EP1351997A2 - Katalysatoren mit verbesserter produktivität und mikrostruktursteuerung - Google Patents

Katalysatoren mit verbesserter produktivität und mikrostruktursteuerung

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Publication number
EP1351997A2
EP1351997A2 EP01992727A EP01992727A EP1351997A2 EP 1351997 A2 EP1351997 A2 EP 1351997A2 EP 01992727 A EP01992727 A EP 01992727A EP 01992727 A EP01992727 A EP 01992727A EP 1351997 A2 EP1351997 A2 EP 1351997A2
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EP
European Patent Office
Prior art keywords
hydrocarbyl
catalyst
substituted
group
ofthe
Prior art date
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EP01992727A
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English (en)
French (fr)
Inventor
Peter Borden Mackenzie
Leslie Shane Moody
James Allen Ponasik, Jr.
Amy Kathryn Farthing
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Eastman Chemical Co
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Eastman Chemical Co
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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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