Classifications

• • 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
  • 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

Definitions

• This application generally relates to olefin polymerization catalyst compositions and olefin polymerization processes using the same.
• Late transition metal complexes as catalysts for olefin polymerization has recently been reviewed by Ittel et al. (Chem. Rev. 2000, 100, 1169). Late transition metal catalysts have also been described in WO 01/07492, WO 01/55231, WO 01/42257, WO 01/21586, and Organometallics 2001, 20, 2321. Notwithstanding the developments described therein, there remains a need for new late transition metal catalysts and processes with improved productivities under cornmercial reactor operating conditions, especially those involving gas phase processes. New catalysts and rocesses for these purposes are described herein.
• Pore-filling agents suitable for use in the present invention include materials that are: (a) compatible with the desired catalysis, by which we mean the pore-filling agent either does not interfere with the desired catalysis, or acts to usefully modify the catalyst activity or selectivity, and (b) (i) low in volatility, by which we mean the pore-filling agent is either sufficiently non- volatile that not all of it is lost before the catalyst is introduced into the olefin polymerization reactor and olefin polymerization is initiated, and enough remains to improve the catalyst productivity in the presence of hydrogen, or (ii) relatively more volatile, but the treated supported catalyst can be handled in such a way that a sufficient amount of the pore-filling agent remains when the supported catalyst is exposed to hydrogen that improved productivity is observed in the presence of hydrogen.
• pore-filling agents include/but are. not limited to, triethylborane, diethylzinc, triethylaluminum, xylene, and triphenylmethane.
• activating supported Group 8-10 metal catalysts in the presence of one or more olefins, but in the absence of hydrogen, can also result in significantly improved productivities upon subsequent exposure to hydrogen.
• improved productivities in the presence of hydrogen can also be achieved by activating the supported Group 8-10 metal catalysts at high partial pressures of ethylene.
• high partial pressures of ethylene we mean partial pressures of at least 400 psig, preferably at least 600 psig.
• the pore-filling agent may be acting to affect the relative concentrations of key reactants at the site of the Group 8- 10 metal catalyst during activation, either by acting as a physical barrier to diffusion or by virtue of the different solubilities of the key reagents in the pore-filling agent.
• the pore-filling agent acts to raise the relative concentration of ethylene to hydrogen at the active site at the time of activation.
• Activating the catalyst in the presence of olefin, but in the absence of hydrogen, may result in a similar effect wherein the polymer itself serves to modify the relative concentrations of key reagents.
• the concentration of the co-catalyst(s) and the concentration of the catalyst itself may also be usefully modified through the use of the specified pore-filling agents.
• Activating the catalyst in the presence of hydrogen at relatively high partial pressures of ethylene may also result in improved catalyst productivity in the presence of hydrogen for the same reason. Without wishing to be bound by theory, we believe that it is important that the activated catalyst react with ethylene or another olefin before it reacts with hydrogen.
• this invention pertains to an improved process for the polymerization of olefins, comprising: contacting one or more olefins with a catalyst comprising a Group 8-10 transition metal complex of a bidentate N,N-, N,O-, N,P-, or P,P-donor ligand, wherein the catalyst is attached to a solid support, wherein the solid support has been treated with a pore-filling agent, either before, during, or after the catalyst and the support have been combined, wherein the pore- filling agent is introduced into the pores of the support either as a pure liquid or as a solution in a suitable solvent.
• suitable solvent we mean a solvent that (a) is itself a useful supported catalyst pore-filling agent, (b) is readily removed prior to polymerization, or (c) is compatible with the process and does not inhibit the catalyst, unless any such inhibition is modest and advantageous in the context of the process, as would be the case, for example, if the catalyst activated more slowly and thereby reduce a tendency for particle overheating in a gas phase reactor. Such overheating can lead to particle agglomeration and reactor fouling.
• the ligand is 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_1 are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, or nitro; and
• R 4a ' b are each independently hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl; in addition, R 4a and R 4b may be linked by a bridging group.
• the catalyst comprises a nickel complex of a bidentate N,N-donor ligand, wherein the N-donor atoms are substituted by aromatic or heteroaromatic rings, wherein the ortho positions of the rings are substituted by bromo, trifluoromethyl, fluoroalkyl, aryl, or heteroaryl groups.
• At least 20%, more preferably at least 40%, even more preferably at least 60%, of the remaining pore volume of the supported catalyst is filled by the pore-filling agent.
• “remaining pore volume” we mean the pore volume of the support minus the volume occupied by the catalyst and any co- catalyst.
• this invention relates to a process for the polymerization of olefins, comprising: contacting one or more olefins with a catalyst comprising a Group 8-10 transition metal complex of a bidentate N,N-, N,O-, N,P-, or P,P-donor, wherein the catalyst is attached to a solid support and wherein the catalyst is first activated in the absence of hydrogen in a first reactor containing one or more olefins, and then introduced into a second reactor containing hydrogen in which the bulk of the polymerization takes place.
• the process comprises a nickel complex of a bidentate N-N-donor ligand, wherein the N-donor atoms are substituted by aromatic or heteroaromatic rings, wherein the ortho positions of the rings are substituted by bromo, trifluoromethyl, fluoroalkyl, aryl, or heteroaryl groups.
• the ligand is selected from Set 2; Set 2
• 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_1 are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, or nitro; and
• R 4a,b are each independently hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl; in addition, R 4a and R 4b may be linked by a bridging group.
• two or three of the ortho positions of the rings are substituted by aryl or heteroaryl groups, and the remainder of the ortho positions are substituted by bromo, trifluoromethyl, or fluoroalkyl groups.
• this invention relates to a process for the polymerization of olefins, comprising: contacting one or more olefins with a catalyst comprising a Group 8-10 transition metal complex of a bidentate N,N-, N,O-, N,P-, or P,P-donor, wherein the catalyst is attached to a solid support, and wherein the catalyst is first activated in the presence of hydrogen at a partial pressure of ethylene greater than 400 psig.
• the partial pressure of ethylene is at least 600 psig.
• Figure 1 is a GPC curve of the polymer prepared in Example 49.
• Figure 2 is a GPC curve of the polymer prepared in Example 50.
• 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, ⁇ o-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: C 1 -C 2 0 alkyl; C ⁇ -C 20 alkyl substituted with one or more groups selected from C ⁇ -C 2 o 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 ⁇ alkyl, C 3 -C 8 cycloalkyl, and aryl; C 6 -C 14 aryl; and C 6 - 4 aryl substituted with one or more groups selected from C ⁇ -C o alkyl, C 3 -C 8 cycloalkyl, and aryl.
• divalent (bridging) hydrocarbyls examples include: -CH 2 -, -CH 2 CH 2 - -CH2CH 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, naphfhyl, 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, 2,6-di(4-phenylphenyl)-4-phenylphenyl, 2,4-dibromo-6- trifluoromethylphenyl, 2,4-bis(4-tert-butylpheny
• 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 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 monoradical which is aromatic; examples include 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, furyl, thienyl, indenyl, i idazolyl, oxazolyl, isoxazolyl, carbazolyl, thiazolyl, pyrirmdinyl, 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 hydrocarbvls include: 2,6-dimethvl-4-methoxvohenvL 2.6-diisonronvl-4- methoxyphenyl, 4-cyano-2,6-dimethylphenyl, 2,6-d methyl-4-nitrophenyl, 2,6- difluorophenyl, 2,6-dibromophenyl, 2,6-dichlorophenyl, 4-methoxycarbonyl-2,6- dimethylphenyl, 2-tert-butyl-6-chloro ⁇ henyl, 2,6-dimethyl-4-phenylsulfonyl ⁇ henyl, 2,6-dimethyl-4-trifluoromethylphenyl, 2,6-di e yl-4-trimethylammoniumphenyl (associated with a weakly coordinated
• 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 of the type E 10 (hydrocarbyl), E 20 H(hydrocarbyl), or E 20 (hydrocarbyl) , 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 2 o alkyl group substituted by one or more fluorine atoms.
• Preferred olefins for such catalysts include ethylene, propylene, butene, hexene, octene, cyclopentene, norbomene, 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, norbomene, substituted norbomenes (e.g., norbomenes 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.
• norbomene substituted norbomenes (e.g., norbomenes substituted at the 5- position with halide, siloxy, silane, halo carbon, ester, acetyl, alcohol, or amino groups)
• 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.
• 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 of the point of attachment of the aromatic or heteroaromatic ring to the 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.
• high productivities in the presence of hydrogen we mean a catalyst productivity, expressed in units of kg polymer per mmole catalyst, which is at least 25% higher, preferably 50% higher, even more preferably 100% higher than that observed under the same conditions using an otherwise similar supported catalyst which has not been treated as described in the first, second, or third aspects of this invention.
• in the presence of hydrogen we mean an amount of hydrogen sufficient to reduce the number average molecular weight of the polymer 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.
• a " ⁇ -allyl” group refers to a monoanionic group with three sp 2 carbon atoms bound to a metal center m a ⁇ -fashion. Any of the three sp carbon atoms may be substituted with a hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or O-silyl group.
• ⁇ -allyl groups examples include:
• ⁇ -benzyl group denotes a ⁇ -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 siliconfTV), boron(ni), N(nJ), P(UJ), 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 abridging group” are directly bonded to one another, in which case the term “bridging group” is meant to refer to that bond.
• 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 of the negative charge of the anion. The importance of such delocalization depends to some extent on the nature of the 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 ) 4 " , than many Group 8-10 transition metal based catalysts, which can in some cases give - active catalysts with BF 4 " 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 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 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 maybe 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 dichlpride with MAO, (ii) the reaction of a Group 4 metallocene dimethyl complex with N,N-c emylamlinium tetrakis(pentafluorophenyl)borate, (iii) the reaction of a Group 8 or-9metal 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) , (v) the reaction of (Me 2 N) 4 Zr with 2 equivalents of an N-ovrrol-1-vlsalicvlimine.
• Additional methods described herein include the reaction of (tridentate N-donor ligand)M(acac)B(C 6 Fs) salts with an alkylalurninum reagent, where M is Fe(U) or Co(Il), and the reaction of (bidentate N-donor hgand)Ni(acac)X salts with an alkylalurninum reagent, where X is a weakly coordinating anion, such as B(C 6 F 5 ) 4 " , 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 of the present invention, n is 1 or 2, M is a Group 8-10 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 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 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 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, al ⁇ minum 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.
• H + X " wherein 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.
• Z la and Z l are both halide or carboxylate, sequential treatment with a metal hydrocarbyl, followed by reaction with a Lewis acid, may be required to generate an active catalyst.
• metal hydrocarbyls 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), 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° maybe the same or different), and Lewis acidic metal oxides.
• alkylalurninum is used to refer to compounds containing at least one alkyl group bonded to Al( ⁇ T), which are capable of reacting with a metal complex of the present invention to generate an active olefin polymerization catalyst.
• this will involve exchanging one or more alkyl groups from the aluminum with a monoanionic atom or group on the metal complex pro-catalyst.
• a hydride may be directly transferred from the ⁇ -carbon of the aginanum alkyl to the 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 pro-catalyst is already a cationic metal complex, the role of the allc laluminum 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 alkyl uminum reagent may, in some cases, simply act as a Lewis acid, to promote conversion of the ⁇ -allyl or ⁇ -benzyl to a ⁇ -allyl or ⁇ -benzyl bonding mode, thereby facilitating binding and insertiori of the olefin monomer.
• a cationic pro-catalyst is used with an alkylduminum activator or co-catalyst, it should also be recognized that the starting counteranion (e.g.
• alkylalurninum reagent may react with the alkylalurninum reagent to generate a new counteranion (or a mixture of several different counteranions) under olefin polymerization reaction conditions.
• alkylalurninum reagents include: MAO, other aluminum sesquioxides, Me 3 Al, EtAlCl 2 , Et 2 AlCl, R Al, R 2 A1C1, RAICI 2 (wherein R is alkyl, and plural groups R may be the same or different), and the like.
• the ligands of the 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 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 the 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. 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( ⁇ i) and Co(U) catalyst precursors to effect olefin polymerization using MAO or other alkylalurninum co-catalysts.
• the catalyst it is advantageous for the catalyst to be attached to a solid support (by "attached to a solid support", we mean ion paired with a component on the surface, adsorbed to the surface or covalently attached to the surface).
• 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.
• 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 a solid support 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 .
• 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.
• Suitable polymerization temperatures are preferably from about 40 °C to about 100 °C, more preferably 60 °C to about 90 °C.
• Suitable polymerization pressures are preferably from about 1 bar to 200 bar, preferably 5 bar to 50 bar, more preferably 10 bar to 50 bar.
• the catalysts of the present invention may be used alone, or in combination with one or more other Group 3-11 olefin polymerization or oligomerization catalysts. 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 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 tackifymg compositions, and as a component of adhesive materials.
• High molecular weight resins are readily processed using conventional extrusion, injection molding, compression molding, and vacuum formmg 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 pore-filling agents used in olefin or vinyl polymers may be used in the new homopolymers and copolymers of this invention.
• Typical pore-filling agents include pigments, colorants, titanium dioxide, carbon black, antioxidants, stabilizers, slip agents, flame retarding agents, and the like.
• 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.
• Triethylaluminum (Aldrich, IM in hexane; 3.0 mL) was added to 0.998 g silylated silica (Crosfield, ES70YS) at 0 °C, followed by 10 mL hexane. The suspension was then agitated for 3 days at room temperature. Volatiles were removed in vacuo. Another flask was then charged with the resulting solid (238 mg) and 3 mL toluene, and cooled to 0 °C. A solution of bbbl (38.3 mg) in 2 mL toluene was added. The suspension was agitated for 15 min and the solvent was removed under reduced pressure at room temperature. The color of the solid turned from red to brown. The resulting solid was used in subsequent polymerization experiments.
• Triethylborane (Aldrich, IM in hexane; 3.0 mL) was added to 1.0 g silylated silica (Crosfield, ES70YS) at 0 °C, followed by 10 mL hexane. The suspension was then agitated for ca. 18 h at room temperature. Volatiles were removed in vacuo. Another flask was then charged with the resulting solid (216 mg) and 3 mL toluene, and cooled to 0 °C. A solution of bbbl (32.3 mg) in 2 mL toluene was added. The suspension was agitated for aboutl5 min and the solvent was removed under reduced pressure at room temperature. The resulting solid was used in subsequent polymerization experiments. 1
• Trimemylarubnum (Aldrich, 2M in hexane; 1.5 mL) was added to 1.0 g sylilated silica (Crosfield ES70YS) at 0 °C, followed by 10 mL hexane. The suspension was then agitated for 3 days at room temperature. Volatiles were removed in vacuo. Another flask was then charged with the resulting solid (220 mg) and 3 mL toluene, and cooled to 0 °C. A solution of bbbl (34.0 mg) in 2 mL toluene was added. The suspension was agitated for about 5 min and the solvent was removed under reduced pressure at room temperature. The resulting solid was used in subsequent polymerization experiments.
• Example 10 Polymerization of ethylene using the catalyst prepared in Example 10 (comparative)
• a 1000-mL Parr ® fixed-head reactor was charged with NaCl (382 g) and a catalyst delivery device containing the catalyst prepared in Example 10 (11.5 mg dispersed in 207 mg silica) was fixed to the head of the reactor.
• the reactor was assembled and purged five times with ethylene (ca. 50 psi).
• Trimethylaluminum Aldrich, 2.0M in hexanes; 10 mL
• the salt was agitated for 30 min at 85 °C.
• the reactor was then purged three times with ethylene (200 psi).
• the reactor was then purged three times with ethylene (200 psi). The catalyst was then delivered while pressurizing the reactor to 100 psi C 2 H
• a 1000-mL Parr ® fixed-head reactor was charged with NaCl (423 g) and a catalyst delivery device containing the catalyst mixture prepared in Example 26 (582 mg) was fixed to the head of the reactor.
• the reactor was assembled and purged five times with ethylene (ca. 50 psi).
• Trimethylaluminum (Aldrich, 2.0M in hexanes; 10 mL) was added to the reactor and the salt was agitated for 30 min at 85 °C.
• the reactor was then purged three times with ethylene (200 psi).
• the catalyst was subsequently delivered while pressurizing the reactor to 100 psi C2H 4 .
• 1,5- Hexadiene (0.11 mL) was then added, followed by tr methylaluminum (Aldrich; 2.0M in hexane; 0.94 mL) at 0 °C.
• the resulting solution was transferred to a flask containing a suspension of 205 mg of the BEt 3 -treated silica in 3 mL toluene at 0 °C.
• the suspension was agitated for 5 min prior to removing the volatiles in vacuo.
• the resulting solid was used in subsequent polymerization experiments.
• the reaction was allowed to proceed at an average temperature of 88 °C for 240 min.
• the reactor was then depressurized.
• Example 29 Polymerization of ethylene using catalyst prepared in Example 29
• a 1000-mL Parr ® fixed-head reactor was charged with NaCl (462 g) and a catalyst delivery device containing the catalyst prepared in Example 29 (10.7 mg dispersed in 188 mg silica) was fixed to the head of the reactor.
• the reactor was assembled and purged four times with ethylene (ca. 50 psi).
• Trimethylaluminum (Aldrich, 2.0M in hexanes; 10 mL) was added to the reactor and the salt was agitated for 30 min at 85 °C.
• the reactor was then purged three times with ethylene (200 psi).
• the catalyst was subsequently delivered while pressurizing the reactor to 100 psi C 2 H .
• Example 29 Polymerization of ethylene using catalyst prepared in Example 29 A 600-mL Parr ® autoclave was charged with NaCl (ca. 300 mL) and the catalyst prepared in Example 28 (25.0 mg). The reactor was assembled and pressurized to 200 psi C 2 H . The reactor was heated up from room temperature to 85-90 °C within 7 min. The reaction was allowed to proceed at an average temperature of 85 °C for 67 min. The reactor was then depressurized.
• Example 33 Polymerization of ethylene using catalyst prepared in Example 29
• a 1000-mL Parr ® fixed-head reactor was charged with NaCl (354 g) and a catalyst delivery device containing the catalyst prepared in Example 29 (8.9 mg dispersed in 138 mg silica) was fixed to the head of the reactor.
• the reactor was assembled and purged five times with ethylene (ca. 50 psi).
• Trimethylaluminum (Aldrich, 2.0M in hexanes; 10 mL) was added to the reactor and the salt was agitated for 30 min at 85 °C.
• the reactor was then purged three times with ethylene (200 psi).
• the catalyst was subsequently delivered while pressurizing the reactor to 200 psi C 2 H 4 . Temperature rose to 89 °C.
• the reaction was allowed to proceed at an average temperature of 88 °C for 240 min.
• the reactor was then depressurized.
• Example 34 Polymerization of ethylene using catalyst prepared in Example 34
• a 1000-mL Parr ® fixed-head reactor was charged with NaCl (378 g) and a catalyst delivery device containing the mixture prepared in Example 34 (566 mg, containing 0.45 mol Ni) was fixed to the head of the reactor.
• the reactor was assembled and purged five times with ethylene (ca. 50 psi).
• Trimethylaluminum (Aldrich, 2.0M in hexanes; 10 mL) was added to the reactor and the salt was agitated for 30 min at 85 °C.
• the reactor was then purged three times with ethylene (200 psi).
• the catalyst was subsequently delivered while pressurizing the reactor to 200 psi C 2 H .
• the reaction was allowed to proceed at an average temperature of 88 °C for 240 min.
• the reactor was then depressurized.
• Example 36 Polymerization of ethylene using catalyst prepared in Example 36
• a 600-mL Parr ® autoclave was charged with the catalyst prepared in Example 36 (60.8 mg) under N 2 .
• the reactor was assembled and hexane (220 mL), pretreated with MAO-treated silica (Witco TA-02794 HL-04), was added to the reactor.
• the suspension was agitated vigorously.
• the reactor was then pressurized to 150 psi with C 2 H 4 , while heating to 75 °C. Once the desired temperature was reached ( ⁇ 3 min), ethylene was added to reach a total reactor pressure of 200 psi.
• the reaction was allowed to proceed for 120 min at 75 °C.
• Example 36 A 600-mL Parr ® autoclave was charged with the catalyst prepared in Example 36 (50.0 mg) under N 2 .
• the reactor was assembled and hexane (220 mL), pretreated with MAO-treated silica (Witco TA-02794 HL-04), was added to the reactor. The suspension was agitated vigorously. The reactor was then pressurized to 60 psi with C 2 ⁇ L 4 . Hydrogen (4 psi) was then added and the reactor immediately pressurized to 150 psi with C 2 H 4 while heating to 75 °C. Once the desired temperature was reached ( ⁇ 3 min), ethylene was added to reach a total reactor pressure of 200 psi. The reaction was allowed to proceed for 120 min at 75 °C.
• Example 4 Polymerization of ethylene using catalyst prepared in Example 4
• a 1000-mL Parr ® fixed-head reactor was charged with NaCl (392 g) and a catalyst delivery device containing a catalyst prepared according to the procedures described in Example 4 (5.8 mg dispersed in 135 mg silica) was fixed to the head of the reactor.
• the reactor was assembled arid purged five times with ethylene (ca. 50 psi).
• Trimethylaluminum Aldrich, 2.0M in hexanes; 10 mL
• the salt was agitated for 30 min at 75 °C.
• the reactor was then purged three times with ethylene (200 psi).
• the catalyst was then delivered while pressurizing the reactor to ca.
• Example 40 Polymerization of ethylene using catalyst prepared in Example 4
• a 1000-mL Parr ® fixed-head reactor was charged with NaCl (407 g) and a catalyst delivery device containing a catalyst prepared according to the procedures described in Example 4 (5.6 mg dispersed in 130 mg silica) was fixed to the head of the reactor.
• the reactor was assembled and purged five times with ethylene (ca. 50 psi).
• Trimethylaluminum (Aldrich, 2.0M in hexanes; 10 mL) was added to the reactor and the salt was agitated for 30 min at 75 °C.
• the reactor was then purged three times with ethylene (200 psi).
• the catalyst was then delivered while pressurizing the reactor to ca. 100 psi C ⁇ Hj.
• a 1000-mL Parr ® fixed-head reactor was charged with NaCl (394 g) and a catalyst delivery device containing a catalyst prepared according to the procedures described in Example 41 (12.2 mg dispersed in 135 mg silica) was fixed to the head of the reactor.
• the reactor was assembled and purged five times with ethylene (ca. 50 psi).
• Trimethylaluminum (Aldrich, 2.0M in hexanes; 10 mL) was added to the reactor and the salt was agitated for 30 min at 85 °C.
• the reactor was then purged three times with ethylene (200 psi).
• the catalyst was then delivered while pressurizing the reactor to 200 psi C. 2 H 4 .
• the reaction was allowed to proceed at an average temperature 89 °C for 210 min.
• the reactor was then depressurized.
• Example 41 Polymerization of ethylene using catalyst prepared in Example 41
• a 1000-mL Parr ® fixed-head reactor was charged with NaCl (418 g) and a catalyst delivery device containing a catalyst prepared according to the procedures described in Example 41 (12.2 mg dispersed in 135 mg silica) was fixed to the head of the reactor.
• the reactor was assembled and purged five times with ethylene (ca. 50 psi).
• Trimethylalurninum Aldrich, 2.0M in hexanes; 10 L
• the salt was agitated for 30 min at 85 °C.
• the reactor was then purged three times with ethylene (200 psi).
• the catalyst was then delivered while pressurizing the reactor to ca. 100 psi C 2 H 4 .
• Example 44 Polymerization of ethylene using catalyst prepared in Example 41
• a 1000-mL Parr ® fixed-head reactor was charged with NaCl (397 g) and a catalyst delivery device containing a catalyst prepared according to the procedures described in Example 41 (14.3 mg dispersed in 192 mg silica) was fixed to the head of the reactor.
• the reactor was assembled and purged five times with ethylene (ca. 50 psi).
• Trimethylaluminum (Aldrich, 2.0M in hexanes; 10 mL) was added to the reactor and the salt was agitated for 30 min at 75 °C.
• the reactor was then purged three times with ethylene (200 psi).
• the catalyst was then delivered while pressurizing the reactor to ca. 100 psi C 2 H .
• Example 3 Polymerization of ethylene using catalyst prepared in Example 3
• a 1000-mL Parr ® fixed-head reactor was charged with NaCl (477 g) and a catalyst dehvery device containing a catalyst prepared according to the procedures described in Example 3 (7.3 mg dispersed in 118 mg silica) was fixed to the head of the reactor.
• the reactor was assembled and purged five times with ethylene (ca. 50 psi).
• Trimethyl uminum Aldrich, 2.0M in hexanes; 10 mL
• the salt was agitated for 30 min at 70 °C.
• the reactor was then purged three times with ethylene (200 psi).
• the catalyst was then delivered while pressurizing the reactor to ca.
• aaalS (98.0 mg, 0J00 mmol; prepared according to procedures similar to those described in WO 00/50470), mckel(II)acetonylacetonate (25.7 mg, 0J00 mmol), and triphenylcarbenium tetrakis(pentafluorophenyl)borate (92.3 mg, 0J00 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.
• Example 50 Polymerization of ethylene in the presence of hydrogen using the catalyst prepared in Example 48
• the catalyst was then delivered while pressurizing the reactor to 200 psi C 2 H 4 . After 30 min at 200 psi the reactor was slowly depressurized and hydrogen (100 mL) was added via a hypodermic syringe. The reactor was then repressurized to 200 psi C 2 H 4 a d the reaction allowed to proceed for 210 min at 85 °C. The reactor was then depressurized.
• a 1000-mL Parr ® fixed-head reactor was charged with NaCl (303 g) and a catalyst delivery device containing the catalyst prepared in Example 48 (15.7 mg dispersed in 188 mg XPO-2402 silica) was fixed to the head of the reactor.
• the reactor was assembled and purged five times with nitrogen (ca. 40 psi).
• Trimethylaluminum (Aldrich, 2.0M in hexanes; 10 mL) was added to the reactor and the salt was agitated for 30 min at 85 °C.
• the reactor was then purged three times with ethylene (200 psi). Hydrogen (16 psi) was then added and the catalyst delivered while pressurizing the reactor to 600 psi C 2 H .
• the reactor was then purged three times with ethylene (200 psi).
• the catalyst was then delivered while pressurizing the reactor to 200 psi C 2 K .
• the reaction was allowed to proceed at an average temperature of 85 °C for 240 min.
• the reactor was then depressurized.
• a flask was charged with silylated silica (Crosfield, ES70YS; 232 mg) and cooled to 0 °C.
• a solution of bbbl (33.5 mg) in 1.5 mL toluene was added.
• the original vial containing bbbl was washed with additional (1.5 mL) toluene, and added to the silica.
• the suspension was agitated for about 5 min and the solvent was removed under reduced pressure at room temperature over 2 h. the resulting solid was used in subsequent polymerization experiments.
• Example 54 Polymerization of Ethylene using the Catalysts Prepared According to the Procedures Described in Example 54 (comparative).
• a 1000-mL Parr ® fixed-head reactor was charged with NaCl (324 g) and a catalyst delivery device containing a catalyst prepared according to the procedures described in Example 54 (21.3 mg dispersed in 233 mg silica) was fixed to the head of the reactor.
• the reactor was assembled and purged under a continuous flow of nitrogen for 60 min. Trimethylaliiminum (5.2M in toluene; 1.0 mL) was added to the reactor.
• the catalyst was then delivered while pressurizing the reactor to 100 psi C 2 H 4 .
• a 1000-mL Parr ® . fixed-head reactor was charged with NaCl (379 g) and a catalyst dehvery device containing a catalyst prepared according to the procedures described in Example 54 (21J mg dispersed in 230 mg sihca) was fixed to the head of the reactor.
• the reactor was assembled and nureed under a r.nntinnnns fln nf r ⁇ rrncreri for 60 min.
• Trimethylaluminum (5.2M in toluene; 1.0 mL) was added to the reactor.
• the catalyst was then delivered while pressurizing the reactor to 200 psi C 2 H 4 .
• the reaction was allowed to proceed at an average temperature of 85 °C for 270 min.
• the reactor was then depressurized.
• a 1000-mL Parr ® fixed-head reactor was charged with NaCl (403 g) and a catalyst delivery device containing a catalyst prepared according to the procedures described in Example 56 (7.8 mg dispersed in 186 mg silica) was fixed to the head of the reactor.
• the reactor was assembled and evacuated/purged three times with nitrogen.
• Trimethylaluminum Aldrich, 2.0M in hexanes; 10 mL was added to the reactor and the salt was agitated for 50 min at 85 °C.
• the reactor was then purged three times with ethylene (200 psi). Hydrogen (210 mL) was added to the reactor while pressuring it to 100 psi with ethylene.
• the catalyst was then delivered while further increasing the reactor pressure to 200 psi with C 2 H .
• the reaction was allowed to proceed at an average temperature of 88 °C for 120 min.
• the reactor was then depressurized.
• a 600-mL Parr ® reactor was charged with 300 mL hexane and BEt 3 (Aldrich, 1.0M in hexane; 1.0 mL) under argon. The reactor was pressurized and depressurized three times with ethylene (ca. 100 psi). Hydrogen (16 psi) was then added. The reactor was pressurized with to about 100 psi with ethylene and then heated to 70 °C. Once the temperature stabilized, the nickel complex bbbl (1.4 ⁇ mol) was then added via an injection loop while further pressurizing the reactor with ethylene to 200 psi. No ethylene uptake was observed. The temperature was then ramped up to 85 °C. No ethylene uptake was observed. The reaction was quenched with acetone at 60 min. No polymer was isolated.

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