WO2002036641A2 - Improved productivity catalysts and microstructure control - Google Patents

Improved productivity catalysts and microstructure control Download PDF

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WO2002036641A2
WO2002036641A2 PCT/US2001/042977 US0142977W WO0236641A2 WO 2002036641 A2 WO2002036641 A2 WO 2002036641A2 US 0142977 W US0142977 W US 0142977W WO 0236641 A2 WO0236641 A2 WO 0236641A2
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hydrocarbyl
catalyst
substituted
group
ofthe
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PCT/US2001/042977
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WO2002036641A3 (en
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Peter Borden Mackenzie
Leslie Shane Moody
James Allen Ponasik, Jr.
Amy Kathryn Farthing
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Eastman Chemical Company
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Publication of WO2002036641A3 publication Critical patent/WO2002036641A3/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/46—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with hetero atoms directly attached to the ring nitrogen atom
    • C07D207/50—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/08—Six-membered rings
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene

Definitions

  • This application generally relates to olefin polymerization catalyst compositions and olefin polymerization processes using the same, and to new polyolefm compositions.
  • Late transition metal complexes as catalysts for olefin polymerization has recently been reviewed by Ittel et al. (Chem. Rev. 2000, 100, 1169). Notwithstanding the many advances described therein, there remains a need for new late transition metal catalysts with improved productivities under commercial reactor operating conditions, and for new methods of microstructure control. Late transition metal catalysts and processes that combine (i) high productivities at elevated temperatures and pressures in the presence of hydrogen as a molecular weight control agent, and (ii) high levels of branching, are especially sought. New catalysts and processes for these purposes are described herein. The distribution of branch lengths obtained using late transition metal catalysts is also important.
  • this invention pertains to a catalyst for olefin polymerization, comprising a Group 3-11 metal complex of a bidentate, tridentate, or tetradentate ligand, wherein the complex comprises at least one N-donor fragment of formula la or lb;
  • M is a Group 3-11 transition metal
  • R 3a"d are each, independently, H, F, CI, Br, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl, nitro, heteroatom connected hydrocarbyl or heteroatom connected substituted hydrocarbyl;
  • Ar la is an aryl or heteroaryl group substituted at one or both ortho positions by a group Q 2 ; wherein Q 2 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl or heteroatom connected substituted hydrocarbyl.
  • M is a Group 8-10 metal.
  • M is nickel, and Q is sufficiently long to extend sufficiently close to the metal M to increase the catalyst productivity at elevated temperatures, or in the presence of hydrogen, or both, relative to an otherwise similar catalyst wherein Q is replaced by H, Me, or Ph.
  • M is nickel, and Q 2 is sufficiently long to extend sufficiently close to the metal M to increase the regioselectivity or stereoselectivity of comonomer incorporation, relative to an otherwise similar catalyst wherein Q 2 is replaced by H, Me, or Ph.
  • M is nickel, and Q 2 is sufficiently long to extend sufficiently close to the metal M to decrease the amount of chain-running, relative to an otherwise similar catalyst wherein Q 2 is replaced by H, Me, or Ph.
  • M is palladium
  • Q 2 is sufficiently long to extend sufficiently close to the metal M to decrease the amount of chain-running, relative to an otherwise similar catalyst wherein Q 2 is replaced by H, Me, or Ph.
  • M is nickel
  • Q 2 is sufficiently long to extend sufficiently close to the metal M to increase the chain-running stereoselectivity, relative to an otherwise similar catalyst wherein Q 2 is replaced by H, Me, or Ph.
  • M is nickel, and Q is sufficiently long to extend sufficiently close to the metal M to decrease the rate of activation ofthe catalyst when an alkylaluminum reagent is used as cocatalyst, relative to an otherwise similar catalyst wherein Q 2 is replaced by H, Me, or Ph.
  • M is a Group 8-10 metal and the catalyst comprises a bidentate ligand selected from Set 1;
  • R 2x ' y are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl; silyl, or ferrocenyl; in addition, R 2x and R 2y may be linked by a bridging group;
  • R 3a"k are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, or nitro;
  • R 4a ' b are each independently hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl; in addition, R 4a and R 4b may be linked by a bridging group;
  • surface refers to a silicon or other atom which is part of, or attached to, a solid support
  • G 1 is a divalent bridging group
  • Ar 2a"m are each independently hydrocarbyl, substituted hydrocarbyl, heteroatom attached hydrocarbyl, heteroatom attached substituted hydrocarbyl, halo, nitro, boryl, or trialkoxysilane.
  • M is iron or cobalt
  • the catalyst comprises a tridentate ligand, and Q 2 which is sufficiently long to extend sufficiently close to the metal M to increase the catalyst productivity at elevated temperatures.
  • the tridentate ligand.of the ninth preferred embodiment of this first aspect is selected from Set 2;
  • R 2x ' y are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl; silyl, or ferrocenyl; and
  • R 3a"k are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, or nitro.
  • the catalyst is a titanium or zirconium complex of a bidentate ligand selected from Set 3;
  • R 2 is H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, silyl, or ferrocenyl;
  • R 3a"J are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, fluoro, chloro, or bromo;
  • Ar 2a"J are each independently hydrocarbyl, substituted hydrocarbyl, heteroatom attached hydrocarbyl, heteroatom attached substituted hydrocarbyl, halo, nitro, boryl, or trialkoxysilane.
  • the catalyst further comprises a solid support.
  • the catalyst ofthe twelfth embodiment is attached to the solid support via a covalent bond to the group Ar la .
  • this invention pertains to a process for the polymerization of olefins, comprising contacting one or more olefins with the catalyst ofthe first aspect. .
  • At least one ofthe olefins is ethylene.
  • the olefin is ethylene
  • M is nickel
  • the temperature is at least 80 °C
  • the pressure is less than about 800 psig
  • sufficient hydrogen is added to reduce the number average molecular weight ofthe polymer by at least 20% relative to an otherwise similar reaction conducted in the absence of hydrogen
  • the catalyst productivity is at least 500 kg polyethylene per g nickel
  • the polymer has a DSC (Differential Scanning Calorimetry) first cycle peak melting point greater than 131 °C.
  • sufficient hydrogen is added to reduce the number average molecular weight ofthe polymer by at least 50% relative to an otherwise similar reaction conducted in the absence of hydrogen, and the polymer has a DSC first cycle peak melting point greater than 133 °C.
  • At least one ofthe olefins is ethylene, M is palladium and the amount of chain running is reduced.
  • this invention pertains to a bidentate, tridentate, or tetradentate ligand ofthe first or second aspects.
  • this invention pertains to a process for the polymerization of olefins, comprising contacting one or niore olefins with a catalyst comprising a Group 8-10 metal complex of a bidentate, N,N-donor ligand, wherein the first ofthe donor nitrogens, N 1 , is substituted by an aromatic or heteroaromatic ring wherein the ortho substituents are aryl or heteroaryl groups, and the second ofthe donor nitrogens, N , is substituted by an aromatic or heteroaromatic ring wherein one or both ofthe ortho substituents are other than aryl or heteroaryl; wherein the catalyst is capable of homopolymerizing ethylene to produce a polymer with a number average molecular weight of at least 20,000 g/mole and at least 20 branch points per 1000 carbons with a catalyst productivity of at least 500 kg polyethylene per g of Group 8-10 metal at a temperature of at least 60 °C at a partial pressure of ethylene of at
  • the metal is nickel
  • N l is substituted by a 2,6-diaryl substituted aryl group or a 2,5-diaryl substituted 1- pyrrolyl group
  • N 2 is substituted by an aromatic or heteroaromatic ring wherein one or both ofthe ortho substituents are other than aryl or heteroaryl.
  • the metal is mckel
  • N 1 is substituted by a 2,6-diaryl substituted aryl group
  • N 2 is substituted by an aromatic ring wherein one or both ofthe ortho substituents are other than aryl or heteroaryl
  • the catalyst productivity is at least 500 kg polyethylene per g nickel at a temperature of at least 70 °C.
  • the process ofthe fourth preferred emodiment ofthe fourth aspect comprises a catalyst wherein N 2 is substituted by an aromatic ring wherein one ofthe ortho substituents is aryl, heteroaryl or bromo, and the other ortho substituent is bromo.
  • the bidentate ligand is selected
  • R 2x ' y are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, silyl, or ferrocenyl; in addition, R 2 and R 2y may be linked by a bridging group;
  • R 3a_1 are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, or nitro;
  • the olefin is ethylene and the polymer is an ethylene homopolymer wherein the average spacing between branch points is such that there is at least a 10% excess of sequences ofthe type - CHR-(CH 2 ) n+2 -CHR-, where R is alkyl and n is 0 or a positive integer, relative to sequences of the type -CHR-(CH 2 ) 2m -CHR-, where R is alkyl and m is a positive integer.
  • the olefin is ethylene
  • N is substituted by a 2-aryl-6-bromo-aryl group
  • the polymer is an ethylene homopolymer wherein there is an excess of isotactic sequences ofthe type -CHR la -(CH 2 ) 4n+2 -CHR lb -, where R la and R l are hydrocarbyl or substituted hydrocarbyl branches and n is 0 or 1, relative to a random distribution.
  • this invention pertains to a polymer prepared according to the process ofthe fourth aspect.
  • this invention pertains to a process for the polymerization of olefins, comprising contacting one or more olefins with a catalyst comprising a Group 8-10 metal complex of a bidentate, tridentate or multidentate ligand, wherein the catalyst is activated using an alkylaluminum compound, wherein the alkylaluminum compound is subsequently selectively deactivated before the bulk of the polymerization has occurred.
  • the alkylaluminum compound is selectively deactivated through the addition of a phenol or substituted phenol.
  • the Group 8-10 metal complex is a cationic nickel complex of a bidentate N,N-donor ligand.
  • the Group 8-10 metal complex is a cationic iron or cobalt complex of a tridentate ligand.
  • this invention pertains to a catalyst for the polymerization of olefins, comprising a nickel complex of a ligand of formula 2a;
  • R 2x ' y are each independently hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or silyl; in addition, R 2x and R 2y may be linked by a bridging group;
  • R 3 "f are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, iodo, cyano, or nitro;
  • R 3x,y are each independently halo or fluoroalkyl; and Ar 2a,b are each independently aryl or heteroaryl.
  • R 2x and R 2y are linked by a bridging group.
  • this invention pertains to a process for the polymerization of olefins comprising contacting ethylene and optionally other olefins with the catalyst ofthe seventh aspect in the presence of sufficient hydrogen to reduce the number average molecular weight ofthe polymer by at least 10% relative to an otherwise similar process carried out in the absence of hydrogen.
  • other olefins we mean 1-alkenes, preferably 1-butene, 1-hexene or 1- octene, or long chain 1-alkene macromonomers.
  • this invention pertains to an ethylene homopolymer having a number average molecular weight of at least 10,000 g/mole, total branching of less than about 70 branches per 1000 carbons, at least 10% saturated hydrocarbon polymer chains, and a ratio of C 5 and longer branches to methyl branches of at least 0.35.
  • the total branching is less than about 60 branches per 1000 carbons; at least 25% ofthe polymer chains are saturated hydrocarbon chains; and the ratio of C 5 and longer branches to methyl branches is at least 0.40.
  • the total branching is less than about 60 branches per 1000 carbons; and the ratio of C 5 and longer branches to methyl branches is at least 0.45.
  • the Differential Scanning Calorimetry (DSC) curve ofthe homopolymer shows a bimodal melt endotherm on the second heat from the melt, with the area ofthe smaller ofthe two peaks representing at least 25% ofthe total melt endotherm.
  • N, O, S, P, and Si stand for nitrogen, oxygen, sulfur, phosphorus, and silicon, respectively, while Me, Et, Pr, 'Pr, Bu, l Bu and Ph stand for methyl, ethyl, propyl, z ' so-propyl, butyl, tert-butyl and phenyl, respectively.
  • a "1-pyrrolyl or substituted 1-pyrrolyl” group refers to a group of formula II below:
  • R 3a"d are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two or more of R 3a"d may be linked by a bridging group or groups to form bicyclic or polycyclic ring systems including carbazol-9-yl and indol-1-yl.
  • a “hydrocarbyl” group means a monovalent or divalent, linear, branched or cyclic group which contains only carbon and hydrogen atoms.
  • monovalent hydrocarbyls include the following: C1-C20 alkyl; C1-C20 alkyl substituted with one or more groups selected from C ⁇ -C 20 alkyl, C 3 -C 8 cycloalkyl, and aryl; C 3 -C 8 cycloalkyl; C 3 -C 8 cycloalkyl substituted with one or more groups selected from Ci-C 2 o alkyl, C 3 -C 8 cycloalkyl, and aryl; C 6 -C 14 aryl; and C 6 -C 1 aryl substituted with one or more groups selected from -C20 alkyl, C 3 -C 8 cycloalkyl, and aryl.
  • divalent (bridging) hydrocarbyls examples include: -CH 2 -, -CH2CH 2 - -CH 2 CH 2 CH 2 - and 1,2-phenylene.
  • aryl refers to an aromatic carbocyclic monoradical, which may be substituted or unsubstituted, wherein the substituents are halo, hydrocarbyl, substituted hydrocarbyl, heteroatom attached hydrocarbyl, heteroatom attached substituted hydrocarbyl, nitro, cyano, fluoroalkyl, sulfonyl, and the like.
  • Examples include: phenyl, naphthyl, anthracenyl, phenanthracenyl, 2,6-diphenylphenyl, 3,5- dimethylphenyl, 4-nitrophenyl, 3-nitrophenyl, 4-methoxyphenyl, 4- dimethylaminophenyl, 2,6-dibromophenyl, 2,4,6-tribromophenyl, 2,4-dibromo-6- phenylphenyl, 2,6-di(4-tert-butylphenyl)phenyl, 2,6-di(4-tert-butylphenyl)-4- phenylphenyl, 2,6-di(4-phenylphenyl)-4-phenylphenyl, 2,4-dibromo-6- trifluoromethylphenyl, 2,4-bis(4-tert-butylphenyl)-6-trifluoromethylphenyl, 2- chloro-4,6-di(4-
  • heterocyclic ring refers to a carbocyclic ring wherein one or more ofthe carbon atoms has been replaced by an atom selected from the group consisting of O, N, S, P, Se, As, Si, B, and the like.
  • a “heteroaromatic ring” refers to an aromatic heterocyclic ring; examples include pyrrole, furan, thiophene, indene, imidazole, oxazole, isoxazole, carbazole, thiazole, pyrimidine, pyridine, pyridazine, pyrazine, benzothiophene, and the like.
  • heteroaryl refers to a heterocyclic ring monoradical which is aromatic; examples include 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, furyl, thienyl, indenyl, imidazolyl, oxazolyl, isoxazolyl, carbazolyl, thiazolyl, pyrimidinyl, pyridyl, pyridazinyl, pyrazinyl, benzothienyl, and the like, and substituted derivatives thereof.
  • sil refers to a SiR 3 group wherein Si is silicon and R is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or silyl, as in Si(SiR 3 ) 3 .
  • a “boryl” group refers to a BR 2 or B(OR) 2 group, wherein R is hydrocarbyl or substituted hydrocarbyl.
  • heteroatom refers to an atom other than carbon or hydrogen.
  • Preferred heteroatoms include oxygen, nitrogen, phosphorus, sulfur, selenium, arsenic, chlorine, bromine, silicon, and fluorine.
  • a “substituted hydrocarbyl” refers to a monovalent, divalent, or trivalent hydrocarbyl substituted with one or more heteroatoms.
  • monovalent substituted hydrocarbyls include: 2,6-dimethyl-4-methoxyphenyl, 2,6-diisopropyl- 4-methoxyphenyl, 4-cyano-2,6-dimethylphenyl, 2,6-dimethyl-4-nitrophenyl, 2,6- difluorophenyl, 2,6-dibromophenyl, 2,6-dichlorophenyl, 4-methoxycarbonyl-2,6- dimethylphenyl, 2-tert-butyl-6-chlorophenyl,-2,6-dimethyl-4-phenylsulfonylphenyl, 2,6-dimethyl-4-trifluoromethylphenyl, 2,6-dimethyl-4-trimethylammoniumphenyl (associated with a weakly coordinated anion), 2,6-dimethyl-4
  • divalent (bridging) substituted hydrocarbyls examples include: 4-methoxy-l,2-phenylene, 1- methoxymethyl-l,2-ethanediyl, l,2-bis(benzyloxymethyl)-l,2-ethanediyl, and l-(4- methoxyphenyl)- 1 ,2-ethanediyl.
  • a "heteroatom connected hydrocarbyl” refers to a group ofthe type
  • E 10 (hydrocarbyl), E 20 H(hydrocarbyl), or E 20 (hydrocarbyl) 2 where E 10 is an atom selected from Group 16 and E is an atom selected from Group 15.
  • a "heteroatom connected substituted hydrocarbyl” refers to a group ofthe type E 10 (substituted hydrocarbyl), E 20 H(substituted hydrocarbyl), or E 20 (substituted hydrocarbyl) 2 , where E 10 is an atom selected from Group 16 and E 20 is an atom selected from Group 15.
  • fluoroalkyl refers to a C 1 -C 2 0 alkyl group substituted by one or more fluorine atoms.
  • Preferred olefins for such catalysts include ethylene, propylene, butene, hexene, octene, cyclopentene, norbornene, and styrene.
  • Lewis basic substituents on the olefin will tend to reduce the rate of catalysis in most cases; however, useful rates of homopolymerization or copolymerization can nonetheless be achieved with some of those olefins.
  • Preferred olefins for such catalysts include ethylene, propylene, butene, hexene, octene, and fluoroalkyl substituted olefins, but may also include, in the case of palladium and some ofthe more functional group tolerant nickel catalysts, norbornene, substituted norbornenes (e.g., norbornenes substituted at the 5-position with halide, siloxy, silane, halo carbon, ester, acetyl, alcohol, or amino groups), cyclopentene, ethyl undecenoate, acrylates, vinyl ethylene carbonate, 4- vinyl-2,2-dimethyl- 1 ,3 -dioxolane, and vinyl acetate.
  • norbornene substituted norbornenes (e.g., norbornenes substituted at the 5-position with halide, siloxy, silane, halo carbon, ester, acetyl, alcohol, or amino groups)
  • cyclopentene
  • the Group 8-10 catalysts can be inhibited by olefins which contain additional olefinic or acetylenic functionality. This is especially likely if the catalyst is prone to "chain-running" wherein the catalyst can migrate up and down the polymer chain between insertions, since this can lead to the formation of relatively unreactive ⁇ -allylic intermediates when the olefin monomer contains additional unsaturation.
  • alpha-olefin functional comonomer we mean an alpha-olefin which contains a functional group containing at least one N or O atom.
  • Preferred functional groups include esters, alkyl ethers, carbonates and nitriles.
  • the term “ortho” is used to refer to substituents attached to the 2- and 6- positions of a 1 -attached, six-membered aromatic or heteroaromatic ring, or the 2- and 5-positions of a 1 -attached, five-membered aromatic or heteroaromatic ring, or more generally the first substitutable positions on either side ofthe point of attachment of said aromatic or heteroaromatic ring to said donor nitrogen.
  • chain running we mean the process by which certain olefin polymerization catalysts, especially those based on Group 8-10 transition metal complexes of bidentate ligands, are capable of migrating along a growing polymer chain between insertion events to form branched polymers from ethylene alone, and give modes of enchainment other than 1,2 enchainment when substituted alkenes are polymerized or copolymerized.
  • olefin rotation we mean rotation by at least 180° about a vector extending from said Group 8-10 metal to the olefin centroid.
  • the rate of olefin rotation may be calculated using Density Field Theory / Molecular Mechanics programs (c.f. Ziegler et al. inJ. Am. Chem. Soc. 1997, 119, 1094 and 6177).
  • isotactic sequences ofthe type -CHR la -(CH 2 ) 4n+2 -CHR lb - we mean polymer chain sequences ofthe type -CHR 1 a -CH 2 -CH 2 -CHR lb - or -CHR la -(CH 2 ) 6 - CHR lb - in which the configuration about the -CHR la - center is the same as that about the -CHR lb - center where R la and R lb are hydrocarbyl or substituted hydrocarbyl branches and n is 0 or 1.
  • the most common type of branch will be methyl with most ofthe catalysts ofthe current invention; however, longer branches will also be present in most cases, especially when the total number of branches is greater than about 10 per 1000 carbons.
  • Elevated temperatures we mean a temperature of at least 60 °C, preferably at least 70 °C, even more preferably at least 80 °C.
  • in the presence of hydrogen we mean an amount of hydrogen sufficient to reduce the number average molecular weight by at least 5%, preferably at least 10%, even more preferably at least 20%, relative to an otherwise similar reaction conducted in the absence of hydrogen.
  • increase the regioselectivity or stereoselectivity of comonomer incorporation we mean an increase of at least 10%, preferably at least 20% in either the regioselectivity or stereoselectivity of comonomer incorporation, relative to that observed for an otherwise similar catalyst with H, Me or Ph in place of group Ar la , under the same reaction conditions.
  • reduce the amount of chain running we mean either a decrease of at least 10%, preferably at least 20%, in the amount of branching observed for a branched polyolefin derived from ethylene alone, or an increase of at least 10%, preferably at least 20%, in the amount of branching observed for a chain- straightened poly-alpha-olefin, relative to that observed for an otherwise similar catalyst with H, Me or Ph in place of group Ar la , under the same reaction conditions.
  • chain-straightened we mean a poly-alpha-olefin with fewer branches than would be observed using an olefin polymerization catalyst which cannot undergo chain-running.
  • increase the chain-running stereoselectivity we mean an . increase of at least 10%, preferably at least 20% in the occurrence of configurational correlation between adjacent substituted carbons along the polymer chain, relative to a purely random distribution.
  • a " ⁇ -allyl” group refers to a monoanionic group with three sp 2 carbon atoms bound to a metal center in a ⁇ -fashion. Any ofthe three sp carbon atoms may be substituted with a hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or O-silyl group. Examples of ⁇ -allyl groups include:
  • ⁇ -benzyl group denotes an ⁇ -allyl group where two ofthe sp 2 carbon atoms are part of an aromatic ring.
  • ⁇ -benzyl groups include:
  • a “bridging group” refers to an atom or group which links two or more groups, which has an appropriate valency to satisfy its requirements as a bridging group, and which is compatible with the desired catalysis. Suitable examples include divalent or trivalent hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, substituted silicon(IV), boron(ni), N(II ⁇ ), P(in), and P(V), -C(O)-, -SO 2 -, -C(S)-, -B(OMe)-, - C(O)C(O)-, O, S, and Se.
  • the groups which are said to be “linked by a bridging group” are directly bonded to one another, in which case the term “bridging group” is meant to refer to that bond.
  • bridging group By “compatible with the desired catalysis,” we mean the bridging group either does not interfere with the desired catalysis, or acts to usefully modify the catalyst activity or selectivity.
  • weakly coordinating anion is well known in the artier se and generally refers to a large bulky anion capable of delocalization ofthe negative charge ofthe anion. The importance of such delocalization depends to some extent on the nature ofthe transition metal comprising the cationic active species, with the Group 4-6 transition metals requiring less coordinating anions, such as B(C 6 F 5 ) " , than many Group 8-10 transition metal based catalysts, which can in some cases give active catalysts with BF " counteranions.
  • the weakly coordinating nature of such anions is known and described in the literature (S. Strauss et al., Chem. Rev., 1993, 93, 927).
  • acac refers to acetylacetonate.
  • substituted acetylacetonates wherein one or more hydrogens in the parent structure have been replaced by a hydrocarbyl, substituted hydrocarbyl, or fluoroalkyl, may be used in place ofthe “acac”.
  • Hydrocarbyl substituted acetylacetonates may be preferred in some cases when it is important, for example, to improve the solubility of a (ligand)Ni(acac)BF 4 salt in mineral spirits.
  • one or more olefins refers to the use of one or more chemically different olefin monomer feedstocks, for example, ethylene and propylene.
  • a variety of protocols may be used to generate active polymerization catalysts comprising transition metal complexes of various nitrogen, phosphorous, oxygen and sulfur donor ligands.
  • Examples include (i) the reaction of a Group 4 metallocene dichloride with MAO, (ii) the reaction of a Group 4 metallocene dimethyl complex with N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, (iii) the reaction of a Group 8 or 9 metal dihalide complex of a tridentate N-donor ligand with an alkylaluminum reagent, (iv) the reaction of a Group 8 or 9 metal dialkyl complex of a tridentate N-donor ligand with MAO or HB(3,5- bis(trifluoromethyl)phenyl) 4 , (v) the reaction of (Me 2 N) 4 Zr with 2 equivalents of an N-pyrrol-1-ylsalicylimine, followed by treatment ofthe product of that reaction with Me 3 SiCl and then a triisobutylaluminum-modified methylaluminoxane, and (vi) the reaction
  • Additional methods described herein include the reaction of (tridentate N-donor ligand)M(acac)B(C 6 F 5 ) 4 salts with an alkylaluminum reagent, where M is Fe(II) or Co(II), and the reaction of (bidentate N-donor ligand)Ni(acac)X salts with an alkylaluminum reagent, where X is a weakly coordinating anion, such as B(C 6 F 5 ) " , BF 4 " , PF 6 “ , SbF 6 " , (F 3 CSO 2 ) 2 N ⁇ (F 3 CSO 2 ) 3 C, and OS(O) 2 CF 3 " .
  • Cationic [(ligand)M( ⁇ -allyl)] complexes with weakly coordinating counteranions, where M is a Group 10 transition metal, are often also suitable catalyst precursors, requiring only exposure to olefin monomer and in some cases elevated temperatures (40-100 °C) or added Lewis acid, or both, to form an • active polymerization catalyst.
  • a variety of (ligand) n M(Z la )(Z lb ) complexes where "ligand” refers to a compound ofthe present invention, n is 1 or 2, M is a Group 4-10 transition metal, and Z la and Z l are univalent groups, or may be taken together to form a divalent group, may be reacted with one or more compounds, collectively referred to as compound Y, which function as co-catalysts or activators, to generate an active catalyst ofthe form [(ligand) n M(T la )(L)] + X " , where n is 1 or 2, T la is a hydrogen atom or hydrocarbyl, L is an olefin or neutral donor group capable of being displaced by an olefin, M is a Group 4-10 transition metal, and X " is a weakly coordinating anion.
  • examples of compound Y include: methylaluminoxane (herein MAO) and other aluminum sesquioxides, R 3 A1, R A1C1, and RA1C1 2 (wherein R is alkyl, and plural groups R may be the same or different).
  • MAO methylaluminoxane
  • R 3 A1, R A1C1, and RA1C1 2 wherein R is alkyl, and plural groups R may be the same or different.
  • examples of a compound Y include: MAO and other aluminum sesquioxides, R 3 A1, R 2 A1C1, RA1C1 2 (wherein R is alkyl, and plural groups R may be the same or different), B(C 6 Fs) 3 , R° 3 Sn[BF 4 ] (wherein R° is hydrocarbyl or substituted hydrocarbyl and plural groups R° may be the same or different), H + X " , wherein X " is a weakly coordinating anion, for example, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and Lewis acidic or Bronsted acidic metal oxides, for example, montmorillonite clay.
  • metal hydrocarbyls include: MAO, other aluminum sesquioxides, R 3 Al, R 2 A1C1, RA1C1 2 (wherein R is alkyl, and plural groups R may be the same or different), Grignard reagents, organolithium reagents, and diorganozinc reagents.
  • Lewis acids examples include: MAO, other aluminum sesquioxides, R 3 A1, R 2 A1C1, RAICI 2 (wherein R is alkyl, and plural groups R may be the same or different), B(C 6 F 5 ) 3 , R° 3 Sn[BF 4 ] (wherein R° is hydrocarbyl or substituted hydrocarbyl and plural groups R° may be the same or different), and Lewis acidic metal oxides.
  • alkylaluminum is used to refer to compounds containing at least one alkyl group bonded to Al(III), which are capable of reacting with a metal complex ofthe present invention to generate an active olefin polymerization catalyst. In general, this will involve exchanging one or more alkyl groups from the aluminum with a monoanionic atom or group on the metal complex pro-catalyst. In some cases, a hydride may be directly transferred from the ⁇ -carbon ofthe aluminum alkyl to said metal complex. Subsequent abstraction of a second monoanionic atom or group from the metal complex may also be required to generate a cationic active catalyst.
  • the role ofthe alkylaluminum may simply be to exchange an alkyl or hydride from the aluminum with a monoanionic group, such as acetylacetonate, attached to the metal complex.
  • the alkylaluminum reagent may, in some cases, simply act as a Lewis acid, to promote conversion ofthe ⁇ -allyl or ⁇ -benzyl to a ⁇ -allyl or ⁇ -benzyl bonding mode, thereby facilitating binding and insertion ofthe olefin monomer.
  • alkylaluminum activator When a cationic pro-catalyst is used with an alkylaluminum activator or co-catalyst, it should also be recognized that the starting counteranion (e.g. BF 4 " ) may react with the alkylaluminum reagent to generate a new counteranion (or a mixture of several different counteranions) under olefin polymerization reaction conditions.
  • alkylaluminum reagents include: MAO, other aluminum sesquioxides, Me Al, EtAlCl 2 , Et 2 AlCl, R 3 A1, R 2 A1C1, RA1C1 2 (wherein R is alkyl, and plural groups R may be the same or different), and the like.
  • the foregoing discussion is intended to illustrate that there are frequently many ways to generate an active catalyst. It is an object of this disclosure to teach that there are a variety of methods wherein the ligands ofthe present invention can be reacted with a suitable metal precursor, and optionally a co-catalyst, to generate an active olefin polymerization catalyst.
  • the active catalyst typically comprises the catalytically active metal, one or more ligands ofthe present invention, the growing polymer chain (or a hydride capable of initiating a new chain), and a site on the metal adjacent to the metal-alkyl bond ofthe chain where ethylene can coordinate, or at least closely approach, prior to insertion.
  • active catalysts comprising the ligands ofthe present invention are formed as the reaction products ofthe catalyst activation reactions disclosed herein, regardless ofthe detailed structures of those active species.
  • Active catalysts may, in some cases, be generated from more than one oxidation state of a given metal.
  • the present invention describes the use of both Co(IH) and Co(II) catalyst precursors to effect olefin polymerization using MAO or other alkylaluminum co-catalysts.
  • oxidation state of a given metal has been specified herein, it is therefore to be understood that other oxidation states ofthe same metal, complexed by the ligands ofthe present invention, can serve as catalyst precursors or active catalysts.
  • the catalysts ofthe present invention may be used in batch and continuous processes, in solution or slurry or gas phase processes. In some cases, it is advantageous to attach the catalyst to a solid support.
  • useful solid supports include: inorganic oxides, such as talcs, silicas, titania, silica/chromia, silica/chromia/titania, silica/alumina, zirconia, aluminum phosphate gels, silanized silica, silica hydrogels, silica xerogels, silica aerogels, montmorillonite clay and silica co-gels, as well as organic support materials such as polystyrene and functionalized polystyrene. (See, for example, S.B.
  • inorganic oxides such as talcs, silicas, titania, silica/chromia, silica/chromia/titania, silica/alumina, zirconia, aluminum phosphate gels, silanized silica, silica hydrogels, silica xerogels, silica aerogels, montmorillonite clay and silica co-gels,
  • the catalysts ofthe present invention are attached to a solid support (by "attached to a solid support” is meant ion paired with a component on the surface, adsorbed to the surface or covalently attached to the surface) that has been pre-treated with an alkylaluminum compound. More generally, the alkylaluminum and the solid support can be combined in any order and any number of alkylaluminum(s) can be utilized.
  • the supported catalyst thus formed may be treated with additional quantities of alkylaluminum.
  • the compounds ofthe present invention are attached to silica that has been pre-treated with an alkylaluminum, for example, MAO, Et 3 Al, i Bu3Al, Et2A101, or Me 3 Al.
  • Such supported catalysts are prepared by contacting the transition metal compound, in a substantially inert solvent (by which is meant a solvent which is either unreactive under the conditions of catalyst preparation, or if reactive, acts to usefully modify the catalyst activity or selectivity) with MAO-treated silica for a sufficient period of time to generate the supported catalyst.
  • substantially inert solvents include toluene, o-difluorobenzene, mineral spirits, hexane, CH 2 C1 2 , arid CHC1 3 .
  • the catalysts ofthe present invention are activated in solution under an inert atmosphere, and then adsorbed onto a silica support which has been pre-treated with a silylating agent to replace surface silanols by trialkylsilyl groups.
  • a silylating agent to replace surface silanols by trialkylsilyl groups.
  • precurors and procedures may be used to generate the activated catalyst prior to said adsorption, including, for example, reaction of a (ligand)Ni(acac)B(C 6 F 5 ) complex with Et 2 AlCl in a toluene/hexane mixture under nitrogen; where "ligand” refers to a compound of the present invention.
  • the catalysts ofthe present invention are covalently attached to a solid support and then activated in a slurry phase process by treatment with an alkylaluminum reagent.
  • Methods of covalent attachment include reaction of a 4-hydroxyphenyl group which is part ofthe ligand with Si(NMe 2 ) 4 , followed by reaction ofthe resultant ligand-O-Si(NMe 2 )3 derivative with silica.
  • metal complexes are depicted herein with square planar, trigonal bipyramidal, or other coordination, however, it is to be understood that no specific geometry is implied.
  • the polymerizations may be conducted as solution polymerizations, as non- solvent slurry type polymerizations, as slurry polymerizations using one or more of the olefins or other solvent as the polymerization medium, or in the gas phase.
  • the catalyst could be supported using a suitable catalyst support and methods known in the art.
  • Substantially inert solvents such as toluene, hydrocarbons, methylene chloride and the like, may be used.
  • Propylene and 1 -butene are excellent monomers for use in slurry-type copolymerizations and unused monomer can be flashed off and reused.
  • Suitable polymerization temperatures are preferably from about 20 °C to about 160 °C, more preferably 60 °C to about 100 °C.
  • Suitable polymerization pressurse range from about 1 bar to about 200 bar, preferably 5 bar to 50 bar, more preferably 10 bar to 50 bar.
  • the catalysts ofthe present invention may be used alone, or in combination with one or more other Group 3-10 olefin polymerization or oligomerization catalysts, in solution, slurry, or gas phase processes. Such mixed catalyst systems are sometimes useful for the production of bimodal or multimodal molecular weight or compositional distributions, which may facilitate polymer processing or final product properties.
  • the polymer can be recovered from the reaction mixture by routine methods of isolation and/or purification.
  • the polymers ofthe present invention are useful as components of thermoset materials, as elastomers, as packaging materials, films, compatibilizing agents for polyesters and polyolefins, as a component of tackifying compositions, and as a component of adhesive materials.
  • High molecular weight resins are readily processed using conventional extrusion, injection molding, compression molding, and vacuum forming techniques well known in the art.
  • Useful articles made from them include films, fibers, bottles and other containers, sheeting, molded objects and the like.
  • Low molecular weight resins are useful, for example, as synthetic waxes and they may be used in various wax coatings or in emulsion form. They are also particularly useful in blends with ethylene/vinyl acetate or ethylene/methyl acrylate- type copolymers in paper coating or in adhesive applications.
  • typical additives used in olefin or vinyl polymers may be used in the new homopolymers and copolymers of this invention.
  • Typical additives include pigments, colorants, titanium dioxide, carbon black, antioxidants, stabilizers, slip agents, flame retarding agents, and the like. These additives and their use in polymer systems are known per se in the art.
  • the molecular weight data presented in the following examples is determined at 135 °C in 1,2,4-trichlorobenzene using refractive index detection, calibrated using narrow molecular weight distribution poly(styrene) standards.
  • Hydrogen was added to the reactor either by direct pressurization to the indicated partial pressure - (for hydrogen partial pressures ⁇ 4 psia), or by pressurizing a 40 mL gas sample loop to 40 or 65 psia with hydrogen, and using ethylene gas to sweep the hydrogen into the reactor (for hydrogen partial pressures ⁇ 4 psia).
  • the autoclave was then heated to the temperature indicated in Table I and pressurized to within about 100 psig ofthe indicated pressure (see Table I) with ethylene gas while being vigorously stirred.
  • Ethylene pressure was then used to inject 2.0 mL of dry, deoxygenated toluene from a sample loop (to clean the loop), followed by 2.0 mL (corresponding to 0.5 micromole of catalyst) of a toluene stock solution of [(ligand)Ni(acac)][B(C 6 F 5 ) 4 ], (see Table I for ligand) followed by another 2.0 mL of dry, deoxygenated toluene (to flush the loop), thereby raising the total reactor pressure to 5-10% over the target pressure, after which the reactor was isolated from the ethylene supply and the pressure was allowed to fall to approximately 5-10% below the target pressure, after which more ethylene was added to raise the pressure back to 5-10% over the target pressure and the cycle was repeated as required.
  • Example 2 Ethylene polymerization using r(w3 ⁇ NhYacac)1B(C 6 Fs) using MAO to activate
  • the procedure of Example 1 was followed using 15.72 psi hydrogen, an average reaction temperature of 90 °C, an average pressure of 400 psig, two catalyst injections, with the last injection at 0.32 min, and a total reaction time of 120 min to obtain 18.0 g polyethylene, corresponding to 6.1 million mol H mol Ni.
  • the reactor pressure was followed as a function of time, and showed an increasing rate of ethylene consumption, for the first 20-30 min, after which the rate stabilized and then slowly decreased until the end ofthe experiment.
  • Example 3 Ethylene polymerization using [Yw3)Ni(acac lB(CfiFs using AlMe 3 to activate The procedure of Example 3 was followed using 14.7 psi hydrogen and 0.36 mmol AlMe 3 in hexane instead of MAO, an average temperature of 81 °C, an average pressure of 399 psig, two injections of catalyst, with the last injection at 0.35 min and a total reaction time of 57 min to obtain 49.9 g polyethylene, corresponding to 1.7 million turnovers. A graph of reactor pressure as a function of time showed a more rapid increase in activity than was observed in Example 3, with full activity apparently being reached within about 5 min.
  • Example 5 Example 5
  • Triphenylmethanol (6.6 g, 25.4 mmol) was suspended in acetic anhydride (70 mL) and warmed until in solution.
  • Tetrafluoroboric acid (48% in water, 4.15 mL, 31.8 mmol) was slowly added dropwise while cooling the exothermic reaction in a room temperature water bath.
  • Diketone wa6-il (10.3 g, 21.2 mmol) was added in portions over a few minutes. Yellow needles ofthe desired pyrylium salt wa6-i2 began to separate from solution within minutes.
  • a sample loop injector was first purged with 2.0 mL dry, deoxygenated dichloromethane (injected into the reactor), and then used to inject 3 x 2.0 mL of a stock solution (corresponding to a total of 3.0 ⁇ mol of pro-catalyst) prepared from 17.34 mL of CH 2 C1 2 and 2.66 mL of a second stock solution prepared from 45.3 mg ligand v22,
  • Example 20 The procedure of Example 20 was followed, except the average temperature was 60.1 C, the average pressure was 605 psig, the partial pressure of hydrogen was 4.49 psi, and the total reaction time was 59.7 min. This afforded 38.6 g amorphous polyethylene, corresponding to 4.6 x 10 5 mol ethylene/mol nickel.
  • Example 22 Ethylene polymerization with the nickel catalyst derived from Nifacac)?. Pfo CsF )-. and ligand v5
  • Example 20 The procedure of Example 20 was followed using 2 ⁇ mol ofthe nickel catalyst derived from Ni(acac) 2 , Ph 3 C(C 6 F 5 ) 4 and ligand v5, and an average temperature of 60.8 C, an average pressure of 397 psig, a partial pressure of hydrogen of 5.12 psi, and a total reaction time of 21.7 min. This afforded 38. g partially crystalline polyethylene, corresponding to 6.8 x 10 5 mol ethylene/mol nickel.
  • Example 23 Example 23
  • Example 20 Ethylene polymerization with the nickel catalyst derived from Nifacac)?, Ph 3 CfC 6 Fs and 2,3-bis(2,6-diisopropylphenylimino butane
  • the procedure of Example 20 was followed using 4.2 ⁇ mol ofthe nickel catalyst derived from Ni(acac) 2 , Ph 3 C(C 6 Fs) 4 and 2,3-bis(2,6-diisopropylphenylimino)- butane, and an average temperature of 60.5 C, an average pressure of 398 psig, a partial pressure of hydrogen of 4.64 psi, and a total reaction time of 60 min. This afforded 18.7 g polyethylene, corresponding to 1.6 x 10 5 mol ethylene/mol nickel.
  • Example 20 The procedure of Example 20 was followed using 2 ⁇ mol ofthe nickel catalyst derived from Ni(acac) 2 , Ph 3 C(C 6 F 5 ) 4 and ligand v4, an initial temperature of 60 °C (the reaction exothermed to 81 °C), an average temperature of 63.7 C, an average pressure of 590 psig, a partial pressure of hydrogen of 4.03 psi, and a total reaction time of 34.5 min. This afforded 33.7 g partially crystalline polyethylene, corresponding to 6.0 x 10 5 mol ethylene/mol nickel.
  • Example 25 Example 25
  • Example 22 The procedure of Example 22 was repeated using 3 ⁇ mol nickel catalyst, 13.32 psi hydrogen, an average temperature of 80.4 C, and an average pressure of 406 psig to obtain 19.9 g polyethylene, corresponding to 2.4 x 10 5 mol ethylene/mol Ni.

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Abstract

Improved Group 3-11 transition metal based catalysts and processes for the polymerization of olefins are described. Some of the ligands are characterized by a preferred substitution pattern which allows for higher productivities of highly branched olefins; substitution patterns which boost productivity or alter the polymer microstructure are also described.

Description

IMPROVED PRODUCTIVITY CATALYSTS AND MICROSTRUCTURE
CONTROL
CROSS REFERENCE TO RELATED APPLICATIONS This application claims the benefit ofthe following applications under 35
USC § 120: Application No. 09/507,492, filed February 18, 2000, and Application No. 09/563,812, filed May 3, 2000, the entire contents of which are incorporated herein by reference; and the benefit ofthe following applications under 35 USC § 119: Provisional Application No. 60/231,920, filed September 11, 2000; Provisional Application No. 60/246,254, filed November 6, 2000; Provisional Application No. 60/246,255, filed November 6, 2000; Provisional Application No. 60/246,178, filed November 6, 2000; and Provisional Application No. 60/298,893, filed June 19, 2001, the entire contents of which are incorporated herein by reference.
FIELD OF THE INVENTION
This application generally relates to olefin polymerization catalyst compositions and olefin polymerization processes using the same, and to new polyolefm compositions.
BACKGROUND OF THE INVENTION
The use of late transition metal complexes as catalysts for olefin polymerization has recently been reviewed by Ittel et al. (Chem. Rev. 2000, 100, 1169). Notwithstanding the many advances described therein, there remains a need for new late transition metal catalysts with improved productivities under commercial reactor operating conditions, and for new methods of microstructure control. Late transition metal catalysts and processes that combine (i) high productivities at elevated temperatures and pressures in the presence of hydrogen as a molecular weight control agent, and (ii) high levels of branching, are especially sought. New catalysts and processes for these purposes are described herein. The distribution of branch lengths obtained using late transition metal catalysts is also important. Previously reported catalysts have tended to give ethylene homopolymers with too few longer branches, relative to methyl branches, to give LLDPE's with adequate film toughness. With the objective of addressing this problem, we have developed catalysts and processes which give ethylene homopolymers with substantially higher ratios of C5 and longer branches to methyl branches. These new catalysts, processes and ethylene homopolymer compositions are also described herein.
SUMMARY OF THE INVENTION In a first aspect, this invention pertains to a catalyst for olefin polymerization, comprising a Group 3-11 metal complex of a bidentate, tridentate, or tetradentate ligand, wherein the complex comprises at least one N-donor fragment of formula la or lb;
Figure imgf000004_0001
1a 1b
wherein: M is a Group 3-11 transition metal;
R3a"d are each, independently, H, F, CI, Br, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl, nitro, heteroatom connected hydrocarbyl or heteroatom connected substituted hydrocarbyl; and
Arla is an aryl or heteroaryl group substituted at one or both ortho positions by a group Q2; wherein Q2 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl or heteroatom connected substituted hydrocarbyl.
In a first preferred embodiment ofthe first aspect, M is a Group 8-10 metal. In a second preferred embodiment, M is nickel, and Q is sufficiently long to extend sufficiently close to the metal M to increase the catalyst productivity at elevated temperatures, or in the presence of hydrogen, or both, relative to an otherwise similar catalyst wherein Q is replaced by H, Me, or Ph.
In a third preferred embodiment, M is nickel, and Q2 is sufficiently long to extend sufficiently close to the metal M to increase the regioselectivity or stereoselectivity of comonomer incorporation, relative to an otherwise similar catalyst wherein Q2 is replaced by H, Me, or Ph. In a fourth preferred embodiment, M is nickel, and Q2 is sufficiently long to extend sufficiently close to the metal M to decrease the amount of chain-running, relative to an otherwise similar catalyst wherein Q2 is replaced by H, Me, or Ph.
In a fifth preferred embodiment, M is palladium, and Q2 is sufficiently long to extend sufficiently close to the metal M to decrease the amount of chain-running, relative to an otherwise similar catalyst wherein Q2 is replaced by H, Me, or Ph.
In a sixth preferred embodiment, M is nickel, and Q2 is sufficiently long to extend sufficiently close to the metal M to increase the chain-running stereoselectivity, relative to an otherwise similar catalyst wherein Q2 is replaced by H, Me, or Ph.
In a seventh preferred embodiment, M is nickel, and Q is sufficiently long to extend sufficiently close to the metal M to decrease the rate of activation ofthe catalyst when an alkylaluminum reagent is used as cocatalyst, relative to an otherwise similar catalyst wherein Q2 is replaced by H, Me, or Ph. In an eighth preferred embodiment, M is a Group 8-10 metal and the catalyst comprises a bidentate ligand selected from Set 1;
Setl
Figure imgf000006_0001
Figure imgf000006_0002
Set 1, cont'd
Figure imgf000007_0001
Figure imgf000007_0002
Set 1, cont'd
Figure imgf000008_0001
Figure imgf000008_0002
Set 1, cont'd
Figure imgf000009_0001
Figure imgf000009_0002
Set 1, cont'd
Figure imgf000010_0001
Figure imgf000010_0002
Set 1, cont'd
Figure imgf000011_0001
Figure imgf000011_0002
Set 1, cont'd
Figure imgf000012_0001
wa14
Figure imgf000012_0002
Set 1, cont'd
Figure imgf000013_0001
Figure imgf000013_0002
Set 1, cont'd
Figure imgf000014_0001
wherein:
R2x'y are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl; silyl, or ferrocenyl; in addition, R2x and R2y may be linked by a bridging group;
R3a"k are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, or nitro; R4a'b are each independently hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl; in addition, R4a and R4b may be linked by a bridging group;
"surface" refers to a silicon or other atom which is part of, or attached to, a solid support;
G1 is a divalent bridging group; and
Ar2a"m are each independently hydrocarbyl, substituted hydrocarbyl, heteroatom attached hydrocarbyl, heteroatom attached substituted hydrocarbyl, halo, nitro, boryl, or trialkoxysilane.
In a ninth preferred embodiment of this first aspect, M is iron or cobalt, the catalyst comprises a tridentate ligand, and Q2 which is sufficiently long to extend sufficiently close to the metal M to increase the catalyst productivity at elevated temperatures.
In a tenth preferred embodiment, the tridentate ligand.of the ninth preferred embodiment of this first aspect is selected from Set 2;
Set 2
Figure imgf000015_0001
Set 2, cont'd
Figure imgf000016_0001
tri2
wherein:
R2x'y are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl; silyl, or ferrocenyl; and
R3a"k are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, or nitro.
In an eleventh preferred embodiment, the catalyst is a titanium or zirconium complex of a bidentate ligand selected from Set 3;
Set 3
Figure imgf000016_0002
da1 Set 3, cont'd
Figure imgf000017_0001
Figure imgf000017_0002
wherein:
R2 is H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, silyl, or ferrocenyl;
R3a"J are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, fluoro, chloro, or bromo; and
Ar2a"J are each independently hydrocarbyl, substituted hydrocarbyl, heteroatom attached hydrocarbyl, heteroatom attached substituted hydrocarbyl, halo, nitro, boryl, or trialkoxysilane. In a twelfth preferred embodiment, the catalyst further comprises a solid support.
In a thirteenth preferred embodiment, the catalyst ofthe twelfth embodiment is attached to the solid support via a covalent bond to the group Arla.
In a second aspect, this invention pertains to a process for the polymerization of olefins, comprising contacting one or more olefins with the catalyst ofthe first aspect. .
In a first preferred embodiment ofthe second aspect, at least one ofthe olefins is ethylene.
In a second preferred embodiment ofthe second aspect, the olefin is ethylene, M is nickel, the temperature is at least 80 °C, the pressure is less than about 800 psig, sufficient hydrogen is added to reduce the number average molecular weight ofthe polymer by at least 20% relative to an otherwise similar reaction conducted in the absence of hydrogen, the catalyst productivity is at least 500 kg polyethylene per g nickel, and the polymer has a DSC (Differential Scanning Calorimetry) first cycle peak melting point greater than 131 °C.
In a third, more preferred embodiment ofthe second embodiment ofthe second aspect, sufficient hydrogen is added to reduce the number average molecular weight ofthe polymer by at least 50% relative to an otherwise similar reaction conducted in the absence of hydrogen, and the polymer has a DSC first cycle peak melting point greater than 133 °C.
In a fourth preferred embodiment ofthe second aspect, at least one ofthe olefins is ethylene, M is palladium and the amount of chain running is reduced. In a third aspect, this invention pertains to a bidentate, tridentate, or tetradentate ligand ofthe first or second aspects.
In a fourth aspect, this invention pertains to a process for the polymerization of olefins, comprising contacting one or niore olefins with a catalyst comprising a Group 8-10 metal complex of a bidentate, N,N-donor ligand, wherein the first ofthe donor nitrogens, N1, is substituted by an aromatic or heteroaromatic ring wherein the ortho substituents are aryl or heteroaryl groups, and the second ofthe donor nitrogens, N , is substituted by an aromatic or heteroaromatic ring wherein one or both ofthe ortho substituents are other than aryl or heteroaryl; wherein the catalyst is capable of homopolymerizing ethylene to produce a polymer with a number average molecular weight of at least 20,000 g/mole and at least 20 branch points per 1000 carbons with a catalyst productivity of at least 500 kg polyethylene per g of Group 8-10 metal at a temperature of at least 60 °C at a partial pressure of ethylene of at least 350 psia at a partial pressure of hydrogen of at least 2 psia. Preferred substituents other than aryl or heteroaryl include Br, CI, CF3 and fluoroalkyl.
In a first preferred embodiment of this fourth aspect, the ligand is such that the calculated rate of olefin rotation in square planar complexes ofthe type (L)M(H)(RlaCH=CHRlb)n+, wherein n = 0 or 1, M is nickel or palladium, L is the bidentate, N,N-donor ligand, Rla is H or Me, and Rl is Me, and RlaCH=CHRlb is trans to N1, is at least 2 times higher than the calculated rate of olefin rotation in the complex wherein RlaCH=CHRl is cis to N1.
In a second, more preferred embodiment, the calculated rate of olefin rotation in the complex ofthe first preferred embodiment ofthe fourth aspect wherein RlaCH=CHRlb is trans to N1 is at least 4 times higher than the calculated rate of olefin rotation in the isomeric complex wherein Rl CH=CHRlb is cis to N1. In a third preferred embodiment of this fourth aspect, the metal is nickel, Nl is substituted by a 2,6-diaryl substituted aryl group or a 2,5-diaryl substituted 1- pyrrolyl group, and N2 is substituted by an aromatic or heteroaromatic ring wherein one or both ofthe ortho substituents are other than aryl or heteroaryl. In a fourth, more preferred embodiment of this fourth aspect, the metal is mckel, N1 is substituted by a 2,6-diaryl substituted aryl group, N2 is substituted by an aromatic ring wherein one or both ofthe ortho substituents are other than aryl or heteroaryl, and the catalyst productivity is at least 500 kg polyethylene per g nickel at a temperature of at least 70 °C.
In a fifth preferred embodiment ofthe fourth aspect, the process ofthe fourth preferred emodiment ofthe fourth aspect comprises a catalyst wherein N2 is substituted by an aromatic ring wherein one ofthe ortho substituents is aryl, heteroaryl or bromo, and the other ortho substituent is bromo.
In a sixth embodiment ofthe fourth aspect, the bidentate ligand is selected
Figure imgf000020_0001
2/36641
20
Set 4
Figure imgf000021_0001
hcr4
Figure imgf000021_0002
hcrl
Figure imgf000021_0003
hcr2 Set 4, cont'd
Figure imgf000022_0001
hcr5
Figure imgf000022_0002
hcr6
Figure imgf000022_0003
hcr7
Figure imgf000022_0004
Set 4, cont'd
Figure imgf000023_0001
hcr9
Figure imgf000023_0002
hcr10
Figure imgf000023_0003
hcr11
Figure imgf000023_0004
Set 4, cont'd
Figure imgf000024_0001
Set 4, cont'd
Figure imgf000025_0001
Figure imgf000025_0002
hcr17
Figure imgf000025_0003
hcr18 Set 4, cont'd
Figure imgf000026_0001
shc
Figure imgf000026_0002
shcr2
Figure imgf000026_0003
shcr3
Figure imgf000026_0004
shcr4
Figure imgf000026_0005
Set 4, cont'd
Figure imgf000027_0001
Figure imgf000027_0002
Set 4, cont'd
Figure imgf000028_0001
Figure imgf000028_0002
s cr9 wherein:
R2x'y are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, silyl, or ferrocenyl; in addition, R2 and R2y may be linked by a bridging group; R3a_1 are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, or nitro; Ar2a"m are each independently aryl or heteroaryl; and Ar3a"c are each independently 4-substituted aryl groups; wherein the 4- substituents are selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted • hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, phenylsulfonyl, and nitro.
In a seventh preferred embodiment ofthe fourth aspect, the olefin is ethylene and the polymer is an ethylene homopolymer wherein the average spacing between branch points is such that there is at least a 10% excess of sequences ofthe type - CHR-(CH2) n+2-CHR-, where R is alkyl and n is 0 or a positive integer, relative to sequences of the type -CHR-(CH2)2m-CHR-, where R is alkyl and m is a positive integer. In an eighth preferred embodiment ofthe fourth aspect, the olefin is ethylene, N is substituted by a 2-aryl-6-bromo-aryl group and the polymer is an ethylene homopolymer wherein there is an excess of isotactic sequences ofthe type -CHRla-(CH2)4n+2-CHRlb-, where Rla and Rl are hydrocarbyl or substituted hydrocarbyl branches and n is 0 or 1, relative to a random distribution. In a fifth aspect, this invention pertains to a polymer prepared according to the process ofthe fourth aspect.
In a sixth aspect, this invention pertains to a process for the polymerization of olefins, comprising contacting one or more olefins with a catalyst comprising a Group 8-10 metal complex of a bidentate, tridentate or multidentate ligand, wherein the catalyst is activated using an alkylaluminum compound, wherein the alkylaluminum compound is subsequently selectively deactivated before the bulk of the polymerization has occurred. In a first preferred embodiment ofthe sixth aspect, the alkylaluminum compound is selectively deactivated through the addition of a phenol or substituted phenol.
In a second preferred embodiment ofthe sixth aspect, the Group 8-10 metal complex is a cationic nickel complex of a bidentate N,N-donor ligand.
In a third preferred embodiment ofthe sixth aspect, the Group 8-10 metal complex is a cationic iron or cobalt complex of a tridentate ligand.
In a seventh aspect, this invention pertains to a catalyst for the polymerization of olefins, comprising a nickel complex of a ligand of formula 2a;
Figure imgf000030_0001
2a
wherein:
R2x'y are each independently hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or silyl; in addition, R2x and R2y may be linked by a bridging group;
R3 "f are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, iodo, cyano, or nitro;
R3x,y are each independently halo or fluoroalkyl; and Ar2a,b are each independently aryl or heteroaryl.
In a first preferred embodiment of this seventh aspect, R2x and R2y are linked by a bridging group.
In an eighth aspect, this invention pertains to a process for the polymerization of olefins comprising contacting ethylene and optionally other olefins with the catalyst ofthe seventh aspect in the presence of sufficient hydrogen to reduce the number average molecular weight ofthe polymer by at least 10% relative to an otherwise similar process carried out in the absence of hydrogen. By "other olefins", we mean 1-alkenes, preferably 1-butene, 1-hexene or 1- octene, or long chain 1-alkene macromonomers.
In a ninth aspect, this invention pertains to an ethylene homopolymer having a number average molecular weight of at least 10,000 g/mole, total branching of less than about 70 branches per 1000 carbons, at least 10% saturated hydrocarbon polymer chains, and a ratio of C5 and longer branches to methyl branches of at least 0.35.
In a first preferred embodiment of this ninth aspect, the total branching is less than about 60 branches per 1000 carbons; at least 25% ofthe polymer chains are saturated hydrocarbon chains; and the ratio of C5 and longer branches to methyl branches is at least 0.40. In a second preferred embodiment, the total branching is less than about 60 branches per 1000 carbons; and the ratio of C5 and longer branches to methyl branches is at least 0.45. In a third preferred embodiment, the Differential Scanning Calorimetry (DSC) curve ofthe homopolymer shows a bimodal melt endotherm on the second heat from the melt, with the area ofthe smaller ofthe two peaks representing at least 25% ofthe total melt endotherm.
DETAILED DESCRIPTION OF THE INVENTION In this disclosure, symbols ordinarily used to denote elements in the Periodic Table and commonly abbreviated groups, take their ordinary meaning, unless otherwise specified. Thus, N, O, S, P, and Si stand for nitrogen, oxygen, sulfur, phosphorus, and silicon, respectively, while Me, Et, Pr, 'Pr, Bu, lBu and Ph stand for methyl, ethyl, propyl, z'so-propyl, butyl, tert-butyl and phenyl, respectively.
A "1-pyrrolyl or substituted 1-pyrrolyl" group refers to a group of formula II below:
Figure imgf000032_0001
wherein R3a"d are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, or nitro; in addition, any two or more of R3a"d may be linked by a bridging group or groups to form bicyclic or polycyclic ring systems including carbazol-9-yl and indol-1-yl.
A "hydrocarbyl" group means a monovalent or divalent, linear, branched or cyclic group which contains only carbon and hydrogen atoms. Examples of monovalent hydrocarbyls include the following: C1-C20 alkyl; C1-C20 alkyl substituted with one or more groups selected from Cι-C20 alkyl, C3-C8 cycloalkyl, and aryl; C3-C8 cycloalkyl; C3-C8 cycloalkyl substituted with one or more groups selected from Ci-C2o alkyl, C3-C8 cycloalkyl, and aryl; C6-C14 aryl; and C6-C1 aryl substituted with one or more groups selected from -C20 alkyl, C3-C8 cycloalkyl, and aryl. Examples of divalent (bridging) hydrocarbyls include: -CH2-, -CH2CH2- -CH2CH2CH2- and 1,2-phenylene. The term "aryl" refers to an aromatic carbocyclic monoradical, which may be substituted or unsubstituted, wherein the substituents are halo, hydrocarbyl, substituted hydrocarbyl, heteroatom attached hydrocarbyl, heteroatom attached substituted hydrocarbyl, nitro, cyano, fluoroalkyl, sulfonyl, and the like. Examples include: phenyl, naphthyl, anthracenyl, phenanthracenyl, 2,6-diphenylphenyl, 3,5- dimethylphenyl, 4-nitrophenyl, 3-nitrophenyl, 4-methoxyphenyl, 4- dimethylaminophenyl, 2,6-dibromophenyl, 2,4,6-tribromophenyl, 2,4-dibromo-6- phenylphenyl, 2,6-di(4-tert-butylphenyl)phenyl, 2,6-di(4-tert-butylphenyl)-4- phenylphenyl, 2,6-di(4-phenylphenyl)-4-phenylphenyl, 2,4-dibromo-6- trifluoromethylphenyl, 2,4-bis(4-tert-butylphenyl)-6-trifluoromethylphenyl, 2- chloro-4,6-di(4-tert-butylphenyl)phenyl, 2,6-di(l-naphthyl)-4-phenylphenyl, and the like. A "heterocyclic ring" refers to a carbocyclic ring wherein one or more ofthe carbon atoms has been replaced by an atom selected from the group consisting of O, N, S, P, Se, As, Si, B, and the like.
A "heteroaromatic ring" refers to an aromatic heterocyclic ring; examples include pyrrole, furan, thiophene, indene, imidazole, oxazole, isoxazole, carbazole, thiazole, pyrimidine, pyridine, pyridazine, pyrazine, benzothiophene, and the like.
A "heteroaryl" refers to a heterocyclic ring monoradical which is aromatic; examples include 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, furyl, thienyl, indenyl, imidazolyl, oxazolyl, isoxazolyl, carbazolyl, thiazolyl, pyrimidinyl, pyridyl, pyridazinyl, pyrazinyl, benzothienyl, and the like, and substituted derivatives thereof.
A "silyl" group refers to a SiR3 group wherein Si is silicon and R is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or silyl, as in Si(SiR3)3.
A "boryl" group refers to a BR2 or B(OR)2 group, wherein R is hydrocarbyl or substituted hydrocarbyl.
A "heteroatom" refers to an atom other than carbon or hydrogen. Preferred heteroatoms include oxygen, nitrogen, phosphorus, sulfur, selenium, arsenic, chlorine, bromine, silicon, and fluorine.
A "substituted hydrocarbyl" refers to a monovalent, divalent, or trivalent hydrocarbyl substituted with one or more heteroatoms. Examples of monovalent substituted hydrocarbyls include: 2,6-dimethyl-4-methoxyphenyl, 2,6-diisopropyl- 4-methoxyphenyl, 4-cyano-2,6-dimethylphenyl, 2,6-dimethyl-4-nitrophenyl, 2,6- difluorophenyl, 2,6-dibromophenyl, 2,6-dichlorophenyl, 4-methoxycarbonyl-2,6- dimethylphenyl, 2-tert-butyl-6-chlorophenyl,-2,6-dimethyl-4-phenylsulfonylphenyl, 2,6-dimethyl-4-trifluoromethylphenyl, 2,6-dimethyl-4-trimethylammoniumphenyl (associated with a weakly coordinated anion), 2,6-dimethyl-4-hydroxyphenyl, 9- hydroxyanthr-10-yl, 2-chloronapth-l-yl, 4-methoxyphenyl, 4-nitrophenyl, 9- nitroanthr-10-yl, -CH2OCH3, cyano, trifluoromethyl, and fluoroalkyl. Examples of divalent (bridging) substituted hydrocarbyls include: 4-methoxy-l,2-phenylene, 1- methoxymethyl-l,2-ethanediyl, l,2-bis(benzyloxymethyl)-l,2-ethanediyl, and l-(4- methoxyphenyl)- 1 ,2-ethanediyl. A "heteroatom connected hydrocarbyl" refers to a group ofthe type
E10(hydrocarbyl), E20H(hydrocarbyl), or E20(hydrocarbyl)2, where E10 is an atom selected from Group 16 and E is an atom selected from Group 15. A "heteroatom connected substituted hydrocarbyl" refers to a group ofthe type E10(substituted hydrocarbyl), E20H(substituted hydrocarbyl), or E20(substituted hydrocarbyl)2, where E10 is an atom selected from Group 16 and E20 is an atom selected from Group 15. The term "fluoroalkyl" as used herein refers to a C1-C20 alkyl group substituted by one or more fluorine atoms.
An "olefin" refers to a compound ofthe formula RlaCH=CHRlb, where Rla and R may independently be H, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl, silyl, O(hydrocarbyl), or O(substituted hydrocarbyl), and where Rla and Rlb may be connected to form a cyclic olefin, provided that in all cases, the substituents Rla and Rlb are compatible with the catalyst. In the case of most Group 4-7 catalysts, this will generally mean that the olefin should not contain good Lewis base donors, since this will tend to severely inhibit catalysis. Preferred olefins for such catalysts include ethylene, propylene, butene, hexene, octene, cyclopentene, norbornene, and styrene. In the case ofthe Group 8-10 catalysts, Lewis basic substituents on the olefin will tend to reduce the rate of catalysis in most cases; however, useful rates of homopolymerization or copolymerization can nonetheless be achieved with some of those olefins. Preferred olefins for such catalysts include ethylene, propylene, butene, hexene, octene, and fluoroalkyl substituted olefins, but may also include, in the case of palladium and some ofthe more functional group tolerant nickel catalysts, norbornene, substituted norbornenes (e.g., norbornenes substituted at the 5-position with halide, siloxy, silane, halo carbon, ester, acetyl, alcohol, or amino groups), cyclopentene, ethyl undecenoate, acrylates, vinyl ethylene carbonate, 4- vinyl-2,2-dimethyl- 1 ,3 -dioxolane, and vinyl acetate.
In some cases, the Group 8-10 catalysts can be inhibited by olefins which contain additional olefinic or acetylenic functionality. This is especially likely if the catalyst is prone to "chain-running" wherein the catalyst can migrate up and down the polymer chain between insertions, since this can lead to the formation of relatively unreactive π-allylic intermediates when the olefin monomer contains additional unsaturation. Such effects are best determined on a case-by-case basis, but may be predicted to some extent through knowledge of how much branching is observed with a given catalyst in ethylene homopolymerizations; those catalysts which tend to give relatively high levels of branching with ethylene will tend to exhibit lower rates when short chain diene co-monomers are used under the same conditions. Longer chain dienes tend to be less inhibitory than shorter chain dienes, when other factors are kept constant, since the catalyst has to migrate farther to form the π-allyl, and another insertion may intervene first. Similar considerations apply to unsaturated esters which are capable of inserting and chain-running to form relatively stable intramolecular chelate structures wherein the Lewis basic ester functionality occupies a coordination, site on the catalyst. In such cases, short chain unsaturated esters, such as methyl acrylate, tend to be more inhibitory than long chain esters, such as ethyl undecenoate, if all other factors are kept constant.
By "alpha-olefin functional comonomer" we mean an alpha-olefin which contains a functional group containing at least one N or O atom. Preferred functional groups include esters, alkyl ethers, carbonates and nitriles. The term "ortho" is used to refer to substituents attached to the 2- and 6- positions of a 1 -attached, six-membered aromatic or heteroaromatic ring, or the 2- and 5-positions of a 1 -attached, five-membered aromatic or heteroaromatic ring, or more generally the first substitutable positions on either side ofthe point of attachment of said aromatic or heteroaromatic ring to said donor nitrogen. By "chain running", we mean the process by which certain olefin polymerization catalysts, especially those based on Group 8-10 transition metal complexes of bidentate ligands, are capable of migrating along a growing polymer chain between insertion events to form branched polymers from ethylene alone, and give modes of enchainment other than 1,2 enchainment when substituted alkenes are polymerized or copolymerized.
By "olefin rotation", we mean rotation by at least 180° about a vector extending from said Group 8-10 metal to the olefin centroid. The rate of olefin rotation may be calculated using Density Field Theory / Molecular Mechanics programs (c.f. Ziegler et al. inJ. Am. Chem. Soc. 1997, 119, 1094 and 6177).
By "isotactic sequences ofthe type -CHRla-(CH2)4n+2-CHRlb-", we mean polymer chain sequences ofthe type -CHR1 a-CH2-CH2-CHRlb- or -CHRla-(CH2)6- CHRlb- in which the configuration about the -CHRla- center is the same as that about the -CHRlb- center where Rla and Rlb are hydrocarbyl or substituted hydrocarbyl branches and n is 0 or 1. When the only olefin monomer is ethylene, the most common type of branch will be methyl with most ofthe catalysts ofthe current invention; however, longer branches will also be present in most cases, especially when the total number of branches is greater than about 10 per 1000 carbons.
By "different (a) comonomer incorporation selectivities, (b) chain running rates, (c) stereoselectivities, or (d) combinations thereof," we mean a difference of at least 10%, preferably at least 20%, more preferably at least 40%. By "increase the catalyst productivity at elevated temperatures, or in the presence of hydrogen, or both", we mean a catalyst productivity, expressed in units of kg polymer per mmole catalyst, which is at least 25% higher, preferably 50% higher, even more preferably 100% higher than that observed with an otherwise similar catalyst with H, Me or Ph in place of group Arl , under the same reaction conditions.
By "elevated temperatures", we mean a temperature of at least 60 °C, preferably at least 70 °C, even more preferably at least 80 °C.
By "in the presence of hydrogen", we mean an amount of hydrogen sufficient to reduce the number average molecular weight by at least 5%, preferably at least 10%, even more preferably at least 20%, relative to an otherwise similar reaction conducted in the absence of hydrogen. By "increase the regioselectivity or stereoselectivity of comonomer incorporation", we mean an increase of at least 10%, preferably at least 20% in either the regioselectivity or stereoselectivity of comonomer incorporation, relative to that observed for an otherwise similar catalyst with H, Me or Ph in place of group Arla, under the same reaction conditions.
By "reduce the amount of chain running", we mean either a decrease of at least 10%, preferably at least 20%, in the amount of branching observed for a branched polyolefin derived from ethylene alone, or an increase of at least 10%, preferably at least 20%, in the amount of branching observed for a chain- straightened poly-alpha-olefin, relative to that observed for an otherwise similar catalyst with H, Me or Ph in place of group Arla, under the same reaction conditions.
By "chain-straightened", we mean a poly-alpha-olefin with fewer branches than would be observed using an olefin polymerization catalyst which cannot undergo chain-running. By "increase the chain-running stereoselectivity", we mean an. increase of at least 10%, preferably at least 20% in the occurrence of configurational correlation between adjacent substituted carbons along the polymer chain, relative to a purely random distribution.
By "decrease the rate of activation ofthe catalyst", we mean the catalyst precursor is converted into active form more slowly than would be observed for otherwise similar catalysts with H, Me or Ph in place of group Arla, under the same reaction conditions. Such slower activation can be advantageous under certain circumstances, including, for example, gas phase fluidized bed processes, where overly rapid activation can lead to over-heating of supported catalyst particles and reactor fouling.
The term "alpha-olefin" is used to refer to an olefin of formula H2C=CHR, where R is a hydrocarbyl group. Preferred alpha-olefins are those with 3-40 carbons. A "π-allyl" group refers to a monoanionic group with three sp2 carbon atoms bound to a metal center in a η -fashion. Any ofthe three sp carbon atoms may be substituted with a hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or O-silyl group. Examples of π-allyl groups include:
Me -C6H5
Figure imgf000038_0001
The term π-benzyl group denotes an π-allyl group where two ofthe sp2 carbon atoms are part of an aromatic ring. Examples of π-benzyl groups include:
Figure imgf000038_0002
A "bridging group" refers to an atom or group which links two or more groups, which has an appropriate valency to satisfy its requirements as a bridging group, and which is compatible with the desired catalysis. Suitable examples include divalent or trivalent hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, substituted silicon(IV), boron(ni), N(IIι), P(in), and P(V), -C(O)-, -SO2-, -C(S)-, -B(OMe)-, - C(O)C(O)-, O, S, and Se. In some cases, the groups which are said to be "linked by a bridging group" are directly bonded to one another, in which case the term "bridging group" is meant to refer to that bond. By "compatible with the desired catalysis," we mean the bridging group either does not interfere with the desired catalysis, or acts to usefully modify the catalyst activity or selectivity.
The term "weakly coordinating anion" is well known in the artier se and generally refers to a large bulky anion capable of delocalization ofthe negative charge ofthe anion. The importance of such delocalization depends to some extent on the nature ofthe transition metal comprising the cationic active species, with the Group 4-6 transition metals requiring less coordinating anions, such as B(C6F5) ", than many Group 8-10 transition metal based catalysts, which can in some cases give active catalysts with BF " counteranions. Weakly coordinating anions, not all of which would be considered bulky, include, but are not limited to: B(C6Fs) ", PF6 ", BF ", SbF6 ", (Ph)4B" wherein Ph = phenyl, and Ar- B" wherein Ar B" = tetrakis[3,5- bis(trifluoromethyl)phenyl]-borate. The weakly coordinating nature of such anions is known and described in the literature (S. Strauss et al., Chem. Rev., 1993, 93, 927).
The abbreviation "acac" refers to acetylacetonate. In general, substituted acetylacetonates, wherein one or more hydrogens in the parent structure have been replaced by a hydrocarbyl, substituted hydrocarbyl, or fluoroalkyl, may be used in place ofthe "acac". Hydrocarbyl substituted acetylacetonates may be preferred in some cases when it is important, for example, to improve the solubility of a (ligand)Ni(acac)BF4 salt in mineral spirits.
By "under the same reaction conditions", we mean the catalyst loading, solvent, solvent volume, agitation, ethylene pressure, co-monomer concentration, reaction time, and other process relevant parameters are sufficiently similar that a valid comparison can be made between two catalysts.
The phrase "one or more olefins" refers to the use of one or more chemically different olefin monomer feedstocks, for example, ethylene and propylene. A variety of protocols may be used to generate active polymerization catalysts comprising transition metal complexes of various nitrogen, phosphorous, oxygen and sulfur donor ligands. Examples include (i) the reaction of a Group 4 metallocene dichloride with MAO, (ii) the reaction of a Group 4 metallocene dimethyl complex with N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, (iii) the reaction of a Group 8 or 9 metal dihalide complex of a tridentate N-donor ligand with an alkylaluminum reagent, (iv) the reaction of a Group 8 or 9 metal dialkyl complex of a tridentate N-donor ligand with MAO or HB(3,5- bis(trifluoromethyl)phenyl)4, (v) the reaction of (Me2N)4Zr with 2 equivalents of an N-pyrrol-1-ylsalicylimine, followed by treatment ofthe product of that reaction with Me3SiCl and then a triisobutylaluminum-modified methylaluminoxane, and (vi) the reaction of a nickel or palladium dihalide complex of a bidentate N-donor ligand with an alkylaluminum reagent. Additional methods described herein include the reaction of (tridentate N-donor ligand)M(acac)B(C6F5)4 salts with an alkylaluminum reagent, where M is Fe(II) or Co(II), and the reaction of (bidentate N-donor ligand)Ni(acac)X salts with an alkylaluminum reagent, where X is a weakly coordinating anion, such as B(C6F5) ", BF4 ", PF6 ", SbF6 ", (F3CSO2)2N\ (F3CSO2)3C, and OS(O)2CF3 ". Cationic [(ligand)M(π-allyl)] complexes with weakly coordinating counteranions, where M is a Group 10 transition metal, are often also suitable catalyst precursors, requiring only exposure to olefin monomer and in some cases elevated temperatures (40-100 °C) or added Lewis acid, or both, to form an • active polymerization catalyst. More generally, a variety of (ligand)nM(Zla)(Zlb) complexes, where "ligand" refers to a compound ofthe present invention, n is 1 or 2, M is a Group 4-10 transition metal, and Zla and Zl are univalent groups, or may be taken together to form a divalent group, may be reacted with one or more compounds, collectively referred to as compound Y, which function as co-catalysts or activators, to generate an active catalyst ofthe form [(ligand)nM(Tla)(L)]+X", where n is 1 or 2, Tla is a hydrogen atom or hydrocarbyl, L is an olefin or neutral donor group capable of being displaced by an olefin, M is a Group 4-10 transition metal, and X" is a weakly coordinating anion. When Zla and Zlb are both halide, examples of compound Y include: methylaluminoxane (herein MAO) and other aluminum sesquioxides, R3A1, R A1C1, and RA1C12 (wherein R is alkyl, and plural groups R may be the same or different). When Zla and Zl are both alkyl, examples of a compound Y include: MAO and other aluminum sesquioxides, R3A1, R2A1C1, RA1C12 (wherein R is alkyl, and plural groups R may be the same or different), B(C6Fs)3, R°3Sn[BF4] (wherein R° is hydrocarbyl or substituted hydrocarbyl and plural groups R° may be the same or different), H+X", wherein X" is a weakly coordinating anion, for example, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and Lewis acidic or Bronsted acidic metal oxides, for example, montmorillonite clay. In some cases, for example, when Zla and Zlb are both halide or carboxylate, sequential treatment with a metal hydrocarbyl, followed by reaction with a Lewis acid, may be required to generate an active catalyst. Examples of metal hydrocarbyls include: MAO, other aluminum sesquioxides, R3 Al, R2A1C1, RA1C12 (wherein R is alkyl, and plural groups R may be the same or different), Grignard reagents, organolithium reagents, and diorganozinc reagents. Examples of Lewis acids include: MAO, other aluminum sesquioxides, R3A1, R2A1C1, RAICI2 (wherein R is alkyl, and plural groups R may be the same or different), B(C6F5)3, R°3Sn[BF4] (wherein R° is hydrocarbyl or substituted hydrocarbyl and plural groups R° may be the same or different), and Lewis acidic metal oxides.
The term "alkylaluminum" is used to refer to compounds containing at least one alkyl group bonded to Al(III), which are capable of reacting with a metal complex ofthe present invention to generate an active olefin polymerization catalyst. In general, this will involve exchanging one or more alkyl groups from the aluminum with a monoanionic atom or group on the metal complex pro-catalyst. In some cases, a hydride may be directly transferred from the β-carbon ofthe aluminum alkyl to said metal complex. Subsequent abstraction of a second monoanionic atom or group from the metal complex may also be required to generate a cationic active catalyst. When the pro-catalyst is already a cationic metal complex, the role ofthe alkylaluminum may simply be to exchange an alkyl or hydride from the aluminum with a monoanionic group, such as acetylacetonate, attached to the metal complex. In the case of a cationic π-allyl or π-benzyl pro- catalyst, the alkylaluminum reagent may, in some cases, simply act as a Lewis acid, to promote conversion ofthe π-allyl or π-benzyl to a σ-allyl or σ-benzyl bonding mode, thereby facilitating binding and insertion ofthe olefin monomer. When a cationic pro-catalyst is used with an alkylaluminum activator or co-catalyst, it should also be recognized that the starting counteranion (e.g. BF4 ") may react with the alkylaluminum reagent to generate a new counteranion (or a mixture of several different counteranions) under olefin polymerization reaction conditions. Examples of alkylaluminum reagents include: MAO, other aluminum sesquioxides, Me Al, EtAlCl2, Et2AlCl, R3A1, R2A1C1, RA1C12 (wherein R is alkyl, and plural groups R may be the same or different), and the like.
The foregoing discussion is intended to illustrate that there are frequently many ways to generate an active catalyst. It is an object of this disclosure to teach that there are a variety of methods wherein the ligands ofthe present invention can be reacted with a suitable metal precursor, and optionally a co-catalyst, to generate an active olefin polymerization catalyst. Without wishing to be bound by theory, the inventors also believe that the active catalyst typically comprises the catalytically active metal, one or more ligands ofthe present invention, the growing polymer chain (or a hydride capable of initiating a new chain), and a site on the metal adjacent to the metal-alkyl bond ofthe chain where ethylene can coordinate, or at least closely approach, prior to insertion. Where specific structures for active catalysts have been implied herein, it should be understood that an object of this invention is to teach and claim that active catalysts comprising the ligands ofthe present invention are formed as the reaction products ofthe catalyst activation reactions disclosed herein, regardless ofthe detailed structures of those active species.
Active catalysts may, in some cases, be generated from more than one oxidation state of a given metal. For example, the present invention describes the use of both Co(IH) and Co(II) catalyst precursors to effect olefin polymerization using MAO or other alkylaluminum co-catalysts. Where only one oxidation state of a given metal has been specified herein, it is therefore to be understood that other oxidation states ofthe same metal, complexed by the ligands ofthe present invention, can serve as catalyst precursors or active catalysts. When different oxidation state complexes ofthe ligands are used, appropriate changes in the ancillary ligands or the counteranion must obviously accompany any change in oxidation level to balance the charge. Examples where multiple oxidation state precurors are especially likely to be encountered include, but are not limited to, Ti(III)/Ti(IN), Fe(III)/Fe(II), and Co(iπ)/Co(II).
The catalysts ofthe present invention may be used in batch and continuous processes, in solution or slurry or gas phase processes. In some cases, it is advantageous to attach the catalyst to a solid support.
Examples of useful solid supports include: inorganic oxides, such as talcs, silicas, titania, silica/chromia, silica/chromia/titania, silica/alumina, zirconia, aluminum phosphate gels, silanized silica, silica hydrogels, silica xerogels, silica aerogels, montmorillonite clay and silica co-gels, as well as organic support materials such as polystyrene and functionalized polystyrene. (See, for example, S.B. Roscoe et al., "Polyolefin Spheres from Metallocenes Supported on Non-Interacting Polystyrene," 1998, Science, 280, 270-273 (1998)). Thus, in a preferred embodiment, the catalysts ofthe present invention are attached to a solid support (by "attached to a solid support" is meant ion paired with a component on the surface, adsorbed to the surface or covalently attached to the surface) that has been pre-treated with an alkylaluminum compound. More generally, the alkylaluminum and the solid support can be combined in any order and any number of alkylaluminum(s) can be utilized. In addition, the supported catalyst thus formed may be treated with additional quantities of alkylaluminum. In another preferred embodiment, the compounds ofthe present invention are attached to silica that has been pre-treated with an alkylaluminum, for example, MAO, Et3Al, iBu3Al, Et2A101, or Me3Al.
Such supported catalysts are prepared by contacting the transition metal compound, in a substantially inert solvent (by which is meant a solvent which is either unreactive under the conditions of catalyst preparation, or if reactive, acts to usefully modify the catalyst activity or selectivity) with MAO-treated silica for a sufficient period of time to generate the supported catalyst. Examples of substantially inert solvents include toluene, o-difluorobenzene, mineral spirits, hexane, CH2C12, arid CHC13.
In another preferred embodiment, the catalysts ofthe present invention are activated in solution under an inert atmosphere, and then adsorbed onto a silica support which has been pre-treated with a silylating agent to replace surface silanols by trialkylsilyl groups. Methods to pre-treat silicas in this way are known to those skilled in the art and may be achieved, for example, by heating the silica with hexamethyldisilazane and then removing the volatiles under vacuum. A variety of precurors and procedures may be used to generate the activated catalyst prior to said adsorption, including, for example, reaction of a (ligand)Ni(acac)B(C6F5) complex with Et2AlCl in a toluene/hexane mixture under nitrogen; where "ligand" refers to a compound of the present invention.
In another, more preferred embodiment, the catalysts ofthe present invention are covalently attached to a solid support and then activated in a slurry phase process by treatment with an alkylaluminum reagent. Methods of covalent attachment include reaction of a 4-hydroxyphenyl group which is part ofthe ligand with Si(NMe2)4, followed by reaction ofthe resultant ligand-O-Si(NMe2)3 derivative with silica.
In several cases, metal complexes are depicted herein with square planar, trigonal bipyramidal, or other coordination, however, it is to be understood that no specific geometry is implied.
The polymerizations may be conducted as solution polymerizations, as non- solvent slurry type polymerizations, as slurry polymerizations using one or more of the olefins or other solvent as the polymerization medium, or in the gas phase. One of ordinary skill in the art, with the present disclosure, would understand that the catalyst could be supported using a suitable catalyst support and methods known in the art. Substantially inert solvents, such as toluene, hydrocarbons, methylene chloride and the like, may be used. Propylene and 1 -butene are excellent monomers for use in slurry-type copolymerizations and unused monomer can be flashed off and reused. Temperature and olefin pressure have significant effects on catalyst activity, and on polymer structure, composition, and molecular weight. Suitable polymerization temperatures are preferably from about 20 °C to about 160 °C, more preferably 60 °C to about 100 °C. Suitable polymerization pressurse range from about 1 bar to about 200 bar, preferably 5 bar to 50 bar, more preferably 10 bar to 50 bar.
The catalysts ofthe present invention may be used alone, or in combination with one or more other Group 3-10 olefin polymerization or oligomerization catalysts, in solution, slurry, or gas phase processes. Such mixed catalyst systems are sometimes useful for the production of bimodal or multimodal molecular weight or compositional distributions, which may facilitate polymer processing or final product properties.
After the reaction has proceeded for a time sufficient to produce the desired . polymers, the polymer can be recovered from the reaction mixture by routine methods of isolation and/or purification. In general, the polymers ofthe present invention are useful as components of thermoset materials, as elastomers, as packaging materials, films, compatibilizing agents for polyesters and polyolefins, as a component of tackifying compositions, and as a component of adhesive materials.
High molecular weight resins are readily processed using conventional extrusion, injection molding, compression molding, and vacuum forming techniques well known in the art. Useful articles made from them include films, fibers, bottles and other containers, sheeting, molded objects and the like.
Low molecular weight resins are useful, for example, as synthetic waxes and they may be used in various wax coatings or in emulsion form. They are also particularly useful in blends with ethylene/vinyl acetate or ethylene/methyl acrylate- type copolymers in paper coating or in adhesive applications.
Although not required, typical additives used in olefin or vinyl polymers may be used in the new homopolymers and copolymers of this invention. Typical additives include pigments, colorants, titanium dioxide, carbon black, antioxidants, stabilizers, slip agents, flame retarding agents, and the like. These additives and their use in polymer systems are known per se in the art.
Other features ofthe invention will become apparent in the following description of working examples, which have been provided for illustration of the invention and are not intended to be limiting thereof.
The molecular weight data presented in the following examples is determined at 135 °C in 1,2,4-trichlorobenzene using refractive index detection, calibrated using narrow molecular weight distribution poly(styrene) standards.
EXAMPLES Example 1
Ethylene polymerization at elevated temperature and pressure. General procedure used to obtain the polymerization data given in Table I The data given in Table I was generated using a procedure substantially similar to the following procedure. A I L Parr® autoclave, Model 4520, was dried by heating under vacuum to 180 °C at 0.6 torr for 16 h, then cooled and refilled with dry. nitrogen. The autoclave was charged with dry, deoxygenated hexane (450 mL) and 1.0 mL of a 10 wt% solution of MAO in toluene (Aldrich®), then purged by pressurizing it to 200 psig with ethylene and venting (3 cycles). Hydrogen was added to the reactor either by direct pressurization to the indicated partial pressure - (for hydrogen partial pressures ≥ 4 psia), or by pressurizing a 40 mL gas sample loop to 40 or 65 psia with hydrogen, and using ethylene gas to sweep the hydrogen into the reactor (for hydrogen partial pressures < 4 psia). The autoclave was then heated to the temperature indicated in Table I and pressurized to within about 100 psig ofthe indicated pressure (see Table I) with ethylene gas while being vigorously stirred. Ethylene pressure was then used to inject 2.0 mL of dry, deoxygenated toluene from a sample loop (to clean the loop), followed by 2.0 mL (corresponding to 0.5 micromole of catalyst) of a toluene stock solution of [(ligand)Ni(acac)][B(C6F5)4], (see Table I for ligand) followed by another 2.0 mL of dry, deoxygenated toluene (to flush the loop), thereby raising the total reactor pressure to 5-10% over the target pressure, after which the reactor was isolated from the ethylene supply and the pressure was allowed to fall to approximately 5-10% below the target pressure, after which more ethylene was added to raise the pressure back to 5-10% over the target pressure and the cycle was repeated as required. In some cases, multiple catalyst injections were made, with the final injection being made at the indicated last injection time. After the indicated total reaction time, 2.0 mL MeOH was injected via the sample loop, and the reactor was promptly cooled, depressurized and opened. The polyethylene product was recovered by filtration, washed with MeOH and then a dilute solution of Irganox™ 1010 (Ciba-Geigy) in acetone, and dried in vacuo at 160 °C, 1 mm Hg. Table I
Figure imgf000047_0001
Pressure injection K PE /mol Ni 1000 Mn
Entry Ligand T (°C) (psig) H2 (psi) t (min) (min) Yield (g) / Ni (xlO-3) carbons (xlO"3) PDI1 Tm (°C)2
1 hcrlO 70 395 2 53.3 0 90.0 307 634 44 63.3 2.58 75.1,113.6
2 wa4 70 400 2 175 72 43.5 756 1560 7.2 127.4 2.15 127.1
3 a4 71 403 2 264 58 24.9 859 1774 129.0
4 br43'4 61 420 4 90 0 39.0 675 1393 109.7 2.52 123.5
5 wa6 70 395 1 160 51 31.0 538 1110 27 127.2 2.05 102
Figure imgf000047_0002
6 wa6 ' 70 790 1 97 31 38.0 644 1330 122.4
7 hcrll 70 418 2 160 90 27.8 482 994 94.9
8 wa5 80 400 15 31 0 48.8 2054 4240 <1 51.4 2.2 137.75,133.6
9 wa5 110 650 16 66 11 29.0 610 1260 7 21.8 1.99 129.2
10 ar43 80 397 18 61 0 65.5 1860 3900 7 40.3 1.9 127.1
11 ar43 110 748 17 46 24 19.8 411 849 13 30.9 1.87 121
12 wa4 70 402 3 175 72 43.5 756 1560 7.2 127.4 2.15 127.1
13 wa4 81 385 0 60 33 20.5 355 732 18.9 69.7 2.49 114.5
14 wa4 81 382 0 45 0 12.0 414 854 14.9 90.7 2.42 116.7
15 wa4 70 411 3 432 84 23.8 819 1690 115.5 2.29 129.0
Table I, cont'd
16 wa4 70 403 3 264 58 24.9 857 1770
17 hcrlO 71 392 0 53 12 36.0 308 636 48.8 292.1 1.98 68.6
18 hcrl2 70 401 2 89 0 64.6 373 769 42 83.4 3.19 76.8,115.1
19 wa6 79 420 0 123 48 15.6 270 557 41.5 340.3 2.01 86.5
20 wa6 70 395 2 160 51 31.0 538 1110 27 127.2 2.05 102.0
21 wa6 70 790 2 97 31 38.0 644 1330 21 161.7 2.56 122.4
22 hcrll 70 418. 3 160 90 27.8 482 994 94.9
23 illl6 70 200 5 335 112 21.9 184 387 41 13.7 1.93
24 hcrll7 80 182 6 107 70 8.6 74 153 52 15.9 2.01 60.8,95.1
25 shcrlO 80 460 7 404. 167 31.6 309 649 13.4 34.3 2.50 122.3
26 shcrll8 60 193 7 229 126 46.3 399 836 35 35.0 2.69 80.5,123
Notes: !PDI = polydispersity index = Mw/Mn. 22nd cycle endothermic maximum. JLigand structure on following page. 4AlMe3 (2 mmol) used in place of MAO; 2,6-di-tert-butyl-4-methylρhenol (9.1 mmol) injected and allowed to react with the AlMe3 at 80 °C for 30 min prior to addition ofthe Ni catalyst. 5lst cycle endothermic maximum. 6Branches per 1000 carbons by 13C NMR: 23.2 Me, 3.2 Et, no detected Pr, 1.8 Bu, 12.6 pentyl and longer; ratio C5 and higher to methyl = 0.54. ' 'Branches per 1000 carbons by 13C NMR: 30.9 Me, 2.6
Et, 3.5 Pr, 0.9 Bu, 13.2 pentyl and longer; ratio C5 and higher to methyl = 0.43. "Branches per 1000 carbons by 13C NMR: 23.7 Me, 1.8
Et, no detected Pr, no detected Bu, 9.2 pentyl and longer; ratio C5 and higher to methyl = 0.39
Example 1, cont'd
Figure imgf000049_0001
Example 2
Preparation of da2, a Ti complex thereof, and ethylene polymerization The requisite aniline is prepared as described for a5 in Example 19 below and reacts with malonyl dichloride to afford the corresponding bis amide, which is reduced with borane to the diamine. The latter is deprotonated and reacted with Me3SiCl to afford the bis(trirnethylsilyi) derivative, which is converted to the corresponding Ti complex and activated in the presence of ethylene following the method of McConville et al. (J. Am. Chem. Soc, 1996, 118, 10008-10009) to afford polyethylene.
Example 3
Ethylene polymerization using r(w3ΪNhYacac)1B(C6Fs) using MAO to activate The procedure of Example 1 was followed using 15.72 psi hydrogen, an average reaction temperature of 90 °C, an average pressure of 400 psig, two catalyst injections, with the last injection at 0.32 min, and a total reaction time of 120 min to obtain 18.0 g polyethylene, corresponding to 6.1 million mol H mol Ni. The reactor pressure was followed as a function of time, and showed an increasing rate of ethylene consumption, for the first 20-30 min, after which the rate stabilized and then slowly decreased until the end ofthe experiment.
Example 4
Ethylene polymerization using [Yw3)Ni(acac lB(CfiFs using AlMe3 to activate The procedure of Example 3 was followed using 14.7 psi hydrogen and 0.36 mmol AlMe3 in hexane instead of MAO, an average temperature of 81 °C, an average pressure of 399 psig, two injections of catalyst, with the last injection at 0.35 min and a total reaction time of 57 min to obtain 49.9 g polyethylene, corresponding to 1.7 million turnovers. A graph of reactor pressure as a function of time showed a more rapid increase in activity than was observed in Example 3, with full activity apparently being reached within about 5 min. Example 5
Synthesis of wa6-il
Figure imgf000051_0001
Benzaldehyde (3.0 g, 28.3 mmol) and 4'-bromoacetophenone (15.0 g, 75.4 mmol) were nearly dissolved in 95% ethanol (60 mL). Solid sodium hydroxide (1 pellet,, ca. 100 mg) was added. The mixture was heated at reflux for ca. 30 s, then allowed to cool. Upon cooling, an orange oil settled. The mixture was again heated at reflux for ca. 1 min. Upon cooling, near-colorless crystals separated from the orange supernatant. Ethanol (150 L) was added, and the large chunky crystals were crushed with a glass rod, then collected by vacuum filtration and washed with ethanol (3 x 20 mL). The desired diketone wa6-il was used without further purification. Crude yield: 10.3 g, 74%.
Example 6
Synthesis of wa6-i2
Figure imgf000051_0002
wa6-i2 Triphenylmethanol (6.6 g, 25.4 mmol) was suspended in acetic anhydride (70 mL) and warmed until in solution. Tetrafluoroboric acid (48% in water, 4.15 mL, 31.8 mmol) was slowly added dropwise while cooling the exothermic reaction in a room temperature water bath. Diketone wa6-il (10.3 g, 21.2 mmol) was added in portions over a few minutes. Yellow needles ofthe desired pyrylium salt wa6-i2 began to separate from solution within minutes. The mixture was stirred at room temperature for 16 h, then vacuum filtered and washed with acetic anhydride (3 x 25 mL) and dried in vacuo at 100 °C to obtain 9.9 g wa6-i2. An additional 540 mg was obtained by treating the filtrate/washings with diethyl ether. Combined yield: 89 %.
Example 7
Synthesis of wa6-i3
Figure imgf000052_0001
wa6-i3
Pyrylium salt wa6-i2 (13.85 g, 25.0 mmol) and 4-nitrophenylacetic acid (9.09 g, 50.2 mmol) were slurried in acetic anhydride (26 mL). The mixture was heated to 70 C under a nitrogen atmosphere then triethylamine (7 mL) was added dropwise with stirring. The dark mixture was stored in the refrigerator for 16 h, then filtered and washed with acetic anhydride, then methanol to obtain the desired nitroarene wa6-i3 as a pale yellow powder (7.89 g), which was used without further purification. Example 8
Synthesis of wa6-i4
Figure imgf000053_0001
wa6-i4
To a suspension of wa6-i3 (11.81 g, 20.2 mmol) and Pd(PPh3)4 (2.67 g, 2.4 mmol) in toluene (201 ml) was added 4-tert-butylρhenylboronic acid (10.77g, 60.5 mmol) as a solution in EtOH (40 ml). 2 M aqueous Na2CO3 (80 ml) was added and the resulting suspension was heated at 85 °C for 41.5 h, then cooled to 23 °C and extracted with Et2O. The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo. The residue was dissolved in toluene and filtered through a plug of silica gel and celite then concentrated in vacuo. The residue was suspended in a small amount of CH2C12 and filtered, washing with heptane. A second amount of precipitate was collected from the filtrate, again washing with heptane. The filtrate was filtered a third time to afford a gray solid, which was adsorbed onto silica gel and eluted through a short plug of silica and celite with CH2C12. The filtrate was combined with the solids obtained previously to afford wa6-i4 (6.14g, 44%), which was used without further purification. Example 9
Synthesis of wa6-i5
Figure imgf000054_0001
wa6-i5
A suspension of wa6-i4 (9.14g, 13.2 mmol) and 5% Pd/C (1.84g) in a mixture of toluene (149 ml) and MeOH (25 ml) was stirred under a balloon of H2 at 55 °C for 17 h. The reaction was cooled to rt, and filtered through a plug of celite, rinsing with toluene. The filtrate was concentrated in vacuo to afford wa6-i5 (8.72 g, 100%), which was used without further purification.
Example 10
Synthesis of wa6-i6
Figure imgf000055_0001
To an ice cold suspension of wa6-i5 (8.72 g, 13.2 mmol) in acetic acid (102 ml) and CH2C12 (20 ml) was added NaOAc (2.18g) in portions. Following the completion of the addition, bromine (1.37 ml) was added via syringe. The ice bath was removed, and the reaction stirred at 23 °C under Ar for 1.5 h then poured over ice, resulting in the formation of a yellow solid (7.96g), which was collected by vacuum filtration. The filtrate was extracted with CH2C12. The organic layer was dried over Na2SO4, filtered and concentrated in vacuo. The residue was combined with the solid collected previously to afford wa6-i6 (10.13 g, 94 %), which was used without further purification.
Example 11
Synthesis of wa6-i7
Figure imgf000056_0001
wa6-i7
To a suspension of wa6-i6 (4.5 g, 5.5 mmol) and Pd(Ph3P) (0.722 g, 0.65 mmol) in toluene (54.6 ml) was added 4-tert-butylphenylboronic acid (2.91 g, 16.4 mmol) and EtOH (10.9 ml). The resulting suspension was treated with 2 M aqueous Na2CO3 (21.7 ml) then heated to 85 °C for 22.5 h. The reaction was cooled to rt, and extracted with toluene. The organic layer was washed with water, dried over Na2SO4, filtered and concentrated in vacuo. The residue was divided into two portions and purified by flash chromatography (SiO2, 5-50% CH2Cl2/heρtane) on two columns to afford wa6-i7 (1.9 g and 2.16 g, total 4.06 g, 80%).
Example 12
Synthesis of wa6-i8
Figure imgf000057_0001
wa6-iδ
To a suspension of wa6-i7 (250 mg, 0.27 mmol) in CH2θ2 (1.5 ml) was added ethyl chlorooxoacetate (0.032 ml, 0.28 mmol). The resulting solution was stirred at 23 °C for 1 h, then diluted with CH2C12 and washed with saturated aqueous NaHCO3 and water. The organic layer was concentrated in vacuo to afford wa6-i8 (277 mg), which was used without further purification.
Example 13
Synthesis of wa-i9
Figure imgf000058_0001
wa6-i9
A suspension of wa6-i8 (246 mg, 0.24 mmol) in 'PrOH (1.7 ml) was treated with 2 M NaOH (1.08 ml). The resulting suspension was heated to 60 °C for lh, then cooled to 23 °C and acidified with 2 M HCl (pH = 2). The solid that formed was filtered, washed with H2O and dried in vacuo to afford wa6-i9 (220 mg, 92 %), which was used without further purification.
Example 14
Synthesis of wa6-il0
Figure imgf000059_0001
Amide/acid a6-i9 (215 mg, 0.215 mmol) was added portionwise to a suspension of NaH (60% in oil, 10 mg, 0.254 mmol) in toluene (2 ml). The resulting suspension was stirred at 23 °C for 15 min then treated with oxalyl chloride (338 μl, 3.88 mmol) and stirred at 23 °C for an additional 15 min. The mixture was concentrated in vacuo, and the residue was treated with wa6-i6 (184 mg, 0.225 mmol) followed by CH2C12 (2 ml). The resulting suspension was stirred at 23 °C for 3 days then concentrated in vacuo to afford crude wa6-il0 (415 mg), which was used without further purification. Example 15
Synthesis of wa6-ill
Figure imgf000060_0001
A suspension of wa6-il0 (385 mg (assume 100% yield from example 10), 0.214 mmol) in o-xylene (1.5 ml) was treated with P4S10 (48 mg, 0.108 mmol). The resulting suspension was heated to 140 °C under Ar for 1.5 h, then cooled to rt. The residue was diluted with toluene and washed with water. The organic layer was dried over Na2SO4, filtered and concentrated in vacuo to afford wa6-ill (413 mg), contaminated with residual xylene. The crude product was not purified further. Example 16
Synthesis of wa6
Figure imgf000061_0001
wa6
To a suspension of wa6-ill (392 mg (assume 100%) yield from example 11), 0.214 mmol,) in 1,2-dibromoethane (2.17 ml) was added 2 M NaOH (2.55 ml) and tetrabutylammonium bromide (12.8 mg, 0.04 mmol). The resulting biphasic mixture was stirred rapidly under Ar at 23 °C for 17 h, then diluted with CH2C12 and washed with H2O. The organic layer was dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified by flash chromatography (SiO2, 20-70% CH2Cl2/heptane) to afford wa6 (280 mg, 70% from wa6-i9). Example 17
Synthesis of wa5-il
Figure imgf000062_0001
A solution of wa6-i7 (329 mg, 0.355 mmol) in CH2C12 (2 ml) was treated with oxalyl chloride (20 μl, 0.22 mmol). The resulting solution was stirred at 23 °C under Ar for 1 h, then poured into MeOH. The precipitate was filtered and dried in vacuo. NMR indicated the crude product contained a significant amount of wa6-i7, so the mixture was redissolved in CH2CI2 (2 ml) and treated with oxalyl chloride (10 μl, 0.11 mmol). The resulting mixture was stirred at 23 °C under Ar for 25.5h, then poured into MeOH. The precipitate was filtered and dried in vacuo to afford wa5-il (319 mg), which was used without further purification. Example 18
Synthesis of wa5-i2
Figure imgf000063_0001
P S10 (37.5 mg, 0.084 mmol) was added to a suspension of wa5-il (319 mg, 0.167 mmol) in o-xylene (1.4 ml). The resulting suspension was heated to 140 °C under Ar for 5.5h, then cooled to 23 °C overnight. TLC indicated the reaction was not complete, so the mixture was heated to 140 °C for an additional 6h. The reaction was cooled to 23 °C and allowed to stand under Ar overnight. The suspension was diluted with toluene and washed with H2O. The organic layer was dired over Na2SO4, filtered and concentrated in vacuo to afford wa5-i2 (242 mg), which was used without further purification. Example 19
Synthesis of wa5
Figure imgf000064_0001
A suspension of wa5-i2 (242 mg, 0.124 mmol) in 1,2-dibromoethane (1.28 ml) was treated with 2 M NaOH (1.5 ml) and tetrabutylammonium bromide (8mg, 0.025 mmol). The resulting biphasic solution was stirred vigorously under Ar for 4 h, then diluted with CH2C12 and washed with H2O. The organic layer was dried over Na2SO , filtered and concentrated in vacuo. The residue was purified by flash chromatography (SiO2, 15-50% CH2Cl2 heptane) to afford wa5, contaminated with a small amount of an unidentified impurity. The impurity was removed by washing with MeOH to afford wa5 (87.3 mg, 25% from wa6-i7). Example 20
Ethylene polymerization with the nickel catalyst derived from Ni(acac ?,
Figure imgf000065_0001
v22
A I L Parr autoclave, Model 4520, was dried by heating under vacuum to 180 C at 0.6 torr for 1 h, then cooled and refilled with dry nitrogen. The autoclave was charged with dry, deoxygenated hexane (450 mL) and 2.0 mL of a 0.25 M solution of triisobutylaluminum in hexanes. The reactor was sealed and heated to 80 °C under nitrogen, then sufficient hydrogen was added to raise the pressure by 8.9 psi, after which ethylene was introduced to raise the total pressure to 250 psig. A sample loop injector was first purged with 2.0 mL dry, deoxygenated dichloromethane (injected into the reactor), and then used to inject 3 x 2.0 mL of a stock solution (corresponding to a total of 3.0 μmol of pro-catalyst) prepared from 17.34 mL of CH2C12 and 2.66 mL of a second stock solution prepared from 45.3 mg ligand v22,
15.0 mg Ni(acac)2, 54 mg Ph3C(C6F5)4 and 19.546 g (14.75 mL) CH2C12, followed by 2.0 mL of CH2C12, using ethylene gas to force the liquids into the autoclave and raise the pressure to ca. 440 psig, after which time the reactor was isolated and the pressure was allowed to fall to about 380 psig. More ethylene was then reintroduced to raise the pressure back to ca. 430 psig, after which the pressure was allowed to fall to ca. 400 psig, to give an average pressure of 402 psig, and an average temperature was 80.4 °C. After 47 min, the reaction was quenched by injection of MeOH, then the reactor was cooled, depressurized and opened. The polyethylene was recovered by concentrating the mixture to dryness under vacuum to obtain
13.01 g amorphous polyethylene, corresponding to 1.55 x 105 mol ethylene/mol Ni. Example 21
Ethylene polymerization with the nickel catalyst derived from Nifacac ?,
Figure imgf000066_0001
The procedure of Example 20 was followed, except the average temperature was 60.1 C, the average pressure was 605 psig, the partial pressure of hydrogen was 4.49 psi, and the total reaction time was 59.7 min. This afforded 38.6 g amorphous polyethylene, corresponding to 4.6 x 105 mol ethylene/mol nickel.
Example 22 Ethylene polymerization with the nickel catalyst derived from Nifacac)?. Pfo CsF )-. and ligand v5
Figure imgf000066_0002
v5
The procedure of Example 20 was followed using 2 μmol ofthe nickel catalyst derived from Ni(acac)2, Ph3C(C6F5)4 and ligand v5, and an average temperature of 60.8 C, an average pressure of 397 psig, a partial pressure of hydrogen of 5.12 psi, and a total reaction time of 21.7 min. This afforded 38. g partially crystalline polyethylene, corresponding to 6.8 x 105 mol ethylene/mol nickel. Example 23
Ethylene polymerization with the nickel catalyst derived from Nifacac)?, Ph3CfC6Fs and 2,3-bis(2,6-diisopropylphenylimino butane The procedure of Example 20 was followed using 4.2 μmol ofthe nickel catalyst derived from Ni(acac)2, Ph3C(C6Fs)4 and 2,3-bis(2,6-diisopropylphenylimino)- butane, and an average temperature of 60.5 C, an average pressure of 398 psig, a partial pressure of hydrogen of 4.64 psi, and a total reaction time of 60 min. This afforded 18.7 g polyethylene, corresponding to 1.6 x 105 mol ethylene/mol nickel.
Example 24
Ethylene polymerization with the nickel catalyst derived from Nifacac)?. PtoCIGJFsk and ligand v4
Figure imgf000067_0001
v4
The procedure of Example 20 was followed using 2 μmol ofthe nickel catalyst derived from Ni(acac)2, Ph3C(C6F5)4 and ligand v4, an initial temperature of 60 °C (the reaction exothermed to 81 °C), an average temperature of 63.7 C, an average pressure of 590 psig, a partial pressure of hydrogen of 4.03 psi, and a total reaction time of 34.5 min. This afforded 33.7 g partially crystalline polyethylene, corresponding to 6.0 x 105 mol ethylene/mol nickel. Example 25
Ethylene polymerization with the nickel catalyst derived from Nifacacb, Ph3C(CfiF5 and ligand v5
The procedure of Example 22 was repeated using 3 μmol nickel catalyst, 13.32 psi hydrogen, an average temperature of 80.4 C, and an average pressure of 406 psig to obtain 19.9 g polyethylene, corresponding to 2.4 x 105 mol ethylene/mol Ni.
Ligand syntheses and metal complex syntheses not given above followed procedures similar to those given above or previously described in the cross- referenced applications.

Claims

WE CLAIM:
1. A catalyst for olefin polymerization, comprising a Group 3-11 metal complex of a bidentate, tridentate, or tetradentate ligand, wherein said complex comprises at least one N-donor fragment of formula la or lb;
Figure imgf000069_0001
wherein:
M is a Group 3-11 transition metal;
R3a"d are each, independently, H, F, CI, Br, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl, nitro, heteroatom connected hydrocarbyl or heteroatom connected substituted hydrocarbyl; and
Arla is an aryl or heteroaryl group substituted at one or both ortho positions by a group Q2; wherein Q2 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl or heteroatom connected substituted hydrocarbyl.
2. The catalyst according to Claim 1 wherein M is a Group 8-10 metal.
3. The catalyst according to Claim 2, wherein M is nickel, and Q2 is sufficiently long to extend sufficiently close to the metal M to increase the catalyst productivity at elevated temperatures, or in the presence of hydrogen, or both, relative to an otherwise similar catalyst wherein Q2 is replaced by H, Me, or Ph.
4. The catalyst according to Claim 2, wherein M is nickel, and Q2 is sufficiently long to extend sufficiently close to the metal M to increase the regioselectivity or stereoselectivity of comonomer incorporation, relative to an otherwise similar catalyst wherein Q2 is replaced by H, Me, or Ph.
5. The catalyst according to Claim 2, wherein M is nickel, and Q2 is sufficiently long to extend sufficiently close to the metal M to decrease the amount of chain-running, relative to an otherwise similar catalyst wherein Q2 is replaced by H, Me, or Ph.
6. The catalyst according to Claim 2, wherein M is palladium, and Q2 is sufficiently long to extend sufficiently close to the metal M to decrease the amount of chain-running, relative to an otherwise similar catalyst wherein Q2 is replaced by H, Me, or Ph.
7. The catalyst according to Claim 2, wherein M is nickel, and Q2 is sufficiently long to extend sufficiently close to the metal M to increase the chain- running stereoselectivity, relative to an otherwise similar catalyst wherein Q2 is replaced by H, Me, or Ph.
8. The catalyst according to Claim 2, wherein M is nickel, and Q2 is sufficiently long to extend sufficiently close to the metal M to decrease the rate of activation of the catalyst when an alkylaluminum reagent is used as cocatalyst, relative to an otherwise similar catalyst wherein Q2 is replaced by H, Me, or Ph.
9. The catalyst according to Claim 2 which comprises a bidentate ligand selected from Set 1;
Setl
Figure imgf000071_0001
Figure imgf000071_0002
Set 1, cont'd
Figure imgf000072_0001
Figure imgf000072_0002
Set 1, cont'd
Figure imgf000073_0001
Figure imgf000073_0002
Set 1, cont'd
Figure imgf000074_0001
Figure imgf000074_0002
Set 1, cont'd
Figure imgf000075_0001
Figure imgf000075_0002
Set 1, cont'd
Figure imgf000076_0001
Figure imgf000076_0002
wa13 Set 1, cont'd
Figure imgf000077_0001
wa14
Figure imgf000077_0002
Set 1, cont'd
Figure imgf000078_0001
Figure imgf000078_0002
Set 1, cont'd
Figure imgf000079_0001
Figure imgf000079_0002
wherein:
R2x'y are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl; silyl, or ferrocenyl; in addition, R2x and R2y may be linked by a bridging group;
R3a"k are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, or nitro; R4a'b are each independently hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl; in addition, R4a and R4b may be linked by a bridging group;
"surface" refers to a silicon or other atom which is part of, or attached to, a solid support;
G1 is a divalent bridging group; and
Ar2a"m are each independently hydrocarbyl, substituted hydrocarbyl, heteroatom attached hydrocarbyl, heteroatom attached substituted hydrocarbyl, halo, nitro, boryl, or trialkoxysilane.
10. The catalyst according to Claim 2, wherein M is iron or cobalt, the catalyst comprises a tridentate ligand, and Q2 which is sufficiently long to extend sufficiently close to the metal M to increase the catalyst productivity at elevated temperatures.
11. The catalyst according to Claim 10, wherein said tridentate ligand is selected from Set 2;
Set 2
Figure imgf000080_0001
Set 2, cont'd
Figure imgf000081_0001
tri2
wherein: R2x,y are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl; silyl, or ferrocenyl; and
R3a"k are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, or nitro.
12. The catalyst according to Claim 1, comprising a titanium or zirconium complex of a bidentate ligand selected from Set 3;
Set 3
Figure imgf000082_0001
wherein:
R2x is H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl; silyl, or ferrocenyl;
R3a"J are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, fluoro, chloro, or bromo; and
Ar2a"J are each independently hydrocarbyl, substituted hydrocarbyl, heteroatom attached hydrocarbyl, heteroatom attached substituted hydrocarbyl, halo, nitro, boryl, or trialkoxysilane.
13. The catalyst according to Claim 1, further comprising a solid support.
14. The catalyst according to Claim 13, which is attached to the solid support via a covalent bond to the group Arla.
15. A process for the polymerization of olefins, comprising contacting one or more olefins with the catalyst of Claim 1.
16. The process according to Claim 15, wherein at least one of said olefins is ethylene.
17. The process according to Claim 15, wherein the olefin is ethylene, M is nickel, the temperature is at least 80 °C, the pressure is less than about 800 psig, sufficient hydrogen is added to reduce the number average molecular weight ofthe polymer by at least 20% relative to an otherwise similar reaction conducted in the absence of hydrogen, the catalyst productivity is at least 500 kg polyethylene per g nickel, and the polymer has a DSC first cycle peak melting point greater than 131 °C,
18. The process according to Claim 17, wherein sufficient hydrogen is added to reduce the number average molecular weight ofthe polymer by at least 50% relative to an otherwise similar reaction conducted in the absence of hydrogen, and the polymer has a DSC first cycle peak melting point greater than 133 °C.
19. The process according to Claim 15, wherein at least one ofthe olefins is ethylene, M is palladium and the amount of chain running is reduced.
20. A bidentate, tridentate, or tetradentate ligand of Set 1, Set 2, or Set 3.
21. A process for the polymerization of olefins, comprising contacting one or more olefins with a catalyst comprising a Group 8-10 metal complex of a bidentate, N,N-donor ligand, wherein the first of said donor nitrogens, N1, is substituted by an aromatic or heteroaromatic ring wherein the ortho substituents are aryl or heteroaryl groups, and the second of said donor nitrogens, N2, is substituted by an aromatic or heteroaromatic ring wherein one or both ofthe ortho substituents are other than aryl or heteroaryl; wherein said catalyst is capable of homopolymerizing ethylene to produce a polymer with a number average molecular weight of at least 20,000 g/mole and at least 20 branch points per 1000 carbons with a catalyst productivity of at least 500 kg polyethylene per g of Group 8-10 metal at a temperature of at least 60 °C at a partial pressure of ethylene of at least 350 psia at a partial pressure of hydrogen of at least 2 psia.
22. The process according to Claim 21, wherein said ligand is such that the calculated rate of olefin rotation in square planar complexes ofthe type (L)M(H)(RlaCH=CHRlb)n+, wherein n = 0 or 1, M is nickel or palladium, L is said , bidentate, N,N-donor ligand, Rla is H or Me, and Rlb is Me, and RlaCH=CHRlb is trans to N1, is at least 2 times higher than the calculated rate of olefin rotation in the complex wherein RlaCH=CHRlb is cis to N1.
23. The process according to Claim 22, wherein the calculated rate of olefin rotation in the complex wherein RlaCH=CHRl is trans to N1 is at least 4 times higher than the calculated rate of olefin rotation in the complex wherein RιaCH=CHRlo is cis to N\
24. The process according to Claim 21, wherein the metal is nickel, N1 is substituted by a 2,6-diaryl substituted aryl group or a 2,5-diaryl substituted 1- pyrrolyl group, and N2 is substituted by an aromatic or heteroaromatic ring wherein one or both ofthe ortho substituents are other than aryl or heteroaryl.
25. The process according to Claim 24, wherein N1 is substituted by a 2,6-diaryl substituted aryl group, N2 is substituted by an aromatic ring wherein one or both ofthe ortho substituents are other than aryl or heteroaryl, and the catalyst . productivity is at least 500 kg polyethylene per g nickel at a temperature of at least 70 °C. ,
26. The process according to Claim 25, wherein N2 is substituted by an aromatic ring wherein one ofthe ortho substituents is aryl, heteroaryl or bromo, and the other ortho substituent is bromo.
27. The process according to Claim 21 , wherein the bidentate ligand is selected from Set 4;
Set 4
Figure imgf000086_0001
hcrl
Figure imgf000086_0002
Figure imgf000086_0003
hcr3
Figure imgf000086_0004
hcr4 Set 4, cont'd
Figure imgf000087_0001
hcr5
Figure imgf000087_0002
hcr6
Figure imgf000087_0003
hcr7
Figure imgf000087_0004
hcr8 Set 4, cont'd
Figure imgf000088_0001
hcr9
Figure imgf000088_0002
hcrlO
Figure imgf000088_0003
hcr11
Figure imgf000088_0004
Set 4, cont'd
Figure imgf000089_0001
Set 4, cont'd
Figure imgf000090_0001
Figure imgf000090_0002
hcr1
Figure imgf000090_0003
hcr18 Set 4, cont'd
Figure imgf000091_0001
shcrl
Figure imgf000091_0002
shcr3
Figure imgf000091_0003
shcrδ Set 4, cont'd
Figure imgf000092_0001
Set 4, cont'd
Figure imgf000093_0001
shcrδ
Figure imgf000093_0002
shcr9 wherein:
R2x'y are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl; silyl, or ferrocenyl; in addition, R2x and R2y may be linked by a bridging group; R3a_1 are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, or nitro; Ar2a"m are each independently aryl or heteroaryl; and Ar3a"c are each independently 4-substituted aryl groups; wherein the 4- substituents are selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, phenylsulfonyl, and nitro.
28. A polymer prepared according to the process of Claim 21.
29. The process according to Claim 21 wherein the olefin is ethylene and the polymer is an ethylene homopolymer wherein the average spacing between branch points is such that there is at least a 10% excess of sequences ofthe type -CHR-(CH2)4n+2-CHR-, where R is alkyl and n is 0 or a positive integer, relative to sequences ofthe type -CHR-(CH2)2ra-CHR-, where R is alkyl and m is a positive integer.
30. The process according to Claim 21 wherein the olefin is ethylene, N2 is substituted by a 2-aryl-6-bromo-aryl group and the polymer is an ethylene homopolymer wherein there is an excess of isotactic sequences ofthe type -CHRla-(CH2)4π+2-CHRlb-, where Rla and Rlb are hydrocarbyl or substituted hydrocarbyl branches and n is 0 or 1, relative to a random distribution.
31. A process for the polymerization of olefins, comprising contacting one or more olefins with a catalyst comprising a Group 8-10 metal complex of a bidentate, tridentate or multidentate ligand, wherein said catalyst is activated using an alkylaluminum compound, wherein said alkylaluminum compound is subsequently selectively deactivated before the bulk of said polymerization has occurred.
32. The process according to Claim 31, wherein said alkylaluminum compound is selectively deactivated through the addition of a phenol or substituted phenol.
33. The process according to Claim 31, wherein said Group 8-10 metal complex is a cationic nickel complex of a bidentate N,N-donor ligand.
34. The process according to Claim 31, wherein said Group 8-10 metal complex is a cationic iron or cobalt complex of a tridentate ligand.
35. A catalyst for the polymerization of olefins, comprising a nickel complex of a ligand of formula 2a;
Figure imgf000095_0001
2a
wherein: R2x'y are each independently hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or silyl; in addition, R2x and R2y may be linked by a bridging group;
R3a"f are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, iodo, cyano, or nitro; R3x'y are each independently halo or fluoroalkyl; and Ar2a'b are each independently aryl or heteroaryl.
36. The catalyst according to Claim 35, wherein R2x and R2y are linked by a bridging group.
37. A process for the polymerization of olefins comprising contacting ethylene and optionally other olefins with the catalyst of Claim 35 in the presence of sufficient hydrogen to reduce the number average molecular weight ofthe polymer by at least 10% relative to an otherwise similar process carried out in the absence of hydrogen.
38. An ethylene homopolymer having a number average molecular weight of at least 10,000 g/mole, total branching of less than about 70 branches per 1000 carbons, at least 10% saturated hydrocarbon polymer chains, and a ratio of C5 and longer branches to methyl branches of at least 0.35.
39. The homopolymer according to Claim 38, wherein the total branching is less than about 60 branches per 1000 carbons; at least 25% ofthe polymer chains are saturated hydrocarbon chains; and the ratio of C5 and longer branches to methyl branches is at least 0.40.
40. The homopolymer according to Claim 38, wherein the total branching is less than about 60 branches per 1000 carbons; and the ratio of C5 and longer branches to methyl branches is at least 0.45.
41. The homopolymer according to Claim 38, having a DSC curve that shows a bimodal melt endotherm on a second heat from the melt, with the area of the smaller ofthe two peaks representing at least 25% ofthe total melt endotherm.
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US7582755B2 (en) 2004-04-27 2009-09-01 Wyeth Cyanopyrrole-containing cyclic carbamate and thiocarbamate biaryls and methods for preparing the same
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7446211B2 (en) 2004-04-27 2008-11-04 Wyeth Coupling process for generating reactive boron-containing derivatives of N-substituted pyrrole-2-carbonitriles to produce biaryls
US7582755B2 (en) 2004-04-27 2009-09-01 Wyeth Cyanopyrrole-containing cyclic carbamate and thiocarbamate biaryls and methods for preparing the same
US8003784B2 (en) 2004-04-27 2011-08-23 Wyeth Llc Cyanopyrrole containing cyclic carbamate and thiocarbamate biaryls and methods for preparing the same
US8129524B2 (en) 2004-04-27 2012-03-06 Wyeth Llc Cyanopyrrole containing cyclic carbamate and thiocarbamate biaryls and methods for preparing the same
US8129523B2 (en) 2004-04-27 2012-03-06 Wyeth Llc Coupling process for generating reactive boron-containing derivatives of N-substituted pyrrole-2-carbonitriles to produce biaryls
CN101440138B (en) * 2008-11-13 2011-08-31 复旦大学 Nickel olefin polymerizing catalyst, and preparation and use thereof
WO2012079678A1 (en) * 2010-12-13 2012-06-21 Merck Patent Gmbh Substituted tetraarylbenzenes
JP2014508114A (en) * 2010-12-13 2014-04-03 メルク パテント ゲーエムベーハー Substituted tetraarylbenzene
US8906893B2 (en) 2010-12-13 2014-12-09 Merck Patent Gmbh Substituted tetraarylbenzenes
US9231220B2 (en) 2010-12-13 2016-01-05 Merck Patent Gmbh Substituted tetraarylbenzenes
JP2016196460A (en) * 2010-12-13 2016-11-24 メルク パテント ゲーエムベーハー Substituted tetraarylbenzenes

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