WO2002022694A1 - Catalysts containing per-ortho aryl substituted aryl or heteroaryl substituted nitrogen donors - Google Patents
Catalysts containing per-ortho aryl substituted aryl or heteroaryl substituted nitrogen donors Download PDFInfo
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- WO2002022694A1 WO2002022694A1 PCT/US2001/028529 US0128529W WO0222694A1 WO 2002022694 A1 WO2002022694 A1 WO 2002022694A1 US 0128529 W US0128529 W US 0128529W WO 0222694 A1 WO0222694 A1 WO 0222694A1
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- hydrocarbyl
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- independently
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- heteroatom
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- IBWPSFGQJIZVDV-IULVPYHESA-N CCCCc(cc1)ccc1-c1cc(/N=C\C)cc(-c2ccc(CCCC)cc2)[o+]1 Chemical compound CCCCc(cc1)ccc1-c1cc(/N=C\C)cc(-c2ccc(CCCC)cc2)[o+]1 IBWPSFGQJIZVDV-IULVPYHESA-N 0.000 description 1
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- C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
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- C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
- C07C257/14—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to acyclic carbon atoms
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- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
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Definitions
- the present invention generally relates to catalyst compositions useful for the polymerization or oligomerization of olefins, and to processes using the catalyst compositions.
- Certain of these catalyst compositions comprise a Group 8-10 metal complex comprising a bidentate or variable denticity ligand comprising one or two nitrogen donor atom or atoms independently substituted by an aromatic or heteroaromatic ring(s), wherein the ortho positions of said ring(s) are substituted by aryl or heteroaryl groups.
- Olefin polymers are used in a wide variety of products, from sheathing for wire and cable to film. Olefin polymers are used, for instance, in injection or compression molding applications, in extruded films or sheeting, as extrusion coatings on paper, for example photographic paper and digital recording paper, and the like. Improvements in catalysts have made it possible to better control polymerization processes and, thus, influence the properties of the bulk material. Increasingly, efforts are being made to tune the physical properties of plastics for lightness, strength, resistance to corrosion, permeability, optical properties, and the like, for particular uses. Chain length, polymer branching and functionality have a significant impact on the physical properties of the polymer. Accordingly, novel catalysts are constantly being sought in attempts to obtain a catalytic process for polymerizing olefins which permits more efficient and better-controlled polymerization of olefins.
- this invention relates to a catalyst composition useful for the polymerization of olefins, which comprises a Group 8-10 metal complex comprising a bidentate or variable denticity ligand comprising two nitrogen donor atoms independently substituted by aromatic or heteroaromatic rings, wherein the ortho positions of the rings are substituted by aryl or heteroaryl groups.
- this invention relates to a catalyst composition
- a catalyst composition comprising either (i) a compound of formula eel, (ii) the reaction product of a metal complex of formula ffl and a second compound Y, or (iii) the reaction product of Ni(l,5-cyclooctadiene) 2 , B(C 6 F 5 ) 3 , a ligand selected from Set 18, and optionally an olefin:
- L 2 is selected from Set 18;
- T is H, hydrocarbyl, substituted hydrocarbyl, or other group capable of inserting an olefin;
- L is an olefin or a neutral donor group capable of being displaced by an olefin; in addition, T and L may be taken together to form a ⁇ -allyl or ⁇ -benzyl group;
- X " is BF “ , B(C 6 F5) “ , BPI1 4 " , or another weakly coordinating anion;
- Q and W are each independently fluoro, chloro, bromo or iodo, hydrocarbyl, substituted hydrocarbyl, heteroatom attached hydrocarbyl, heteroatom attached substituted hydrocarbyl, or collectively sulfate, or may be taken together to form a ⁇ -allyl, ⁇ -benzyl, or acac group, in which case a weakly coordinating counteranion X " is also present;
- Y is either (i) a metal hydrocarbyl capable of abstracting acac from ffl in exchange for alkyl or another group capable of inserting an olefin, (ii) a neutral
- Lewis acid capable of abstracting Q " or W " from ffl to form a weakly coordinating anion, a cationic Lewis acid whose counterion is a weakly coordinating anion, or a Bronsted acid whose conjugate base is a weakly coordinating anion, or (iii) a Lewis acid capable of reacting with a ⁇ -allyl or ⁇ -benzyl group, or a substituent thereon, in ffl to initiate olefin polymerization;
- R 3a ' b are each independently H, alkyl, hydrocarbyl, substituted hydrocarbyl, 2,4,6-triphenylphenyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or fluoroalkyl;
- Ar la"d are each independently phenyl, 4-alkylphenyl, 4-tert-butylphenyl, 4- trifluoromethylphenyl, 4-hydroxyphenyl, 4-(heteroatom attached hydrocarbyl)- phenyl, 4-(heteroatom attached substituted hydrocarbyl)-phenyl, or 1-naphthyl.
- the metal complex of formula ffl is selected from Set 19; Set 19
- R >3a,'b are each independently H, methyl, phenyl, 4-methoxyphenyl, or 4-tert- butylphenyl;
- Ar la_d are each independently phenyl, 4-methylphenyl, 4-tert-buty ⁇ phenyl, 4- trifiuoromethylphenyl, 1-naphthyl, 2-naphthyl, or 4-phenylphenyl; and
- X " is BF 4 " , B(C 6 F 5 ) 4 " , BPh* " , or another weakly coordinating anion.
- the substituents Ar la"d are 4-tert-butylphenyl or 1-naphthyl.
- the catalyst composition further comprises a solid support.
- this invention relates to a process for the polymerization of olefins, comprising contacting one or more olefins with the catalyst composition of the second aspect.
- the second compound Y is trimethylaluminum, and the metal complex is contacted with the trimethylaluminum in a gas phase olefin polymerization reactor.
- this invention relates to a compound of formula iil;
- R 3a ' b are each independently H, methyl, phenyl, 4-methoxyphenyl, or 4-tert- butylphenyl;
- Ar la"d are each independently phenyl, 4-methylphenyl, 4-tert-butylphenyl, 4- trifluoromethylphenyl, 1-naphthyl, 2-naphthyl, or 4- ⁇ henylphenyl.
- Compounds of this formula are useful as ligands in constituting the catalysts of the present invention.
- the invention relates to a process for the polymerization of olefins, comprising contacting one or more olefins with a catalyst composition comprising a Group 8-10 transition metal complex which comprises a ligand selected from Set 20;
- R 2x,y are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl; in addition, R 2x and R 2y may be linked by a bridging group;
- R 3a"f are each independently H, alkyl, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or fluoroalkyl;
- Ar la"d are each independently phenyl, 4-alkylphenyl, 4-tert-butylphenyl, 4- trifluoromethylphenyl, 4-hydroxyphenyl, 4-(heteroatom attached hydrocarbyl)- phenyl, 4-(heteroatom attached substituted hydrocarbyl)-phenyl, 1-naphthyl, 2- naphthyl, 9-anthracenyl, or aryl.
- this invention relates to a compound selected from Set 21; Set 21
- R 2x ' y are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl; in addition, R 2x and R 2y may be linked by a bridging group;
- R 3a"f are each independently H, alkyl, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or fluoroalkyl;
- Ar la"d are each independently phenyl, 4-alkylphenyl, 4-tert-butylphenyl, 4- trifluoromethylphenyl, 4-hydroxyphenyl, 4-(heteroatom attached hydrocarbyl)- phenyl, 4-(heteroatom attached substituted hydrocarbyl)-phenyl, 1-naphthyl, 2- naphthyl, 9-anthracenyl, or aryl. These compounds are are useful as ligands in constituting the catalysts of the present invention.
- this invention relates to a catalyst composition useful for the polymerization of olefins, which comprises a Group 8-10 transition metal complex comprising a N,N-donor ligand of the formula kkl or kk2;
- a ⁇ a ' h are each independently aromatic or heteroaromatic groups wherein the ortho positions are substituted by aryl or heteroaryl groups;
- M 1 is a metal selected from Groups 3, 4, 5, 6, 13, or 14, or is Cu, P or As;
- L n are ancillary ligands or groups which satisfy the valency of M 1 , such that M 1 is either a neutral, monoanionic or cationic metal center, or is a neutral or cationic P or As, with suitable counterions such that said catalyst composition has no net charge.
- M'L ⁇ may also be an active site for olefin polymerization.
- the compounds of formula kk2 are capable of ligating to two Group 8-10 metal centers, which may be the same or different, where one or both of said Group 8-10 metal centers may be active sites for olefin polymerization.
- this invention relates to a process for the polymerization of olefins, comprising contacting one or more olefins with the catalyst composition the seventh aspect.
- the catalyst compositions of the present invention can provide improved stability in the presence of an amount of hydrogen effective to achieve chain transfer, a total productivity greater than 28,000 kg polyethylene per mole of catalyst at an operating temperature of at least 60 °C (preferably greater than 56,000 kg PE/mol catalyst), and/or a higher productivity in the presence of an amount of hydrogen effective to achieve chain transfer, relative to the productivity observed in the absence of hydrogen.
- 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, isO-propyl, butyl, tert-butyl and phenyl, respectively.
- 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: C ⁇ -C 20 alkyl; C ⁇ -C 20 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 C ⁇ -C 20 alkyl, C 3 -C 8 cycloalkyl, and aryl; C 6 - 4 aryl; and C 6 -C ⁇ 4 aryl substituted with one or more groups selected from C ⁇ -C 20 alkyl, C 3 -C 8 cycloalkyl, and aryl.
- divalent (bridging) hydrocarbyls examples include: -CH 2 -, -CH 2 CH 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, and the like.
- a “heterocyclic ring” refers to a carbocyclic ring wherein one or more of the 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 heterocycle; examples include pyrrole, furan, thiophene, indene, imidazole, oxazole, isoxazole, carbazole, thiazole, pyrimidine, pyridine, pyridazine, pyrazine, benzothiophene, and the like.
- heteroaryl refers to a heterocyclic 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 group wherein Si is silicon and R is hydrocarbyl or substituted 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.
- 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.
- 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-
- 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)-l,2-ethanediyl.
- Examples of trivalent hydrocarbyls include methine and phenyl-substituted methane.
- a “heteroatom connected hydrocarbyl” refers to a group of the type E 10 (hydrocarbyl), E 20 H(hydrocarbyl), or E 0 (hydrocarbyl) 2 , where E 10 is an atom selected from Group 16 and E 20 is an atom selected from Group 15.
- a “heteroatom connected substituted hydrocarbyl” refers to a group of the 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 ⁇ -C 20 alkyl group substituted by one or more fluorine atoms.
- 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.
- 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 of the 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-l,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.
- a " ⁇ -allyl” group refers to a monoanionic group with three sp 2 carbon atoms bound to a metal center in a ⁇ 3 -fashion. Any of the three sp 2 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 of the sp 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(III), N(III), P(III), and P(V), -C(O)-, -S0 2 -, -C(S)-, -B(OMe)-, - C(O)C(0)-, 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 is meant to refer to that bond.
- compatible with the desired catalysis we mean a bridging group or substituent which 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 art per se and generally refers to a large bulky anion capable of delocalization of the negative charge of the anion.
- Ar 4 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).
- ortho is used herein in the context of the ligands of the present invention to denote the positions which are adjacent to the point of attachment of the aromatic or heteroaromatic ring to the ligated nitrogen(s).
- a 1 -attached, 6-membered ring we mean the 2- and 6-positions.
- a 1 -attached, 5-membered ring we mean the 2- and 5-positions.
- variable denticity is used herein in the context of otherwise bidentate ligands to refer to the reversible formation of a third binding interaction between the ligand and the Group 8-10 transition metal center to which it is complexed.
- abbreviation “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 of the "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 salt in mineral spirits.
- an amount of hydrogen effective to achieve chain transfer refers to the ability of hydrogen to react with an olefin polymerization catalyst to cleave off a growing polymer chain and initiate a new chain. In most cases, this is believed to involve hydrogenolysis of the metal-carbon bond of the growing polymer chain, to form a metal hydride catalytic intermediate, which can then react with the olefin monomer to initiate a new chain.
- an effective amount is considered to be that amount of hydrogen which reduces both the number average molecular weight and the weight average molecular weight of the polymer by at least 10%, relative to an otherwise similar reaction conducted in the absence of hydrogen.
- the productivity P r ogen is defined as the grams of polymer produced per mole of catalyst in the presence of an amount of hydrogen effective to achieve chain transfer, in an otherwise similar reaction conducted for the same period of time.
- Catalysts lacking the novel ortho-aryl substitution pattern of the catalyst compositions of the current invention typically exhibit ratios P h dr o ei P less than or equal to 0.05 under substantially non-mass transport limited conditions.
- the phrase "improved stability in the presence of an amount of hydrogen effective to achieve chain transfer" means that the ratio Phy i r oge n /P is at least 0J under substantially non-mass transport limited conditions.
- Preferred catalysts of the present invention exhibit a ratio P ⁇ )y d r ogcn/P greater than or equal to 0.2 under substantially non-mass transport limited conditions.
- Especially preferred catalysts of the present invention exhibit a ratio P h yd r oge n /P greater than or equal to 0.5 under substantially non-mass transport limited conditions.
- one or more olefins refers to the use of one or more chemically different olefin monomer feedstocks, for example, ethylene and propylene.
- the degree of steric hindrance at the active catalyst site required to give slow chain transfer, and thus form polymer depends on a number of factors and is often best determined by experimentation. These factors include: the exact structure of the catalyst, the monomer or monomers being polymerized, whether the catalyst is in solution or attached to a solid support, and the temperature and pressure.
- polymer is defined herein as corresponding to a degree of polymerization, DP, of 10 or more; oligomer is defined as corresponding to a DP of 2 to 10.
- total productivity is defined in the context of ethylene polymerization as the number of kilograms of polyethylene per mole of catalyst and is the maximum weight of polyethylene that can be produced using a given catalyst.
- suitable counterions we mean weakly coordinating ions with sufficient charge to give the overall catalyst complex no net charge.
- ancillary ligands are atoms or groups which serve to satisfy the valency of M without interfering with the desired catalysis.
- the compounds of Sets 18-21 and formula iil may be prepared as described in the examples contained herein, or by methods described in the references cited by Ittel et al. (Chem. Rev. 2000, 100, 1169); or in United States Patent Application Nos. 09/507,492, filed on February 18, 2000, 09/563,812, filed on May 3, 2000, and 09/231,920, filed on September 11, 2000; or in United States Provisional Application Nos. 60/246,254, 60/246,255, and 60/246,178, all filed on November 6, 2000.
- 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 Ni(II), Pd(II), Co(II) or Fe(II) dihalide complex of a bidentate N,N-donor ligand with an alkylaluminum reagent, for example, the reaction of (bidentate N,N-donor ligand)Ni(acac)X salts with an alkylaluminum reagent, where X is a weakly coordinating anion, such as BF 4 " , PF 6 " , SbF 6 ⁇ and OS(0) 2 CF 3 " , (ii) the reaction of a bidentate N,N-donor ligand with bis(l,5-cyclooctadiene)nickel(0) and [H(OEt 2 ) 2 ] + [B(3,5-(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.
- ligand refers to a compound of the present invention and is a bidentate or variable denticity ligand comprising one or two nitrogen donor atom or atoms independently substituted by an aromatic or heteroaromatic ring(s), wherein the ortho positions of the ring(s) are substituted by aryl or heteroaryl groups, n is 1 or 2, M is a Group 8-10 transition metal, and Z la and Z lb 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 of the 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
- examples of compound Y include: methylaluminoxane (herein MAO) and other aluminum sesquioxides, R 3 A1, R 2 A1C1, and RA1C1 2 (wherein R is alkyl, and plural groups R may be the same or different).
- MAO methylaluminoxane
- R 3 A1, R 2 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 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), 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 A1, R 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, RA1C1 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.
- the active catalyst typically comprises the catalytically active metal, one or more ligands of the 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 of said chain where ethylene can coordinate, or at least closely approach, prior to insertion.
- active catalysts comprising the ligands of the present invention are formed as the reaction products of the catalyst activation reactions disclosed herein, regardless of the detailed structures of those active species. 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 fimctionalized polystyrene. (See, for example, S.B. Roscoe et al., "Polyolefin Spheres from Metallocenes Supported on Non-Interacting Polystyrene," 1998, Science, 280, 270-273 (1998)).
- inorganic oxides such as talcs, silicas, titania, silica/chromia, silica chromia/titania, silica/alumina
- the catalysts of the 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 a compound Y.
- the compound Y and the solid support can be combined in any order and any number of compound(s) Y can be utilized.
- the supported catalyst thus fonned may be treated with additional quantities of compound Y.
- the compounds of the present invention are attached to silica that has been pre-treated with an alkylaluminum compound Y, for example, MAO, Et 3 Al, 'BusAl, Et 2 AlCl, 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 umeactive 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 , and CHC1 3 .
- the catalysts of the 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 adso ⁇ tion, 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 polymerizations may be conducted in batch or continuous processes, 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 20 °C to 160 °C, more preferably 60 °C to 100 °C.
- Suitable polymerization pressures range from 1 bar to 200 bar, preferably 5 bar to 50 bar, and more preferably from 10 bar to 50 bar.
- the catalyst concentration in solution, or loading on a support is adjusted to give a level of activity suitable for the process and desired polymer.
- suitable catalyst concentrations are typically in the range of 0.01 to 100 micromoles/L, preferably 0J to 10 micromoles/L, even more preferably 0.2 to 2 micromoles/L. Higher loadings tend to reduce the solution phase concentration of ethylene at a given temperature, pressure and agitation rate, and can therefore result in relatively more chain running and branching in some cases.
- the catalysts of the present invention may acquire new hydrocarbyl substituents, attached to the ligand or counteranion, or both, under the conditions of the olefin polymerization reaction.
- a bidentate N,N-donor ligand of the current invention underwent cyclometallation to form a tridentate ligand with a nickel-carbon bond, insertion of one or more ethylenes into this bond, followed by hydrogenolysis or by ⁇ -H elimnation, could result in a new hydrocarbyl side chain attached to said ligand.
- the ligand could comprise an olefinic side chain substituent prior to polymerization, and this side chain could undergo copolymerization in the presence of ethylene to attach an oligomeric or polymeric group to the ligand.
- the reaction product of (i) bis(l,5-cyclooctadiene)nickel(0), (ii) a ligand of the present invention and (iii) B(C 6 F 5 ) 3 may comprise a cycloctadiene-derived hydrocarbyl bridge between cationic nickel and anionic boron, and subsequent ethylene insertion may result in the attachment of a polyethylene chain to the borate counteranion.
- the catalysts of the 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 catalysts 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 of the 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 er se in the art.
- a suspension of aaal3 (4.4 g, 4.78 mmol) in ort/zo-xylene (20 ml) was treated with phosphorus pentasulfide (1J g, 2.39 mmol).
- the flask was fitted with a reflux condenser, and immersed in a 180 °C oil bath.
- the resulting suspension was refluxed under nitrogen for ca. 3h, then cooled to rt, then diluted with ca. 35 mL methylene chloride.
- the heterogeneous mixture was poured onto a column of silica (10" x 50 mm) and eluted with methylene chloride/hexane, collecting only the forerunning orange band.
- aaal4 crystallized from solution as orange needles (2 g), and was collected by filtration.
- the filtrate was concentrated to give more aaal4 as an orange crystalline powder (1.8 g).
- aaal5 (98.0 mg, OJOO mmol), nickel(II)acetonylacetonate (25.7 mg, OJOO mmol), and triphenylcarbenium tetrakis(pentafluorophenyl)borate (92.3 mg, OJOO mmol) were weighed to a Schlenk flask. On the Schlenk line, 10 mL dry diethyl ether was added to give a dark red solution. Dry hexane (4 mL) was added and dark crystals separated. The supernatant was removed via filer paper-tipped cannula. The dark bronze crystals were washed (2 x 10 mL) with a hexane/ether (1/1) mixture, then dried several hours in vacuo to afford 163.3 mg (89%) bbbl.
- Ligand aaa9 (1.00 g) was treated with nickel(II)acetonylacetonate and triphenylcarbenium tetrakis(pentafluorophenyl)borate according to the procedure given in Example 16 to afford 1.71 g (84%) bbb2.
- Example 18 Polymerization of ethylene using the catalyst prepared in Example 18 A catalyst delivery device was charged with the catalyst prepared in Example 18 (2.5 mg; 0J9 ⁇ mol Ni, dispersed in 130 mg Grace Davison XPO-2402 silica) and fixed to the head of a 1000-mL Parr ® reactor. The device was placed under vacuum. The reactor was then charged with NaCl (298 g) that had been dried in vacuum at 130 °C for several hours, closed, evacuated and backfilled with nitrogen five times. The leak rate of the reactor was tested by pressurizing to ca. 200 psi C 2 E ; for 5 min.
- the reactor was then depressurized, and the salt treated with trimethylaluminum (10 mL; 2.0 M in hexane) and agitated at 75 °C for 30 min.
- the reactor was subsequently pressurized with ethylene (200 psi) and depressurized to atmospheric pressure three times.
- the catalyst was then introduced in the reactor with appropriate agitation.
- the reaction was allowed to proceed for 60 min at 75 °C.
- the reactor was then depressurized.
- the polymer was isolated by washing the content of the reactor with hot water.
- Example 21 Polymerization of ethylene using the catalyst prepared in Example 20
- a catalyst delivery device was charged with the catalyst prepared in Example 20 (3.8 mg; 0.33 ⁇ mol Ni) dispersed in 122 mg silica (Grace Davison XPO-2402) and fixed to the head of a 1000-mL Parr (trademark) reactor. The device was placed under vacuum. The reactor was then charged with NaCl (315 g) that had been dried in vacuum at 130 °C for several hours, closed, evacuated and backfilled with nitrogen five times. The leak rate of the reactor was tested by pressurizing to ca. 200 psi C ⁇ for ca. 5 min. The reactor was then depressurized, and the salt treated with trimethylaluminum (10 mL; 2.0 M in hexane) and agitated at 86 °C for 30 min.
- the reactor was subsequently pressurized with ethylene (200 psi) and depressurized to atmospheric pressure three times.
- the catalyst was then introduced in the reactor with appropriate agitation.
- the reaction was allowed to proceed for 240 min at 90 C.
- the reactor was then depressurized.
- the polymer was isolated by washing the content of the reactor with hot water.
- a catalyst delivery device was charged with the catalyst prepared in Example 20 (3.8 mg; 0.33 ⁇ mol Ni) dispersed in 122 mg silica (Grace Davison XPO-2402) and fixed to the head of a 1000-mL Parr (trademark) reactor. The device was placed under vacuum. The reactor was then charged with NaCl (372 g) that had been dried in vacuum at 130 °C for several hours, closed, evacuated and backfilled with nitrogen five times. The salt was then treated with trimethylaluminum (10 mL; 2.0 M in hexane) and agitated at 85 °C for 30 min. The reactor was subsequently pressurized with ethylene (200 psi) and depressurized to atmospheric pressure three times.
- a catalyst delivery device was charged with the catalyst prepared in Example 20 (14.9 mg; 1.3 ⁇ mol Ni) dispersed in 152 mg silica (Grace Davison XPO-2402) and fixed to the head of a 1000-mL Parr (trademark) reactor. The device was placed under vacuum. The reactor was then charged with NaCl (363 g) that had been dried in vacuum at 130 °C for several hours, closed, evacuated and backfilled with nitrogen five times. The salt was then treated with trimethylaluminum (10 mL; 2.0 M in hexane) and agitated at 85 °C for 30 min. The reactor was subsequently pressurized with ethylene (200 psi) and depressurized to atmospheric pressure three times.
- Ph 3 CB(C 6 F 5 ) 4 (14.5 mg; 15.7 ⁇ mol) was added to a solution of aaal6 (12.6 mg; 16.0 ⁇ mol, prepared by methods similar to those described above, from the 2,6- di ⁇ henyl-4-(4-methoxyphenyl)-aniline, with the methoxy group being de-O- methylated as the last step) and Ni(acac) 2 (4J mg; 16 ⁇ mol) in acetone to result in a Ni concentration of 9.4 ⁇ mol/mL. An aliquot (0.75 mL) of the resulting solution was collected and the volatiles removed in vacuo.
- Example 25 Polymerization of ethylene using the catalyst prepared in Example 24
- a 600-mL Parr (trademark) reactor was charged with the catalyst prepared in Example 24. Toluene (150 mL) was added to the reactor before pressurizing to 200 psi ethylene to saturate the mixture. The reactor was then depressurized and MMAO type 4 (1.5 mL; 7J4 wt % Al; Akzo Nobel) was added. The reactor was repressurized with ethylene (200 psi) and the temperature quickly ramped up to 85 °C. The reaction was allowed to proceed under those conditions for 120 min before being quenched by addition of methanol. The mixture was treated with 6M HC1.
- the reactor was sealed and heated to 80 °C under nitrogen, then sufficient hydrogen was added to raise the pressure by 15.5 psi, after which sufficient ethylene was introduced to raise the total pressure to 300 psig.
- a sample loop injector was first purged with 2.0 mL dry, deoxygenated dichloromethane (injected into the reactor), and then used to inject 2.0 mL of a stock solution (corresponding to 0.60 ⁇ mol of pro-catalyst) prepared from 17.09 mL of CH 2 C1 2 and 2.91 mL of a stock solution prepared from 42 mg ligand a52, 10J mg Ni(acac) 2 , 20.0 mg B(C 6 F 5 ) 3 , 36 mg Ph 3 C(C 6 F 5 ) 4 and a total of 23.964 g CH 2 C1 2 (with the 1 st three reagents being combined in CH 2 C1 2 and then added to a solution of the trityl salt in CH 2 C1 2 ), followed by 2.0 mL of CH2C12, using ethylene gas to force the liquids into the autoclave and raise the pressure to ca.
- a stock solution corresponding to 0.60 ⁇ mol of pro-catalyst
- Example 26 A procedure similar to that described in Example 26 was followed, using 450 mL hexane, 4.0 mL MMAO, 14.0 psig hydrogen, sufficient ethylene pressure to give 660 psig total pressure, a reaction temperature of 100 °C, a single injection of 0.6 ⁇ mol of bbbl in CH 2 C1 2 solution, and a reaction time of 58 min to obtain 27.0 g polyethylene, corresponding to 1.61 (10) 6 mol C2H4/mol Ni.
- Example 20 Polymerization of ethylene using the catalyst prepared in Example 20. with hydrogen as a chain-transfer agent
- a catalyst delivery device was charged with the catalyst prepared in Example 20 (7.0 mg; 0.61 ⁇ mol Ni) dispersed in 160 mg silica (Grace Davison XPO-2402) and fixed to the head of a 1000-mL Parr (trademark) reactor. The device was placed under vacuum. The reactor was then charged with NaCl (324 g) that had been dried in vacuum at 130 °C for several hours, closed, evacuated and backfilled with nitrogen five times. The salt was then treated with trimethylaluminum (10 mL; 2.0 M in hexane) and agitated at 85 °C for 30 min.
- a catalyst delivery device was charged with the catalyst prepared in Example 20 (5.5 mg; 0.48 ⁇ mol Ni) dispersed in 148 mg silica (Grace Davison XPO-2402) and fixed to the head of a 1000-mL Parr (trademark) reactor. The device was placed under vacuum. The reactor was then charged with NaCl (350 g) that had been dried in vacuum at 130 °C for several hours, closed, evacuated and backfilled with nitrogen five times. The salt was then treated with trimethylaluminum (10 mL; 2.0 M in hexane) and agitated at 85 °C for 30 min. The reactor was subsequently pressurized with ethylene (200 psi) and depressurized to atmospheric pressure three times.
- ethylene 200 psi
- the catalyst was then introduced in the reactor with appropriate agitation. The reaction was allowed to proceed for 3 min at 85 °C under 200 psi ethylene. The reactor was then depressurized and hydrogen (100 mL) was syringed in. The reactor was then repressurized with ethylene (200 psi) and the reaction allowed to proceed for a total reaction time of 120 min. The reactor was depressurized to atmospheric pressure. The polymer was isolated by washing the content of the reactor with hot water.
- 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 toal of 3.0 ⁇ mol of pro-catalyst) prepared from 17.34 mL of CH 2 C1 2 and 2.66 mL of a stock solution prepared from 45.3 mg ligand v22, 15.0 mg Ni(acac) 2 , 54 mg Ph 3 C(C 6 F 5 ) 4 and a total of 19.546 g (14.75 mL) CH 2 C1 2 , followed by 2.0 mL of CH 2 CI 2 , using ethylene gas to force- the liquids into the autoclave and raise the pressure to ca.
- a stock solution corresponding to a toal of 3.0 ⁇ mol of pro-catalyst
- Example 30 The procedure of Example 30 was followed without change, except the average temperature was 60J °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 amo ⁇ hous polyethylene, corresponding to 460,000 mol ethylene/mol nickel.
Abstract
Description
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CA002421054A CA2421054A1 (en) | 2000-09-11 | 2001-09-11 | Catalysts containing per-ortho aryl substituted aryl or heteroaryl substituted nitrogen donors |
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US20020049135A1 (en) | 2002-04-25 |
US6844446B2 (en) | 2005-01-18 |
US6946532B2 (en) | 2005-09-20 |
JP2004516339A (en) | 2004-06-03 |
US6579823B2 (en) | 2003-06-17 |
CA2421054A1 (en) | 2002-03-21 |
US20030228978A1 (en) | 2003-12-11 |
US20050090381A1 (en) | 2005-04-28 |
EP1317490A1 (en) | 2003-06-11 |
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