borate, methyldi(hexadecyl)ammonium (4-diethylaluminumoxyphenyl) tris(pentafluorophenyl)borate, methyldi(octadecyl)ammonium (4-diethylaluminumoxyphenyl) tris(pentafluorophenyl) borate, and mixtures thereof. The foregoing complexes are disclosed in U.S. Pat. Nos. 5,834,393 and 5,783,512.
Another suitable ion-forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula:
(Oxe+)c)(Ad-)e, wherein
Oxe+ is a cationic oxidizing agent having a charge of e+; d is an integer from 1 to 3; e is an integer from 1 to 3; and
Ad- is as previously defined.
Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Pb+2 or Ag+. Preferred embodiments of A^- are those anions previously defined with respect to the Bronsted acid containing activating cocatalysts, especially tetrakis(pentafluorophenyl)borate.
Another suitable ion-forming, activating cocatalyst comprises a compound which is a salt of a carbenium ion and a noncoordinating, compatible anion represented by the formula
@+A" wherein:
@+ is a C-j-20 carbenium ion; and
A" is a noncoordinating, compatible anion having a charge of -1. A preferred carbenium ion is the trityl cation, especially triphenylmethylium.
Preferred carbenium salt activating cocatalysts are triphenylmethylium tetrakis(pentafluorophenyl)borate, triphenylmethylium tetrakis(nonafluorobiphenyl)borate, tritolylmethylium tetrakis(pentafluorophenyl)borate and ether substituted adducts thereof.
A further suitable ion-forming, activating cocatalyst comprises a compound which is a salt of a silylium ion and a noncoordinating, compatible anion represented by the formula R3Si+A" wherein:
R is C-i-10 hydrocarbyl; and
A" is as previously defined.
Preferred silylium salt activating cocatalysts are trimethylsilylium tetrakis(pentafluorophenyl)borate, trimethylsilylium tetrakis(nonafluorobiphenyl)borate, triethylsilylium tetrakis(pentafluorophenyl)borate and other substituted adducts thereof. Silylium salts have been previously generically disclosed in J. Chem Soc. Chem. Comm., 1993, 383-384, as well as Lambert, J. B., et al., Organometallics, 1994, 13, 2430-2443. The use of the above silylium salts as activating cocatalysts for addition polymerization catalysts is claimed in U.S. Pat. No. 5,625,087.
Certain complexes of alcohols, mercaptans, silanols, and oximes with tris(pentafluorophenyl)borane are also effective catalyst activators and may be used according to the present invention. Such activators are disclosed in U.S. Pat. No. 5,296,433.
The activating cocatalysts may also be used in combination. An especially preferred combination is a mixture of a tri(hydrocarbyl)aluminum or tri(hydrocarbyl)borane compound having from 1 to 4 carbons in each hydrocarbyl group with an oligomeric or polymeric alumoxane compound.
The molar ratio of catalyst/activator employed preferably ranges from 1 :10,000 to 10:1 , more preferably from 1 :5000 to 10:1 , most preferably from 1 :2500 to 1 :1. Alumoxane, when used by itself as an activating cocatalyst, is preferably employed in large molar ratio, generally at least 50 times the quantity of metal complex on a molar basis. Tris(pentafluorophenyl)borane, where used as an activating cocatalyst, is preferably employed in a molar ratio to the metal complex of from 0.5:1 to 10:1 , more preferably from 1 :1 to 6:1 most preferably from 1 :1 to 5:1. The remaining activating cocatalysts are generally preferably employed in approximately equimolar quantity with the metal complex.
If the above-mentioned ion-forming compound comprising a compatible non- coordinating or poorly coordinating anion is used as the activator, it is preferable for the metal complex according to the invention to be alkylated (that is, one of the X groups of the metal complex is an alkyl or aryl group). Activators comprising boron are preferred. Most preferred are activators comprising tetrakis(pentafluorophenyl)borate, tris(pentafluorophenyl)borane, tris(o-nonafluorobiphenyl)borane, tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, tris(pentafluorophenyl)alumane, tris(o- nonafluorobiphenyl)alumane.
The molar ratio of the activator relative to the metal center in the metal complex in the case an organometallic compound is selected as the activator, usually is in a range of from 1 :10 to 10,000:1 , more preferably from 1 :10 to 5000:1 and most preferably in a range of from 1 :1 to 2,500:1. If a compound containing or yielding a non-coordinating or poorly coordinating anion is selected as activator, the molar ratio usually is in a range of from 1 :100 to 1 ,000:1 , and preferably is in range of from 1 :2 to 250:1.
Especially desirable activating cocatalysts for use herein are combinations of neutral optional Lewis acids, especially the combination of a trialkyl aluminum compound having from 1 to 4 carbons in each alkyl group with one or more C-j_3rj hydrocarbyl-substituted
Group 13 Lewis acid compounds, especially halogenated tetrakis(hydrocarbyl)boron or- aluminum compounds having from 1 to 20 carbons in each hydrocarbyl group, especially tetrakis(pentafluorophenyl)borate, tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, further combinations of a single neutral Lewis acid, especially tetrakis(pentafluorophenyl)borate or tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, with a polymeric or oligomeric alumoxane. A benefit according to the present invention is the discovery that the most efficient catalyst activation using such a combination of tetrakis(pentafluorophenyl)borane/ alumoxane mixture occurs at reduced levels of alumoxane.
Preferred molar ratios of the metal complex : tetrakis(pentafluorophenylborane : alumoxane from 1 :1 :1 to 1 :5:1.000, more preferably from 1 :1 :1.5 to 1 :5:500. The surprising efficient use of lower levels of alumoxane with the present invention allows for the production of diene polymers with high catalytic efficiencies using less of the expensive alumoxane activator. Additionally, polymers with lower levels of aluminum residue, and hence greater clarity, are obtained. Preferred molar ratios of the metal complex:tetrakis(pentafluorophenylborane:neutral optional Lewis acids especially trialkyl aluminum or dialkyl aluminum hydride compounds are from 1 :1 :10 to 1 :10:1000, more preferably from 1 :1 :20 to 1 :5:500. Also in this case are polymers with lower levels of aluminum residue, and hence greater clarity, obtained.
Especially desirable activating cocatalysts for use herein are neutral optional Lewis acids, especially the combination of a trihydrocarbonyl aluminum compound, more especially trialkyl aluminum compound having from 1 to 5 carbons in each alkyl group with neutral Lewis acids containing at least one metal halide bond, especially perhalogenated metals or transition metals, especially boron trifluoride, boron trichloride, boron tribromide, aluminum trifluoride, aluminum trichloride, aluminum tribromide, scandium trifluoride, titanium tetrafluoride, further combinations of a single neutral Lewis acid, especially boron trifluoride, boron trichloride, boron tribromide, aluminum trifluoride, aluminum trichloride, aluminum tribromide, scandium trifluoride, titanium tetrafluoride, with a polymeric or oligomeric alumoxane in a molar ratio of the metal complex : metal fluoride : alumoxane from 1 :1 :1 to 1 :5:10.000, more preferably from 1 :1 :10 to 1 :5:5.000; and further combinations of a single neutral Lewis acid, especially boron trifluoride, boron trichloride, boron tribromide, aluminum trifluoride, aluminum trichloride, aluminum tribromide, scandium trifluoride, titanium tetrafluoride, with trialkyl aluminum or dialkyl aluminum hydride compounds in a molar ratio of the metal complex : neutral Lewis acid : trialkyl aluminum or dialkyl aluminum hydride compound from 1 :1 :10 to 1 :10:1000, more preferably from 1 :1 :20 to 1 :5:500.
In addition to the metal complex according to the invention and the activator, the catalyst composition can also contain a small amount of another organometallic compound that is used as a so-called scavenger agent. The scavenger agent is added to react with or passivate activity-decreasing impurities in the reaction mixture. It may be added at any time, but normally is added to the reaction mixture before addition of the metal complex and the activator (cocatalyst). Usually organoaluminum compounds are used as scavenger agents. Examples of suitable scavengers are trioctylaluminum, triethylaluminum, diethylaluminum chloride, tri-isobutylaluminum, methylalumoxane or MMAO. The metal complex as well as the activator can be present in the catalyst composition as a single component or as a mixture of several components. For instance, a mixture may be desired where there is a need to influence the molecular properties of the polymer, such as molecular weight distribution.
The reaction system optionally contains a solid material, which serves as carrier or support material for the activator component and/or the metal complex. The carrier material can be chosen from one of the following materials: clay, silica, charcoal (activated carbon), graphite, expanded clay, expanded graphite, carbon black, layered silicates, and alumina. Clays and layered silicates include, but are not limited to, magadiite, montmorillonite, hectorite, sepiolite, attapulgite, smectite, and laponite. Supported catalyst systems of the invention may be prepared by several methods. The metal complex and optionally the activator can be combined before the addition of the support material. The mixture may be prepared in conventional solution in a normally liquid alkane or aromatic solvent. The solvent is preferably also suitable for use as a polymerization diluent for the liquid phase polymerization of an olefin monomer. Alternatively, the activator can be placed on the support material followed by the addition of the metal complex or conversely, the metal complex may be applied to the support material followed by the addition of the activator. The supported catalyst maybe prepolymerized. In addition, third components can be added during any stage of the preparation of the supported catalyst. Third components can be defined as compounds containing Lewis acidic or basic functionalities exemplified by, but not limited to, compounds such as N,N-dimethylaniline, tetraethoxysilane, phenyltriethoxysilane, and bis-tert-butylhydroxytoluene (BHT). The catalyst can be supported onto the carrier material using techniques such as the solid-phase immobilization (SPI) technique described by H.C.L. Abbenhuis in Angew. Chem. Int. Ed. 37 (1998) 356-58 and by M. Buisio et al., in Microporous Mater., 5 (1995) 211 and by J.S. Beck et al., in J. Am. Chem. Soc, 114 (1992) 10834, as well as the pore volume impregnation (PVI) technique (see WO 97/24344). The isolation of the impregnated carrier can be done by filtration or by removing the volatile material present (that is, solvent) under reduced pressure or by heating.
The support, if present, is preferably employed in an amount to provide a weight ratio of catalyst (based on metal) :support from 1 :100,000 to 1 :10, more preferably from 1 :50,000 to 1 :20, and most preferably from 1 :10,000 to 1 :30. Suitable gas phase reactions may utilize condensation of the monomer or monomers employed in the reaction, or of an inert diluent to remove heat from the reactor.
In the polymerization process the catalyst is used in a catalytically effective amount, that is, any amount that successfully results in the formation of polymer. Such amounts may be readily determined by routine experimentation by the worker skilled in the art, but typically the molar ratio of catalyst:polymerizable compounds employed is from 10"12;1 to
10"1 :1, more preferably from 10-12:1 to 10~3:1.
The catalysts may be used to homopolymerize or copolymerize ethylenically unsaturated addition polymerizable monomers having from 2 to 100,000 carbon atoms either alone for homopolymers or in combination with a different type of ethylenically unsaturated addition polymerizable monomer for copolymers. Preferred monomers include α-olefins selected from ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1- pentene,1-octene, styrene, alpha methylstyrene, divinyl benzene, acrylonitrile, acrylic acid ester, methyl meth acrylate, ethylmethacrylate and n-butylmethacrylate and conjugated dienes chosen from the group comprising internal conjugated olefins, cyclic conjugated olefins and non-cyclic conjugated olefins. Preferred conjugated dienes are 1 ,3-butadiene, isoprene (2-methyl-1 ,3-butadiene), 2,3-dimethyl-1 ,3-butadiene, 1 ,3-pentadiene, 2,4- hexadiene, 1 ,3-hexadiene, 1 ,4-hexadiene, 1 ,3-heptadiene, 1 ,3-octadiene, 2-methyl-2,4- pentadiene, cyclopentadiene, 2,4-hexadiene, 1 ,3-cyclooctadiene. More preferably butadiene, isoprene and/or cyclopentadiene is used as conjugated diene and ethylene, propene and styrene is used as α-olefin.
Especially desirably formed polymers using the catalyst in the polymerization process of the invention are homo-, co- and terpolymers of conjugated ethylenically unsaturated addition polymerizable monomers, especially conjugated dienes, especially butadiene or isoprene, and random or block copolymers of at least one conjugated diene, especially butadiene, with at least one different type of conjugated diene, especially isoprene, or with an α-olefin, especially ethylene, propene and styrene. Especially preferred are homopolymerization of butadiene or isoprene and random or block copolymerization, optionally terpolymerization, of at least one conjugated diene, especially butadiene with at least one different type of conjugated diene, especially isoprene, or with at least one α-olefin, especially styrene. Highly preferred homopolymers comprise butadiene and highly preferred copolymers comprise conjugated dienes chosen from butadiene or isoprene or comprise butadiene and styrene.
In general, the homopolymerization of the conjugated diene or the copolymerization of one type the conjugated diene monomers with a second type of monomer, an α-olefin or a conjugated diene monomer may be accomplished at conditions well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, such as temperatures from -50 - 250° C. The polymerization or copolymerization can be effected at atmospheric pressure, at sub-atmospheric pressure, or at elevated pressures of up to, or even higher than 500 MPa, continuously or discontinuously. Preferably, the homo- or copolymerization is performed at pressures between 0.01 and 500 MPa, most preferably between 0.01 and 10 MPa, in particular between 0.1-2 MPa. Higher pressures can be applied. In such a high- pressure process the metal complex according to the present invention can also be used with good results. Slurry and solution polymerizations normally take place at lower pressures, preferably below 10 MPa. The polymerization can be carried out in the gas phase as well as in a liquid reaction medium. The polymerization is generally conducted under batch, continuous or semicontinuous polymerization conditions. The polymerization process can be conducted as a gas phase polymerization (for example, in a fluidized bed or stirred bed reactor), as a solution polymerization, wherein the homopolymer or copolymer formed is substantially soluble in the reaction mixture, a suspension/slurry polymerization, wherein the polymer formed is substantially insoluble in the reaction medium, as a solid phase powder polymerization or as a so-called bulk polymerization process, in which an excess of monomer to be polymerized is used as the reaction medium.
The catalysts may also be utilized in combination with at least one additional homogeneous or heterogeneous polymerization catalyst in the same or in separate reactors connected in series or in parallel to prepare polymer blends having desirable properties. An example of such a process is disclosed in WO 94/00500, equivalent to U.S. Ser. No. 07/904,770, as well as U.S. Pat. No. 5,844,045.
The quantity of catalyst to be used generally is such that its concentration in the solvent or dispersion agent amounts to 10"8 -10"3 mol/L, preferably 10"7 - 10"4 mol/L.
Suitable solvents, dispersion agents or diluents for the polymerization or copolymerization process via a solution or slurry process are typically noninterfering, inert liquids and can be chosen from the group comprising, but not limited to, straight and branched-chain hydrocarbons such as propane, butane, isobutane, pentane, hexane, heptane, octane, cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, and xylene and isomers of the foregoing and mixtures thereof as well as pentamethyl heptane or mineral oil fractions such as light or regular petrol, naphtha, kerosine or gas oil. Fluorinated hydrocarbon fluids such as perfluorinated C4-1 Q alkanes are also suitable. Further suitable solvents include liquid olefins which may act as comonomers in the polymerization process including cyclopentadiene, butadiene isoprene, butene, pentene, hexene and cyclooctadiene, including isomers of the foregoing. Mixtures of the foregoing are also suitable. Aromatic hydrocarbons, for instance benzene and toluene, can also be used. Out of cost considerations it is preferred therefore to use low-priced aliphatic hydrocarbons or mixtures thereof in polymerization processes on a technical scale as marketed by the petrochemical industry as solvent. If an aliphatic hydrocarbon is used as solvent, the solvent may optionally contain minor quantities of aromatic hydrocarbon, for instance toluene. Thus, if for instance methyl aluminoxane (MAO) is used as activator, toluene can be used as solvent for the MAO in order to supply the MAO in dissolved form to the polymerization reactor. Drying or purification of the solvents is desirable if such solvents are used; this can be done without problems by known methods by one skilled in the art.
Preferably the polymerization or copolymerization is conducted under batch, continuous or semicontinous solution or bulk polymerization conditions in hydrocarbons such as propylene, propane, butane, butene, pentane, hexane, heptane, cyclohexane, benzene, toluene, including isomers of the foregoing and mixtures thereof at temperatures from -10°C and 200°C, preferably from 0° to 130°C. The polymerization may be conducted n one or more continuous stirred reactors or fluidized bed, gas phase reactors, connected n series or parallel. Monomer and/or solvent may be added to the reactor as is well known n the art. The catalyst may also be supported and/or prepolymerized prior to use. A continuous process is preferred, in which event advantageously the mixture of reaction components of catalyst, solvent and dienes is substantially supplied continuously or at frequent intervals into the reactor system and is continuously monitored so as to ensure an efficient reaction and the desired product which is continuously removed therefrom. For example, it is well known that many supported coordination catalysts and catalyst systems for polymerization processes are highly sensitive, in varying degrees, to catalyst poisons such as water, oxygen, carbon oxides, acetylenic compounds and sulfur compounds. Introduction of such compounds may result in reactor upset and production of off-grade product. Typically, computer control systems may be used to maintain process variables within acceptable limits, often by measuring variables such as temperature, viscosity, molecular weight, exotherm, flow rates or catalyst productivity. If the polymerization process is carried out under suspension or gas phase polymerization conditions, the temperatures typically are below 150°C.
Utilizing the catalysts of the present invention, high molecular weight polymers can be readily attained by use of the present catalysts, even at elevated reactor temperatures. This result is highly desirable because the molecular weight of diene polymers can be readily reduced by the use of hydrogen, di- and trihydrocarbylaluminum compounds (such as but not limited to triisopropylaluminum, diisopropylaluminum hydride, triethylaluminum, trioctylaluminum, diethylaluminum chloride and diisopropylaluminum chloride), 1 ,5- cyclooctadiene or similar chain transfer agent. In addition high molecular weights can be reduced using aromatic monomers such as but not limited to styrene. In addition, productivity is increased due to improved polymer solubility, decreased solution viscosity, and a higher polymer concentration.
Utilizing the catalysts of the present invention, homopolymers and copolymers having different comonomer incorporation may be readily prepared.
The polymers of the invention such as but not limited to polybutadiene, polyisoprene, polystyrene, polyethylene and polypropylene preferably polybutadiene, polyisoprene and polystyrene, even more preferably polybutadiene and polyisoprene can be prepared as completely amorphous polymers or as polymers comprising more or less expanded crystalline areas. For example but not limited to it the polybutadiene prepared with metal complex 2 and modified methylalumoxane had much more expanded crystalline areas when nonpolar solvents such as cyclohexane were used as polymerization solvents. The use of more polar solvents such as toluene resulted in a much more amorphous polybutadiene.
Preferably the percentage of one type of monomers in the copolymer, preferably of one type of conjugated diene is higher than 0 and less than 100 percent. The polybutadiene content of the polybutadiene homopolymer or of the butadiene copolymers preferably comprises high cis-1 ,4-polybutadiene.
The polymer resulting from the polymerization or copolymerization can be worked up by a method known per se. In general the catalyst is deactivated at some point during the processing of the polymer in a manner known per se, for example, by means of water or an alcohol. Removal of the catalyst residues can mostly be omitted because the quantity of catalyst in the polymer or copolymer, in particular the content of halogen and metal, is very low owing to the use of the catalyst system according to the invention. If desired, however, the level of catalyst residues in the polymer can be reduced in a known manner, for example, by washing. The deactivation step can be followed by a stripping step (removal of organic solvent(s) from the copolymer). The polymerization or copolymerization can also be performed in several steps, in series as well as in parallel. If required, the catalyst composition, temperature, hydrogen concentration, pressure, residence time, etc., may be varied from step to step. In this way it is also possible to obtain products with a wide property distribution, for example, molecular weight distribution. By using the catalysts of the present invention for the polymerization of olefins, polymers may be obtained with molecular weights between 50,000 and 1 ,500,000 g/mol preferably between 100,000 and 1 ,000,000 g/mol and polydispersities (Mw/Mn) of 1.0 - 50, preferably polydispersities of 1.0 - 20.
The polymerization or copolymerization of conjugated dienes by an addition polymerization mechanism results in the formation of residual olefinic vinyl, E (entgegen) and Z (zusammen) double bonds. In the case of butadiene, these are designated vinyl (or 1 ,2-, or 1 ,2-polybutadiene ), trans (or trans-1 ,4- or trans-1 ,4-polybutadiene ) and cis (or cis- 1 ,4- or cis-1 ,4-polybutadiene ) double bonds. An advantage of the invention is the possibility to prepare high cis content polybutadiene polymers or copolymers. Preferably the fraction of the residual olefinic double bonds in the polymer or copolymer resulting from the polymerization of the conjugated dienes that are Z or cis units ranges from 50 — 100 percent, even more preferably from 60 to 100 percent, yet still more preferably from 85 — 99 percent and yet still more preferably from 90 -99 percent of the total amount of residual olefinic double bonds resulting from the polymerization of the conjugated dienes. Advantageously the conjugated diene polymers having high cis-1 ,4- content also have a vinyl content (1 ,2-polybutadiene and/or 1 ,2- and 3,4- polyisoprene) between 0 and 30 percent, preferably between 0 and 20 percent, more preferably the 1 ,2-polybutadiene content of the polybutadiene fraction of the homo- or copolymer is between 0 and 10 percent, even more preferably between 0 and 5 percent. Advantageously according to the invention the cis content of polybutadiene can be very high such as for example but not limited to 97.0 percent (see Runs 1 , 4 and 6).
Formed copolymerization products of one type of conjugated diene monomer with a second ethylenically unsaturated addition polymerizable monomer preferably can be chosen to be a random or block copolymer, even more preferably the copolymer comprises butadiene and styrene or butadiene and isoprene.
Such polymers of the invention are well-suited for use in the modification of plastics, particularly polystyrene in the preparation of HIPS (high impact polystyrene).
The polymerization process of the invention allows the production of tailor-made copolymers. In particular, the choice of the activator and of the metal complex and also the manner of preparation of catalyst, as well as the solvent used for the polymerization reaction (nonaromatic or aromatic), the concentration of the diene monomers and the polymerization temperature enable an adjustment of the molecular weight of the resulting polymer, the molecular weight distribution and the polymerization activity of a given catalyst. Non-limiting examples are the following:
In one example, the average molecular weight (Mw) was 910,000 g/mol when the neodymium complex 4 was combined with modified methylalumoxane (MMAO) (Run 5) while a much lower average molecular weight of Mw = 275.000 g/mol resulted when metal complex 6 was combined with modified methylalumoxane (MMAO) (Run 7).
The molecular weight distribution can vary over a wide range; in one example it was 2.31 , typical for a single site polymerization process (Run 2) while in another example it was 4.9 (see Run 5).
Advantageously, the cis content is generally very high regardless of the polarity of the polymerization solvent. For example the cis content of polybutadiene amounted to 97.0 percent when complex 2 was combined with modified methylalumoxane (MMAO) in cyclohexane (see Run 1) and the cis content amounted to 95 percent when complex 2 was combined with modified methylalumoxane (MMAO) in toluene (see Run 2).
Another advantage which was already mentioned before is the possibility to avoid catalyst aging (see above).
Another advantage of the invention for diene polymerization reactions is that the manner of preparation of the catalyst (for example, order of addition of the catalyst components and catalyst aging) can favorably influence the polymer properties such as the polymer microstructure and the molecular weight.
The polymers of the invention may be used in the production of many useful shapes, molded parts, films, foams, golf balls, tires, hoses, conveyor and other belts, gaskets, seals, shoes and in the modification of plastics, such as the manufacture of high impact polystyrene or impact-modified polypropylene.
Examples:
It is understood that the present invention is operable in the absence of any component which has not been specifically disclosed. The following examples are provided in order to further illustrate the invention and are not to be constructed as limiting. Unless stated to the contrary, all parts and percentages are expressed on a weight basis. The term "overnight", if used, refers to a time of approximately 16-18 hours, "room temperature", if used, refers to a temperature of 20-25°C.
All tests in which organometallic compounds were involved were carried out in an inert nitrogen atmosphere, using standard Schlenk equipment and techniques or in a glovebox. In the following THF' stands for tetrahydrofuran, 'Me' stands for 'methyl', 'MMAO' or 'MMAO-3a' stands for 'modified methyl alumoxane' purchased from AKZO Nobel. Pressures mentioned are absolute pressures. The polymerizations were performed under exclusion of moisture and oxygen in a nitrogen atmosphere. The products were characterized by means of SEC (size exclusion chromatography), elemental analysis, NMR (Avance 400 device (1H=400 MHz; 13CH00 MHz) of Bruker Analytic GmbH) and IR (IFS 66 FT-IR spectrometer of Bruker Optics GmbH). The IR samples were prepared using CS2 as swelling agent and using a two or fourfold dissolution. DSC (differential scanning calorimetry) was measured using a DSC 2920 of TA Instruments. Mn and Mw are molecular weights and were determined by universal calibration of SEC. The ratio between the 1 ,4-cis-, 1 ,4-trans- and 1 ,2-polydiene content of the butadiene or isoprene polymers was determined by IR and 13C NMR-spectroscopy. The glass transition temperatures of the polymers were determined by DSC determination. 1. Synthesis of the transition metal complexes
Figure imgf000054_0001
1.1. Preparation of compound 1a.
10 mmol of 2,6-diisopropylaniline were refluxed with 5 mmol of diacetylpyridine in the presence of a few drops of CF3COOH in methanol for 12 hours. Compound 1 precipitated out and was collected by filtration and washed afterwards with methanol and diethylether.
4.5 mmol (2.1 g) of compound 1 (90 percent yield) were recovered.
1.2.
Figure imgf000054_0002
The neutral ligand CssH^Ns (2.0 g, 4.15 mmol) was stirred with LiCH2Si(CH3)3 (0.85 g, 9.03 mmol) in THF (40 mL) at r.t. overnight. After the solvent was evaporated at reduced pressure, the residue was washed with two portions of hexane (20 mL) and dried under vacuum to leave a yellow powder of 1 (2.73 g, 3.20 mmol, 77 percent). 1H NMR (C6D6, 500 MHz) δ 1.27 (m, 20H, OCH2CH2), 1.32 (d, J= 7.0 Hz, 12H, (CH3)2CH), 1.57 (d, J= 6.9 Hz, 12H, (CH3)2CH), 3.18 (m, 20H, OCH2CH2), 3.41 (br. s, 2H, NC=CW2), 3.74 (quint, J= 6.9 Hz, 4H, (CH3)2CH), 4.05 (br. s, 2H, NC=CH2), 7.17 (t, J= 7.7 Hz, 1 H, p-C5H3N), 7.24 (t, J=
7.6 Hz, 2H, p-C6H3'Pr2), 7.39 (d, J= 7.6 Hz, 4H, m-C6H3Vr2) , 7.76 (d, J= 7.7 Hz, 2H, m- C5 /3N). 13C{1Hj NMR (C6D6, 126 MHz), δ 25.52 ((CH3)2CH)), 25.54 ((CH3)2CH)), 25.78 (OCH2CH2), 28.56 ((CH3)2CH), 68.54 (OCH2CH2), 71.74 (NC=CH2), 118.06 (m-C5H3N), 121.93 (p-C6H3'Pr2), 123.69 (m-C6HjPr2), 136.72 (p-C5H3N), 144.18 (o-CβHg'Prz), 153.61 (/pso-CβHa'Prz), 160.31 (o-C5H3N), 163.36 (NOCH2).
Figure imgf000055_0001
1.3. Preparation of neodymium complex NdfC^HAiN^fTHFKu-CDfu-CH^LKTHFlg 2.
To a suspension of NdCI3(THF)3 (1.45 g, 3.1 mmol) and the neutral ligand C33H43N3 1 (1.50 g, 3.1 mmol) in THF (60 mL), an Et2O solution of CH3Li (1.4 M, 6.7 mL, 9.4 mmol) was added at 0°C. The mixture was allowed to warm to room temperature and stirred overnight. After solvent evaporation at reduced pressure, the residue was extracted with Et2O (50 mL) and centrifuged to remove the insoluble material (mainly LiCI). After evaporation of Et2O at reduced pressure, the residue was redissolved into THF (6 mL), and precipitated by addition of hexane (80 mL) affording 2 as a brown powder (1.25 g, 1.4 mmol, 51 percent).
Figure imgf000055_0002
1.4. Preparation of neodymium complex 3.
A suspension of diiminopyridine ligand 1 (0.48 g, 1.0 mmol) in THF (40 mL) was treated with neodymium powder (0.22 g, 1.5 mmol) and iodine (0.25 g, 1.0 mmol). The initial brown color of iodine gradually disappeared to form a gray precipitate of neodimium (III) iodide. The color of mixture turned into brown and then dark purple upon stirring at 50°C overnight. The mixture was centrifuged to remove unreacted neodymium metal. The solvent was evaporated and the residue extracted with toluene and centrifuged to remove insoluble materials. The combined extracts were concentrated to ca 1/3 of volume. Layering of hexane resulted in the formation of pink crystals of Nd(diiminopyridine)l2(THF) (0.314 g, 0.33 mmol, 33 percent)
Figure imgf000056_0001
1.5. Preparation of neodymium complex 4.
7.803 g (31.14 mmol) of neodymium chloride was added slowly to a flask containing 250 mL of THF to avoid clumping. The resulting slurry was refluxed for about 6 hours, then was allowed to cool to ambient temperature. The slurry was then cooled to -35°, then 15.000 g (31.14 mmol) of 1 and 200 mL of additional THF were added. After chilling anew for 4 hours at -35°, 39.9 mL of 1.6 M (63.83 mmol) methyl lithium were slowly added dropwise. The yellow-green slurry gradually became darker green during the course of the addition and gas bubbles, presumably methane, were evolved. After stirring overnight at ambient temperature, additional 40 mL of MeLi was added at ambient temperature (total: 127.7 mmol). The reaction mixture was stirred overnight again, then filtered. The volatiles were removed under reduced pressure and the residue was extracted with toluene, then filtered. The volatiles were removed under reduced pressure and the residue was triturated with hexane, then dried under reduced pressure. Yield of brown-green powder was 18.97 g, 69.7 percent
Figure imgf000057_0001
A suspension of NdCI3(THF)3 (0.82 g, 1.8 mmol) was stirred with 1b (1.50 g, 1.8 mmol) in THF (60 mL) at room temperature overnight. After THF was evaporated, the residue was extracted with Et2O (80 mL) and centrifuged to remove LiCI. Et2O was again evaporated, and the residue was recrystallized from THF (10 mL)/ hexane (80 mL) to give orange crystals of Nd(C33H4ιN3)(THF)(μ-CI)2Li(THF)2 (5) (1.69g, 1.8 mmol, >99 percent, as 0.5 hexane solvate).
Figure imgf000057_0002
1.7. Preparation of yttrium complex YfCggHAiNsXTHFH U-CI)9LKTHF)P 6.
YCI33THF (2.87 g, 7.0 mmol) and neutral ligand 1 (3.35 g, 7.0 mmol) were mixed and stirred in 80 ml of THF at room temperature overnight. The pale yellow mixture was cooled to -50°C and treated with a solution of MeLi in Ether (15 ml , 1.4M, 21 mmol). The mixture did not change its color at low temperature. After the temperature slowly increased to -25°C, the mixture became green, and finally dark green after reaching room temperature. The mixture was stirred overnight. After removal of some insoluble precipitate, the dark green solution was concentrated and treated with hexane (5 mL). The solution was kept at room temperature overnight upon which greenish yellow crystalline 6 was obtained (5.2 g , 6.0 mmol, 86 percent) (Note: single crystals of 6 have orange red appearance), μΘtf = 3.25 B.M.
1.8. Preparation of lanthanum complex La(C3^H 1Ng)(THF)(u-CI)pLi(THF)97. The preparation was carried out following an identical procedure as above by using LaCI3(THF)3 (0.81 g, 1.7 mmol) with 1b (1.50 g, 1.8 mmol). Complex 7 was isolated as yellow-orange crystals (0.93 g, 1.0 mmol, 55 percent).
1.9. Preparation of samarium complex Sm(CaaHd N3)(THF)(u-CI)?Li(THF)p_ 8. SmCI33THF (1.87 g, 3.9 mmol) and 1b (3.37 g, 3.9 mmol) were mixed together inside a reaction vessel. The mixture was cooled to -78°C, and THF was slowly added. After 10 min, the cooling bath was removed. The mixture was slowly warmed to room temperature and stirred for additional 3 hrs. The mixture formed a dark-red solution. After evaporation of the solvent under reduce pressure, toluene (80 ml) was added to the solid residue. After removal of the insoluble residue, the clear red toluene solution was concentrated and layered with hexane overnight at room temperature. Orange yellow crystals of 8 separated (3.5 g, 3.8 mmol, 96 percent). μen = 3.62 μB
1.10. Preparation of samarium complex Sm(C33H 1Ng)(THF)(u-Me)pLi(THF) 9.
A suspension of SmCI33THF (0.61 g, 1.3 mmol) and neutral ligand 1a (0.62 g, 1.3 mmol) in 80 ml of THF was cooled to -50°C. A solution of MeLi in ether (6 ml, 1.4M, 7.7 mmol) was added. The mixture remained yellow at low temperature. When the cooled bath was removed and the temperature rose to -30°C, the mixture was starting to become green. When the temperature rose to — 20°C, the mixture rapidly became dark green. After 2hrs at room temperature, the dark green solution was evaporated to dryness in vacuo and treated with 150 ml of hexane. After one hour of vigorous stirring, the insoluble residue was extracted with additional 50 ml of hexane. The combined dark green hexane extracts were concentrated and allowed to stand at room temperature upon which, orange red crystals of 9 were formed (0.85 g, 0.96 mmol, 74 percent).
Figure imgf000058_0001
Note: The orange red crystals directly formed from hexane extraction have free hexane molecular in the lattice. So that the crystal is monoclinic, unit cell is a=18.7804 A, b=13.0745 A, c=20.9406 A, β=100.76°
1.11. Preparation of yttrium complex rWC.^H^Na((Me)9irMeU(THBq1(THR 10. YCI33THF (4.9 g, 11.8 mmol) and neutral ligand 1a (5.7 g, 11.8 mmol) were mixed together in 150 ml of THF. The suspension was cooled to- 60°C. A solution of MeLi in ether was slowly added (51 mL, 1.4 M, 7.1 mmol). The resulting color of the cold mixture was yellow greenish. When the temperature was increased to -35°C, the reaction mixture become green and quickly darkened at -20°C . When the temperature reached ambient value, a dark green solution was formed. The mixture was stirred overnight and then evaporated to dryness. The dark green solid residue was treated with a large amount of hexane, the mixture was stirred for a few hours in hexane. After centrifuge, the dark hexane solution was separated; the precipitate was extracted with additional 80 ml of hexane. The hexane solutions were combined. The residue was then extracted with 100 ml and 50 ml of toluene twice. The toluene dark orange extract were combined with the hexane extracts and evaporated to dryness. The solid residue was recrystallized from THF with a small amount of hexane. Large orange crystals of 10 formed (9.2 g, 85 percent). X-ray: (sg2176):
Figure imgf000059_0001
1.12. Preparation of praseodymium complex 11.
A suspension of diiminopyridine ligand 1 (0.48 g, 1.0 mmol) in THF (40 mL) was treated with praseodymium powder (0.21 g, 1.5 mmol) and iodine (0.25 g, 1.0 mmol). The initial brown color of iodine gradually disappeared to form a gray precipitate of praseodimium (III) iodide. The color of mixture turned into brown and then dark purple upon stirring at 50°C overnight. The mixture was centrifuged to remove unreacted praseodymium metal. The solvent was evaporated and the residue extracted with toluene and centrifuged to remove insoluble materials. The combined extracts were concentrated to ca 1/3 of volume. Layering of hexane resulted in the formation of pink crystals of Nd(diiminopyridine)l2(THF) 11 (0.24 g, 0.26 mmol, 26 percent)
1.13. Preparation of praseodymium complex 12.
A 250 mL Schlenk flask was charged with NdCI3(THF)3 (0.467 g, 1.0 mmol) and LiCH2Si(CH3)3 (0.377 g, 4.0 mmol). A mixture of hexane (30 mL) and Et2O (10 mL) was added while cooling at -60SC and stirring during a period of 30 min. The mixture became an emerald green suspension. To this mixture, a THF (40 mL) solution of 2,6-diiminopyridine ligand 1 (0.482 g, 1.0 mmol) was added affording color change to brown. The mixture was allowed to warm to room temperature and stirring was continued overnight to give a dark orange mixture. The solvent was evaporated under reduced pressure. The residue was extracted with hexane (60 mL) and then centrifuged to remove insoluble materials. The resulting green solution was concentrated to half of the volume and cooled to -36eC to give yellowish -green micro crystals of 11 (0.191 g, 0.22 mmol, 22 percent).
2. Polymerization
2.1 Description of the polymerization procedure 1
The polymerizations were performed in a double wall 2 L steel reactor, which was purged with nitrogen before the addition of organic solvent, metal complex, activator(s), Lewis acids or other components. The polymerization reactor was tempered to 50°C unless stated otherwise. The following components were then added in the following order: organic solvent, the activator 1 , conjugated diene monomer(s) and the mixture was allowed to stir for one hour. Then the following components were added in the following order into the 2 L steel reactor: optionally a second activator component and/or Lewis acid and subsequently the metal complex was added to start the polymerization. The polymerization was performed at 50°C unless stated otherwise. The polymerization time varied depending on the experiment. For the termination of the polymerization process, the polymer solution was transferred into a separate double wall steel reactor containing 50 mL of methanol and Irganox 1520 as stabilizer for the polymer (1 L of methanol contains 2 g of Irganox). This mixture was stirred for 15 minutes. The recovered polymer was then stripped with steam for 1 hour to remove solvent and other volatiles and dried in an oven at 45°C for 24 hours.
2.2 Description of the polymerization procedure 2
The polymerizations were performed in a double wall 2 L steel reactor, which was purged with nitrogen before the addition of organic solvent, metal complex, activator(s), Lewis acids or other components. The polymerization reactor was tempered to 50°C unless stated otherwise. The following components were then added in the following order: organic solvent and the activator 1 and the mixture was allowed to stir for one hour. Then the following components were added in the following order into the 2 L steel reactor: optionally a second activator component and/or Lewis acid and subsequently the metal complex was added and the reaction mixture was stirred for a short period. Afterwards the conjugated diene monomer(s) was added to start the polymerization. The polymerization was performed at 50°C unless stated otherwise. The polymerization time varied depending on the experiment.
For the termination of the polymerization process, the polymer solution was transferred into a separate double wall steel reactor containing 50 mL of methanol and Irganox 1520 as stabilizer for the polymer (1 L of methanol contains 2 g of Irganox). This mixture was stirred for 15 minutes. The recovered polymer was then stripped with steam for 1 hour to remove solvent and other volatiles and dried in an oven at 45°C for 24 hours.
3 Polymerization Examples:
3.1 Homopolymerization of 1 ,3-butadiene
A) Polymerization of 1 ,3-butadiene using complex 2 and MMAO-3a (Run 1) The experiment was carried out according to the general polymerization procedure described above (2.1). The polymerization was carried out in 500 g of cyclohexane solvent. Thus 500 g of cyclohexane, 54.1 g (1.0 mol) of 1 ,3-butadiene monomer and MMAO (11.8 g of a heptane solution containing 30.3 mmol of MMAO) were added into the polymerization reactor and stirred for two hours and 22 minutes. Afterwards 90.3 mg (0.1 mmol) of neodymium complex 2 dissolved in 4.3 g cyclohexane were added into the polymerization reactor to start the polymerization reaction. After 33 minutes the polymerization reaction was terminated as described above (see 2.1.). At this point, the conversion level of the monomers into polybutadiene was 77.3 percent. 41.8 g of polybutadiene were recovered as result of the stripping process. The polymer contained 97.0 percent cis-1 ,4-; 2.5 percent trans-1 ,4-, 0.5 percent 1 ,2- polybutadiene according to 13C-NMR and IR determination. The molecular weight of the polymer amounted to 659,000 g/mol and the polydispersity (molecular weight distribution) amounted to 2.5. (Mn = 263,000; Mz = 1 ,220,000). The Mooney value amounted to 119.6, the melt enthalpy (ΔHSL) amounts to 38.8 J/g, the glass transition temperature amounted to -108.3°C and the melting points are at -74 and -8°C.
B) Polymerization of 1 ,3-butadiene using complex 2 and MMAO-3a (Run 2)
The experiment was carried out according to the general polymerization procedure described above (2.1). The polymerization was carried out in 500 g of toluene solvent. Thus 500 g of toluene, 54.1 g (1.0 mol) of 1 ,3-butadiene monomer and MMAO (11.8 g of a heptane solution containing 30.3 mmol of MMAO) were added into the polymerization reactor and stirred for one hour and 27 minutes. Afterwards 90.3 mg (0.1 mmol) of neodymium complex 2 dissolved in 4.1 g toluene were added into the polymerization reactor to start the polymerization reaction.
After one hour 34 minutes the polymerization reaction was terminated as described above (see 2.1. ). At this point, the conversion level of the monomers into polybutadiene was 67.5 percent. 36.5 g of polybutadiene were recovered as result of the stripping process. The polymer contained 95.0 percent cis-1 ,4-; 4.5 percent trans-1 ,4-, 0.5 percent 1 ,2- polybutadiene according to 13C-NMR and IR determination. The molecular weight of the polymer amounted to 380,000 g/mol and the polydispersity (molecular weight distribution) amounted to 2.31. (Mn = 164,000; Mz = 715,000). The Mooney value amounted to 61.9, the melt enthalpy (ΔHSL) amounts to 33.2 J/g, the glass transition temperature amounted to - 108.5°C and the melting points are at -70 and -12°C.
C) Polymerization of 1 ,3-butadiene using complex 2 and MMAO-3a (Run 3)
The experiment was carried out according to the general polymerization procedure described above (2.2). The polymerization was carried out in 3515 g of toluene solvent. Thus 3.515 kg of toluene and MMAO (82.5 g of a heptane solution containing 0.211 mol of MMAO) were added into the polymerization reactor and stirred for 46 minutes. Afterwards 0.62 g (0.686 mmol) of neodymium complex 2 dissolved in 10.3 g toluene were added into the polymerization reactor and stirred for four minutes. Then 379.0 g (7.0 mol) of 1 ,3- butadiene monomer were added into the polymerization reactor to start the polymerization reaction. After one hour 33 minutes the polymerization reaction was terminated as described above (see 2.2.). At this point, the conversion level of the monomers into polybutadiene was 84.8 percent. 321 g of polybutadiene were recovered as result of the stripping process. The polymer contained 96.1 percent cis-1 ,4-; 4.5 percent trans-1 ,4-, 3.4 percent 1 ,2- polybutadiene according to IR determination. The molecular weight of the polymer amounted to 385,000 g/mol and the polydispersity (molecular weight distribution) amounted to 2.34. (M„ = 164,000; Mz = 727,000). The Mooney value amounted to 66.2.
D) Polymerization of 1 ,3-butadiene using complex 3 and MMAO-3a (Run 4)
The experiment was carried out according to the general polymerization procedure described above (2.1). The polymerization was carried out in 500 g of cyclohexane solvent. Thus 500 g of cyclohexane, 53.9 g (1.0 mol) of 1 ,3-butadiene monomer and MMAO (11.8 g of a heptane solution containing 30.3 mmol of MMAO) were added into the polymerization reactor and stirred for two hours and 5 minutes. Afterwards 95.1 mg (0.1 mmol) of neodymium complex 3 dissolved in 8.1 g cyclohexane were added into the polymerization reactor to start the polymerization reaction.
After one hour and 16 minutes the polymerization reaction was terminated as described above (see 2.1.). At this point, the conversion level of the monomers into polybutadiene was 16.6 percent. 9.0 g of polybutadiene were recovered as result of the stripping process. The polymer contained 97.0 percent cis-1 ,4-; 2.2 percent trans-1 ,4-, 0.8 percent 1 ,2- polybutadiene according to IR determination.
E) Polymerization of 1 ,3-butadiene using complex 4 and MMAO-3a (Run 5)
The experiment was carried out according to the general polymerization procedure described above (2.1). The polymerization was carried out in 500 g of cyclohexane solvent. Thus 500 g of cyclohexane, 54.2 g (1.0 mol) of 1 ,3-butadiene monomer and MMAO (11.8 g of a heptane solution containing 30.3 mmol of MMAO) were added into the polymerization reactor and stirred for two hours and 48 minutes. Afterwards 89.6 mg (0.1 mmol) of neodymium complex 4 dissolved in 6.6 g cyclohexane were added into the polymerization reactor to start the polymerization reaction.
After one hour and 4 minutes the polymerization reaction was terminated as described above (see 2.1.). At this point, the conversion level of the monomers into polybutadiene was 31.7 percent. 17.2 g of polybutadiene were recovered as result of the stripping process.
The polymer contained 95.9 percent cis-1 ,4-; 3.3 percent trans-1 ,4-, 0.8 percent 1 ,2- polybutadiene according to IR determination. The molecular weight of the polymer amounted to 910,000 g/mol and the polydispersity (molecular weight distribution) amounted to 5.9. (Mn = 155,000; Mz = 2,200,000).
F) Polymerization of 1 ,3-butadiene using complex 5 and MMAO-3a (Run 6)
The experiment was carried out according to the general polymerization procedure described above (2.1). The polymerization was carried out in 503 g of cyclohexane solvent. Thus 503 g of cyclohexane, 54.1 g (1.0 mol) of 1 ,3-butadiene monomer and MMAO (11.8 g of a heptane solution containing 30.3 mmol of MMAO) were added into the polymerization reactor and stirred for one hour and 42 minutes. Afterwards 96.1 mg (0.1 mmol) of neodymium complex 5 dissolved in 3.6 g cyclohexane were added into the polymerization reactor to start the polymerization reaction.
After one hour 47 minutes the polymerization reaction was terminated as described above (see 2.1.). At this point, the conversion level of the monomers into polybutadiene was 78.6 percent. 42.5 g of polybutadiene were recovered as result of the stripping process. The polymer contained 97.0 percent cis-1 ,4-; 2.3 percent trans-1 ,4-, 0.7 percent 1 ,2- polybutadiene according to IR determination. The molecular weight of the polymer amounted to 725,000 g/mol and the polydispersity (molecular weight distribution) amounted to 2.8. (Mn = 262,000; Mz = 1 ,440,000). The Mooney value amounted to 108.5.
G) Polymerization of 1 ,3-butadiene using complex 6 and MMAO-3a (Run 7)
The experiment was carried out according to the general polymerization procedure described above (2.1). The polymerization was carried out in 500 g of cyclohexane solvent. Thus 499 g of cyclohexane, 54.2 g (1.0 mol) of 1 ,3-butadiene monomer and MMAO (11.8 g of a heptane solution containing 30.3 mmol of MMAO) were added into the polymerization reactor and stirred for one hour and 53 minutes. Afterwards 84.5 mg (0.1 mmol) of neodymium complex 6 dissolved in 5.9 g cyclohexane were added into the polymerization reactor to start the polymerization reaction.
After one hour and 10 minutes the polymerization reaction was terminated as described above (see 2.1.). At this point, the conversion level of the monomers into polybutadiene was 24.6 percent. 13.3 g of polybutadiene were recovered as result of the stripping process.
The polymer contained 96.6 percent cis-1 ,4-; 2.7 percent trans-1 ,4-, 0.7 percent 1 ,2- polybutadiene according to IR determination. The molecular weight of the polymer amounted to 275,000 g/mol and the polydispersity (molecular weight distribution) amounted to 4.7. (Mπ = 58,000; M2 = 1 ,345,000).
Figure imgf000065_0001
.measured after 15 minutes; .... measured after 10 minutes;
3.4 Molecular weight - Comparison
Figure imgf000065_0002
3.5 Molecular weight distribution (MWG) & Mooney viscosity - Comparison
Figure imgf000065_0003
3.6 Microstructure - Polybutadiene Fraction Comparison
Figure imgf000065_0004

Claims

Claims:
1. Metal complexes according to the Formula
Figure imgf000066_0001
Formula 1 wherein
M is yttrium, a group 4 metal of the Periodic Table of the elements, a lanthanide or actinide metal;
M1 is a group 1 or group 2 metal of the Periodic Table of the elements;
T independently each occurrence is nitrogen or phosphorus;
Rc independently each occurrence is hydrogen or a group having from 1 to 80 atoms not counting hydrogen, which is halide, nitro, nitrile, hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy, oxygen-substituted hydrocarbyl; amino, hydrocarbylamino, nitrogen-substituted hydrocarbyl; hydrocarbylsilyl, silicon- substituted hydrocarbyl; or two Rc groups are joined together forming a divalent ligand group;
RB independently each occurrence is a hydrogen or a group having from 1 to 80 atoms not counting hydrogen, which is hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl, hydrocarbyloxy, amino, hydrocarbylamino;
X independently each occurrence is an anionic ligand group having up to 60 atoms, provided however that in no occurrence is X a cyclic, delocalized, aromatic group that is π-bonded to M, and optionally two X groups together form a divalent ligand group;
D independently each occurrence is a neutral Lewis base ligand having up to 30 nonhydrogen atoms; x is the number 1 , 2 or 3; x' is the number 1 or 2; t is a number from 0 to 3; t' is a number from 0 to 3; r is the number 0 or 1 ; and o is the number 1 or 2. 2. Metal complexes according to claim 1 having the Formula la, lb or Ic:
Figure imgf000067_0001
Formula la
Figure imgf000067_0002
Formula lb
Figure imgf000067_0003
Formula Ic wherein:
M1 is lithium, sodium, potassium or magnesium;
M is yttrium, a group 4 metal of the Periodic Table of the elements, a lanthanide metal or an actinide metal;
T independently each occurrence is nitrogen or phosphorus;
RA and RD independently each occurrence are hydrogen or groups having from 1 to 80 atoms not counting hydrogen, which is halide, hydrocarbyl, hydrocarbylsilyl, halo- substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino- substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl, hydrocarbyloxy, amino, hydrocarbylamino;
X independently each occurrence is hydrogen or a group having from 1 to 60 atoms not counting hydrogen, which is hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl, hydrocarbyloxy, hydrocarbylcarboxylate, hydrocarbylsulfide, hydrocarbylsiloxy, hydrocarbylamido, cyanide, acetylacetonate, dithiocarbamate, dithiocarboxylate and halide, provided however that in no occurrence is X a cyclic, delocalized, aromatic group that is π- bonded to M;
D independently each occurrence is selected from carbon monoxide; phosphines,
PR'3, and phosphites, P(OR')3, wherein R' independently each occurrence is hydrocarbyl; silyl; thioethers; ethers and polyethers; amines and polyamines; olefins; conjugated dienes having from 4 to 40 carbon atoms; alcohols; nitriles; and esters; for Formulas la and lb, r is the number 0 or 1 ; for Formula Ic, r is the number 1 ;
RB, Rc, x, x', t, t\ and o have the same meaning as defined in claim 1 ; and the formula weight of the metal complex is less than 25,000 g/mol.
3. Metal complexes according to claim 2 wherein:
M1, M, T; D, r, x, x', t, t' and o are as defined in Claim 2; and
RA, Rc and RD groups are hydrogen, halide, hydrocarbyl, hydrocarbylsilyl, amino, hydrocarbylamino, hydrocarbyloxy, or hydrocarbylsiloxy;
RB groups are hydrocarbyl; hydrocarbylsilyl and hydrocarbylamino;
X groups are selected from hydrogen and halide and hydrocarbyl X groups having from 1 to 20 atoms other than hydrogen; and the formula weight of the metal complex is less than 20,000 g/mol.
4. Metal complexes according to claim 3 wherein:
RA, RB, Rc, RD, X, D, x, t and t' are as defined in Claim 3;
M is yttrium, a lanthanide metal or a group IV metal;
M' is lithium, sodium or potassium;
T is nitrogen; and x' is the number 1 ; o is the number 1 ; and r is the number 1.
5. Metal complexes according claim 1 or 2, wherein the metal complex corresponds to the Formula lla, lib or He:
Figure imgf000069_0001
Formula lla
Figure imgf000069_0002
Formula lib
Figure imgf000070_0001
Formula He
wherein
M is a lanthanide metal or a group IV metal,
M1 is lithium, sodium or potassium;
N is nitrogen;
RA or RD independently each occurrence is hydrogen or C1-6 alkyl;
Rc independently each occurrence is hydrogen, halide or C1-6 alkyl;
X independently each occurrence is halide, hydrogen, C1-10 hydrocarbyl, or d.-io hydrocarbylsilylhydrocarbyl; x is the 1 , 2 or 3; x' is the number 1 t is the number zero, one or two;
D is THF, DME, TEA, TMEDA, Et O; t' is a number from zero to two; o is the number one; and r is the number one.
Metal complexes according to claim 5, wherein
M is lanthanum, cerium, praseodymium, neodymium, promethium, samarium, titanium or zirconium;
M1 is lithium, sodium or potassium;
RA or RD independently each occurrence is hydrogen, methyl, ethyl, 1-methylethyl, t- butyl or cyclohexyl;
Rc independently each occurrence is hydrogen, chloride, methyl, ethyl, 1-methylethyl or cyclohexyl;
X independently each occurrence fluoride, chloride, bromide, iodide, methyl, ethyl, benzyl, neopentyl or trimethylsilylmethyl; and
M1, N, x, x', t, D, t', o and r are as defined in claim 5.
7. Metal complexes according to claim 5 or 6, wherein the metal complex corresponds to ([2,6-bis-(1-(hydrocarbylamido)-2-RA-2-RD-ethylidene)-4-Rc-)pyridine]MXxDt *
(M'Xx rDf) of Formula lla in which M, M1, RA, RD, Rc, X, x, x', t, D, f, and r are as previously defined.
8. Metal complexes according any one of the preceding claims, wherein M is neodymium.
9. A process for making metal complexes comprising reacting a compound corresponding to Formula IVa or IVb:
Figure imgf000071_0001
Formula IVa
Figure imgf000071_0002
Formula IVb with more than 0.5 and less than 1.5 equivalents of a metal compound corresponding to Formula III:
M(X)mDt Formula III, and with between 1 and 4 equivalents of a metal compound corresponding to the Formula V:
'X -l REn Formula V wherein:
T independently each occurrence is nitrogen or phosphorus;
RA and RD independently each occurrence are hydrogen or groups having from 1 to 80 atoms not counting hydrogen, which is halide, hydrocarbyl, hydrocarbylsilyl, halo- substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino- substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl, hydrocarbyloxy, amino, hydrocarbylamino;
Rc independently each occurrence is hydrogen or a group having from 1 to 80 atoms not counting hydrogen, which is halide, nitro, nitrile, hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy, oxygen-substituted hydrocarbyl; amino, hydrocarbylamino, nitrogen-substituted hydrocarbyl; hydrocarbylsilyl, silicon- substituted hydrocarbyl; or two Rc groups are joined together forming a divalent ligand group;
RB independently each occurrence is a hydrogen or a group having from 1 to 80 atoms not counting hydrogen, which is hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl, hydrocarbyloxy, amino, hydrocarbylamino; m is the number 3 or 4;
M is yttrium, a group 4 metal of the Periodic Table of the elements, a lanthanide metal or an actinide metal;
X independently each occurrence is hydrogen or a group having from 1 to 60 atoms not counting hydrogen, which is hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl, hydrocarbyloxy, hydrocarbylcarboxylate, hydrocarbylsulfide, hydrocarbylsiloxy, hydrocarbylamido, cyanide, acetylacetonate, dithiocarbamate, dithiocarboxylate and halide, provided however that in no occurrence is X a cyclic, delocalized, aromatic group that is π- bonded to M; D independently each occurrence is selected from carbon monoxide; phosphines,
PR'3, and phosphites, P(OR')3, wherein R' independently each occurrence is hydrocarbyl; silyl; thioethers; ethers and polyethers; amines and polyamines; olefins; conjugated dienes having from 4 to 40 carbon atoms; alcohols; nitriles; and esters; and t is a number from 0 to 3;
M1 is lithium, sodium, potassium or magnesium; x' is the number 1 or 2;
X" is chloro, bromo or iodo;
RE independently each occurrence is hydrogen or a group having from 1 to 80 atoms not counting hydrogen, which is hydrocarbyl; oxygen-substituted hydrocarbyl; nitrogen- substituted hydrocarbyl; hydrocarbylsilyl; or NR2 wherein R independently each occurrence is hydrogen or C-|_25 hydrocarbyl; n is the number 1 or 2; and the sum of n and x'-1 is equal to the oxidation state of M1.
10. A metal complex obtainable according to the process of claim 9.
11. A catalyst composition for homopolymerization of one type of ethylenically unsaturated addition polymerizable monomers and copolymerization of one type of ethylenically unsaturated addition polymerizable monomers with at least one different type of ethylenically unsaturated addition polymerizable monomers characterized in that a metal complex catalyst composition is used comprising: a) at least one metal complex according to any one of Claims 1 to 8 and 10, b) one or more activator compounds, and c) optionally a catalyst support.
12. The catalyst composition of claim 11 , wherein the activator compounds are selected from (a) C-|_3o organoboron or organoaluminum compounds, (b) polymeric or oligomeric alumoxanes, (c) nonpolymeric, compatible, noncoordinating, ion-forming compounds, and (d) hydrocarbyl sodium, hydrocarbyl lithium, hydrocarbyl zinc, hydrocarbyl magnesium halide, dihydrocarbyl magnesium.
13. The catalyst composition according to claim 11 or 12, wherein the activator compounds comprise a combination of: a) a trialkyl aluminum compound having from 1 to 4 carbon atoms in each alkyl group and b) a halogenated tri(hydrocarbyl)boron compound or halogenated tetrakis(hydrocarbyl)boron or -aluminum compound, each having from 1 to 20 carbons in each hydrocarbyl group.
14. The catalyst composition according to claim 11 or 12, wherein the activator compounds comprise a combination of: a) a tris(pentafluorophenyl)borane, tetrakis(pentafluorophenyl)borate or tetrakis(3,5- bis(trifluoromethyl)phenyl)borate with b) a polymeric or oligomeric alumoxane.
15. The catalyst composition according to claim 11 or 12, wherein the activator compounds comprise a combination of: a) a trialkyl aluminum or dialkyl aluminum hydride compound with b) boron trifluoride, boron trichloride, boron tribromide, aluminum trifluoride, aluminum trichloride, aluminum tribromide, scandium trifluoride, titanium tetrafluoride.
16. A process for the homopolymerization of one type of ethylenically unsaturated addition polymerizable monomer and copolymerization of one type of ethylenically unsaturated addition polymerizable monomers with at least one different of ethylenically unsaturated addition polymerizable monomer characterized in that a catalyst composition according to any one of claims 11 to 15 is used.
17. The process according to claim 16, wherein the ethylenically unsaturated addition polymerizable monomers are chosen from the group comprising ethene, propene, styrene, alpha-methylstyrene, 1 ,3-butadiene and isoprene.
18. The process according to claim 16 or 17, wherein the percentage of the fraction of residual olefinic double bonds in the (homo)polymer or copolymer that are Z or cis units is more than 90 percent and less than or equal to 99 percent and the percentage of 1 ,2 polybutadiene is less than or equal to 5 percent.
19. A polymer obtainable according to the process of claim 18.
20. Use of the polymer according to claim 19 for the production of golf balls, tires, hoses, belts, gaskets, seals, or shoes, or for the manufacture of high impact polystyrene or impact-modified polypropylene.
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