WO2020046785A1 - Complexes de métaux de transition de phénolate pontés, production et utilisations associées - Google Patents

Complexes de métaux de transition de phénolate pontés, production et utilisations associées Download PDF

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WO2020046785A1
WO2020046785A1 PCT/US2019/048086 US2019048086W WO2020046785A1 WO 2020046785 A1 WO2020046785 A1 WO 2020046785A1 US 2019048086 W US2019048086 W US 2019048086W WO 2020046785 A1 WO2020046785 A1 WO 2020046785A1
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substituted
aromatic
transition metal
group
independently
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PCT/US2019/048086
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Crisita Carmen H. ATIENZA
David A. Cano
Catherine A. Faler
Margaret T. WHALLEY
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Exxonmobil Chemical Patents Inc.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • 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 System

Definitions

  • the present disclosure provides catalysts containing bridged phenolate transition metal complexes, production, and uses thereof.
  • Polyolefins are widely used commercially because of their robust physical properties. For example, various types of polyethylenes, including high density, low density, and linear low density polyethylenes, are some of the most commercially useful. Polyolefins are typically prepared with a catalyst that polymerizes olefin monomers. Therefore, there is interest in finding new catalysts and catalyst systems that provide polymers having improved properties.
  • Low density polyethylene is generally prepared at high pressure using free radical initiators, or in gas phase processes using Ziegler-Natta or vanadium catalysts.
  • Low density polyethylene typically has a density in the range of 0.916 to 0.940 g/cmA
  • Typical low density polyethylene produced using free radical initiators is known in the industry as "LDPE”.
  • LDPE is also known as “branched” or “heterogeneously branched” polyethylene because of the relatively large number of long chain branches extending from the main polymer backbone.
  • Polyethylene in the same density range e.g., 0.916 to 0.940 g/cniT which is linear and does not contain long chain branching, is known as "linear low density polyethylene” (“LLDPE”) and is typically produced by conventional Ziegler-Natta catalysts or with metallocene catalysts.
  • Linear means that the polyethylene has few, if any, long chain branches, typically referred to tiS 3. g vis value of 0.97 or above, such as 0.98 or above.
  • Polyethylenes having still greater density are the high density polyethylenes (“HDPEs”), e.g., polyethylenes having densities greater than 0.940 g/cmV and are generally prepared with Ziegler-Natta catalysts or chrome catalysts.
  • HDPEs high density polyethylenes
  • VLDPEs Very low density polyethylenes
  • VLDPEs can be produced by a number of different processes yielding polyethylenes having a density less than 0.916 g/cm-L typically 0.890 to 0.915 g/cnH or 0.900 to 0.915 g/cm ⁇ .
  • High molecular weight is defined as a number average molecular weight (Mn) value of 100,000 or more.
  • Low molecular weight is defined as an Mn value of less than
  • polyolefin compositions formed by catalysts capable of forming high molecular weight polyolefins typically also have a broad molecular weight distribution, as indicated by high polydispersity indices, and/or the polyolefins are of such high molecular weight (e.g., Mn of 1,500,000) as to have processing difficulty due to hardness.
  • catalysts capable of forming high molecular weight polyolefins typically have low polymer productivity.
  • the present disclosure provides transition metal catalysts and the respective bridged phenolate ligands contained on the catalyst, as well as, catalyst systems and polymerization processes.
  • the bridged phenolate ligands are asymmetrical due in part to two linking diyl groups that are different lengths.
  • the ligand is represented by Formula (I) and the transition metal complex is represented by Formula (II):
  • M is a Group 4 transition metal
  • each Q is independently a Group 15 atom or a Group 16 atom
  • each n is independently 0 or 1, wherein n is 0 if Q is a Group 16 atom or n is 1 if Q is a Group 15 atom;
  • each X 1 and X 2 is independently a substituted or unsubstituted linear, branched, cyclic, polycyclic, aromatic, or polyaromatic hydrocarbyl, a heteroatom, or a heteroatom- containing group; or X 1 and X 2 are joined together to form a C4-C62 cyclic, polycyclic, heterocyclic, or aromatic group;
  • R 1 is a substituted or unsubstituted linear, branched, cyclic, polycyclic, heterocyclic, or aromatic Ci-Cie diyl; each R 2 is independently a hydrogen, a halogen, a substituted or unsubstituted C 1-C40 hydrocarbyl, or a heteroatom-containing group; or two or more adjacent R 2 groups are joined together to form a C4-C62 cyclic, polycyclic, or heterocyclic group that is not aromatic;
  • each R 3 is independently a hydrogen, a substituted or unsubstituted linear, branched, cyclic, polycyclic, aromatic, or polyaromatic C1-C40 hydrocarbyl, or a heteroatom- containing group;
  • each R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 is independently a hydrogen, a halogen, a substituted or unsubstituted linear, branched, cyclic, polycyclic, aromatic, or poly aromatic C 1-C40 hydrocarbyl, or a heteroatom-containing group; or two or more adjacent R 4 -R n groups are joined together to form a C4-C62 cyclic, polycyclic, heterocyclic, or aromatic group.
  • the present disclosure provides a catalyst system that includes a catalyst compound represented by Formula (II), one or more activators, and an optional catalyst support.
  • the present disclosure provides a polymerization process that includes contacting one or more olefin monomers with a catalyst system of the present disclosure and recovering an olefin polymer.
  • the present disclosure provides catalysts containing bridged phenolate transition metal complexes, production, and uses thereof.
  • Catalysts of the present disclosure are transition metal complexes that have a bridged phenolate ligand located on the transition metal and provide catalytic activity values of greater than 100 kg/mmol-hr, such as greater than 400 kg/mmol-hr or greater than 500 kg/mmol-hr.
  • the relatively high catalytic activity is at least in part due to the asymmetry of the bridged phenolate ligands caused by two linking diyl groups differing in the number of bridging atoms.
  • the specification describes catalysts that can be transition metal complexes.
  • the term complex is used to describe molecules in which an ancillary ligand is coordinated to a central transition metal atom.
  • the ligand is bulky and stably bonded to the transition metal so as to maintain its influence during use of the catalyst, such as polymerization.
  • the ligand may be coordinated to the transition metal by covalent bonds, electron donation coordination, and/or intermediate bonds.
  • the transition metal complexes are generally subjected to activation to perform their polymerization or oligomerization function using an activator which is believed to create a cation as a result of the removal of an anionic group, often referred to as a leaving group, from the transition metal.
  • a "Group 4 metal” is an element from Group 4 of the Periodic Table, e.g., Hf, Ti, or Zr.
  • substituted means that at least one hydrogen atom has been replaced with at least a non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR* 2 , -AsR* 2 , -SbR* 2 , -SR*, -BR* 2 , -SiR* 3 , -GeR* 3 , -SnR* 3 , -PbR* 3 , and the like, where each R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or where at least one heteroatom has been
  • hydrocarbyl radical is defined to be Ci-Cioo radicals, that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic.
  • radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like including their substituted analogues.
  • Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom of the hydrocarbyl radical has been substituted with at least a non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as -NR* 2 , -OR*, -SeR*, -TeR*, -PR* 2 , -AsR* 2 , -SbR* 2 , -SR*, -BR* 2 , -SiR* 3 , -GeR* 3 , -SnR* 3 , -PbR* 3 , and the like, or where at least one heteroatom has been inserted within a hydrocarbyl ring.
  • a non-hydrogen group such as a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as halogen
  • diyl is defined to be C1-C40 divalent groups, that may be substituted or unsubstituted linear, branched, cyclic, polycyclic, heterocyclic, or aromatic.
  • diyls can be or include, but are not limited to, C1-C40 diyls, Ci-C 25 diyls, C1-C18 diyls, Ci-Ci 2 diyls, C1-C10 diyls, and C1-C5 diyls.
  • Examples of a C1-C5 diyl can be or include, but are not limited to, methanediyl (-CH2-), ethanediyl (-CH2CH2-), propanediyl (-CH2CH2CH2-), butanediyl (-CH2(CH2)2CH2-), and pentanediyl (-CH2(CH2)3CH2-), isomers thereof, halide-substituted analogues thereof, or other substituted analogues thereof.
  • alkenyl means a straight-chain, branched-chain, or cyclic hydrocarbon radical having one or more carbon-carbon double bonds. These alkenyl radicals may be substituted. Examples of suitable alkenyl radicals include, but are not limited to, ethenyl, propenyl, allyl, 1 ,4-butadienyl cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloctenyl and the like including their substituted analogues.
  • arylalkenyl means an aryl group where a hydrogen has been replaced with an alkenyl or substituted alkenyl group.
  • styryl indenyl is an indene substituted with an arylalkenyl group (a styrene group).
  • alkoxy or "alkoxide” means an alkyl ether or aryl ether radical wherein the term alkyl is as defined above.
  • suitable alkyl ether radicals include, but are not limited to, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert- butoxy, phenoxy, and the like.
  • aryl or "aryl group” means a carbon-containing aromatic ring and the substituted variants thereof, including but not limited to, phenyl, 2-methyl-phenyl, xylyl, 4- bromo-xylyl.
  • heteroaryl means an aryl group where a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, such as N, O, or S.
  • aromatic also refers to pseudoaromatic heterocycles which are heterocyclic substituents that have similar properties and structures (nearly planar) to aromatic heterocyclic ligands, but are not by definition aromatic; likewise, the term aromatic also refers to substituted aromatics.
  • arylalkyl means an aryl group where a hydrogen has been replaced with an alkyl or substituted alkyl group.
  • 3,5'-di-tert-butyl-phenyl indenyl is an indene substituted with an arylalkyl group.
  • alkylaryl means an alkyl group where a hydrogen has been replaced with an aryl or substituted aryl group.
  • ethylbenzyl indenyl is an indene substituted with an ethyl group bound to a benzyl group.
  • references to an alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer expressly discloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl), unless otherwise indicated.
  • ring atom means an atom that is part of a cyclic ring structure.
  • a benzyl group has six ring atoms and tetrahydrofuran has 5 ring atoms.
  • a heterocyclic ring is a ring having a heteroatom in the ring structure as opposed to a heteroatom substituted ring where a hydrogen on a ring atom is replaced with a heteroatom.
  • tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatom substituted ring.
  • a heterocyclic ring is a ring having a heteroatom in the ring structure as opposed to a heteroatom substituted ring where a hydrogen on a ring atom is replaced with a heteroatom.
  • tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatom substituted ring.
  • catalyst system is defined to mean a complex/activator pair.
  • Catalyst system means the unactivated catalyst complex (precatalyst) together with an activator and, optionally, a co-activator.
  • it means the activated complex and the activator or other charge-balancing moiety.
  • the transition metal compound may be neutral as in a precatalyst, or a charged species with a counter ion as in an activated catalyst system.
  • Catalysts of the presented disclosure represented by Formula (II) are intended to embrace ionic forms in addition to the neutral forms of the compounds.
  • Complex as used herein, is also often referred to as catalyst precursor, precatalyst, catalyst, catalyst compound, transition metal compound, or transition metal complex. These words are used interchangeably. Activator and cocatalyst are also used interchangeably.
  • a scavenger is a compound that is typically added to facilitate polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. A co-activator, that is not a scavenger, may also be used in conjunction with an activator in order to form an active catalyst. In some embodiments a co-activator can be pre mixed with the transition metal compound to form an alkylated transition metal compound.
  • Noncoordinating anion means an anion either that does not coordinate to the catalyst metal cation or that does coordinate to the metal cation, but only weakly.
  • NCA is also defined to include multicomponent NCA-containing activators, such as N,N- dimethylanilinium tetrakis(pentafluorophenyl)borate, that contain an acidic cationic group and the non-coordinating anion.
  • NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, that can react with a catalyst to form an activated species by abstraction of an anionic group.
  • NCA coordinates weakly enough that a neutral Lewis base, such as an olefmically or acetylenically unsaturated monomer can displace it from the catalyst center.
  • a neutral Lewis base such as an olefmically or acetylenically unsaturated monomer can displace it from the catalyst center.
  • Any metal or metalloid that can form a compatible, weakly coordinating complex may be used or contained in the noncoordinating anion. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus, and silicon.
  • the term non-coordinating anion activator includes neutral activators, ionic activators, and Lewis acid activators.
  • Catalyst productivity is a measure of how many grams of polymer (P) are produced using a polymerization catalyst containing W g of catalyst (cat), over a period of time of T hours; and may be expressed by the following formula: P/(T x W) and expressed in units of gPgcar'hr 1 .
  • Conversion is the amount of monomer that is converted to polymer product, and is reported as mol% and is calculated based on the polymer yield and the amount of monomer fed into the reactor.
  • Catalyst activity is a measure of the level of activity of the catalyst and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kgP/molcat).
  • an "olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound containing carbon and hydrogen having at least one double bond.
  • alkene is a linear, branched, or cyclic compound containing carbon and hydrogen having at least one double bond.
  • the olefin present in such polymer or copolymer is the polymerized form of the olefin.
  • a copolymer when a copolymer is said to have a "propylene" content of 35 wt% to 55 wt%, it is understood that the mer unit in the copolymer is derived from propylene in the polymerization reaction and the derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer.
  • a "polymer” has two or more of the same or different monomer (“mer”) units.
  • a “homopolymer” is a polymer having mer units that are the same.
  • a “copolymer” is a polymer having two or more mer units that are different from each other.
  • a “terpolymer” is a polymer having three mer units that are different from each other. "Different” in reference to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically. Accordingly, the definition of copolymer, as used herein, includes terpolymers and the like.
  • An oligomer is typically a polymer having a low molecular weight, such an Mn of less than 25,000 g/mol, or less than 2,500 g/mol, or a low number of mer units, such as 75 mer units or less or 50 mer units or less.
  • An "ethylene polymer” or “ethylene copolymer” is a polymer or copolymer containing at least 50 mol% ethylene derived units
  • a "propylene polymer” or “propylene copolymer” is a polymer or copolymer containing at least 50 mol% propylene derived units, and so on.
  • Mn is number average molecular weight
  • Mw is weight average molecular weight
  • Mz is z average molecular weight
  • wt% is weight percent
  • mol% is mole percent.
  • Molecular weight distribution also referred to as polydispersity index (PDI)
  • PDI polydispersity index
  • continuous means a system that operates without interruption or cessation for a period of time, where reactants are continually fed into a reaction zone and products are continually or regularly withdrawn without stopping the reaction in the reaction zone.
  • a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn.
  • a “solution polymerization” means a polymerization process in which the polymerization is conducted in a liquid polymerization medium, such as an inert solvent or monomer(s) or their blends.
  • a solution polymerization is typically homogeneous.
  • a homogeneous polymerization is one where the polymer product is dissolved in the polymerization medium.
  • Such systems are not turbids as described in Oliveira, J. V. el al. (2000)“High-Pressure Phase Equilibria for Polypropylene-Hydrocarbon Systems,” Ind. Eng. Chem. Res. v.39(l2), pp. 4627-4633.
  • a bulk polymerization means a polymerization process in which the monomers and/or comonomers being polymerized are used as a solvent or diluent using little or no inert solvent or diluent.
  • a small fraction of inert solvent might be used as a carrier for catalyst and scavenger.
  • a bulk polymerization system contains less than about 25 wt% of inert solvent or diluent, such as less than about 10 wt%, such as less than about 1 wt%, such as 0 wt%.
  • the present disclosure provides one or more ligands that can be contained in a transition metal complex or catalyst, as discussed and described herein.
  • a ligand can be represented by the Formula (I):
  • R 1 is a linker or bridge between the two Q groups.
  • R 1 is a substituted or unsubstituted linear, branched, cyclic, polycyclic, heterocyclic, or aromatic diyl linking the two Q groups.
  • R 1 can be a substituted or unsubstituted C1-C30 diyl, such as a substituted or unsubstituted Ci-Cie diyl, a substituted or unsubstituted Ci-Cio diyl, a substituted or unsubstituted C1-C6 diyl, or a substituted or unsubstituted C1-C5 diyl.
  • the R 1 can be or include an unsubstituted organic diyl group that can be or include methanediyl (-CH2-), ethanediyl (-CH2CH2-), propanediyl (-CH2CH2CH2-), butanediyl (-CH2(CH2)2CH2-), pentanediyl (-CH2(CH2)3CH2-), hexanediyl (-CH2(CH2)4CH2-), heptanediyl (-CH2(CH2)5CH2-), octanediyl (-CH2(CH2)6CH2-), nonanediyl (-CH2(CH2)7CH2-), decanediyl (-C H 2/ C Fh)xC H 2-).
  • methanediyl -CH2-
  • ethanediyl propanediyl
  • -CH2(CH2)2CH2- propanediyl
  • R 1 can be a substituted or unsubstituted linear or branched C1-C6 diyl, for example, an unsubstituted methanediyl, ethanediyl, propanediyl, a butanediyl, or a pentanediyl.
  • R 1 can be a substituted or unsubstituted cyclic, polycyclic, heterocyclic, or aromatic Ci-Cie or C1-C10 diyl.
  • R 1 can be or include a phenyl diyl, a benzyl diyl, a cyclohexyl diyl, a cyclooctyl diyl, or substitutes thereof.
  • the group R 1 can be or include a substituted or unsubstituted heterocyclic diyl group that can be or include one or more aminos, iminos, ethers, thioethers, silyls, boryls, phosphinos, phosphines, or any combination thereof.
  • Each Q is independently a Group 15 atom (e.g., N or P) or a Group 16 atom (e.g., O, S, or Se).
  • R 3 is not present thereon.
  • each n is independently either 0 or 1, hence n is 0 if Q is a Group 16 atom or n is 1 if Q is a Group 15 atom.
  • Q is O, N, S, or P.
  • the linker L 1 is a substituted or unsubstituted methanediyl group
  • Each R 2 is independently a hydrogen, a halogen or halide (e.g., F, Br, Cl, or I), a substituted or unsubstituted C 1-C40 hydrocarbyl, or a heteroatom-containing group.
  • the substituted or unsubstituted C1-C40 hydrocarbyl can be or include a substituted or unsubstituted branched C3-C40 hydrocarbyl or a substituted or unsubstituted cyclic, polycyclic, aromatic, or polyaromatic C4-C40 hydrocarbyl.
  • each R 2 is independently methyl, ethyl, ethenyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclohexyl, cyclooctyl, phenyl, benzyl, naphthyl, phenanthryl, anthracenyl, carbazolyl, fluorenyl, adamantly, indolyl, indolinyl, imidazolyl, indenyl, indanyl, isomers thereof, halide- substituted analogues thereof, or other substitutes thereof.
  • the heteroatom-containing group can be or include amino, imino, ether, thioether, silyl, boryl, phosphino, or any combination thereof.
  • two or more adjacent R 2 groups are joined together to form a C4- C62 cyclic, polycyclic, or heterocyclic group that is not aromatic.
  • two or more adjacent R 2 groups are joined together to form a C5-C62, C10-C50, or C12-C40 cyclic, polycyclic, or heterocyclic group that is not aromatic.
  • the linker L 2 is a substituted or unsubstituted organic diyl group
  • the substituted or unsubstituted organic diyl group can have two or more -CR2- groups, such as where y is an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.
  • y can be an integer in a range of 2-12, 2-10, 2-8, or 2-5.
  • L 2 is ethanediyl (-CH2CH2-), propanediyl (-CH2CH2CH2-), butanediyl (-CH 2 (CH 2 )2CH2-), pentanediyl (-CH 2 (CH 2 )3CH2-), hexanediyl (-CH 2 (CH 2 )4CH2-), heptanediyl (-CFhtCFkjsCFh-), octanediyl (-CFktCFhjeCFh-), nonanediyl (-CH2(CH2)7CH2-), decanediyl (-CFktCFhjsCFk-), undecanediyl (-CFktCFkjiCFh-), dodecanediyl (-CFktCFhjioCFh-), isomers thereof, or halide-substituted analogues thereof.
  • L 1 is an un
  • each R 2 is independently a hydrogen or a substituted or unsubstituted C1-C10 hydrocarbyl.
  • L 2 has y as an integer of 2, 3, 4, or 5, and for both L 1 and L 2 , each R 2 is independently a hydrogen or a substituted or unsubstituted C1-C6 hydrocarbyl.
  • L 2 has y as an integer of 2 or 3
  • each R 2 on L 1 is a hydrogen, or a substituted or unsubstituted C1-C3 hydrocarbyl
  • each R 2 on L 2 is independently a hydrogen or a substituted or unsubstituted C1-C3 hydrocarbyl.
  • the bridged phenolate ligand is asymmetrical due to the different carbon chain lengths of L 1 and L 2 .
  • L 1 has fewer linker atoms than L 2 since L 1 is a methanediyl and L 2 is at least as long as an ethanediyl, or longer.
  • the relatively high catalytic activity of the catalyst (the transition metal complex) and/or the catalyst system is attributed, at least in part, to the asymmetrical linkage or bridging provided by L 1 and L 2 .
  • Each R 3 is independently a hydrogen, a substituted or unsubstituted C1-C40 hydrocarbyl, or a heteroatom-containing group.
  • the substituted or unsubstituted C 1-C40 hydrocarbyl can be or include a substituted or unsubstituted branched C3- C40 hydrocarbyl or a substituted or unsubstituted cyclic, polycyclic, aromatic, or polyaromatic C4-C40 hydrocarbyl.
  • the heteroatom-containing group can be or include amino, imino, ether, thioether, silyl, boryl, phosphino, or any combination thereof.
  • each R 3 is independently a hydrogen or a substituted or unsubstituted C1-C 10 hydrocarbyl.
  • Each R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 is independently a hydrogen, a halogen or halide (e.g., F, Br, Cl, or I), a substituted or unsubstituted C1-C40 hydrocarbyl, or a heteroatom- containing group.
  • the substituted or unsubstituted C1-C40 hydrocarbyl can be or include a substituted or unsubstituted branched C3-C40 hydrocarbyl or a substituted or unsubstituted cyclic, polycyclic, aromatic, or polyaromatic C4-C40 hydrocarbyl.
  • the heteroatom-containing group can be or include amino, imino, ether, thioether, silyl, boryl, phosphino, or any combination thereof.
  • each of the R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 groups can be or include methyl, ethyl, ethenyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclohexyl, cyclooctyl, phenyl, benzyl, naphthyl, phenanth
  • two or more adjacent groups of R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 are joined together to form a C4-C62 cyclic, polycyclic, heterocyclic, or aromatic group.
  • two or more adjacent R 4 -R n groups are joined together to form a C5-C62, C10-C50, or C 12-C40 cyclic, polycyclic, heterocyclic, or aromatic group.
  • each R 4 and R 8 is independently halogen, phenyl, naphthyl, phenanthryl, anthracenyl, carbazolyl, fluorenyl, adamantly, indolyl, indolinyl, imidazolyl, indenyl, indanyl, or substitutes thereof.
  • R 4 can be carbazolyl, fluorenyl, adamantly, or a substitute thereof and R 8 can be a halogen, such as Br.
  • each R 5 , R 6 , R 7 , R 9 , R 10 , and R 11 group can independently be a hydrogen or a substituted or unsubstituted linear or branched C1-C10 hydrocarbyl.
  • each R 5 , R 7 , R 9 , and R 11 can be a hydrogen and each R 6 and R 10 can be a substituted or unsubstituted linear or branched Ci- C4 hydrocarbyl.
  • the linker L 1 is an unsubstituted methanediyl group and the linker L 2 is an unsubstituted ethanediyl group
  • the ligand can be represented by the Formula (III):
  • the ligand represented by Formula (III) can be referred to as a Ci,C2-bridged ONNO ligand.
  • the ligand which may be contained in a transition metal catalyst, can be represented by the Formula (IV(a)):
  • the linker or group R 1 is an unsubstituted ethanediyl group and both R 3 are methyl groups in the Formula (III)
  • the ligand can be represented by Formulas (IV(b )-(!) as follows:
  • the present disclosure provides catalysts that are bridged phenolate transition metal complexes that include any of the ligands represented by Formulas (I), (III), and (IV(a)-(l)) ligated to a transition metal atom.
  • the bridged phenolate ligand can undergo deprotonation of the phenol groups when ligating to the metal, as further discussed below.
  • the transition metal complex or catalyst is represented by Formula (II):
  • the metal M can be any transition metal.
  • the metal M is a Group 4 transition metal, such as titanium, hafnium, or zirconium. In one or more examples, M is hafnium or zirconium.
  • Each of X 1 and X 2 is independently a hydrogen, a halogen or halide (e.g., F, Br, Cl, or I), a substituted or unsubstituted C1-C40 hydrocarbyl, a heteroatom, or a heteroatom- containing group.
  • the substituted or unsubstituted C1-C40 hydrocarbyl can be or include a substituted or unsubstituted branched C3-C40 hydrocarbyl or a substituted or unsubstituted cyclic, polycyclic, aromatic, or polyaromatic C4-C40 hydrocarbyl.
  • the heteroatom-containing group can be or include amino, imino, ether, thioether, silyl, boryl, phosphino, or any combination thereof.
  • X 1 and X 2 are joined together to form a C4-C62 cyclic, polycyclic, heterocyclic, or aromatic group that is not aromatic.
  • X 1 and X 2 are joined together to form a C5-C62, C10-C50, or C12-C40 cyclic, polycyclic, heterocyclic, or aromatic group.
  • each of X 1 and X 2 is independently a substituted or unsubstituted C1-C20 hydrocarbyl.
  • each of X 1 and X 2 can independently be or include a substituted or unsubstituted Ci-Ce alkyl, a phenyl, a benzyl, a naphthyl, a cyclohexyl, or halide-substituted analogues thereof.
  • each of X 1 and X 2 is a benzyl.
  • the group R 1 is a linker or bridge between the two Q groups.
  • R 1 is a substituted or unsubstituted linear, branched, cyclic, polycyclic, heterocyclic, or aromatic diyl linking the two Q groups.
  • R 1 can be a substituted or unsubstituted C1-C40 diyl, such as a substituted or unsubstituted C1-C30 diyl, as a substituted or unsubstituted Ci-Cie diyl, a substituted or unsubstituted C1-C10 diyl, a substituted or unsubstituted C1-C6 diyl, or a substituted or unsubstituted C1-C5 diyl.
  • C1-C40 diyl such as a substituted or unsubstituted C1-C30 diyl, as a substituted or unsubstituted Ci-Cie diyl, a substituted or unsubstituted C1-C10 diyl, a substituted or unsubstituted C1-C6 diyl, or a substituted or unsubstituted C1-C5 diyl.
  • the R 1 can be or include an unsubstituted organic diyl group that can be or include methanediyl (-CH2-), ethanediyl (-CH2CH2-), propanediyl (-CH2CH2CH2-), butanediyl (-CFhiGFh ⁇ CFh-), pentanediyl (-CH2(CH2)3CH2-), hexanediyl (-CFhiGFh ⁇ CFh-), heptanediyl (-CFEiGFhjsCFh-), octanediyl (-CFhiGFhjeCFh-), nonanediyl (-CFhiGFEjvCFh-), decanediyl (-CH2(CH2)8CH2-), undecanediyl (-CFhiGFhjiCFh-), dodecanediyl (-CFhiGFhjioCFh-), isomers thereof
  • R 1 can be a substituted or unsubstituted linear or branched C1-C6 diyl, for example, an unsubstituted methanediyl, ethanediyl, propanediyl, a butanediyl, a pentanediyl, or a hexanediyl.
  • R 1 can be a substituted or unsubstituted cyclic, polycyclic, heterocyclic, or aromatic Ci-Cie or C1-C10 diyl.
  • R 1 can be or include a phenyl diyl, a benzyl diyl, a cyclohexyl diyl, a cyclooctyl diyl, or substitutes thereof.
  • the group R 1 can be or include a substituted or unsubstituted heterocyclic diyl group that can be or include one or more aminos, iminos, ethers, thioethers, silyls, boryls, phosphinos, phosphines, or any combination thereof.
  • Each Q is independently a Group 15 atom (e.g., N or P) or a Group 16 atom (e.g., O, S, or Se).
  • R 3 is not present thereon.
  • each n is independently either 0 or 1, hence n is 0 if Q is a Group 16 atom or n is 1 if Q is a Group 15 atom.
  • Q is O, N, S, or P.
  • the linker L 1 is a substituted or unsubstituted methanediyl group
  • Each R 2 is independently a hydrogen, a halogen or halide (e.g., F, Br, Cl, or I), a substituted or unsubstituted C 1-C40 hydrocarbyl, or a heteroatom-containing group.
  • the substituted or unsubstituted C1-C40 hydrocarbyl can be or include a substituted or unsubstituted branched C3-C40 hydrocarbyl or a substituted or unsubstituted cyclic, polycyclic, aromatic, or poly aromatic C4-C40 hydrocarbyl.
  • each R 2 is independently methyl, ethyl, ethenyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclohexyl, cyclooctyl, phenyl, benzyl, naphthyl, phenanthryl, anthracenyl, carbazolyl, fluorenyl, adamantly, indolyl, indolinyl, imidazolyl, indenyl, indanyl, isomers thereof, halide- substituted analogues thereof, or other substitutes thereof.
  • the heteroatom-containing group can be or include amino, imino, ether, thioether, silyl, boryl, phosphino, or any combination thereof.
  • two or more adjacent R 2 groups are joined together to form a C4- C62 cyclic, polycyclic, or heterocyclic group that is not aromatic.
  • two or more adjacent R 2 groups are joined together to form a C5-C62, C10-C50, or C 12-C40 cyclic, polycyclic, or heterocyclic group that is not aromatic.
  • the linker L 2 is a substituted or unsubstituted organic diyl group
  • the substituted or unsubstituted organic diyl group can have two or more -CR2- groups, such as where y is an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.
  • y can be an integer in a range of 2-12, 2-10, 2-8, or 2-5.
  • L 2 can be ethanediyl (-CH2CH2-), propanediyl (-CH2CH2CH2-), butanediyl (-CH2(CH2)2CH2-), pentanediyl (-CFkiGFhjsCFh-), hexanediyl (-CFhiGFh ⁇ CFh-), heptanediyl (-CFhiGFBjsCFh-), octanediyl (-CFBiGFhjeCFh-), nonanediyl (-CH2(CH2)7CH2-), decanediyl (-C H 2 C FhjxC H 2-).
  • L 1 can be an unsubstituted methanediyl and L 2 can be a substituted or unsubstituted ethanediyl.
  • each R 2 is independently a hydrogen or a substituted or unsubstituted C 1-C 10 hydrocarbyl.
  • L 2 can have y as an integer of 2, 3, 4, or 5, and for both L 1 and L 2 , each R 2 is independently a hydrogen or a substituted or unsubstituted C 1-C5 hydrocarbyl.
  • L 2 can have y as an integer of 2 or 3
  • each R 2 on L 1 is a hydrogen or a substituted or unsubstituted C 1-C3 hydrocarbyl
  • each R 2 on L 2 is independently a hydrogen or a substituted or unsubstituted C 1-C3 hydrocarbyl.
  • Each R 3 is independently a hydrogen, a substituted or unsubstituted C1-C40 hydrocarbyl, or a heteroatom-containing group.
  • the substituted or unsubstituted C 1-C40 hydrocarbyl can be or include a substituted or unsubstituted branched C3- C40 hydrocarbyl or a substituted or unsubstituted cyclic, polycyclic, aromatic, or polyaromatic C4-C40 hydrocarbyl.
  • the heteroatom-containing group can be or include amino, imino, ether, thioether, silyl, boryl, phosphino, or any combination thereof.
  • each R 3 is independently a hydrogen or a substituted or unsubstituted C1-C 10 hydrocarbyl.
  • Each of the R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 groups is independently a hydrogen, a halogen or halide (e.g., F, Br, Cl, or I), a substituted or unsubstituted C 1-C40 hydrocarbyl, or a heteroatom-containing group.
  • the substituted or unsubstituted Ci- C40 hydrocarbyl can be or include a substituted or unsubstituted branched C3-C40 hydrocarbyl or a substituted or unsubstituted cyclic, polycyclic, aromatic, or polyaromatic C4-C40 hydrocarbyl.
  • the heteroatom-containing group can be or include amino, imino, ether, thioether, silyl, boryl, phosphino, or any combination thereof.
  • each of the R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 groups can be or include methyl, ethyl, ethenyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclohexyl, cyclooctyl, phenyl, benzyl, naphthyl, phenanth
  • two or more adjacent groups of R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 are joined together to form a C4-C62 cyclic, polycyclic, heterocyclic, or aromatic group.
  • two or more adjacent R 4 -R n groups are joined together to form a C5-C62, C10-C50, or C12-C40 cyclic, polycyclic, heterocyclic, or aromatic group.
  • each of R 4 and R 8 is independently halogen, phenyl, naphthyl, phenanthryl, anthracenyl, carbazolyl, fluorenyl, adamantly, indolyl, indolinyl, imidazolyl, indenyl, indanyl, or substitutes thereof.
  • R 4 can be carbazolyl, fluorenyl, adamantly, or a substitute thereof and R 8 can be a halogen, such as Br.
  • each of R 5 , R 6 , R 7 , R 9 , R 10 , and R 11 group can independently be a hydrogen or a substituted or unsubstituted linear or branched Ci-Cio hydrocarbyl.
  • each of R 5 , R 7 , R 9 , and R 11 can be a hydrogen and each R 6 and R 10 can be a substituted or unsubstituted linear or branched C1-C4 hydrocarbyl.
  • the transition metal catalyst is represented by Formula (V):
  • the transition metal catalyst is represented by Formula (VI):
  • transition metal complex or catalyst is represented by Formula (VII(a)):
  • metal M is titanium, hafnium, or zirconium.
  • the ligand can be represented by Formulas (Vll(b)-(l)) as follows:
  • metal M is titanium, hafnium, or zirconium.
  • All air sensitive syntheses are carried out in nitrogen or argon purged dry boxes. All solvents are available from commercial sources.
  • Ozone is generated by an ozone generator.
  • ligands of Formulas (I), (III), and (IV(a)-(l)) can be synthesized according to the schematic reaction procedure described in Schemes 1-3 and transition metal catalysts of Formulas (II), (V), (VI), (VII(a)-(l)) can be synthesized according to the schematic reaction procedure described in Scheme 4.
  • catalyst systems may be formed by combining the catalysts with activators in any suitable manner, including by supporting them for use in slurry or gas phase polymerization.
  • the catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in the monomer, such as, without solvent).
  • the catalyst system typically contains a transition metal complex as described above and an activator such as alumoxane or a non-coordinating anion activator.
  • Activation may be performed using alumoxane solution including an alkyl alumoxane such as methyl alumoxane, referred to as MAO, as well as modified MAO, referred to herein as MMAO, which contains some higher alkyl groups to improve the solubility.
  • MAO alkyl alumoxane
  • MMAO modified MAO, referred to herein as MMAO, which contains some higher alkyl groups to improve the solubility.
  • MAO can be purchased from Albemarle Corporation, Baton Rouge, Louisiana, typically in a 10 wt% solution in toluene.
  • activators that can be used in the catalyst system can be or include one or more alumoxanes, one or more aluminum alkyls, and other aluminum compounds.
  • Exemplary activators that can be used in the catalyst system can be or include, but are not limited to, methyl alumoxane, ethyl alumoxane, isobutyl alumoxane, isobutyl alumoxane, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum, N,N-dimethylanilinium tetra(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N- dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetra
  • the catalyst-to-activator molar ratio is from about 1 :3,000 to about 10: 1; such as about 1 :2,000 to about 10: 1; such as about 1: 1,000 to about 10: 1; such as about 1 :500 to about 1 : 1; such as about 1 :300 to about 1: 1; such as about 1 :200 to about 1: 1; such as about 1 : 100 to about 1 : 1; such as about 1 :50 to about 1: 1; such as about 1 : 10 to about 1 : 1.
  • alumoxane When the activator is an alumoxane (modified or unmodified), some embodiments select the maximum amount of activator at a 5,000-fold molar excess over the catalyst (per metal catalytic site). The minimum activator-to-catalyst ratio can be 1 : 1 molar ratio.
  • Another useful alumoxane is solid polymethylaluminoxane as described in US Patent Nos. 8,404,880; 8,975,209; and 9,340,630.
  • NCA non-coordinating anions
  • NCA's non-coordinating anions
  • NCA may be added in the form of an ion pair using, for example, [DMAH]+ [NCA]- in which the N,N- dimethylanilinium (DMAH) cation reacts with a basic leaving group on the transition metal complex to form a transition metal complex cation and [NCA]-.
  • the cation in the precursor may, alternatively, be trityl.
  • the transition metal complex may be reacted with a neutral NCA precursor, such as B(C6F5)3, which abstracts an anionic group from the complex to form an activated species.
  • Useful activators include N,N-dimethylanilinium tetrakis (pentafluorophenyl)borate ([PhNMe2H]B(C6F5)4) and N,N-dimethylanilinium tetrakis (heptafluoronaphthyl)borate, where Ph is phenyl, and Me is methyl.
  • activators useful herein include those described in US Patent No. 7,247,687 at column 169, line 50 to column 174, line 43, particularly column 172, line 24 to column 173, line 53.
  • non-coordinating anion activator is represented by the following formula (1):
  • Z is (L-H) or a reducible Lewis acid, L is a neutral Lewis base, H is hydrogen and (L-H) + is a Bronsted acid;
  • a d is a non-coordinating anion having the charge d-; and d is an integer from 1 to 3.
  • the cation component may include Bronsted acids such as protonated Lewis bases capable of protonating a moiety, such as an alkyl or aryl, from the catalyst precursor, resulting in a cationic transition metal species, or the activating cation (L-H) d+ is a Bronsted acid, capable of donating a proton to the catalyst precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof, or ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro- N,N-
  • Z is a reducible Lewis acid
  • it may be represented by the formula: (AnC+).
  • Ar is aryl or aryl substituted with a heteroatom, or a Ci to C40 hydrocarbyl
  • the reducible Lewis acid may be represented by the formula: (Ph 3 C+), where Ph is phenyl or phenyl substituted with a heteroatom, and/or a Ci to C40 hydrocarbyl.
  • the reducible Lewis acid is triphenyl carbenium.
  • Each Q may be a fluorinated hydrocarbyl radical having 1 to 20 carbon atoms, or each Q is a fluorinated aryl radical, or each Q is a pentafluoryl aryl radical.
  • suitable Ad- components also include diboron compounds as disclosed in US Patent No. 5,447,895, which is fully incorporated herein by reference.
  • the present disclosure also provides a method to polymerize olefins including contacting olefins (such as propylene) with a catalyst complex as described above and an NCA activator represented by the Formula (2):
  • R is a monoanionic ligand; M** is a Group 13 metal or metalloid; ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclic aromatic ring, or aromatic ring assembly in which two or more rings (or fused ring systems) are joined directly to one another or together; and n is 0, 1, 2, or 3.
  • the NCA containing an anion of Formula 2 also contains a suitable cation that is essentially non-interfering with the ionic catalyst complexes formed with the transition metal compounds, or the cation is Zd+ as described above.
  • R is a Ci to C30 hydrocarbyl radical.
  • Ci to C30 hydrocarbyl radicals may be substituted with one or more Ci to C20 hydrocarbyl radicals, halide, hydrocarbyl substituted organometalloid, dialkylamido, alkoxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido, arylphosphide, or other anionic substituent; fluoride; bulky alkoxides, where bulky means Cr to C20 hydrocarbyl radicals; -SRa, -NRa 2 , and -PRa 2 , where each Ra is independently a monovalent C4 to C 2 o hydrocarbyl radical having a molecular volume greater than or equal to the molecular volume of an isopropyl substitution or a C4 to C 2 o hydro
  • the NCA in any of the NCA's containing an anion represented by Formula 2 described above, also includes cation containing a reducible Lewis acid represented by the formula: (AnC+). where Ar is aryl or aryl substituted with a heteroatom, and/or a Ci to C40 hydrocarbyl, or the reducible Lewis acid represented by the formula: (Ph3C+), where Ph is phenyl or phenyl substituted with one or more heteroatoms, and/or Ci to C40 hydrocarbyls.
  • a reducible Lewis acid represented by the formula: (AnC+) where Ar is aryl or aryl substituted with a heteroatom, and/or a Ci to C40 hydrocarbyl, or the reducible Lewis acid represented by the formula: (Ph3C+), where Ph is phenyl or phenyl substituted with one or more heteroatoms, and/or Ci to C40 hydrocarbyls.
  • the NCA may also contain a cation represented by the formula, (L-H) d+ , wherein L is an neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or 3, or (L-H) d+ is a Bronsted acid selected from ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof.
  • an activator can be or include a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the Formula (3):
  • OX e+ is a cationic oxidizing agent having a charge of e+; e is 1, 2 or 3; d is 1, 2 or 3; and A d is a non-coordinating anion having the charge of d- (as further described above).
  • cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag + , or Pb +2 .
  • Suitable embodiments of A d include tetrakis(pentafluorophenyl)borate.
  • Activators useful in catalyst systems can be or include one or more of: trimethylammonium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, trimethylammonium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(per£luorobiphenyl)borate, and the types disclosed in US Patent No. 7,297,653, which is fully incorporated by reference herein.
  • Suitable activators also include: N,N-dimethylanibnium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanibnium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanibnium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Ph3C + ][B(C6F5)4 ], [Me3NH + ][B(C6F5)4 ];
  • the activator can be or include one or more of a triaryl carbonium (such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2, 3,4,6- tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate).
  • a triaryl carbonium such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(
  • an activator can be or include one or more of N,N- dimethylanibnium tetra(perfluorophenyl)borate; N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate; N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate; N,N-dimethylanibnium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; triphenylcarbenium tetrakis(perfluoronaphthyl)borate; triphenylcarbenium tetrakis(perfluorobiphenyl)borate; triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; triphenylcarbenium tetra(perfluorophenyl)borate; trimethylammoni
  • two NCA activators may be used in the polymerization and the molar ratio of the first NCA activator to the second NCA activator can be any ratio.
  • the molar ratio of the first NCA activator to the second NCA activator is 0.01 : 1 to 10,000: 1, or 0.1 : 1 to 1,000: 1, or 1: 1 to 100: 1.
  • the NCA activator-to-catalyst ratio is a 1:1 molar ratio, or 0.1:1 to 100:1, or 0.5:1 to 200:1, or 1:1 to 500:1 or 1:1 to 1,000:1.
  • the NCA activator-to-catalyst ratio is 0.5:1 to 10:1, or 1:1 to 5:1.
  • the transition metal catalysts can be combined with combinations of alumoxanes and NCA's (see for example, US 5,153,157, US 5,453,410, EP 0573120 Bl, WO 1994/007928, and WO 1995/014044 which discuss the use of an alumoxane in combination with an ionizing activator, all of which are incorporated by reference herein).
  • the catalyst-to-activator molar ratio is typically from 1:10 to 1:1; 1:10 to 10:1; 1:10 to 2:1; UlOto 3:1; ElOto 5:1; 1:2 to 1.2:1; 1:2 to 10:1; 1:2 to 2:1; 1:2 to 3:1; 1:2 to 5:1; 1:3 to 1.2:1; 1:3 to 10:1; 1:3 to 2:1; 1:3 to 3:1: 1:3 to 5:1; 1:5 to 1:1; 1:5 to 10:1; 1:5 to 2:1; 1:5 to 3:1; 1:5 to 5:1; 1:1 to 1:1.2.
  • a co-activator such as a group 1, 2, or 13 organometallic species (e.g., an alkyl aluminum compound such as tri-n-octyl aluminum), may be used in the catalyst system herein.
  • the catalyst-to-co-activator molar ratio is from 1:100 to 100:1; 1:75 to 75:1; 1:50 to 50:1; 1:25 to 25:1; 1:15 to 15:1; 1:10 to 10:1; 1:5 to 5:1; 1:2 to 2:1; 1:100 to 1:1; 1:75 to 1:1; 1:50 to 1:1; 1:25 to 1:1; 1:15 to 1:1; UlOto 1:1; 1:5 to 1:1; 1:2 to 1:1; UlOto 2:1.
  • the catalyst system can include an inert support material.
  • the supported material is a porous support material, for example, talc, or inorganic oxides.
  • Other support materials include zeolites, clays, organoclays, or any other suitable organic or inorganic support material and the like, or mixtures thereof.
  • the support material is an inorganic oxide.
  • Suitable inorganic oxide materials for use in transition metal catalyst systems herein include Groups 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof.
  • Other inorganic oxides that may be employed either alone or in combination with the silica, or alumina are magnesia, titania, zirconia, and the like.
  • Other suitable support materials can be employed, for example, functionalized polyolefins, such as polyethylene. Supports include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, and the like.
  • support materials may be used, for example, silica-chromium, silica-alumina, silica- titania, and the like.
  • Support materials can include, but are not limited to AI2O3, Zr0 2 , S1O2, S1O2/AI2O3, Si02/Ti02, silica clay, silicon oxide/clay, or any mixture thereof.
  • the support material such as an inorganic oxide, can have a surface area in the range from about 10 m 2 /g to about 700 m 2 /g, pore volume in the range from about 0.1 cc/g to about 4.0 cc/g and average particle size in the range from about 5 pm to about 500 pm.
  • the surface area of the support material is in the range from about 50 m 2 /g to about 500 m 2 /g, pore volume of from about 0.5 cc/g to about 3.5 cc/g and average particle size of from about 10 pm to about 200 pm. In one or more embodiments, the surface area of the support material is in the range is from about 100 m 2 /g to about 400 m 2 /g, pore volume from about 0.8 cc/g to about 3.0 cc/g and average particle size is from about 5 pm to about 100 pm.
  • the average pore size of the support material useful in the present disclosure is in the range from 10 A to 1,000 A, such as 50 A to about 500 A, such as 75 A to about 350 A.
  • Silicas are marketed under the tradenames of DAVISON 952 or DAVISON 955 by the Davison Chemical Division of W.R. Grace and Company. In other embodiments, DAVISON 948 is used.
  • the support material should be dry, that is, substantially free of absorbed water. Drying of the support material can be effected by heating or calcining at about l00°C to about l,000°C, such as at least about 600°C. When the support material is silica, it is heated to at least 200°C, such as about 200°C to about 850°C, such as at about 600°C; and for a time of about 1 minute to about 100 hours, from about 12 hours to about 72 hours, or from about 24 hours to about 60 hours.
  • the calcined support material should have at least some reactive hydroxyl (OH) groups to produce supported catalyst systems of the present disclosure. The calcined support material is then contacted with at least one polymerization catalyst containing one or more transition metal catalyst and an activator.
  • the support material having reactive surface groups, typically hydroxyl groups, is slurried in a non-polar solvent and the resulting slurry is contacted with a solution of a transition metal catalyst and an activator.
  • the slurry of the support material is first contacted with the activator for a period of time in the range from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.
  • the solution of the transition metal catalyst is then contacted with the isolated support/activator.
  • the supported catalyst system is generated in situ.
  • the slurry of the support material is first contacted with the catalyst compound for a period of time in the range from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.
  • the slurry of the supported transition metal catalyst is then contacted with the activator solution.
  • the mixture of the catalyst, activator and support is heated to about 0°C to about 70°C, such as to about 23°C to about 60°C, such as at room temperature.
  • Contact times typically range from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.
  • Suitable non-polar solvents are materials in which all of the reactants used herein, e.g., the activator, and the catalyst compound, are at least partially soluble and which are liquid at room temperature.
  • Non-limiting example non-polar solvents are alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, cycloalkanes, such as cyclohexane, aromatics, such as benzene, toluene, and ethylbenzene.
  • the support material contains a support material treated with an electron-withdrawing anion.
  • the support material can be silica, alumina, silica- alumina, silica-zirconia, alumina-zirconia, aluminum phosphate, heteropoly tungstates, titania, magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereof; and the electron- withdrawing anion is selected from fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, or any combination thereof.
  • the electron- withdrawing component used to treat the support material can be any component that increases the Lewis or Bronsted acidity of the support material upon treatment (as compared to the support material that is not treated with at least one electron-withdrawing anion).
  • the electron-withdrawing component is an electron- withdrawing anion derived from a salt, an acid, or other compound, such as a volatile organic compound, that serves as a source or precursor for that anion.
  • Electron-withdrawing anions can be sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phospho-tungstate, or mixtures thereof, or combinations thereof.
  • An electron-withdrawing anion can be fluoride, chloride, bromide, phosphate, triflate, bisulfate, or sulfate, or any combination thereof, at least one embodiment of this disclosure.
  • the electron-withdrawing anion is sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, or combinations thereof.
  • the support material suitable for use in the catalyst systems of the present disclosure can be one or more of fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica- alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or combinations thereof.
  • the activator-support can be or include fluorided alumina, sulfated alumina, fluorided silica-alumina, sulfated silica-alumina, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or combinations thereof.
  • the support material includes alumina treated with hexafluorotitanic acid, silica-coated alumina treated with hexafluorotitanic acid, silica-alumina treated with hexafluorozirconic acid, silica-alumina treated with trifluoroacetic acid, fluorided boria- alumina, silica treated with tetrafluoroboric acid, alumina treated with tetrafluoroboric acid, alumina treated with hexafluorophosphoric acid, or combinations thereof.
  • any of these activator-supports optionally can be treated with a metal ion.
  • Exemplary cations suitable for use in the present disclosure in the salt of the electron-withdrawing anion include ammonium, trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H + , [H(OEt2)2] + , or combinations thereof.
  • combinations of one or more different electron-withdrawing anions can be used to tailor the specific acidity of the support material to a desired level.
  • Combinations of electron-withdrawing components can be contacted with the support material simultaneously or individually, and in any order that provides a desired chemically- treated support material acidity.
  • two or more electron-withdrawing anion source compounds in two or more separate contacting steps.
  • a process by which a chemically-treated support material is prepared can include contacting a selected support material, or combination of support materials, with a first electron-withdrawing anion source compound to form a first mixture; such first mixture can be calcined and then contacted with a second electron- withdrawing anion source compound to form a second mixture; the second mixture can then be calcined to form a treated support material.
  • the first and second electron- withdrawing anion source compounds can be either the same or different compounds.
  • the method by which the oxide is contacted with the electron-withdrawing component can include gelling, co-gelling, impregnation of one compound onto another, or combinations thereof.
  • the contacted mixture of the support material, electron-withdrawing anion, and optional metal ion can be calcined.
  • the support material can be treated by a process that includes: (i) contacting a support material with a first electron- withdrawing anion source compound to form a first mixture; (ii) calcining the first mixture to produce a calcined first mixture; (iii) contacting the calcined first mixture with a second electron-withdrawing anion source compound to form a second mixture; and (iv) calcining the second mixture to form the treated support material.
  • the present disclosure provides polymerization processes where monomer (e.g., ethylene and/or propylene), and optionally comonomer, are contacted with a catalyst system containing one or more transition metal catalysts and one or more activators, as described above.
  • the catalyst compound and activator may be combined in any order, and are combined typically prior to contacting with the monomer.
  • a polymerization process includes a) contacting one or more olefin monomers with a catalyst system containing: i) an activator and ii) a catalyst compound.
  • the activator may be an alumoxane or a non-coordination anion activator.
  • the one or more olefin monomers can be or include, but are not limited to, ethylene, propylene, butylene, or any combination thereof.
  • the polymerization process further includes heating the one or more olefin monomers and the catalyst system to 70°C or more to form polyethylene, polypropylene, or a copolymer containing both polyethylene and polypropylene.
  • Monomers useful herein include substituted or unsubstituted C2 to C40 alpha olefins, such as C2 to C20 alpha olefins, such as C2 to C 12 alpha olefins, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof.
  • C2 to C40 alpha olefins such as C2 to C20 alpha olefins, such as C2 to C 12 alpha olefins, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof.
  • the monomer contains ethylene and an optional comonomers containing one or more ethylene or C4 to C40 olefins, such as C4 to C20 olefins, such as C6 to C12 olefins.
  • the C4 to C40 olefin monomers may be linear, branched, or cyclic.
  • the C4 to C40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.
  • the monomer contains ethylene and an optional comonomers containing one or more C3 to C40 olefins, such as C4 to C20 olefins, such as G, to C12 olefins.
  • the C3 to C40 olefin monomers may be linear, branched, or cyclic.
  • the C3 to C40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.
  • Exemplary C2 to C40 olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbomene, norbomadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbomadiene, substituted derivatives thereof, and isomers thereof, such as hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, l,5-cyclooctadiene, l-hydroxy-4-cyclooctene, l-acetoxy-4-cyclo
  • one or more dienes are present in the polymer produced herein at up to 10 weight% (wt%), such as at about 0.00001 wt% to about 1.0 wt%, such as about 0.002 wt% to about 0.5 wt%, such as about 0.003 wt% to about 0.2 wt%, based upon the total weight of the composition.
  • wt% weight%
  • 500 ppm or less of diene is added to the polymerization, such as 400 ppm or less, such as 300 ppm or less.
  • at least 50 ppm of diene is added to the polymerization, or 100 ppm or more, or 150 ppm or more.
  • Diolefm monomers include any hydrocarbon structure, such as Cr to C30, having at least two unsaturated bonds, wherein at least two of the unsaturated bonds are readily incorporated into a polymer by either a stereospecific or a non-stereospecific catalyst(s).
  • the diolefm monomers can be selected from alpha, omega-diene monomers (e.g., di-vinyl monomers).
  • the diolefm monomers are linear di-vinyl monomers, such as those containing from 4 carbon atoms to 30 carbon atoms.
  • dienes examples include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, l,6-heptadiene, l,7-octadiene, l,8-nonadiene, 1 ,9-decad
  • Cyclic dienes include cyclopentadiene, vinylnorbomene, norbomadiene, ethylidene norbomene, divinylbenzene, dicyclopentadiene or higher ring containing diolefms with or without substituents at various ring positions.
  • Polymerization processes of the present disclosure can be carried out in any suitable manner. Any suitable suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization process can be used. Such processes can be run in a batch, semi-batch, or continuous mode. Homogeneous polymerization processes and slurry processes can be performed. For example, a homogeneous polymerization process is one where at least 90 wt% of the product is soluble in the reaction media. A bulk homogeneous process can be used. For example, a bulk process is one where monomer concentration in all feeds to the reactor is 70 volume % or more.
  • the process is a slurry polymerization process.
  • slurry polymerization process means a polymerization process where a supported catalyst is employed and monomers are polymerized on the supported catalyst particles. At least 95 wt% of polymer products derived from the supported catalyst are in granular form as solid particles (not dissolved in the diluent).
  • Suitable diluents/solvents for polymerization include non-coordinating, inert liquids.
  • examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (IsoparTM); perhalogenated hydrocarbons, such as peril uorinated C4-C 10 alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene.
  • straight and branched-chain hydrocarbons such as is
  • Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1 -butene, 1 -hexene, l-pentene, 3- methyl-l-pentene, 4-methyl- l-pentene, l-octene, l-decene, and mixtures thereof.
  • aliphatic hydrocarbon solvents are used as the solvent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof.
  • the solvent is not aromatic, such that aromatics are present in the solvent at less than 1 wt%, such as less than 0.5 wt%, such as less than 0 wt% based upon the weight of the solvents.
  • the feed concentration of the monomers and comonomers for the polymerization is 60 vol% solvent or less, such as 40 vol% or less, such as 20 vol% or less, based on the total volume of the feedstream.
  • the polymerization can be performed in a bulk process.
  • Polymerizations can be performed at any temperature and/or pressure suitable to obtain the desired polymers, such as ethylene and or propylene polymers.
  • Typical temperatures and/or pressures include a temperature of about 0°C to about 300°C, such as about 20°C to about 200°C, such as about 35°C to about l50°C, such as about 40°C to about l20°C, such as about 45°C to about 80°C, for example about 74°C, and at a pressure of about 0.05 MPa to about 1,500 MPa, about 1.7 MPa to about 30 MPa, or in some embodiments, such as under supercritical conditions, about 15 MPa to about 1,500 MPa.
  • the run time of the reaction is up to 300 minutes, such as in the range from about 5 minutes to about 250 minutes, such as about 10 minutes to about 120 minutes.
  • hydrogen is present in the polymerization reactor at a partial pressure of about 0.001 psig to about 50 psig (about 0.007 kPa to about 345 kPa), such as from about 0.01 psig to about 25 psig (about 0.07 kPa to about 172 kPa), such as about 0.1 psig to about 10 psig (about 0.7 kPa to about 70 kPa).
  • the productivity of a catalyst of the present disclosure is from about 1,000 gPgcar'hr' to about 20,000 gPgcar'hr'. such as from about 2,000 gPgcar'hr' to about 15,000 gPgcar'hr 1 . such as from about 4,000 gPgcar'hr 1 to about 14,000 gPgcat ⁇ hr 1 , such as from about 6,000 gPgcar'hr' to about 13,000 gPgcar'hr'. such as from about 8,000 gPgcar'hr' to about 12,000 gPgcar'hr'.
  • the catalyst system, the transition metal complex, and/or the catalyst has a catalytic activity of about 10 kg/mmol-hr, about 20 kg/mmol-hr, about 40 kg/mmol-hr, about 50 kg/mmol-hr, about 70 kg/mmol-hr, about 80 kg/mmol-hr, about 90 kg/mmol-hr, or about 100 kg/mmol-hr to about 120 kg/mmol-hr, about 150 kg/mmol-hr, about 180 kg/mmol-hr, about 200 kg/mmol-hr, about 250 kg/mmol-hr, about 300 kg/mmol-hr, about 350 kg/mmol-hr, about 400 kg/mmol-hr, about 450 kg/mmol-hr, about 500 kg/mmol-hr, about 550 kg/mmol-hr, about 600 kg/mmol-hr, about 700 kg/mmol-hr, about 800 kg/mmol-hr
  • the catalyst system, the transition metal complex, and/or the catalyst has a catalytic activity of about 10 kg/mmol-hr to about 2,000 kg/mmol-hr, about 10 kg/mmol-hr to about 1,500 kg/mmol-hr, about 10 kg/mmol-hr to about 1,000 kg/mmol-hr, about 10 kg/mmol-hr to about 800 kg/mmol-hr, about 10 kg/mmol-hr to about 700 kg/mmol-hr, about 10 kg/mmol-hr to about 600 kg/mmol-hr, about 10 kg/mmol-hr to about 500 kg/mmol-hr, about 10 kg/mmol-hr to about 400 kg/mmol-hr, about 10 kg/mmol- hr to about 300 kg/mmol-hr, about 50 kg/mmol-hr to about 1,500 kg/mmol-hr, about 50 kg/mmol-hr to about 1,000 kg/mmol-hr, about 50 kg/mmol-h
  • the catalyst system, the transition metal complex, and/or the catalyst has a catalytic activity of in a range from about 10 kg/mmol-hr to about 1,000 kg/mmol-hr, about 100 kg/mmol-hr to about 1,000 kg/mmol-hr, about 100 kg/mmol-hr to about 600 kg/mmol-hr, about 200 kg/mmol-hr to about 600 kg/mmol-hr, about 400 kg/mmol-hr to about 600 kg/mmol-hr, or alternatively, about 100 kg/mmol-hr to about 200 kg/mmol-hr.
  • the conversion of olefin monomer is at least 10%, based upon polymer yield and the weight of the monomer entering the reaction zone, such as 20% or more, such as 30% or more, such as 50% or more, such as 80% or more.
  • a catalyst of the present disclosure has an activity of 150,000 to about 600,000 g/mmol/hour.
  • a catalyst of the present disclosure such as a compound of Formulas (II), (V), (VI), and (VII(a)-(l)) is capable of producing a polymer or a copolymer, such as polyethylene or polyethylene-octene, having an Mw of about 30,000, about 50,000, about 70,000, or about 80,000 to about 90,000, about 100,000, about 120,000, about 140,000, about 150,000, about 180,000, about 200,000, about 250,000, about 500,000, or about 1,000,000.
  • the polymer has an Mw in a range from about 30,000 to about 1,000,000, about 50,000 to about 500,000, about 60,000 to about 300,000, or about 80,000 to about 200,000.
  • a catalyst of the present disclosure is capable of producing a polymer or a copolymer, such as polyethylene or polyethylene-octene, having an Mn of about 20,000, about 25,000, about 30,000, or about 35,000 to about 40,000, about 45,000, about 50,000, about 60,000, about 70,000, about 80,000, about 90,000, about 100,000, about 120,000, or about 150,000.
  • the polymer has an Mn in a range from about 20,000 to about 150,000, about 25,000 to about 120,000, about 30,000 to about 100,000, or about 40,000 to about 100,000.
  • a catalyst of the present disclosure is capable of producing a polymer or a copolymer, such as polyethylene or polyethylene-octene, having an Mw/Mn value from about 1 to about 5, for example, about 1.5 to about 4, about 1.5 to about 3, about 1.5 to about 2.5.
  • alumoxane is used in the process to produce the polymers.
  • Alumoxane can be present at zero mol%, alternatively the alumoxane is present at a molar ratio of aluminum to transition metal less than 500:1, such as less than 300: 1, such as less than 100: 1, such as less than 1 :1.
  • scavenger such as trialkyl aluminum
  • Scavenger can be present at zero mol%, alternately the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100: 1, such as less than 50: 1, such as less than 15: 1, such as less than 10:1.
  • the polymerization 1) is conducted at temperatures of about 0°C to about 300°C (such as about 25°C to about l50°C, such as about 40°C to about l20°C, such as about 70°C to about H0°C); 2) is conducted at a pressure of atmospheric pressure to 10 MPa (such as about 0.35 MPa to about 10 MPa, such as from about 0.45 MPa to about 6 MPa, such as from about 0.5 MPa to about 4 MPa); 3) is conducted in an aliphatic hydrocarbon solvent (such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof;
  • the catalyst system used in the polymerization includes no more than one catalyst compound.
  • a "reaction zone” also referred to as a "polymerization zone” is a vessel where polymerization takes place, for example a batch reactor. When multiple reactors are used in either series or parallel configuration, each reactor is considered as a separate polymerization zone. For a multi-stage polymerization in both a batch reactor and a continuous reactor, each polymerization stage is considered as a separate polymerization zone. In one or more embodiments, the polymerization occurs in one reaction zone.
  • additives may also be used in the polymerization, as desired, such as one or more scavengers, promoters, modifiers, chain transfer agents (such as diethyl zinc), reducing agents, oxidizing agents, hydrogen, aluminum alkyls, or silanes.
  • a “chain transfer agent” is any agent capable of hydrocarbyl and/or polymeryl group exchange between a coordinative polymerization catalyst and the metal center of the chain transfer agent during a polymerization process.
  • the chain transfer agent can be any desirable chemical compound such as those disclosed in WO 2007/130306.
  • the chain transfer agent can be selected from Group 2, 12, or 13 alkyl or aryl compounds, such as zinc, magnesium, or aluminum alkyls or aryls.
  • the alkyl is a C1-C30 alkyl, a C2- C20 alkyl, or a C3-C12 alkyl.
  • Exemplary alkyls for the CTA can be or include, but are not limited to, methyl, ethyl, propyl, butyl, isobutyl, tertbutyl, pentyl, hexyl, cyclohexyl, phenyl, octyl, nonyl, decyl, undecyl, dodecyl, isomers thereof, or any combination thereof.
  • the chain transfer agent is selected from dialkyl zinc compounds, where each alkyl can independently be methyl, ethyl, propyl, butyl, isobutyl, tertbutyl, pentyl, hexyl, cyclohexyl, or phenyl.
  • the chain transfer agent is selected from trialkyl aluminum compounds, where each alkyl can independently be methyl, ethyl, propyl, butyl, isobutyl, tertbutyl, pentyl, hexyl, or cyclohexyl.
  • the chain transfer agent is selected from tri aryl aluminum compounds where the aryl is selected from phenyl and substituted phenyl.
  • the chain transfer process may be characterized by the transfer of at least 0.5 polymer chains (e.g., 0.5 to 3) polymer chains, where n is the maximum number of polymer chains that can be transferred to the chain transfer agent metal, such as n is 1 to 3 for trivalent metals (such as Al) and 1 to 2 for divalent metals (such as Zn), such as n is 1.5 to 3 for trivalent metals (such as Al) and 1.5 to 2 for divalent metals (such as Zn).
  • n is the maximum number of polymer chains that can be transferred to the chain transfer agent metal, such as n is 1 to 3 for trivalent metals (such as Al) and 1 to 2 for divalent metals (such as Zn), such as n is 1.5 to 3 for trivalent metals (such as Al) and 1.5 to 2 for divalent metals (such as Zn).
  • the number of chains transferred per metal is the slope of the plot of moles of polymer produced versus the moles of the chain transfer agent metal (as determined from at least four points, CTA metal: catalyst transition metal of 20: 1, 80: 1, 140: 1 and 200: 1, using least squares fit (MicrosoftTM Excel 2010, version 14.0.7113.5000 (32bit)) to draw the line.
  • Useful chain transfer agents are typically present at from 10 or 20 or 50 or 100 equivalents to 600 or 700 or 800 or 1,000 or 2,000 or 4,000 equivalents relative to the catalyst component.
  • the chain transfer agent is preset at a catalyst complex-to-CTA molar ratio of from about 1 : 12,000 to 10: 1; alternatively 1:6,000; alternatively, 1 :3,000 to 10: 1; alternatively 1:2,000 to 10: 1; alternatively 1 : 1,000 to 10: 1; alternatively, 1 :500 to 1: 1; alternatively 1:300 to 1 :1; alternatively 1 :200 to 1 : 1; alternatively 1 : 100 to 1: 1; alternatively 1 :50 to 1 : 1; alternatively 1: 10 to 1 : 1.
  • Exemplary chain transfer agents can be or include a compound represented by the formula AIR3, MgR.2, or ZnR.2, where each R is, independently, a Ci-Cx hydrocarbyl, such as methyl, ethyl, propyl, butyl, phenyl, hexyl, octyl, or an isomer thereof.
  • Exemplary chain transfer agents can be or include, but are not limited to, diethylzinc, tri-n-octyl aluminum, trimethylaluminum, triethylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethyl aluminum chloride, methyl alumoxane, dibutyl zinc, di-n-propylzinc, di-n-hexylzinc, di-n-pentylzinc, di-n-decylzinc, di-n-dodecylzinc, di-n-tetradecylzinc, di-n- hexadecylzinc, di-n-octadecylzinc, diphenylzinc, diisobutylaluminum hydride, diethylaluminum hydride, di-n-octylaluminum hydride, dibut
  • two or more complexes are combined with diethyl zinc and/or tri-n-octylaluminum in the same reactor with monomer(s).
  • one or more complexes is/are combined with another catalyst and diethyl zinc and/or tri-n-octylaluminum in the same reactor with monomers.
  • one or more complexes is/are combined with a mixture of diethyl zinc and an aluminum reagent in the same reactor with monomer(s). Alternately, one or more complexes is/are combined with two chain transfer agents in the same reactor with monomers.
  • compositions of matter which can be produced by the methods described herein.
  • the process described herein produces ethylene homopolymers or ethylene copolymers, such as propylene-ethylene and/or ethylene-alphaolefin (such as C4 to C20) copolymers (such as ethylene-hexene copolymers or ethylene-octene copolymers) having an Mw/Mn of greater than 1 to 4 (such as greater than 1 to 3).
  • ethylene-ethylene and/or ethylene-alphaolefin (such as C4 to C20) copolymers such as ethylene-hexene copolymers or ethylene-octene copolymers having an Mw/Mn of greater than 1 to 4 (such as greater than 1 to 3).
  • the process of the present disclosure produces olefin polymers, such as polyethylene and polypropylene homopolymers and copolymers.
  • the polymers produced herein are homopolymers of ethylene or propylene, are copolymers of ethylene such as copolymer of ethylene having from 0 mol% to about 25 mol% (such as from about 0.5 mol% to about 20 mol%, such as from about 1 mol% to about 15 mol%, such as from about 3 mol% to about 10 mol%) of one or more C3 to C20 olefin comonomer (such as C3 to C 12 alpha-olefin, such as propylene, butene, hexene, octene, decene, dodecene, such as propylene, butene, hexene, octene), or are copolymers of propylene such as copolymers of propylene having from 0 mol% to about 25 mol%
  • the monomer is ethylene and the comonomer is hexane or octene, such as from about 1 wt% to about 15 wt% of hexane or octene, for example, about 1 wt% to about 10 wt% of hexane or octene or about 2 wt% to about 8 wt% of hexane or octene.
  • the polymer produced herein has a unimodal or multimodal molecular weight distribution as determined by Gel Permeation Chromatography (GPC).
  • GPC Gel Permeation Chromatography
  • unimodal is meant that the GPC trace has one peak or inflection point.
  • multimodal is meant that the GPC trace has at least two peaks or inflection points.
  • An inflection point is that point where the second derivative of the curve changes in sign (e.g., from negative to positive or vice versus).
  • a bimodal polymer such as a bimodal polyethylene (e.g., formed by a catalyst system having a catalyst represented by Formulas (II), (V), (VI), and (Vll(a)-(l)) and another type of catalyst, such as, for example, a metallocene catalyst) has an Mw/Mn value from about 1 to about 10, for example, about 1.5 to about 8, about 2 to about 4, or about 2 to about 3.
  • the polymer produced herein has a composition distribution breadth index (CDBI) of 50% or more, such as 60% or more, such as 70% or more.
  • CDBI is a measure of the composition distribution of monomer within the polymer chains and is measured by the procedure described in PCT publication WO 1993/003093, published February 18, 1993, specifically columns 7 and 8 as well as in Wild et al., J. Poly. Sci., Poly. Phys. Ed., v.20, p. 441 (1982) and US Patent No. 5,008,204, including that fractions having a weight average molecular weight (Mw) below 15,000 are ignored when determining CDBI.
  • Mw weight average molecular weight
  • the polymer (such as polyethylene or polypropylene) produced herein is combined with one or more additional polymers prior to being formed into a film, molded part or other article.
  • additional polymers include polyethylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, LDPE, LLDPE, HDPE, random copolymer of ethylene and propylene, and/or butene, hexene, poly butene, ethylene vinyl acetate, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene-l, isotactic polybutene, ABS resins, ethylene- propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic block cop
  • the polymer (such as polyethylene or polypropylene) is present in the above blends, at from 10 to 99 wt%, based upon the weight of the polymers in the blend, such as 20 to 95 wt%, such as at least 30 to 90 wt%, such as at least 40 to 90 wt%, such as at least 50 to 90 wt%, such as at least 60 to 90 wt%, such as at least 70 to 90 wt%.
  • the blends described above may be produced by mixing the polymers of the present disclosure with one or more polymers (as described above), by connecting reactors together in series to make reactor blends or by using more than one catalyst in the same reactor to produce multiple species of polymer.
  • the polymers can be mixed together prior to being put into the extruder or may be mixed in an extruder.
  • the blends may be formed using conventional equipment and methods, such as by dry blending the individual components and subsequently melt mixing in a mixer, or by mixing the components together directly in a mixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin-screw extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization process, which may include blending powders or pellets of the resins at the hopper of the film extruder. Additionally, additives may be included in the blend, in one or more components of the blend, and/or in a product formed from the blend, such as a film, as desired.
  • a mixer such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin-screw extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization
  • additives are well known in the art, and can include, for example: fillers; antioxidants (e.g., hindered phenolics such as IRGANOXTM 1010 or IRGANOXTM 1076 available from Ciba-Geigy); phosphites (e.g., IRGAFOSTM 168 available from Ciba-Geigy); anti-cling additives; tackifiers, such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosins; UV stabilizers; heat stabilizers; anti-blocking agents; release agents; anti-static agents; pigments; colorants; dyes; waxes; silica; fillers; and talc.
  • antioxidants e.g., hindered phenolics such as IRGANOXTM 1010 or IRGANOXTM 1076 available from Ciba-Geigy
  • any of the foregoing polymers such as the foregoing polyethylenes or blends thereof, may be used in a variety of end-use applications.
  • Such applications include, for example, mono- or multi-layer blown, extruded, and/or shrink films.
  • These films may be formed by any number of extrusion or coextrusion techniques, such as a blown bubble film processing technique, wherein the composition can be extruded in a molten state through an annular die and then expanded to form a uniaxial or biaxial orientation melt prior to being cooled to form a tubular, blown film, which can then be axially slit and unfolded to form a flat film.
  • Films may be subsequently unoriented, uniaxially oriented, or biaxially oriented to the same or different extents.
  • One or more of the layers of the film may be oriented in the transverse and/or longitudinal directions to the same or different extents.
  • the uniaxially orientation can be accomplished using typical cold drawing or hot drawing methods.
  • Biaxial orientation can be accomplished using tenter frame equipment or a double bubble processes and may occur before or after the individual layers are brought together.
  • a polyethylene layer can be extrusion coated or laminated onto an oriented polypropylene layer or the polyethylene and polypropylene can be coextruded together into a film then oriented.
  • oriented polypropylene could be laminated to oriented polyethylene or oriented polyethylene could be coated onto polypropylene then optionally the combination could be oriented even further.
  • the films are oriented in the Machine Direction (MD) at a ratio of up to 15, such as between 5 and 7, and in the Transverse Direction (TD) at a ratio of up to 15, such as 7 to 9.
  • MD Machine Direction
  • TD Transverse Direction
  • the film is oriented to the same extent in both the MD and TD directions.
  • the films may vary in thickness depending on the intended application; however, films of a thickness from about 1 pm to about 50 pm are usually suitable. Films intended for packaging are usually from about 10 pm to about 50 pm thick. The thickness of the sealing layer is typically about 0.2 pm to about 50 pm. There may be a sealing layer on both the inner and outer surfaces of the film or the sealing layer may be present on only the inner or the outer surface.
  • one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwave.
  • one or both of the surface layers is modified by corona treatment.
  • This invention further relates to:
  • each Q is independently a Group 15 atom or a Group 16 atom, each n is independently 0 or 1, wherein n is 0 if Q is a Group 16 atom or n is 1 if Q is a Group 15 atom;
  • R 1 is a substituted or unsubstituted linear, branched, cyclic, polycyclic, heterocyclic, or aromatic C1-C18 diyl;
  • each R 2 is independently a hydrogen, a halogen, a substituted or unsubstituted C 1-C40 hydrocarbyl, or a heteroatom-containing group; or two or more adjacent R 2 groups are joined together to form a C4-C62 cyclic, polycyclic, or heterocyclic group that is not aromatic;
  • each R 3 is independently a hydrogen, a substituted or unsubstituted linear, branched, cyclic, polycyclic, aromatic, or polyaromatic C1-C40 hydrocarbyl, or a heteroatom-containing group;
  • each R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 is independently a hydrogen, a halogen, a substituted or unsubstituted linear, branched, cyclic, polycyclic, aromatic, or poly aromatic Ci- C40 hydrocarbyl, or a heteroatom-containing group; or two or more adjacent R 4 -R n groups are joined together to form a C4-C62 cyclic, polycyclic, heterocyclic, or aromatic group.
  • M is a Group 4 transition metal
  • each Q is independently a Group 15 atom or a Group 16 atom
  • each n is independently 0 or 1, wherein n is 0 if Q is a Group 16 atom or n is 1 if Q is a Group 15 atom;
  • each X 1 and X 2 is independently a substituted or unsubstituted linear, branched, cyclic, polycyclic, aromatic, or polyaromatic hydrocarbyl, a heteroatom, or a heteroatom-containing group; or X 1 and X 2 are joined together to form a C4-C62 cyclic, polycyclic, heterocyclic, or aromatic group;
  • R 1 is a substituted or unsubstituted linear, branched, cyclic, polycyclic, heterocyclic, or aromatic Ci-Cie diyl; each R 2 is independently a hydrogen, a halogen, a substituted or unsubstituted C 1-C40 hydrocarbyl, or a heteroatom-containing group; or two or more adjacent R 2 groups are joined together to form a C4-C62 cyclic, polycyclic, or heterocyclic group that is not aromatic;
  • each R 3 is independently a hydrogen, a substituted or unsubstituted linear, branched, cyclic, polycyclic, aromatic, or polyaromatic C1-C40 hydrocarbyl, or a heteroatom-containing group;
  • each R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 is independently a hydrogen, a halogen, a substituted or unsubstituted linear, branched, cyclic, polycyclic, aromatic, or poly aromatic Ci- C40 hydrocarbyl, or a heteroatom-containing group; or two or more adjacent R 4 -R n groups are joined together to form a C4-C62 cyclic, polycyclic, heterocyclic, or aromatic group.
  • each R 2 is independently a hydrogen or a substituted or unsubstituted C1-C10 hydrocarbyl.
  • each R 2 is independently a hydrogen or a substituted or unsubstituted C 1-C5 hydrocarbyl, and wherein y is an integer of 2, 3, 4, or 5.
  • each R 2 on L 1 and L 2 is independently a hydrogen or a substituted or unsubstituted C 1-C3 hydrocarbyl, and wherein y is an integer of 2 or 3.
  • each X 1 and X 2 is independently a substituted or unsubstituted C1-C20 hydrocarbyl.
  • each X 1 and X 2 is independently a substituted or unsubstituted C i-Cx alkyl, a phenyl, a benzyl, a cyclohexyl, or halide-substituted analogues thereof.
  • each X 1 and X 2 is independently a halide.
  • R 1 is a substituted or unsubstituted linear, branched, cyclic, polycyclic, heterocyclic, or aromatic Ci-Cio diyl.
  • each R 4 and R 8 is independently halogen, carbazolyl, fluorenyl, adamantly, indolyl, indolinyl, imidazolyl, indenyl, indanyl, or substitutes thereof.
  • each R 5 , R 6 , R 7 , R 9 , R 10 , and R 11 is independently a hydrogen or a substituted or unsubstituted linear or branched Ci-Cio hydrocarbyl.
  • each R 5 , R 7 , R 9 , and R 11 is a hydrogen and each R 6 and R 10 is a substituted or unsubstituted linear or branched C1-C4 hydrocarbyl.
  • a catalyst system comprising an activator and the transition metal complex according to any one of paragraphs 2-19.
  • a polymerization process to produce polyolefin comprising:
  • M is a Group 4 transition metal
  • each X 1 and X 2 is independently a substituted or unsubstituted linear, branched, cyclic, polycyclic, aromatic, or polyaromatic hydrocarbyl, a heteroatom, or a heteroatom-containing group; or X 1 and X 2 are joined together to form a C4-C62 cyclic, polycyclic, heterocyclic, or aromatic group;
  • R 1 is a substituted or unsubstituted linear, branched, cyclic, polycyclic, heterocyclic, or aromatic Ci-Cie diyl;
  • each R 3 is independently a hydrogen, a substituted or unsubstituted linear, branched, cyclic, polycyclic, aromatic, or polyaromatic C1-C40 hydrocarbyl, or a heteroatom-containing group;
  • each R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 is independently a hydrogen, a halogen, a substituted or unsubstituted linear, branched, cyclic, polycyclic, heterocyclic, or aromatic Ci- C40 hydrocarbyl, or a heteroatom-containing group; or two or more adjacent R 4 -R n groups are joined together to form a C4-C62 cyclic, polycyclic, heterocyclic, or aromatic group.
  • M is Ti, Zr, or Hf
  • each X 1 and X 2 is independently a substituted or unsubstituted linear, branched, cyclic, polycyclic, aromatic, or polyaromatic hydrocarbyl, a heteroatom, or a heteroatom-containing group; or X 1 and X 2 are joined together to form a C4-C62 cyclic, polycyclic, heterocyclic, or aromatic group;
  • each R 3 is independently a hydrogen, a substituted or unsubstituted linear, branched, cyclic, polycyclic, aromatic, or polyaromatic C1-C40 hydrocarbyl, or a heteroatom-containing group;
  • each R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 is independently a hydrogen, a halogen, a substituted or unsubstituted linear, branched, cyclic, polycyclic, aromatic, or poly aromatic Ci- C40 hydrocarbyl, or a heteroatom-containing group; or two or more adjacent R 4 -R n groups are joined together to form a C4-C62 cyclic, polycyclic, heterocyclic, or aromatic group.
  • M is Ti, Zr, or Hf.
  • 1 H NMR for Ligand and Catalyst Characterization Chemical structures are determined by 1H NMR. 1H NMR data are collected at room temperature (e.g., 23°C) in a 5 mm probe using either a 400 or 500 MHz Bruker spectrometer with deuterated methylene chloride or deuterated benzene.
  • Metallation In a nitrogen atmosphere, the ligand F was dissolved in 4 mL of toluene in a 20 mL vial. Tetrabenzyl zirconium or hafnium was dissolved in 4 mL of toluene in a separate vial. The solutions were combined and stirred at room temperature for one hour then filtered through a 0.2 pm syringe filter and concentrated. The residue was washed with pentane and dried under vacuum.
  • l-octene (C8) and 1 -hexene (C6) (98%, Aldrich Chemical Company) were dried by stirring over NaK overnight followed by filtration through basic alumina (Aldrich Chemical Company, Brockman Basic 1).
  • Polymerization-grade ethylene (C2) was used and further purified by passing the gas through a series of columns: 500 cc Oxyclear cylinder from Labclear (Oakland, CA) followed by a 500 cc column packed with dried 3 A mole sieves (8-12 mesh; Aldrich Chemical Company) and a 500 cc column packed with dried 5 A mole sieves (8-12 mesh; Aldrich Chemical Company).
  • TNOAL tri-n-octylaluminum
  • the autoclaves were prepared by purging with dry nitrogen at H0°C or 1 l5°C for 5 hours and then at 25°C for 5 hours.
  • Ethylene Homopolymerization (HDPE) and Ethylene-Octene Copolymerization (EOY) A pre-weighed glass vial insert and disposable stirring paddle were fitted to each reaction vessel of the reactor, which contains 48 individual reaction vessels. The reactor was then closed and purged with ethylene. Each vessel was charged with enough solvent (typically isohexane) to bring the total reaction volume, including the subsequent additions, to the desired volume, typically 5 mL. l-octene, if required, was injected into the reaction vessel and the reactor was heated to the set temperature and pressurized to the predetermined pressure of ethylene, while stirring at 800 rpm.
  • solvent typically isohexane
  • the aluminum and/or zinc compound in toluene was then injected as scavenger and/or chain transfer agent followed by addition of the activator solution (typically 1.0- 1.2 molar equivalents of /V,/V-dimethyl anilinium tetrakis-pentafluorophenyl borate - Activator 1).
  • the activator solution typically 1.0- 1.2 molar equivalents of /V,/V-dimethyl anilinium tetrakis-pentafluorophenyl borate - Activator 1.
  • the catalyst solution (typically 0.020-0.080 pmol of metal complex) was injected into the reaction vessel and the polymerization was allowed to proceed until a pre-determined amount of ethylene (quench value is about 20 psi) had been used up by the reaction. Alternatively, the reaction may be allowed to proceed for a set amount of time (maximum reaction time is about 30 minutes). Ethylene was added continuously (through the use of computer controlled solenoid valves) to the autoclaves during polymerization to maintain reactor gauge pressure (+1-2 psig) and the reactor temperature was monitored and typically maintained within +/-l°C. The reaction was quenched by pressurizing the vessel with compressed air.
  • the glass vial insert containing the 30 polymer product and solvent was removed from the pressure cell and the inert atmosphere glove box, and the volatile components were removed using a Genevac HT-12 centrifuge and Genevac VC3000D vacuum evaporator operating at elevated temperature and reduced pressure.
  • the vial was then weighed to determine the yield of the polymer product.
  • the resultant polymer was analyzed by Rapid GPC (see below) to determine the molecular weight, by FT-IR (see below) to determine percent octene incorporation, and by DSC (see below) to determine melting point (Tm).
  • Ethylene-Propylene Copolymerization (EP).
  • the reactor was prepared as described above and purged with propylene. Isohexane was then injected into each vessel at room temperature followed by a predetermined amount of propylene gas. The reactor was heated to the set temperature and pressurized with the required amount of ethylene while stirring at 800 rpm.
  • the scavenger, activator (typically D4-DMAH) and catalyst solutions were injected sequentially to each vessel and the polymerization was allowed to proceed as described previously.
  • PP Propylene Homopolymerization
  • the reactor was prepared as described above and purged with propylene. Isohexane was then injected into each vessel at room temperature followed by a predetermined amount of propylene gas. The reactor was heated to the set temperature while stirring at 800 rpm, and the scavenger, activator (typically D4-DMAH) and catalyst solutions were injected sequentially to each vessel. The polymerization was allowed to proceed as described previously.
  • scavenger, activator typically D4-DMAH
  • the MAO solution was injected into the vessel after the addition of isohexane. No additional aluminum reagent was used as scavenger during these runs.
  • Polymer sample solutions were prepared by dissolving polymer in 1, 2, 4-tri chlorobenzene (TCB, 99+% purity from Sigma- Aldrich) containing 2,6-di- tertbutyl- 4-methylphenol (BHT, 99% from Aldrich) at l65°C in a shaker oven for approximately 3 hours.
  • the typical concentration of polymer in solution was between 0.1 to 0.9 mg/mL with a BHT concentration of 1.25 mg BHT/mL of TCB.
  • the GPC system was calibrated using polystyrene standards ranging from 580 - 3,390,000 g/mol.
  • the system was operated at an eluent flow rate of 2.0 mL/minutes and an oven temperature of l65°C. 1, 2, 4-tri chlorobenzene was used as the eluent.
  • the polymer samples were dissolved in 1, 2, 4-tri chlorobenzene at a concentration of 0.28 mg/mL and 400 pL of a polymer solution was injected into the system.
  • the concentration of the polymer in the eluent was monitored using an evaporative light scattering detector.
  • the molecular weights presented are relative to linear polystyrene standards and are uncorrected, unless indicated otherwise.
  • DSC Differential Scanning Calorimetry
  • the weight percent of ethylene incorporated in polymers was determined by rapid FTIR spectroscopy on a Bruker Equinox 55+ IR in reflection mode. Samples were prepared in a thin film format by evaporative deposition techniques. FT-IR methods were calibrated using a set of samples with a range of known wt% ethylene content. For ethylene- l-octene copolymers, the wt% octene in the copolymer was determined via measurement of the methyl deformation band at about 1,375 cm 1 . The peak height of this band was normalized by the combination and overtone band at about 4,321 cm 1 , which corrects for path length differences.
  • the wt% ethylene is determined via measurement of the methylene rocking band (about 770 cm 1 to about 700 cm 1 ). The peak area of this band is normalized by sum of the band areas of the combination and overtone bands in the range of about 4,500 cm 1 to about 4,000 cm 1 .
  • the wt% ethylene was determined by ⁇ NMR spectroscopy or estimated from the polymer Tm.
  • Vinyl end-groups were measured as the number of vinyls per 1,000 carbon atoms using the resonances between 5.9-5.65 and between 5.3-4.85 ppm. Vinylidene end-groups were measured as the number of vinylidenes per 1,000 carbon atoms using the resonances between 4.85-4.65 ppm.
  • Table 1 provides the reaction conditions for ethylene homopolymerization (HDPE) and ethyleneoctene copolymerization (EO) using Activator 1 or MAO.
  • Table 2 provides catalyst activity and polymer properties for ethylene homopolymerization (HDPE) and ethylene-octene copolymerization (EO) using Activator 1 or MAO.
  • Experiments 1-11 utilized the catalyst represented by Formula (VII(a)) containing zirconium (Zr-VIIa catalyst) and
  • Experiments 12-21 utilized the catalyst represented by Formula (VII(a)) containing hafnium (Hf-VIIa catalyst).
  • Experiments 1-5 and 12-15 included the scavenger TNOAL at a concentration of 0.5 pmol, while the remainder experiments did not contain a scavenger.
  • the catalytic activities in Experiments 1-5 were in a range from about 100-174 kg/mmol-hr, with the exception of Exp. 2 that had a catalytic activity of about 16 kg/mmol-hr.
  • the catalytic activities in Experiments 6-11 were in a range from about 460-563 kg/mmol-hr, which were the greatest values in the present experiments.
  • the catalytic activities in Experiments 12-21 were less than 100 kg/mmol-hr, such as in a range from about 9-53 kg/mmol-hr.
  • the Zr-VIIa catalyst outperformed the Hf-VIIa catalyst throughout all but one of these experiments.
  • the Zr-VIIa catalyst at a low concentration (0.02 pmol) and in the presence of the activator MAO and no scavenger achieved the greatest catalytic activities of 563, 527, 481, 504, 460, and 470 kg/mmol-hr, respectively.
  • Catalysts, catalyst systems, and methods of the present disclosure can provide catalytic activity values of greater than 100 kg/mmol-hr, such as greater than 400 kg/mmol-hr or greater than 500 kg/mmol-hr.
  • compositions, an element or a group of elements are preceded with the transitional phrase “comprising”, it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of, “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.

Abstract

La présente invention concerne des catalyseurs de métaux de transition et des ligands de phénolate pontés respectifs contenus sur le catalyseur, ainsi que des systèmes de catalyseurs et des procédés de polymérisation pour la production de polyoléfines. Les catalyseurs et les systèmes de catalyseur permettent de fournir des valeurs d'activité catalytique supérieures à 100 kg/mmol-hr, par exemple, supérieures à 400 kg/mmol-hr ou supérieures à 500 kg/mmol-hr.
PCT/US2019/048086 2018-08-28 2019-08-26 Complexes de métaux de transition de phénolate pontés, production et utilisations associées WO2020046785A1 (fr)

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Citations (4)

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Publication number Priority date Publication date Assignee Title
WO2002036638A2 (fr) * 2000-11-06 2002-05-10 Ramot University Authority For Applied Research & Industrial Development Ltd. Precatalyseur actif non metallocene pour polymerisation catalytique tactique de monomeres alpha-olefiniques
WO2003091292A2 (fr) * 2002-04-24 2003-11-06 Bp Chemicals Limited Catalyseur de polymerisation
WO2014022010A2 (fr) * 2012-08-03 2014-02-06 Exxonmobil Chemical Patents Inc. Catalyseurs non symétriques comprenant des ligands salan
KR20140129871A (ko) * 2013-04-30 2014-11-07 주식회사 엘지화학 포스트 메탈로센형 리간드 화합물, 유기 금속 화합물 및 이를 이용한 올레핀 중합체의 제조방법

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Publication number Priority date Publication date Assignee Title
WO2002036638A2 (fr) * 2000-11-06 2002-05-10 Ramot University Authority For Applied Research & Industrial Development Ltd. Precatalyseur actif non metallocene pour polymerisation catalytique tactique de monomeres alpha-olefiniques
WO2003091292A2 (fr) * 2002-04-24 2003-11-06 Bp Chemicals Limited Catalyseur de polymerisation
WO2014022010A2 (fr) * 2012-08-03 2014-02-06 Exxonmobil Chemical Patents Inc. Catalyseurs non symétriques comprenant des ligands salan
KR20140129871A (ko) * 2013-04-30 2014-11-07 주식회사 엘지화학 포스트 메탈로센형 리간드 화합물, 유기 금속 화합물 및 이를 이용한 올레핀 중합체의 제조방법

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SEGAL, S. ET AL.: "Zirconium and Titanium Diamine Bis(phenolate) Catalysts for alpha-Olefin Polymerization: From Atactic Oligo(1-hexene) to Ultrahigh-Molecular-Weight Isotactic Poly(1-hexene", ORGANOMETALLICS, vol. 24, no. 2, 2005, pages 200 - 202, XP001236750, DOI: 10.1021/om049556b *

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