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WO2024253863A1 - Catalyseurs de polymérisation d'oléfines supportés comprenant des composés 2-hydroxythiophène substitués - Google Patents

Catalyseurs de polymérisation d'oléfines supportés comprenant des composés 2-hydroxythiophène substitués Download PDF

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WO2024253863A1
WO2024253863A1 PCT/US2024/030820 US2024030820W WO2024253863A1 WO 2024253863 A1 WO2024253863 A1 WO 2024253863A1 US 2024030820 W US2024030820 W US 2024030820W WO 2024253863 A1 WO2024253863 A1 WO 2024253863A1
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scs
ethylene
spray
catalyst system
supported catalyst
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PCT/US2024/030820
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Andrew M. Camelio
Rhett A. BAILLIE
Matthew L. KRAUSE
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Dow Global Technologies Llc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer

Definitions

  • Olefin polymerization catalysts materials, and methods.
  • INTRODUCTION Polyolefins are made by generally known methods comprising polymerizing one or more olefin monomers in solution phase catalyzed by homogeneous catalysts, or in slurry phase or gas phase catalyzed by heterogeneous catalysts.
  • Homogeneous catalysis generally refers to reactions where a soluble catalyst and a reactant it acts upon are in the same phase (same state of matter), and in unrestricted contact.
  • Liquid phase olefin polymerizations mean solution reactions where a homogeneous olefin polymerization catalyst and the reactant—one or more olefin monomers—are dissolved and react in a same hydrocarbon solvent.
  • the polymerizations are run in hydrocarbon solutions at temperatures from 120° to 250° C., and usually 150° to 190° C., which is above the 115° to 135° C. melting temperature range of polyethylenes.
  • Homogeneous olefin polymerization catalysts must have at least partial solubility in the hydrocarbon solvent so that, at the relatively low catalyst concentrations and high temperatures used, the entire amount of the catalyst is dissolved in solution. In practice these catalysts are free (unsupported) ligand-metal complex molecules and the hydrocarbon solvent is alkanes or aromatic hydrocarbons.
  • Structures of free ligand-metal complex molecules may be precisely determined using small molecule structure characterization techniques such as proton-nuclear and carbon- nuclear magnetic resonance ( 1 H-NMR and/or 13 C-NMR) spectroscopy or x-ray crystallography. This knowledge design modifications to the homogeneous catalyst to study its structure-activity relationships and structure-product property relationships.
  • Heterogeneous catalysis generally refers to reactions where an insoluble catalyst and a reactant it acts upon are in different phases (different states of matter). Reaction occurs at interfaces between phases.
  • Heterogeneous catalysts may be made by a general strategy of heterogenization of homogeneous catalysts or homogeneous precatalysts and activators onto solid supports to yield heterogeneous catalysts in the form of supported catalyst systems.
  • Different supported catalyst systems may require different support materials.
  • Ziegler-Natta catalysts use magnesium chloride and supported metallocene catalysts use silica. Supported catalyst structures cannot be precisely determined.
  • gas phase polymerizations In gas phase/solid phase olefin polymerizations, called gas phase polymerizations, the supported catalyst system (a heterogeneous olefin polymerization catalyst) is in a solid phase and the reactant—one or more olefin monomers—is in a gas or vapor phase.
  • supported catalyst systems produce significantly different performance results and product properties than those of their counterpart homogeneous olefin polymerization catalysts.
  • homogeneous olefin polymerization catalysis/solution phase polymerizations are not predictive of heterogeneous olefin polymerization catalysis/gas or slurry phase polymerizations.
  • SUMMARY [0013] We claim a supported catalyst system comprising a substituted 2-hydroxythiophene compound and a support material; and a method of making the supported catalyst system. Also claimed are a gas phase or slurry phase polymerization process employing the supported catalyst system; and a polyolefin made by the gas phase or slurry phase polymerization process.
  • Figure 1 shows Scheme 1 directed to a synthesis of an intermediate compound.
  • Figure 2 shows Scheme 2 directed to a synthesis of a substituted 2-hydroxythiophene compound (I).
  • Figure 3 shows Scheme 3 directed to a synthesis of a precatalyst of formula (II).
  • Figure 4 shows Scheme 4 directed to the making of a spray-dried supported catalyst system (III) or a conventionally-dried supported catalyst system (IV).
  • Figure 5 shows Mark-Houwink plots of ethylene/1-hexene copolymers produced from spray-dried supported catalyst system 1 (SCS 1) and a comparative polyethylene homopolymer.
  • Figure 6 shows Mark-Houwink plots of ethylene/1-hexene copolymers produced from SCS 1 and a comparative polyethylene homopolymer.
  • Figure 7 shows Mark-Houwink plots of ethylene/1-hexene copolymers produced from spray-dried supported catalyst system 3 (SCS 3) and a comparative polyethylene homopolymer.
  • Figure 8 shows Mark-Houwink plots of ethylene/1-hexene copolymers produced from SCS 3 and a comparative polyethylene homopolymer.
  • Figure 9 shows Mark-Houwink plots of ethylene/1-hexene copolymers produced from spray-dried supported catalyst system 5 (SCS 5) and a comparative polyethylene homopolymer.
  • Figure 10 shows Mark-Houwink plots of ethylene/1-hexene copolymers produced from SCS 5 and a comparative polyethylene homopolymer.
  • Figure 11 shows Mark-Houwink plots of ethylene/1-hexene copolymers produced from spray-dried supported catalyst system 7 (SCS 7) and a comparative polyethylene homopolymer.
  • Figure 12 shows Mark-Houwink plots of ethylene/1-hexene copolymers produced from spray-dried supported catalyst system 9 (SCS 9) and a comparative polyethylene homopolymer.
  • Figure 13 shows Mark-Houwink plots of ethylene/1-hexene copolymers produced from spray-dried supported catalyst system 11 (SCS 11) and a comparative polyethylene homopolymer.
  • Figure 14 shows Mark-Houwink plots of ethylene/1-hexene copolymers produced from SCS 11 and a comparative polyethylene homopolymer.
  • Figure 15 shows Mark-Houwink plots of ethylene/1-hexene copolymers produced from SCS 13 and a comparative polyethylene homopolymer.
  • Figure 16 shows Scheme 4 directed to a synthesis of a bis(iodophenoxy)propylene compound.
  • Figure 17 has pictorial illustrations of representative chain structures of LLDPE, LDPE, and HDPE.
  • DETAILED DESCRIPTION [0031] We claim a supported catalyst system comprising a substituted 2-hydroxythiophene compound and a support material; and a method of making the supported catalyst system. Also claimed are a gas phase or slurry phase polymerization process employing the supported catalyst system; and a polyolefin made by the gas phase or slurry phase polymerization process. Also claimed are the substituted 2-hydroxythiophene compound and a precatalyst comprising the substituted 2-hydroxythiophene compound, a metal atom, and a leaving group.
  • Synthesis of the Supported Catalyst System There are two general strategies for making the supported catalyst system comprising a substituted 2-hydroxythiophene compound.
  • a first strategy comprises heterogenizing a homogeneous olefin polymerization precatalyst comprising the substituted 2- hydroxythiophene compound (“homogenous precatalyst”).
  • a second strategy comprises heterogenizing a homogeneous olefin polymerization catalyst comprising the substituted 2- hydroxythiophene compound (“homogeneous catalyst”).
  • a first route comprises contacting a solution of the homogeneous precatalyst in a hydrocarbon solvent onto a solid support that has been pretreated with an activator (also called a cocatalyst), yielding the supported catalyst system.
  • an activator also called a cocatalyst
  • An example of the solid support that has been pretreated with an activator is the spray-dried methylaluminoxane/hydrophobic fumed silica (“SMAO”), which may be used as a convenient way of making an embodiment of the supported catalyst system for use in slurry phase polymerization.
  • SMAO spray-dried methylaluminoxane/hydrophobic fumed silica
  • a second route comprises contacting an activator with solid support that has been pretreated with the homogeneous precatalyst, yielding the supported catalyst system.
  • a third contacting route is used for the second heterogenization strategy comprising heterogenizing the homogeneous catalyst. This third route comprises contacting a solution of the homogeneous precatalyst in a hydrocarbon solvent with an activator to give the homogeneous catalyst dissolved in hydrocarbon solvent, and then contacting the solution with the solid support, yielding the supported catalyst system.
  • the second and third contacting routes are disfavored for use with solid supports that give side reactions with either the homogeneous precatalyst or homogeneous catalyst.
  • the first heterogenization strategy comprising the first contacting route usually does not suffer from this potential problem.
  • the heterogenization strategies and contacting routes independently make the supported catalyst system as a suspension of solid particles thereof in a liquid consisting essentially of the hydrocarbon solvent and any hydrocarbon-soluble compounds.
  • the hydrocarbon-soluble compounds may include unreacted activator (e.g., methyl aluminoxane or triethylaluminum) and/or by-products and side products from the heterogenization reaction and/or the activation reaction.
  • the suspension, including any hydrocarbon-soluble compounds, from the contacting route is fed into a gas phase or slurry phase polymerization reactor to polymerize olefin monomer.
  • the suspension Prior to or during the feeding step the suspension may or may not be stored for a period of time in a storage tank and/or may or may not be diluted with additional hydrocarbon solvent, which may be the same as or different than the hydrocarbon solvent used in the contacting route.
  • additional hydrocarbon solvent which may be the same as or different than the hydrocarbon solvent used in the contacting route.
  • the separating step comprises physically removing the supported catalyst system solids from the liquid portion of the suspension obtained from the contacting route, or vice versa physically removing the liquid portion from the supported catalyst system solids.
  • the separating step comprises a filtering step, a decanting step, or an evaporating step.
  • the separating step may also comprise a combination of any two or more separating steps.
  • the filtering step may comprise contacting the suspension with a filter to yield a filtrate consisting of the liquid portion and a filtercake consisting of the supported catalyst system (solids). The filtercake may be washed with fresh hydrocarbon solvent and/or dried.
  • the decanting step may comprise pouring off or suctioning off the liquid portion of the suspension, yielding a decanted or suctioned liquid and the supported catalyst system (solids) as a “paste” consisting of the supported catalyst system (solids) and a small remainder of undecanted or unsuctioned liquid.
  • the paste may be used as is in a polymerization or dried or slurried with fresh hydrocarbon solvent.
  • the drying step may comprise removing volatile constituents from the suspension, yielding the supported catalyst system (solids) as a dry powder.
  • the volatile constituents may include any volatile components of the hydrocarbon-soluble compounds mentioned earlier, such as any volatile unreacted activator and/or volatile by-products and side products from the heterogenization reaction and/or the activation reaction.
  • the drying step may comprise slowly evaporating volatile constituents from the suspension, which is slowly concentrated, yielding a “conventionally-dried” embodiment of the dry powder of the supported catalyst system.
  • the drying step may comprise spray-drying the suspension so as to rapidly remove (flash off) volatile constituents from the suspension, yielding a “spray-dried” embodiment of the dry powder of the supported catalyst system.
  • the combination of any two or more separating steps may comprise, for example, the decanting step followed by the evaporating step or two sequential decanting steps.
  • the spray-dried supported catalyst system embodiments can have higher catalyst efficiencies, higher catalyst productivities, faster light-offs, and can produce polyethylene polymers having different properties in gas phase polymerizations than the conventionally- dried embodiments of the supported catalyst system have in gas phase polymerizations.
  • the spray-dried supported catalyst system embodiments may be preferred over the conventionally-dried supported catalyst system embodiments for gas phase polymerizations. Nonetheless, the conventionally-dried supported catalyst system embodiments are also completely useful and effective for gas phase polymerizations.
  • any given spray-dried supported catalyst system, or any given conventionally-dried supported catalyst system may perform quite differently in gas phase polymerizations than in slurry phase polymerizations.
  • All dry powder embodiments of the supported catalyst system are versatile for gas phase and slurry phase polymerizations because they can be fed as a dry powder, or suspended in alkanes or mineral oil and the resulting suspension fed, into gas phase or slurry phase olefin polymerization reactors. Catalyst feeders for both methods are commercially available.
  • the supported catalyst system no matter its physical constitution (e.g., as dry powder or as a powder suspended in hydrocarbon solvent) is useful for catalyzing gas phase or a slurry phase olefin polymerization of one or more olefin monomers to make polyolefins such as polyethylene polymers.
  • Technical Advantages [0048] Homogeneous olefin polymerization catalysis in a solution phase reaction with the counterpart homogeneous catalyst comprising a substituted 2-hydroxythiophene compound is quite different than heterogeneous olefin polymerization catalysis in a gas phase or slurry phase reaction with the supported catalyst system.
  • the technical advantages of the inventive supported catalyst system, comprising the substituted 2-hydroxythiophene compound, in gas phase or slurry phase polymerizations are functions of one or more of the following factors: (a) effects of the solid support, (b) performance differences between different embodiments of the supported catalyst system depending on if the embodiment was made via heterogenization according to the first, second, or third route, (c) the different effects of the conventional drying method versus the spray-drying method used to make dried powders of the supported catalyst system, (d) the effects of differences in process conditions between solution phase versus gas phase or slurry phase, (e) performance differences between different embodiments of the supported catalyst system in their gas phase reactor behavior, or (f) any combination of two or more of effects (a) to (e).
  • the (c) effects of the drying method used to make the dry powder of the supported catalyst system may vary depending on whether or not the drying step is employed and the type of the drying step, e.g., conventional drying versus spray-drying. In some embodiments the inventive method comprises spray-drying.
  • the differences in (d) process conditions comprise reaction temperature differences. Solution phase polymerizations of ethylene are run at temperatures from 140° to 250° C., typically 150° to 190° C., whereas gas phase and slurry phase polymerizations of ethylene are run at lower temperatures, from 70° to 120° C., usually from 75° to 115° C.
  • the performance differences between different embodiments of the supported catalyst system in (e) gas phase reactor behavior comprise kinetics of the supported catalyst system on its light-off kinetics for freshly fed catalyst, maximum temperature reached after feed (temperature will increase due to exothermic nature of olefin polymerization reactions), or the amount of ethylene uptake per unit weight of catalyst.
  • the (f) combinations of two or more of factors (a) to (e) are a further technical advantage of the inventive heterogeneous olefin polymerization catalyst comprising the substituted 2-hydroxythiophene compound and the polyolefin made via gas phase or slurry phase olefin polymerization catalyzed thereby.
  • the supported catalyst system comprising the substituted 2- hydroxythiophene compound has an improved activity in a gas phase and slurry phase polymerization reaction relative to that activity of its counterpart homogeneous olefin polymerization catalyst.
  • the improved activity may be an increased catalyst efficiency and/or an increased catalyst productivity.
  • the supported catalyst system also makes a polyethylene product with one or more improved properties relative to those properties of a polyethylene product made by its counterpart homogeneous olefin polymerization catalyst in solution phase polymerization.
  • the improved property may be an increased weight-average molecular weight (M w ); an increased content of ultra-high molecular weight (“UHMW”) constituents, e.g., M w greater than 1,000,000 grams per mole (g/mol); a z-average molecular weight greater than 2,000,000 grams per mole; a broader molecular weight distribution (MWD) or polydispersity index (PDI), e.g., M w /M n ; an increased long chain branching (LCB) content; or a combination of any two or more thereof.
  • UHMW ultra-high molecular weight
  • M w ultra-high molecular weight
  • PDI polydispersity index
  • LCB long chain branching
  • Another embodiment is a substituted 2-hydroxythiophene compound of formula (I):
  • the catalyst is useful for polymerizing one or more olefin monomers.
  • Another embodiment is a supported catalyst system comprising the precatalyst of formula (II), a support material, and an activator.
  • Another embodiment is a method of making the supported catalyst system, the method comprising step (a) or comprising steps (b) and (c): (a) spray drying a mixture of an inert hydrocarbon solvent, the precatalyst of formula (II), the support material, and the activator to make the supported catalyst system; or (b) spray drying a mixture of an inert hydrocarbon solvent, the support material and the activator to make a spray-dried supported activator, and (c) mixing the precatalyst of formula (II) with the spray-dried supported activator and an inert hydrocarbon solvent to make the supported catalyst system.
  • Another embodiment is a method of polymerizing an olefin monomer, the method comprising contacting the olefin monomer with the supported catalyst system, thereby making a polyolefin.
  • the method may comprise a gas phase polymerization in a gas phase reactor under gas phase conditions or a slurry phase polymerization in a slurry phase reactor under slurry phase conditions.
  • Another embodiment is the polyolefin made by the method of polymerizing.
  • R 1 and R 2 independently are H or a halogen. In some embodiments R 1 and R 2 are different, or R 1 and R 2 are identical. In some embodiments R 1 and H.
  • R 1 and R 2 are F.
  • R 3 and R 4 independently are H, a halogen, a (C 1 -C 15 )hydrocarbyl, a (C 1 -C 10 )alkoxy, or a Si((C 1 -C 10 )alkyl) 3 .
  • R 3 and R 4 are different, or R 3 and R 4 are identical.
  • R 3 and R 4 are a halogen, a (C 1 -C 15 )hydrocarbyl, a (C 1 -C 10 )alkoxy, or a Si((C 1 -C 10 )alkyl) 3 .
  • R 3 and R 4 are H. In other embodiments R 3 and R 4 are F. In some embodiments R 3 and R 4 are a (C 1 -C 15 )hydrocarbyl. In other embodiments R 3 and R 4 are a (C 1 - C 10 )alkoxy. In other embodiments R 3 and R 4 are a Si((C 1 -C 10 )alkyl) 3 .
  • R 3 and R 4 are identical and are both H, or both F, or both -C(CH 3 ) 3 , or both -C(CH 2 CH 3 ) 3 , or both -C(CH 3 ) 2 CH 2 C(CH 3 ) 3 , or both -OCH 3 , or both -O(CH 2 ) 2 C(CH 3 ) 3 , or both -O(CH 2 ) 7 CH 3 , or both 4-i(tert-butyl)phenyl, or both 1,3-di(tert-butyl)phenyl, or both -Si(CH 3 ) 2 (CH 2 ) 7 CH 3 .
  • each (C 1 -C 15 )hydrocarbyl independently is a (C 1 -C 15 )alkyl, a (C 1 -C 5 )alkyl, a (C 6 -C 10 )alkyl, a (C 6 -C 15 )aryl (e.g., phenyl or naphthyl), a (C 7 -C 15 )aralkyl (e.g., benzyl, 2-phenylethyl, or 1-phenylprop-1-yl), or a (C 7 -C 15 )alkaryl (e.g., 4-methylphenyl or 2,6-diisopropylphenyl).
  • R 5 and R 6 independently are H or a halogen. In some embodiments R 5 and R 6 are different, or R 5 and R 6 are identical. In some embodiments R 5 and R 6 are H. In some embodiments R 5 and R 6 are F.
  • R 7 and R 8 independently are H or a halogen. In some embodiments R 7 and R 8 are different, or R 7 and R 8 are identical. In some embodiments R 7 and R 8 are H. In some embodiments R 7 and R 8 are F.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are H.
  • R 2 , R 7 , and R 8 are H.
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are F and R 7 and R 8 are H.
  • R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are F and R 1 and R 2 are H.
  • each R 9 is H and each R 10 is a (C 1 -C 15 )hydrocarbyl, alternatively a (C 1 -C 10 )alkyl or a (C 1 -C 5 )alkyl, phenyl, or substituted phenyl; or each R 10 is H and each R 9 is a (C 1 -C 15 )hydrocarbyl, alternatively a (C 1 -C 10 )alkyl or a (C 1 -C 5 )alkyl, phenyl, or substituted phenyl.
  • each R 9 is H and each R10 is a -Si((C 1 -C 10 )alkyl) 3 , (C 10 -C 18 )aryl, or substituted (C 10 -C 18 )aryl; or each R 10 is H and each R 9 is a -Si((C 1 -C 10 )alkyl) 3 , (C 10 -C 18 )aryl, or substituted (C 10 - C 18 )aryl.
  • Each substituted phenyl has from 1 to 3 substituent groups independently selected from F, (C 1 -C 10 )alkyl, and (C 1 -C 10 )alkoxy; or F and (C 1 -C 10 )alkoxy; or (C 1 -C 10 )alkyl.
  • each R 9 is H and each R 10 is tertiary-butyl, 4-tert-butylphenyl, 4- triethylmethylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, or 3,5-difluoro-4- octyloxyphenyl.
  • each R 10 is H and each R 9 is 3,5-di-tert-butylphenyl.
  • R 1 and R 2 are different, or R 1 and R 2 are identical; or R 1 and R 2 are H; or R 1 and R 2 are F; or R 3 and R 4 are different, or R 3 and R 4 are identical, or R 3 and R 4 are a halogen, a (C 1 -C 15 )hydrocarbyl, a (C 1 -C 10 )alkoxy, or a Si((C 1 -C 10 )alkyl) 3 , or R 3 and R 4 are a (C 1 -C 10 )alkyl or a (C 1 -C 10 )alkoxy; or R 5 and R 6 are different, or R 5 and R 6 are identical, or R 5 and R 6 are H, or R 5 and R 6 are F; or R 7 and R 8 are different, or R 7 and R 8 are identical, or R 7 and R 8 are H
  • M is Ti, Hf, or Zr. In some embodiments M is Hf or Zr, or M is Ti, or M is Hf, or M is Zr. [0077] Independently in formula (II), subscript n is 1, 2, or 3. In some embodiments subscript n 1 or 2, or n is 2 or 3, or n is 1, or n is 2, or n is 3. [0078] Independently in formula (II), each X independently is a leaving group, at least one of which is displaceable when precatalyst (II) is contacted with an activator.
  • each X independently is selected from a monodentate ligand independently chosen from a hydrogen atom, a (C 1 ⁇ C 50 )hydrocarbyl, a (C 1 ⁇ C 50 )heterohydrocarbyl, a (C 1 ⁇ C 50 )organoheteryl, a halogen atom, a dialkylamino, or a dialkyl carbamate.
  • Each heteroatom in a heterohydrocarbyl or organoheteryl may be O, N, S, Si, or P. In some embodiments each heteroatom is O, N, or Si, or each heteroatom is Si.
  • each X a halogen, a (C 1 ⁇ C 8 )alkyl group, a Si((C 1 ⁇ C 8 )alkyl) 3 group, a CH 2 Si((C 1 ⁇ C 10 )alkyl) 3 group, or benzyl.
  • each X is benzyl or each X is Cl and subscript n is 2; or each X is benzyl and subscript n is 2. [0079] The subscript n and X are chosen so that the precatalyst of formula (II) is overall (i.e., formally) charge-neutral.
  • R 1 and R 2 are identical, R 3 and R 4 are identical, R 5 and R 6 are identical, R 7 and R 8 are identical, each R 9 is identical, each R 10 is identical, each R 11 is identical, and each R 12 is identical.
  • R 1 and R 2 are H;
  • R 3 and R 4 are a halogen, a (C 1 -C 15 )hydrocarbyl, a (C 1 - C 10 )alkoxy, or a Si((C 1 -C 10 )alkyl) 3 ;
  • R 5 and R 6 are H; and R 7 and R 8 are H.
  • R 3 and R 4 are as defined earlier.
  • each X is identical.
  • M is Hf.
  • M is Zr.
  • R 1 and R 2 are H
  • R 3 and R 4 are each a (C 1 -C 15 )alkyl or a (C 1 -C 10 )alkoxy
  • R 5 and R 6 are H
  • R 7 and R 8 are H
  • each R 9 is H
  • each R 10 is the same and is tertiary-butyl, 4-tert-butylphenyl, 4- triethylmethylphenyl, 3,5-dimethylphenyl, or 3,5-di-tert-butylphenyl.
  • R 1 and R 2 are H, R 3 and R 4 are a (C 7 -C 9 )alkyl or a (C 7 -C 9 )alkoxy, R 5 and R 6 are H, R 7 and R 8 are H, each R 9 is H, and each R 10 is tertiary-butyl.
  • each R 3 and R 4 is (CH 3 ) 3 CCH 2 C(CH 3 ) 2 - or CH 3 (CH 2 ) 7 O-.
  • R 1 and R 2 are F, or R 5 and R 6 are F, or R 7 and R 8 are F, or at least four thereof are F.
  • R 1 and R 2 are the same, R 3 and R 4 are the same, R 5 and R 6 are the same, R 7 and R 8 are the same, each R 9 is the same, each R 10 is the same, and, in formula (II), each X is the same.
  • the substituted 2-hydroxythiophene compound of formula (I) is free of a Group 1 or Group 2 metal, i.e., has the structure drawn for formula (I).
  • the substituted 2-hydroxythiophene compound is the Group 1 or Group 2 metal salt thereof.
  • the Group 1 or Group 2 metal salt may be made by replacing the hydrogen atom of one of the hydroxyl groups or replacing each of the hydrogen atoms of both hydroxyl groups, of the substituted 2-hydroxythiophene compound in formula (I) with a Group 1 or Group 2 metal atom. This may be done by reacting the compound of formula (I) with a Group 1 or Group 2 metal reactant.
  • the Group 1 or Group 2 metal reactant may be a Group 1 or Group 2 metal hydroxide, a Group 1 or Group 2 metal hydride, a Group 1 or Group 2 metal alkoxide, or an alkyl Group 1 or Group 2 metal.
  • the Group 1 or Group 2 metal atom or metal atoms independently is Li, Na, K, Ca, or Mg.
  • the quantity of Group 1 or Group 2 metal reactant is chosen so that the Group 1 or Group 2 metal salt of the precatalyst of formula (I) is overall (i.e., formally) charge-neutral.
  • the substituted 2-hydroxythiophene compound of formula (I) is selected from the group consisting of compounds 1 to 6 in TABLE 1: [0087] TABLE 1: Cmpd R 1 / R 2 R 3 / R 4 R 5 / R 6 R 7 / R 8 No.
  • precatalyst of formula (II) selected from the group consisting of precatalyst numbers 1 to 13 in TABLE 2: [0090] TABLE 2: Precatalyst Make from Formula (I) No. Compound No.
  • M X each is n 1 1 Zr Benzyl 2 2 1 Hf Benzyl 2 3 2 Zr Benzyl 2 4 2 Hf Benzyl 2 5 3 Zr Benzyl 2 6 3 Hf Benzyl 2 7 4 Zr Benzyl 2 8 4 Hf Benzyl 2 9 5 Zr Benzyl 2 10 5 Hf Benzyl 2 11 6 Zr Benzyl 2 12 6 Hf Benzyl 2 13 2 Zr Cl 2 [0091] In some embodiments is the supported catalyst system selected from the group consisting of spray-dried supported catalyst system numbers SCS 1 to SCS 13 and undried supported catalyst system numbers SCS 14 to SCS 16 in TABLE 3: [0092] TABLE 3: Make from Formula Catalyst Drying SCS No.
  • the supported catalyst system is that which has been shown to make by gas phase polymerization an ethylene/1-hexene copolymer having a weight-average molecular weight greater than 1,000,000 grams per mole and/or a z-average molecular weight greater than 2,000,000 grams per mole.
  • the substituted 2-hydroxythiophene compound of formula (I) is selected from Cmpd. nos.1 to 6; or from any five of Cmpd. Nos.1 to 6; or from Cmpd. nos.1 and 2; or from Cmpd. nos.3 and 4; or from Cmpd. nos.5 and 6..
  • the precatalyst of formula (II) is selected from Precat. nos.1 to 12; or from any eleven of Precat. Nos.1 to 13 ; or from Precat. nos.1 to 9, 11, and 12; or from Precat. nos.1 and 2; or from Precat. nos.3 and 4; or from Precat. nos.5 and 6; or from Precat. nos.7 and 8; or from Precat. nos.9 and 10; or from Precat. nos.11 and 12; or Precat. No.13.
  • the spray-dried supported catalyst system is selected from SCS nos.1 to 13; or from any thirteen of SCS nos.1 to 13; or from SCS nos.1 to 9, 11, and 12; or from SCS nos.1 and 2; or from SCS nos.3 and 4; or from SCS nos.5 and 6; or from SCS nos.7 and 8; or from SCS nos.9 and 10; or from SCS nos.11 and 12, or SCS no.13.
  • the supported catalyst system is an undried supported catalyst system selected from SCS nos.14 to SCS 16; or from any three of SCS nos.14 to SCS 16; or from SCS nos. 14 and 15; or SCS no.16.
  • Embodiments also include a method of making a polyolefin in a gas phase polymerization process, the method comprising contacting one or more olefin monomers with the supported catalyst system, described above, in a gas phase polymerization reactor under gas phase polymerization conditions to make a polyolefin polymer.
  • the one or more olefin monomers comprise ethylene or propylene and optionally a 1-alkene having from 4 to 20 carbon atoms (“(C 4 -C 20 )1-alkene”) and the polyolefin polymer that is made comprises a polyethylene polymer selected from a polyethylene homopolymer or an ethylene/(C 4 -C 20 )1-alkene copolymer or a polypropylene polymer selected from a polypropylene homopolymer or a propylene/(C 4 -C 20 )1-alkene copolymer.
  • the one or more olefin monomers comprises ethylene and 1-butene, 1-hexene, or 1-octene and the polyethylene polymer is an ethylene/1-butene copolymer, an ethylene/1- hexene copolymer, or an ethylene/1-octene copolymer.
  • the polyethylene polymer has a weight-average molecular weight greater than 1,000,000 grams per mole and/or a z-average molecular weight greater than 2,000,000 grams per mole.
  • the method of polymerizing comprises gas phase polymerization and has any one of limitations (i) to (v): (i) wherein the one or more olefin monomers comprises ethylene or a combination of ethylene and propylene or a combination of ethylene and a (C 4 -C 20 )alpha-olefin and wherein the polyolefin polymer is an ethylene homopolymer or an ethylene/propylene copolymer or an ethylene/(C 4 -C 20 )alpha-olefin copolymer; (ii) wherein the one or more olefin monomers comprises ethylene or a combination of ethylene and a (C 4 -C 20 )alpha-olefin and the polyolefin polymer is an ethylene homopolymer or an ethylene/(C 4 -C 20 )alpha-olefin copolymer; wherein the ethylene homopolymer or an ethylene/(C 4 -C 20 )alpha-
  • Embodiments also include a method of making a polyolefin in a slurry phase polymerization process, the method comprising contacting one or more olefin monomers with the supported catalyst system, described above, in a slurry phase polymerization reactor under slurry phase polymerization conditions to make a polyolefin polymer.
  • the method has any one of limitations (i) and (ii): (i) wherein the one or more olefin monomers comprises ethylene or a combination of ethylene propylene or a combination of ethylene and a (C 4 -C 20 )alpha-olefin and the polyolefin polymer comprises an ethylene homopolymer or an ethylene/propylene copolymer of an ethylene/(C 4 -C 20 )alpha-olefin copolymer.
  • the one or more olefin monomers comprises a combination of ethylene and 1-hexene and the polyolefin polymer comprises an ethylene/1-hexene copolymer.
  • step A compound (1) is saponified with sodium hydroxide (NaOH) in aqueous 1,4-dioxane at 80° C. to give 3-bromo- 2-hydroxy-thiophene-1-carboxylate sodium salt.
  • the carboxylate was heated with concentrated hydrochloric acid at 60° C. to give 3-bromo-2-hydroxythiophene.
  • step B the 3- bromo-2-hydroxythiophene was reacted with lithium hydroxide monohydrate (LiOH ⁇ H 2 O), ethoxychloromethane (ClCH 2 OCH 2 CH 3 ) in 1,4-dioxane/tetrahydrofuran (1:4, v/v) at 0° C.
  • step C 1.0 mole equivalent of compound (2) was reacted with 2.20 mole equivalents of 3,6-di-t-butylcarbazole (3), 2.00 mole equivalents of cuprous oxide (Cu 2 O), 10 mole equivalents of potassium carbonate (K 2 CO 3 ), and 4.0 mole equivalents of N,N ⁇ -dimethylethylenediamine (“DMEDA”) in deoxygenated anhydrous xylenes at 140 °C to make the 2-ethoxymethyloxy-3-carbazolyllthiophene (4).
  • DMEDA N,N ⁇ -dimethylethylenediamine
  • step D 1 mole equivalent of compound (4) was reacted with 1.25 mole equivalents of n-butyl lithium at -35° C for 4 hours, and then 2.0 mole equivalents of neat isopropoxyboropinacolate ester (“i-PrOBPin”) were added and the temperature allowed to warm to room temperature to make intermediate compound (5).
  • i-PrOBPin isopropoxyboropinacolate ester
  • Step E 3 mole equivalents of compound (5) were reacted with 1 mole equivalent of a 1,3- bis(iodophenoxy)propylene (6) wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are as defined for formula (I) in the presence of a catalyst (e.g., bis(di-tert-butyl(4- dimethylaminophenyl)phosphine)dichloropalladium(II)) or “Pd(AmPhos)Cl 2 ”) and 9 mole equivalents of potassium phosphate tribasic (K3PO4) to make a bis(ethoxymethyl)-protected compound.
  • a catalyst e.g., bis(di-tert-butyl(4- dimethylaminophenyl)phosphine)dichloropalladium(II)
  • Pd(AmPhos)Cl 2 9 mole equivalents of potassium
  • Step F The bis(ethoxymethyl)-protected compound was used in Step F comprising deprotective hydrolysis with concentrated hydrochloric acid in dichloromethane/1,4-dioxane (1:1, v/v) under nitrogen at 23° C. to make the substituted 2-hydroxythiophene compound of formula (I).
  • Figure 3 depicts synthetic Scheme 3 showing the conversion of the substituted 2- hydroxythiophene compound of formula (I) to an embodiment of the precatalyst of formula (II).
  • Step G 1.0 mole equivalent of the substituted 2-hydroxythiophene compound of formula (I) is azeotropically dried using toluene..
  • Examples of the Group 4 metal salt of formula M(X) n+2 are zirconium tetrachloride (ZrCl 4 ), zirconium dibenzyl dichloride (ZrBn 2 Cl 2 ), zirconium tetrabenzyl (ZrBn 4 ), hafnium tetrachloride (HfCl 4 ), hafnium dibenzyl dichloride (HfBn2Cl2), and hafnium tetrabenzyl (HfBn 4 ).
  • Benzyl, abbreviated “Bn” is phenylmethyl, which is a monoradical of formula -CH 2 C 6 H 5 .
  • the ZrCl 4 , ZrBn 2 Cl 2 , HfCl 4 , or HfBn 2 Cl 2 make embodiments of the precatalyst of formula (II) wherein M is Zr or Hf and each X is Cl. These embodiments may be converted to other embodiments of the precatalyst of formula (II). For example, the embodiments of the precatalyst of formula (II) wherein each X is Cl may be reacted with n mole equivalents of an alkylmagnesium halide or of an alkyl lithium to make the precatalyst of formula (II) wherein each X is alkyl.
  • inventions of the precatalyst of formula (II) wherein M is Zr or Hf and each X is benzyl (Bn) are made directly from the ZrBn 4 or HfBn 4 .
  • the embodiments of the precatalyst of formula (II) wherein M is Zr or Hf and each X is benzyl (Bn) may be made from the embodiments of the precatalyst of formula (II) wherein M is Zr or Hf and each X is Cl by reacting them with n mole equivalents of a benzylmagnesium halide or benzyl lithium.
  • Figure 4 depicts synthetic Scheme 4.
  • Step H of Scheme 4 the precatalyst of formula (II) is activated by an activator and supported on a support material in an inert hydrocarbon liquid, such as alkanes or toluene, to make a supported catalyst system suspended in the inert hydrocarbon liquid.
  • the suspension of the supported catalyst system is spray-dried as described herein to make a spray-dried supported catalyst system (“sd-SCS”) embodiment.
  • the suspension of the supported catalyst system is conventionally dried as described herein to make a conventionally-dried supported catalyst system (“cd-SCS”) embodiment.
  • FIG. 16 depicts synthetic Scheme 5.
  • the 1,3- bis(iodophenoxy)propylene compound (6) shown in Scheme 2 in Figure 2 is made from phenols (6a) and (6c) and 1,3-dibromopropane or 1,3-bistosylatepropane (6b) in the presence of potassium carbonate (K 2 CO 3 ) in acetone (Me 2 CO) at 60° C.
  • the supported catalyst system is a heterogeneous olefin polymerization catalyst.
  • the heterogenization of the precatalyst of formula (II) with support material and activator to make the supported catalyst system may be carried out according to any one of the heterogenization routes described earlier.
  • the supported catalyst system is formulated for use in gas phase or slurry phase polymerizations of olefin monomers.
  • the supported catalyst system is made from the precatalyst of formula (II), an activator, and a solid support.
  • the supported catalyst system may comprise additional components such as by-products and side products of the preparation of the supported catalyst system and any unreacted activator that may remain in preparations that use an excess amount of activator relative to the amount of the precatalyst of formula (II).
  • the catalysts of the supported catalyst system may be unsupported when contacted with an activator, which may be the same or different for the different catalysts.
  • the catalysts may be disposed by spray-drying onto a solid support material prior to being contacted with the activator(s).
  • the solid support material may be uncalcined or calcined prior to being contacted with the catalysts.
  • the solid support material may be a hydrophobic fumed silica (e.g., a fumed silica treated with dimethyldichlorosilane, which is ((CH 3 ) 2 SiCl 2 ), which is commercially available from Cabot Corporation as CabosilTM TS-610 fumed silica.
  • the bimodal (unsupported or supported) catalyst system may be in the form of a powdery, free- flowing particulate solid.
  • Support Material [00110]
  • the support material used in the supported catalyst system may be an inorganic oxide solid.
  • support”, “solid support”, “support material”, and “solid support material” mean the same thing as used herein and refer to a porous inorganic substance or organic substance.
  • the support material may be an inorganic oxide, which includes Group 2, 3, 4, 5, 13 or 14 metal oxides, alternatively Group 13 or 14 metal oxides.
  • inorganic oxide-type support materials are silica, magnesia, alumina, titania, zirconia, thoria, and mixtures of any two or more of such inorganic oxides. Examples of such mixtures are silica-chromium, silica-alumina, and silica-titania.
  • the support material may be untreated or the support material may be treated with a hydrophobing agent. In some embodiments the support material is a hydrophobic fumed silica.
  • the inorganic oxide support material is porous and has variable surface area, pore volume, and average particle size.
  • the surface area is from 50 to 1000 square meter per gram (m 2 /g) and the average particle size is from 1 to 300 micrometers ( ⁇ m), alternatively 20 to 300 ⁇ m.
  • the pore volume is from 0.5 to 6.0 cubic centimeters per gram (cm 3 /g) and the surface area is from 200 to 600 m 2 /g.
  • the pore volume is from 1.1 to 1.8 cm 3 /g and the surface area is from 245 to 375 m 2 /g.
  • the pore volume is from 2.4 to 3.7 cm 3 /g and the surface area is from 410 to 620 m 2 /g.
  • the pore volume is from 0.9 to 1.4 cm 3 /g and the surface area is from 390 to 590 m 2 /g.
  • the support material may comprise silica, alternatively amorphous silica (not quartz), alternatively a high surface area amorphous silica (e.g., from 500 to 1000 m 2 /g).
  • Such silicas are commercially available from several sources including the Davison Chemical Division of W.R.
  • the silica may be in the form of spherical particles, which may be obtained by a spray-drying process.
  • MS3050 product is a silica from PQ Corporation that is not spray-dried. As procured, these silicas are not calcined (i.e., not dehydrated). Silica that is calcined prior to purchase may also be used as the support material.
  • the solid support is a hydrophobic fumed silica.
  • the hydrophobic fumed silica is made by contacting an untreated fumed silica, having surfaces containing silicon-bonded hydroxyl groups (Si-OH groups), with a hydrophobing agent, described later.
  • the hydrophobing agent is a silicon-based hydrophobing agent, containing on average per molecule one or more functional groups reactive with a Si-OH group, to give the hydrophobic fumed silica.
  • the silicon-based hydrophobing agent may be selected from (CH 3 ) 2 SiCl 2 , a polydimethylsiloxane, hexamethyldisilazane (HMDZ), and a (C 1 -C 10 )alkylSi((C 1 -C 10 )alkoxy) 3 (e.g., an octyltrialkoxysilane such as octyltriethoxysilane, i.e., CH 3 (CH 2 ) 7 Si(OCH 2 CH 3 ) 3 ).
  • the silicon-based hydrophobing agent is dimethyldichlorosilane, i.e., (CH 3 ) 2 SiCl 2 .
  • the support material is a dimethyldichlorosilane-treated fumed silica, such as that sold as product TS-610 from Cabot Corporation.
  • the support material may be uncalcined or calcined.
  • the calcined support material is made prior to being contacted with a precatalyst, activator, and/or hydrophobing agent, by heating the support material in air to give a calcined support material.
  • the calcining comprises heating the support material at a peak temperature from 350° to 850° C., alternatively from 400° to 800° C., alternatively from 400° to 700° C., alternatively from 500° to 650° C.
  • the hydrophobing agent is an organic compound or an organosilicon compound that forms a stable reaction product with surface hydroxyl groups of a fumed silica.
  • the polydiorganosiloxane compound such as a polydimethylsiloxane, contains backbone Si- O-Si groups wherein the oxygen atom can form a stable hydrogen bond to a surface hydroxyl group of fumed silica.
  • the silicon-based hydrophobing agent may be trimethylsilyl chloride, dimethyldichlorosilane, a polydimethylsiloxane fluid, hexamethyldisilazane, an octyltrialkoxysilane (e.g., octyltrimethoxysilane), and a combination of any two or more thereof.
  • Activator [00116]
  • the activator used in the heterogenization method may be any compound capable of reacting with the precatalyst of formula (II) to yield an active olefin polymerization catalyst.
  • the activator may be a Lewis acid, a non-coordinating ionic activator, or an ionizing activator, or a Lewis base.
  • the activator is an aluminum based activator.
  • the molar ratio of activator’s metal (Al) to a particular catalyst compound’s metal (Group 4 metal, e.g., Ti, Zr, or Hf) may be 7,000:1 to 0.5:1, alternatively 3,500:1 to 1:1, alternatively 1,000:1 to 0.5:1, alternatively 300:1 to 1:1, alternatively 150:1 to 1:1.
  • Suitable activators are commercially available.
  • the aluminum based activator is an alkylaluminum or an alkylaluminoxane (alkylalumoxane). Any alkyl group may be used.
  • each alkyl of the alkylaluminum or alkylaluminoxane independently may be a (C 1 -C 8 )alkyl, alternatively a (C 1 -C 7 )alkyl, alternatively a (C 1 -C 6 )alkyl, alternatively a (C 1 -C 4 )alkyl.
  • the alkylaluminum may be a trialkylaluminum, alkylaluminum halide, or alkylaluminum alkoxide (diethylaluminum ethoxide).
  • the trialkylaluminum may be trimethylaluminum, triethylaluminum (“TEAl”), tripropylaluminum, or tris(2- methylpropyl)aluminum.
  • the alkylaluminum halide may be diethylaluminum chloride.
  • the alkylaluminum alkoxide may be diethylaluminum ethoxide.
  • the alkylaluminoxane may be a methylaluminoxane (MAO), ethylaluminoxane, 2- methylpropyl-aluminoxane, or a modified methylaluminoxane (MMAO).
  • the activator is the MAO.
  • an active catalyst species and an activator species are made in situ.
  • the active catalyst species comprises a ligand derived from the substituted 2-hydroxythiophene compound of formula (I) and an activator species.
  • the activator species has a different structure or composition than the activator from which it is derived.
  • the activation reaction may also generate one or more by-products.
  • the corresponding activator species may be a derivative of the Lewis acid, non-coordinating ionic activator, ionizing activator, Lewis base, alkylaluminum, or alkylaluminoxane, respectively.
  • An example of the derivative of the by-product is a methylaluminoxane species that is formed by devolatilizing during spray-drying of a supported catalyst system made with methylaluminoxane.
  • the supported catalyst system may be made by the heterogenization routes described earlier. These routes typically include use of an inert hydrocarbon liquid as solvent or carrier.
  • the precatalyst and support material are contacted together in the inert hydrocarbon liquid to give a suspension of a supported precatalyst in the inert hydrocarbon liquid, then the suspension is contacted with the activator to give a suspension of the supported catalyst system in the inert hydrocarbon liquid, and then the inert hydrocarbon liquid is removed to give the supported catalyst system.
  • the precatalyst and activator are contacted together in an inert hydrocarbon liquid to give a solution of a catalyst in the inert hydrocarbon liquid, then the solution is contacted with the support material to give a suspension of the supported catalyst system in the inert hydrocarbon liquid, and then the inert hydrocarbon liquid is removed to give the supported catalyst system.
  • the activator and the support material are contacted together in an inert hydrocarbon liquid to give a suspension of a supported activator in the inert hydrocarbon liquid, then the suspension is contacted with the precatalyst to give a suspension of the supported catalyst system in the inert hydrocarbon liquid, and then the inert hydrocarbon liquid is removed to give the supported catalyst system.
  • the precatalyst, activator, and support material are contacted together simultaneously in an inert hydrocarbon liquid to give a suspension of the supported catalyst, and then the inert hydrocarbon liquid is removed to give the supported catalyst system.
  • the removing of the inert hydrocarbon liquid from the suspension of the supported catalyst system may include a step of decanting some of the inert hydrocarbon liquid from the suspension.
  • the decanting method comprises pouring off excess inert hydrocarbon liquid from the suspension to give a concentrated suspension of the supported catalyst system.
  • the removing of the inert hydrocarbon liquid from the suspension of the supported catalyst system may comprise a step of drying the supported catalyst system.
  • the drying step may comprise a conventional drying method or a spray-drying method.
  • the conventional drying method comprises a method of slowly increasing the mass or molar amount of less volatile chemical constituent(s) per unit volume of a continuous mixture comprising more volatile and less volatile chemical constituent(s) by gradually removing the more volatile chemical constituent(s) from the less volatile constituent(s) of the continuous mixture to give a concentrate having a higher mass or molar amount of the less volatile chemical constituent(s) per unit volume than did the continuous mixture, wherein the rate of gradual removing is limited by a relatively small evaporative surface area to mass ratio (compared to spray-drying).
  • the concentrate may be a precipitated solid.
  • the spray-drying method comprises rapidly forming a particulate solid comprising less volatile chemical constituents via aspiration of a bulk mixture of the less volatile chemical constituents and more volatile chemical constituents through a nebulizer using a hot gas, wherein the aspiration forms particulates collectively having a large evaporative surface area to mass ratio compared to that of concentrating.
  • the particle size and shape of the particulate solid formed by spray-drying may be different than those of a precipitated solid.
  • the spray-dried supported catalyst system may be made at laboratory scale according to the following spray-drying procedure in a nitrogen-purged glove box: charge an oven-dried glass jar with anhydrous deoxygenated toluene and a solid support material. The contents are stirred at room temperature until well dispersed as a slurry. To the slurry is added a 10 % solution by weight of methylaluminoxane (MAO) in toluene. The resulting mixture is stirred for 15 minutes, then a quantity of the precatalyst of formula (II) is added.
  • MAO methylaluminoxane
  • the resulting reaction mixture is stirred at room temperature for an additional 30 to 60 minutes to activate the precatalyst, yielding the supported catalyst system suspended in toluene.
  • This suspension is spray-dried using a spray drier apparatus (e.g., a Büchi Mini Spray Dryer model B-290 from BUCHI Corporation, New Castle, Delaware, USA) with the following parameters: Set Temperature 140° C., Outlet Temperature 75° C. (minimum), aspirator setting 95 rotations per minute (rpm), and pump speed 150 rpm.
  • the spray-drying process yields the spray-dried supported catalyst system as an anhydrous solid powder.
  • the solid support material that has been treated with a hydrophobing agent such as a hydrophobic fumed silica that has been treated with dimethyldichlorosilane.
  • a hydrophobing agent such as a hydrophobic fumed silica that has been treated with dimethyldichlorosilane.
  • the foregoing procedure may be scaled up to manufacturing size quantities using generally known methods. Comparing Advantages of Undried, Conventionally-Dried, and Spray-Dried Embodiments of the Supported Catalyst System [00132]
  • the present invention contemplates both the conventionally dried supported catalyst system embodiments, the spray-dried supported catalyst system embodiments, and the decanted but undried supported catalyst system embodiments.
  • the decanted but undried supported catalyst system embodiments are useful in catalyzing slurry phase polymerizations and are convenient form for adding the supported catalyst system to a slurry phase reactor.
  • the conventionally dried supported catalyst system embodiments may have higher catalyst efficiencies, and thus greater polyolefin productivities, than do comparative unsupported catalysts made from the same precatalyst and activator in the absence of the support material.
  • the spray-dried supported catalyst system embodiments may have higher catalyst efficiencies, and thus greater polyolefin productivities, than do the conventionally dried supported catalyst system embodiments.
  • the spray-dried embodiments of the supported catalyst system may have still higher catalyst efficiencies, and thus still greater polyolefin productivities, than do comparative unsupported catalysts made from the same precatalyst and activator in the absence of the support material.
  • Many spray-dried supported catalyst system embodiments also make polyolefins having improved resin properties. For example, some spray-dried supported catalyst system embodiments make polyolefins having increased content of long chain branching (LCB), whereas other spray-dried supported catalyst system embodiments and the conventionally dried catalyst system embodiments do not.
  • LCB long chain branching
  • some spray-dried supported catalyst system embodiments make polyolefins having ultrahigh molecular weight contents, whereas other spray-dried supported catalyst system embodiments and the conventionally dried catalyst system embodiments do not.
  • the supported catalyst system may be used in slurry phase or gas phase olefin polymerization reactions to enhance the rate of polymerization of monomer and/or comonomer(s).
  • the olefin polymerization reaction is conducted in a gas phase reactor in the gas phase, or in a slurry phase reactor in the slurry phase.
  • the method comprising contacting the olefin monomer with the supported catalyst system, thereby making a polyolefin, wherein the olefin polymerization is conducted in a gas phase reactor under gas phase process conditions or the olefin polymerization is conducted in a slurry phase reactor under slurry phase conditions.
  • the method comprises polymerizing ethylene only and makes a polyethylene homopolymer.
  • the method comprises polymerizing ethylene and propylene and makes an ethylene/propylene copolymer, or polymerizing ethylene and a (C 4 -C 8 )alpha-olefin and makes an ethylene/(C 4 -C 8 )alpha- olefin copolymer.
  • the (C 4 -C 8 )alpha-olefin is 1-butene, 1-hexene, or 1- octene; or 1-butene or 1-hexene; or 1-butene; or 1-hexene; or 1-octene; and the ethylene/(C 4 - C 8 )alpha-olefin copolymer is ethylene/1-butene copolymer, ethylene/1-hexene copolymer, or ethylene/1-octene copolymer; or ethylene/1-butene copolymer or ethylene/1-hexene copolymer; or ethylene/1-butene copolymer; or ethylene/1-hexene copolymer; or ethylene/1- octene copolymer.
  • the method of polymerizing an olefin monomer may be carried out in any gas phase olefin polymerization reactor or slurry phase olefin polymerization reactor and under any gas phase polymerization process conditions or slurry phase polymerization conditions.
  • Reactors and process conditions for gas phase and slurry phase olefin polymerization reactions are well-known.
  • slurry phase reactors and process conditions include those described in US 3,324,095.
  • the gas phase polymerization reactor and process conditions may employ stirred-bed gas-phase polymerization reactor (SB-GPP reactor) or a fluidized-bed gas-phase polymerization reactor (FB-GPP reactor).
  • the gas phase reactor and process conditions may include an induced condensing agent and be conducted in condensing mode polymerization such as described in US 4,453,399; US 4,588,790; US 4,994,534; US 5,352,749; US 5,462,999; and US 6,489,408.
  • the gas phase reactor and process conditions may be a fluidized bed reactor/method as described in US 3,709,853; US 4,003,712; US 4,011,382; US 4,302,566; US 4,543,399; US 4,882,400; US 5,352,749; US 5,541,270; EP-A-0802202; and Belgian Patent No. 839,380.
  • gas phase polymerization processes wherein the polymerization medium is either mechanically agitated or fluidized by the continuous flow of the gaseous monomer and diluent.
  • Other useful gas phase processes include series or multistage polymerization processes such as described in US 5,627,242; US 5,665,818; US 5,677,375; EP-A-0794200; EP-B1-0649992; EP-A-0 802202; and EP-B-634421.
  • the gas phase reactor and process conditions comprise a single gas phase reactor and single set of process conditions.
  • the gas phase reactor and process conditions comprise two gas phase reactors in series and two sets of process conditions.
  • a first olefin polymerization is conducted in a first gas phase reactor under a first gas phase process conditions, then the resulting polyolefin is transferred into a second gas phase reactor, wherein a second olefin polymerization reaction is conducted under a second set of process conditions.
  • the supported catalyst system may be used in the first olefin polymerization and not the second olefin polymerization, or in the second olefin polymerization and not the first olefin polymerization, or in both the first and second olefin polymerizations.
  • the supported catalyst system used in both the first and second olefin polymerizations may be the same embodiment or different embodiments.
  • the olefin polymerization comprises a slurry phase reactor and process conditions and a gas phase reactor and process conditions in series, or vice versa.
  • a first olefin polymerization is conducted in the slurry phase reactor under the slurry phase process conditions, then the slurry phase polyolefin is transferred into the gas phase reactor and a second olefin polymerization is conducted under gas phase conditions.
  • the supported catalyst system may be used in the first olefin polymerization and not the second olefin polymerization, or in the second olefin polymerization and not the first olefin polymerization, or in both the first and second olefin polymerizations.
  • the supported catalyst system used in both the first and second olefin polymerizations may be the same embodiment or different embodiments.
  • Polyolefin [00143]
  • the product of the olefin polymerization method is a polyolefin.
  • the polyolefin is a low-density polyethylene (LDPE), linear low- density polyethylene (LLDPE), a medium-density polyethylene (MDPE), or a high-density polyethylene (HDPE).
  • LDPE low-density polyethylene
  • LLDPE linear low- density polyethylene
  • MDPE medium-density polyethylene
  • HDPE high-density polyethylene
  • an LLDPE is distinguished from LDPE by the initiator or catalyst and the polymerization process conditions used to make them, which leads to differences in their amounts of long chain branching.
  • LDPE is made by a free radical polymerization process (e.g., initiated by small amounts of organic peroxide) at high pressure and as such LDPE inherently has a significant amount of long chain branching as shown in Figure 17.
  • LLDPEs that are made using traditional Ziegler-Natta catalysts, which do not generate long chain branching, are linear and free of long chain branching as illustrated in Figure 17.
  • an LLDPE is distinguished from HDPE by density and by the amount of short chain branching (SCB).
  • LLDPEs have densities less than 0.940 g/cm 3
  • HDPE has densities greater than or equal to 0.940 g/cm 3
  • LLDPEs have a significant amount of short chain branching
  • HDPEs have far lesser amounts of short chain branching; see Figure 17.
  • the polyethylene may have no detectable long-chain branching content, i.e., 0 long-chain branches (“LCB”) per 1000 carbon atoms.
  • the polyethylene may have a long-chain branching content from 0.01 to 2 long-chain branches (“LCB”) per 1000 carbon atoms (LCB/1000C), alternatively from 0.01 LCB/1000C to 1.0 LCB/1000C, alternatively from 0.1 LCB/1000C to 1.0 LCB/1000C.
  • LCB content means having an amount of long chain branching that is detectable by the 13 C- NMR spectroscopy, which currently has a lower detection limit of 0.004 LCB/1000C.
  • LCB content from greater than 0.000 LCB/1000C to less than 0.010 LCB/1000C are excluded herein.
  • the long chain branching content of the inventive polyolefin may be directly or indirectly characterized by any one of the following measurements (i) to (iv): (i) directly by carbon-13 nuclear magnetic resonance (NMR) spectroscopy; (ii) indirectly by a melt flow ratio (I 21 /I 2 ) equation described below; (iii) indirectly by a melt flow ratio (I 21 /I 2 ) range; or (iv) Mark- Houwink analysis using a triple detector gel permeation chromatography (triple detector GPC).
  • NMR carbon-13 nuclear magnetic resonance
  • the characterization may comprise a combination of measurements (i) and (ii), a combination of measurements (i) and (iv), a combination of measurements (i) and (iii), a combination of measurements (ii) and (iii), a combination of measurements (ii) and (iv), a combination of measurements (iii) and (iv), or a combination of measurements (i), (ii), (iii), and (iv).
  • the polyethylene may have ultrahigh molecular weight (“UHMW”) content.
  • UHMW tail in a GPC plot may be ultrahigh molecular weight
  • the UHMW content of these polyethylene embodiments may be measured by GPC, and is a polymer weight average molecular weight of 1,000,000 g/mol or greater.
  • the UHMW tail is any one of limitations (i) to (iii): (i) a z-average molecular weight of 1,000,000 g/mol or greater, (ii) a ratio of z-average molecular weight to weight-average molecular weight (Mz/Mw) of 3.5 or greater, or (iii) both limitations (i) and (ii).
  • the polyolefin may be formulated with one or more additives useful in polyethylene articles, such as but not limited to, additives useful in polyethylene films, additives useful in polyethylene pipes, or additives useful in blow molded polyethylene articles.
  • the one or more additives comprise additives useful for films such as one or more antioxidants, one or more ultraviolet (UV) light stabilizers, one or more colorants, and/or one or more anti-microbial agents.
  • Activator a compound for converting a precatalyst having no or negligible catalytic activity into a catalyst having orders of magnitude higher catalytic activity.
  • Dry may also refer to being free of an organic solvent such as toluene or hexanes when used to describe an embodiment of a supported catalyst system as a dry powder.
  • Fumed silica a pyrogenic silica produced in a flame. An amorphous silica powder made by fusing microscopic droplets into branched, chainlike, three-dimensional secondary particles, which agglomerate into tertiary particles. Not quartz.
  • Heteroatoms as used herein, generic heteroatom-containing organic groups wherein the specific heteroatom or heteroatoms is not or are not explicitly or implicitly indicated, such as is the case for “heterohydrocarbyl” groups and “organoheteryl” groups, inherently contain one or more heteroatoms selected from the group consisting of O, S, N, P, and Si; or O, S, N, and Si; or O, N, and Si; or O and N; or O; or N; or Si: or S; or P.
  • heteroatom-containing organic groups wherein the heteroatom is explicitly or implicitly indicated are: alkoxy groups wherein the heteroatom implicitly is O’ and amino groups wherein the heteroatom implicitly is N; alkylO- groups wherein the heteroatom explicitly is O; and - CH 2 Si(alkyl) 3 groups wherein the heteroatom explicitly is Si.
  • Hydrocarbyl, heterohydrocarbyl, and organoheteryl have their IUPAC Gold Book meanings.
  • the hydrocarbyl is a monovalent radical that in unsubstituted embodiments consists of one or more carbon atoms and hydrogen atoms, wherein the monovalent radical is on a carbon atom. Examples are alkyl and aryl.
  • the heterohydrocarbyl group is a monovalent radical that in unsubstituted embodiments consists of one or more carbon atoms and at least one heteroatom, wherein the monovalent radical is a carbon atom. Examples are ethoxymethyl and -CH 2 Si(alkyl) 3 .
  • the organoheteryl group is a monovalent radical that in unsubstituted embodiments consists of one or more carbon atoms and at least one heteroatom, wherein the monovalent radical is a heteroatom. Examples alkoxy and -Si(alkyl) 3 . [00157] Inert: not (appreciably) reactive.
  • inert as applied to the purge gas or olefin monomer feed means a molecular oxygen (O 2 ) content from 0 to less than 5 parts per million based on total parts by weight of the purge gas or olefin monomer feed.
  • O 2 molecular oxygen
  • hydrocarbon (unsubstituted) solvent means free of carbon-carbon double and triple bonds, free of molecular oxygen (0 to less than 5 ppm O 2 ), and free of moisture (“dry”, 0 to less than 5 ppm H 2 O).
  • hydrocarbon solvents that may be inerted (dried and purged of O 2 ) are unsubstituted alkanes (e.g., hexanes and heptane), unsubstituted arenes (e.g., benzene and naphthalene), and unsubstituted alkylarenes (e.g., toluene, xylenes, and fluorene).
  • Metallocene catalyst Homogeneous or heterogeneous molecule that contains an unsubstituted- or substituted-cyclopentadienyl ligand-metal complex and enhances olefin polymerization reaction rates.
  • typically unsupported metallocene catalyst molecules are substantially single site or dual site and supported metallocene catalysts are multi-sited, meaning two or more sites or speciations.
  • the unsubstituted cyclopentadienyl is a monoanion of formula [C 5 H 5 ]-.
  • substituted cyclopentadienyl includes monocyclic derivatives of cyclopentadienyl, such as propylcyclopentadienyl and pentamethylcyclopentadienyl, and multicyclic derivatives of cyclopentadienyl, such as bicyclic derivatives indenyl and tetrahydroindenyl and tricyclic derivatives fluorenyl, tetrahydrofluorenyl, and octahydrfluorenyl, and substituted derivatives thereof.
  • monocyclic derivatives of cyclopentadienyl such as propylcyclopentadienyl and pentamethylcyclopentadienyl
  • multicyclic derivatives of cyclopentadienyl such as bicyclic derivatives indenyl and tetrahydroindenyl and tricyclic derivatives fluorenyl, tetrahydrofluorenyl, and octahydrfluoren
  • substituted-cyclopentadienyl ligands are unsubstituted indenyl, alkyl- substituted indenyl, unsubstituted 4,5,6,7-tetrahydroindenyl, alkyl-substituted 4,5,6,7- tetrahydroindenyl, unsubstituted fluorenyl, and alkyl-substituted fluorenyl, unsubstituted 1,2,3,4-tetrahydrofluorenyl, alkyl-substituted 1,2,3,4-tetrahydrofluorenyl, unsubstituted 1,2,3,4,5,6,7,8-octahydrofluorenyl, and alkyl-substituted 1,2,3,4,5,6,7,8-octahydrofluorenyl.
  • the modality of the polyolefin may be unimodal (only 1 peak between log(MW) 3.0 and log(MW) 7.0) or multimodal (2 or more peaks between log(MW) 3.0 and log(MW) 7.0).
  • the modality of the multimodal polyolefin may be bimodal (only 2 peaks between log(MW) 3.0 and log(MW) 7.0), trimodal (only 3 peaks between log(MW) 3.0 and log(MW) 7.0), or higher modal (4 or more peaks between log(MW) 3.0 and log(MW) 7.0).
  • Multi-site catalyst any catalyst that makes a polyethylene having a polydispersity index (PDI, M w /M n ) greater than 2.0.
  • Olefin monomer unsubstituted hydrocarbon containing a carbon-carbon double bond.
  • Precatalyst a catalyst precursor compound, also called a “precatalyst”.
  • a precatalyst has none or very little catalytic activity itself, but upon being contacted with an activator the precatalyst is converted into a catalyst compound.
  • the precatalyst may be a ligand-metal complex such as the precatalysts described herein.
  • Single-site catalyst An organic ligand-metal complex useful for enhancing rates of polymerization of olefin monomers and having at most two discreet binding sites at the metal available for coordination to an olefin monomer molecule prior to insertion on a propagating polymer chain.
  • Single-site non-metallocene catalyst A single-site catalyst that is free of an unsubstituted or substituted cyclopentadienyl ligand.
  • LCB Value Test Method the amount of the LCB occurring in the EB LLDPE resins can be measured using a combination of nuclear magnetic resonance (NMR) techniques described in Z. Zhou, S. Pesek, J. Klosin, M. Rosen, S. Mukhopadhyay, R. Cong, D. Baugh, B. Winniford, H. Brown, K. Xu, “Long chain branching detection and quantification in LDPE with special solvents, polarization transfer techniques, and inverse gated 13 C NMR spectroscopy”, Macromolecules, 2018, 51, 8443; Z. Zhou, C. Anklin, R. Cong, X. Qiu, R.
  • Melt flow index values of polyethylenes were measured via the rate of extrusion of molten polymers through a die of specified length and diameter, under prescribed conditions of temperature, load, piston position in the barrel and duration, employing a melt indexer and test methods according to ASTM D1238-13 at 190° C.
  • the load is 2.16 kg (“I 2 ”), 5.0 kg (“I 5 ”), or 21.6 kg (“I 21 ”).
  • I 2 2.16 kg
  • I 5 5.0 kg
  • I 21 21.6 kg
  • Differential Scanning Calorimetry Test Method Melt temperature was determined via Differential Scanning Calorimetry according to ASTM D 3418-08. In general, a scan rate of 10° C/min on a sample of 10 milligrams (mg) was used, and the second heating cycle was used to determine T m .
  • the various transfer lines, columns, and differential refractometer were contained in an oven maintained at 160°C.
  • the solvent for the experiment was prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1, 2, 4 trichlorobenzene (TCB).
  • TCB Aldrich reagent grade 1, 2, 4 trichlorobenzene
  • the TCB mixture was then filtered through a 0.1 ⁇ m Teflon filter.
  • the TCB was then degassed with an online degasser before entering the GPC instrument.
  • the polymer solutions were prepared by placing dry polymer in glass vials, adding the desired amount of TCB, then heating the mixture at 160 °C with continuous shaking for about 2 hours. All quantities were measured gravimetrically.
  • the injection concentration was from 0.5 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
  • the DRI detector Prior to running each sample the DRI detector was purged. The flow rate in the apparatus was then increased to 1.0 ml/minute, and the DRI was allowed to stabilize for 8 hours before injecting the first sample.
  • the molecular weight was determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards.
  • PS monodispersed polystyrene
  • the mass recovery was calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume. All molecular weights are reported in g/mol unless otherwise noted.
  • the GPC-DRI procedure immediately above shall be used.
  • the comonomer content i.e., 1- hexene
  • weight % was determined by rapid FT-IR spectroscopy on the dissolved polymer in a GPC measurement.
  • Comonomer content can be determined with respect to polymer molecular weight by use of an infrared detector such as an IR5 detector in a gel permeation chromatography measurement, as described in Analytical Chemistry 2014, 86(17), 8649-8656.
  • weight-average molecular weight (Mw), number- average molecular weight (Mn), and z-average molecular weight (Mz) were measured using a chromatographic system consisting of a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infra-red detector (IR5) and 4-capillary viscometer (DV) coupled to a Precision Detectors (Now Agilent Technologies) 2- angle laser light scattering (LS) detector Model 2040. For all absolute Light scattering measurements, the 15 degree angle is used for measurement. The autosampler oven compartment was set at 165o Celsius and the column compartment and detectors were set at 155o Celsius.
  • the polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000.
  • the polystyrene standards were pre-dissolved at 80 oC with gentle agitation for 30 minutes then cooled and the room temperature solution is transferred cooled into the autosampler dissolution oven at 160oC for 30 minutes.
  • the plate count for the chromatographic system should be greater than 12,000 for the 4 TOSOH TSKgel GMHHR-H (30) HT 30-micron particle size, mixed pore size columns.
  • Samples were prepared in a semi-automatic manner with the PolymerChar “Instrument Control” Software, wherein the samples were weight-targeted at 1 mg/ml, and the solvent (contained 200ppm BHT) was added to a pre nitrogen-sparged septa-capped vial, via the PolymerChar high temperature autosampler. The samples were dissolved for 3 hours at 165o Celsius under “low speed” shaking.
  • Flowrate(effective) Flowrate(nominal) * (RV(FM Calibrated) / RV(FM Sample)) (EQ 5).
  • RAD Dow Robot Assisted Delivery
  • IR5 PolymerChar infrared detector
  • Agilent PLgel Mixed A columns Decane (10 ⁇ L) was added to each sample for use as an internal flow marker.
  • Samples were first diluted in 1,2,4-trichlorobenzene (TCB) stabilized with 300ppm butylated hydroxyl toluene (BHT) at a concentration of 10mg/mL and dissolved by stirring at 160°C for 120 minutes. Prior to injection samples were further diluted with TCB stabilized with BHT to a concentration of 2 mg/mL. Samples (250 ⁇ L) were eluted through one PL-gel 20 ⁇ m (50 x 7.5mm) guard column followed by two PL-gel 20 ⁇ m (300 x 7.5mm) Mixed-A columns maintained at 160 °C with TCB stabilized with BHT at a flowrate of 1.0 mL/min. The total run time was 24 minutes.
  • TCB 1,2,4-trichlorobenzene
  • BHT butylated hydroxyl toluene
  • Example 1 synthesis of 3-bromo-2-hydroxythiophene (example of step A).
  • reaction mixture was removed from the mantle, allowed to gradually cool to 23 °C, and placed in an ice water bath for 60 minutes. Then concentrated HCl (175 mL, 37%) was added over 10 minutes, and the resulting white heterogeneous mixture was removed from the ice water bath, placed in a mantle heated to 60 °C, and stirred vigorously (1000 rpm) for 5 hours.
  • Example 2 synthesis of 3-bromo-2-ethoxymethyloxythiophene (2) (example of step B). [00197] The solution of the 3-bromo-2-hydroxythiophene in 1,4-dioxane (100 mL) from Step A was diluted with non-anhydrous, non-deoxygenated THF (400 mL). Then H 2 O (6 mL) was added.
  • Example 3 synthesis of 2-ethoxymethyloxy-3-(3’,6’-di-tert-butylcarbazolyl)lthiophene bromothiophene (2) (5.883 g, 24.811 mmol, 1.00 eq), 3,6-di-t-butylcarbazole (15.252 g, 54.585 mmol, 2.20 eq), Cu2O (7.100 g, 49.622 mmol, 2.00 eq), and K2CO3 (34.290 g, 248.11 mmol, 10.00 eq) was suspended in deoxygenated anhydrous xylenes (200 mL), N,N-DMEDA (10.7 mL, 99.244 mmol, 4.00 eq) was added, the mixture was equipped with a reflux condenser and a rubber septa, removed from the glovebox, placed under nitrogen, placed in a mantle heated to 140 °C, stirred vigorously (
  • Example 4 synthesis of 2-ethoxymethyloxy-3-(3’,6’-di-tert-butylcarbazolyl)-2- 1.00 eq) in anhydrous deoxygenated Et2O (75 mL) in a nitrogen filled continuous purge glovebox was placed in the freezer (-35 °C), and allowed to precool for 14 hours upon which a precooled solution of normal-butyl lithium (n-Butyllithium or n-BuLi) (3.50 mL, 8.608 mmol, 1.25 eq, titrated 2.5 M in hexanes) was added in a quick dropwise manner.
  • normal-butyl lithium n-Butyllithium or n-BuLi
  • Example 6 synthesis of 1,3-bis[2-iodo-4-(1 ⁇ ,1 ⁇ ,3 ⁇ ,3 ⁇ - tetramethylbutyl)phenoxy]propane. g, mmol, 1.00 eq), the mixture was equipped with a reflux condenser, placed under nitrogen, placed in a mantle heated to 60 °C, and stirred (500 rpm) for 48 hours.
  • the mixture was then removed from the mantle, allowed to cool to ambient temperature, diluted with CH2Cl2 (20 mL), the mixture was suction filtered through a pad of diatomaceous earth, rinsed with CH2Cl2 (4 x 20 mL), the pale golden brown filtrate solution was poured into a separatory funnel, washed with aqueous NaOH (2 x 20 mL, 1N), residual organics were extracted from the aqueous using CH2Cl2 (2 x 20 mL), dried over Na2SO4, decanted, the pale golden brown solution was concentrated onto diatomaceous earth, and purified via silica gel chromatography using an ISCO; hexanes – 30% CH2Cl2 in hexanes to afford the bisiodide as a white solid (2.091 g, 2.968 mmol, 84%).
  • Example 7 synthesis of 4-octyloxyphenol. mmol, 1.00 eq) and K 2 CO 3 (100.40 g, 726.56 mmol, 4.00 eq) in DMSO (600 mL) was added 1-bromooctane (40.8 mL, 236.13 mmol, 1.30 eq).
  • the mixture was placed under nitrogen, placed in a mantle heated to 90 °C, stirred (500 rpm) for 36 hours, removed from the mantle, allowed to cool to ambient temperature, water (200 mL) and KH2PO4 (100 grams) were added, and stirred for approximately 10 mins.
  • Example 8 Synthesis of 4-octyloxyphenolmethyl ethyl ether. mol, 1.00 eq) in THF upon which an aqueous solution of NaOH (13.2 mL, 0.500 mol, 6.00 eq, 50 % w/w) was added via syringe in a quick dropwise manner. After stirring (500 rpm) for 60 mins at 23 °C, neat chloromethyl ethyl ether (23.0 mL, 0.24835 mol, 3.00 eq) was added via syringe in a quick dropwise manner to the clear pale yellow solution.
  • the now white heterogeneous mixture was diluted with aqueous NaOH (100 mL, 1 N), THF was removed via rotary evaporation, the resultant white biphasic mixture was diluted with CH2Cl2 (100 mL), poured into a separatory funnel, partitioned, organics were washed with aqueous NaOH (2 x 100 mL, 1 N), residual organics were extracted from the aqueous using CH 2 Cl 2 (2 x 50 mL), combined, dried over solid Na2SO4, decanted, and concentrated.
  • Example 9 Synthesis of 2-iodo-4-octyloxyphenolmethyl ethyl ether. x 10 mL). A clear, colorless solution of the bisether (4.359 g, 15.545 mmol, 1.00 eq) in anhydrous deoxygenated THF (150 mL) in a continuous purge nitrogen filled glovebox was placed in a freezer (-35 °C) for 16 hours.
  • n-BuLi (10.9 mL, 27.204 mmol, 1.75 eq, 2.5 M in hexanes) was added, the dark amber solution was allowed to sit in the freezer for 20 hours, 2-iodo-1,1,1-trifluoroethane (3.8 mL, 38.863 mmol, 2.50 eq) was added neat in a quick dropwise manner, the now golden brown solution was allowed to remain in the freezer for 30 mins, removed, stirred (500 rpm) for 4 hours at 23 °C, the mixture was removed from the glovebox, neutralized with H2O (50 mL), and THF was removed via rotary evaporation.
  • the brown mixture was diluted with CH 2 Cl 2 (50 mL) and water (50 mL), poured into a separatory funnel, partitioned, organics were extracted with CH 2 Cl 2 (2 x 50 mL), combined, dried over Na 2 SO 4 , decanted, concentrated onto diatomaceous earth, and purified by silica gel chromatography using an ISCO; hexanes – 20% CH2Cl2 in hexanes to afford the iodide as a clear colorless oil (5.208 g, 12.818 mmol, 82%). NMR indicated product.
  • Example 10 Synthesis of 2-iodo-4-octyloxyphenol. 0.04310 mol, 1.00 eq) in 1,4-dioxane (50 mL) and CH 2 Cl 2 (50 mL) under nitrogen at 23 °C was added conc. HCl (25 mL).
  • the now golden brown mixture was diluted with water (100 mL) and CH2Cl2 (50 mL), poured into a separatory funnel, partitioned, organics were extracted from the aqueous using CH2Cl2 (2 x 25 mL), combined, dried over Na2SO4, decanted, concentrated, CH 2 Cl 2 (20 mL) was added, the dark brown solution was suction filtered over a pad of silica gel, rinsed with CH 2 Cl 2 (4 x 25 mL), and the filtrate was concentrated to afford the iodophenol as a clear amber oil (14.810 g, 0.04253 mol, 99%).
  • Example 11 synthesis of 1,3bis-[2-iodo-4-(octyloxy)phenoxy]propane. .20 eq), K2CO3 . g, . , . q, y . g, .
  • Example 12 synthesis of 2-iodo-4-(triethylmethyl)phenol.
  • Residual organics were extracted from the aqueous layer using CH2Cl2 (1 x 20 mL), combined, dried over solid Na2SO4, decanted, and concentrated onto diatomaceous earth, and purified via silica gel chromatography; hexanes – 15% CH 2 Cl 2 to afford the 2-iodo-4- (triethylmethyl)phenol as a clear colorless amorphous foam (1.246 g, 3.916 mmol, 43%). NMR is consistent with pure 2-iodo-4-(triethylmethyl)phenol.
  • the mixture was then removed from the mantle, allowed to cool to ambient temperature, diluted with CH 2 Cl 2 (20 mL), the mixture was suction filtered through a pad of diatomaceous earth, rinsed with CH 2 Cl 2 (4 x 20 mL), the pale golden brown filtrate solution was poured into a separatory funnel, washed with aqueous NaOH (2 x 20 mL, 1N), residual organics were extracted from the aqueous using CH2Cl2 (2 x 20 mL), dried over Na2SO4, decanted, the pale golden brown solution was concentrated onto diatomaceous earth, and purified via silica gel chromatography using an ISCO; hexanes – 30% CH 2 Cl 2 in hexanes to afford the bisiodide as a white solid (4.125 g, 6.098 mmol, 90%).
  • Example 14 synthesis of 2-iodo-4-(3 ⁇ ,5 ⁇ -di-t-butylphenyl)phenol.
  • the now white heterogeneous mixture was diluted with aqueous NaOH (100 mL, 1 N), THF was removed via rotary evaporation, the resultant white biphasic mixture was diluted with CH2Cl2 (100 mL), poured into a separatory funnel, partitioned, organics were washed with aqueous NaOH (2 x 50 mL, 1 N), residual organics were extracted from the aqueous (2 x 25 mL), combined, dried over solid Na2SO4, decanted, and concentrated.
  • Example 15 Synthesis of 4-(3,5-di-t-butylphenyl)phenoxymethyl ethyl ether. (1.645 g, 7.118 mmol, 1.00 eq), NaOH(1.281 g, 32.031 mmol, 4.50 eq), and Pd(PPh3)4 (0.823 g, 0.7118 mmol, 0.10 eq) in a flask equipped with a reflux condenser was evacuated, back-filled with nitrogen, and the evacuation/refill process was repeated 3x more.
  • Example 16 Synthesis of 2-iodo-4-(3,5-di-t-butylphenyl)phenoxymethyl ethyl ether. [00225] Prior to use, the ether was azeotropically dried using toluene (4 x 10 mL).
  • n-BuLi (3.20 mL, 7.934 mmol, 1.30 eq, 2.5 M in hexanes) was added, the amber solution was allowed to sit in the freezer for 12 hours, then 2-iodo-1,1,1-trifluoroethane (0.90 mL, 9.155 mmol, 1.50 eq) was added neat in a quick dropwise manner, the now golden brown solution was allowed to remain in the freezer for 60 mins, removed, stirred (500 rpm) for 2 hours at 23 °C, the mixture was removed from the glovebox, neutralized with H2O (50 mL), and THF was removed via rotary evaporation.
  • the golden brown mixture was diluted with CH2Cl2 (50 mL) and water (50 mL), poured into a separatory funnel, partitioned, organics were extracted with CH2Cl2 (2 x 25 mL), combined, dried over Na2SO4, decanted, concentrated onto diatomaceous earth, and purified by silica gel chromatography using an ISCO; 5% – 75% CH 2 Cl 2 in hexanes to afford the iodide as a white foam (2.783 g, 5.967 mmol, 98%). NMR indicated product.
  • Example 17 Synthesis of 2-iodo-4-(3,5-di-t-butylphenyl)phenol. and CH 2 Cl 2 (25 mL) under nitrogen at 23 °C was added conc.
  • Example 18 synthesis of 1,3-bis(2-iodo-4-(3 ⁇ ,5 ⁇ -di-t-butylphenyl)phenoxy)propane. g, . mmo, . eq) n aceone ( m ) was a e , - romopropane ( . m , .166 mmol, 1.00 eq), the mixture was equipped with a reflux condenser, placed under nitrogen, placed in a mantle heated to 60 °C, and stirred (500 rpm) for 48 hours.
  • the mixture was then removed from the mantle, allowed to cool to ambient temperature, diluted with CH2Cl2 (20 mL), the mixture was suction filtered through a pad of diatomaceous earth, rinsed with CH2Cl2 (4 x 20 mL), the pale golden brown filtrate solution was poured into a separatory funnel, washed with aqueous NaOH (2 x 20 mL, 1N), residual organics were extracted from the aqueous using CH 2 Cl 2 (2 x 20 mL), dried over Na 2 SO 4 , decanted, the pale golden brown solution was concentrated onto diatomaceous earth, and purified via silica gel chromatography using an ISCO; hexanes – 30% CH 2 Cl 2 in hexanes to afford the bisiodide as a white solid (0.844 g, 0.9852 mmol, 84%).
  • Example 19 synthesis of 2-iodo-4-(dimethyl-octyl-silyl)phenoxymethyl ethyl ether. using anhydrous toluene (4 x 10 mL).
  • the now golden yellow mixture was stirred (300 rpm) at 23 °C in the glovebox for 3 hours, removed from the glovebox, diluted with an aqueous saturated mixture of NaHCO 3 (50 mL) and Et 2 O (50 mL), poured into a separatory funnel, partitioned, residual organics were washed with an aqueous saturated mixture of NaHCO3 (2 x 25 mL), residual organics were extracted from the aqueous using Et2O (2 x 25 mL), combined, dried over solid Na2SO4, suction filtered through silica gel, rinsed with Et2O (3 x 25 mL), and the clear pale yellow solution was concentrated to afford the protected phenol as a clear pale yellow oil (4.498 g, 13.945 mmol, 80%).
  • Example 21 Synthesis of 2-iodo-4-(dimethyl-octyl-silyl)phenol. enol (0.600 g, 1.338 mmol, 1.00 eq) y 2 2 g s added a solution of BCl3 (2.70 mL, 2.676 mmol, 2.00 eq, 1 M in CH2Cl2).
  • Example 22 synthesis of 1,3-bis[2-iodo-4-(dimethyl-octyl-silyl)phenoxy]propane.
  • bromide , , 4 (0.510 g, 0.4411 mmol, 0.10 eq) in a flask equipped with a reflux condenser was evacuated, back- filled with nitrogen, and the evacuation/refill process was repeated 3x more.
  • n-BuLi (2.50 mL, 6.323 mmol, 1.30 eq, 2.5 M in hexanes) was added, the amber solution was allowed to sit in the freezer for 10 hours, then 2-iodo-1,1,1-trifluoroethane (0.72 mL, 7.2296 mmol, 1.50 eq) was added neat in a quick dropwise manner, the now golden brown solution was allowed to remain in the freezer for 60 mins, removed, stirred (500 rpm) for 2 hours at 23 °C, the mixture was removed from the glovebox, neutralized with H2O (50 mL), and THF was removed via rotary evaporation.
  • the golden brown mixture was diluted with CH 2 Cl 2 (50 mL) and water (50 mL), poured into a separatory funnel, partitioned, organics were extracted with CH 2 Cl 2 (2 x 25 mL), combined, dried over Na 2 SO 4 , decanted, concentrated onto diatomaceous earth, and purified by silica gel chromatography using an ISCO; 5% – 75% CH2Cl2 in hexanes to afford the iodide as a clear colorless oil (1.557 g, 3.442 mmol, 71%). NMR indicated product.
  • Example 27 Synthesis of 2-iodo-4-(4’-triethylmethylphenyl)phenol. eq) in 1,4- dioxane (10 mL) and CH2Cl2 (10 mL) under nitrogen at 23 °C was added conc.
  • the mixture was then removed from the mantle, allowed to cool to ambient temperature, diluted with CH 2 Cl 2 (20 mL), the mixture was suction filtered through a pad of diatomaceous earth, rinsed with CH2Cl2 (4 x 20 mL), the pale golden brown filtrate solution was poured into a separatory funnel, washed with aqueous NaOH (2 x 20 mL, 1N), residual organics were extracted from the aqueous using CH2Cl2 (2 x 20 mL), dried over Na2SO4, decanted, the pale golden brown solution was concentrated, CH2Cl2 (10 mL) was added, the solution was suction filtered through a pad of silica gel, rinsed with CH 2 Cl 2 (4 x 20 mL), and the filtrate was concentrated to afford the bisiodide as a white solid (2.150 g, 2.595 mmol, 97%).
  • Example 30 synthesis of Compound 2: a compound of formula (I) wherein R 1 , R 2 , [00253] A solid mixture of the boropinacolate ester (17.973 g, 22.403 mmol, 3.00 eq, ⁇ 70% pure), bis-iodide (5.500 g, 7.468 mmol, 1.00 eq), Pd(AmPhos)Cl2 (1.058 g, 1.494 mmol, 0.20 eq), and solid K3PO4 (14.267 g, 67.212 mmol, 9.00 eq) in a round-bottom flask equipped with a reflux condenser sealed with a rubber septa was evacuated, back-filled with nitrogen, the evacuation/nitrogen re-fill process was repeated 3x more, then freshly sparged deoxygenated 1,4-dioxane (70 mL) and H 2 O (7 mL) were added via syringe, and the resultant canary
  • Example 31 synthesis of Compound 3: a compound of formula (I) wherein R 1 , R 2 , and R 5 to R 9 are H, R 3 and R 4 are each triethylmethyl,
  • Example 32 synthesis of Compound 4: a compound of formula (I) wherein R 1 , R 2 , and R 5 to R 9 are R 3 and R 4 are each di-tert- di and each (0.390 g, 0.4552 mmol, 1.00 eq), Pd(AmPhos)Cl2 (65.0 mg, 0.09104 mmol, 0.20 eq), and solid K 3 PO 4 (0.870 g, 4.097 mmol, 9.00 eq) in a round-bottom flask equipped with a reflux condenser sealed with a rubber septa was evacuated, back-filled with nitrogen, the evacuation/nitrogen re-fill process was repeated 3x more, then freshly sparged deoxygenated 1,4-dioxane (20 mL) and H2O (2.0 mL) were added via syringe, and the resultant canary yellow mixture was placed in a mantle heated to 50 °C.
  • R 1 , R 2 , and R 5 to R 9 are R 3
  • Example 33 synthesis of Compound 5: a compound of formula (I) wherein R 1 , R 2 , and R 5 to R 9 are H, R 3 and R 4 are each CH 3 (CH 2 ) 7 ,(CH 3 ) 2 Si- (octyl-dimethyl-silyl),and each R 10 is tertiary-butyl. eq, approx.
  • Example 34 synthesis of Compound 6: a compound of formula (I) wherein R 1 , R 2 , 60% pure), bis-iodide (0.300 g, 0.3620 mmol, 1.00 eq), Pd(AmPhos)Cl2 (51.3 mg, 0.07240 mmol, 0.20 eq), and solid K 3 PO 4 (0.768 g, 3.620 mmol, 9.00 eq) in a round-bottom flask equipped with a reflux condenser sealed with a rubber septa was evacuated, back-filled with nitrogen, the evacuation/nitrogen re-fill process was repeated 3x more, then freshly sparged deoxygenated 1,4-dioxane (15 mL) and H2O (1.5 mL) were added via syringe, and the resultant canary yellow mixture was placed in a mantle heated to 50 °C.
  • Examples 35 and 36 synthesis of Precatalyst 1: a precatalyst of formula (II) wherein R 1 , R 2 , and R 5 to R 9 are H, R 3 and R 4 are each (CH 3 ) 3 CCH 2 C(CH 3 ) 2 - (“t-Octyl”), each R 10 is tertiary-butyl, M is Zr, each X is benzyl, and subscript n is 2; and Precatalyst 2: a precatalyst of formula (II) wherein R 1 , R 2 , and R 5 to R 9 are H, R 3 and R 4 are each each X is benzyl, and [00263] The thiophene ligand was azeotropically dried using PhMe (4 x 10 mL) prior to use.
  • Examples 37 and 38 synthesis of Precatalyst 3: a precatalyst of formula (II) wherein is of formula (II) wherein R 1 , R 2 , and R 5 to R 9 are H, R 3 and R 4 are each CH 3 (CH 2 ) 7 O- (octyloxy), each R 10 is tertiary-butyl, M is Hf, each X is benzyl, and subscript n is 2. mL) in a continuous purge, nitrogen filled glovebox at 23 °C was added a solution of ZrBn4 (62.1 mg, 0.1362 mmol, 1.10 eq) in PhMe (5.0 mL) in a dropwise manner.
  • formula (II) is of formula (II) wherein R 1 , R 2 , and R 5 to R 9 are H, R 3 and R 4 are each CH 3 (CH 2 ) 7 O- (octyloxy), each R 10 is tertiary-butyl,
  • the thiophene ligand was azeotropically dried using PhMe (4 x 10 mL) prior to use.
  • PhMe x 10 mL
  • Examples 39 and 40 synthesis of Precatalyst 5: a precatalyst of formula (II) wherein R 1 , R 2 , and R 5 to R 9 are H, R 3 and R 4 are each triethylmethyl, each R 10 is tertiary-butyl, M is Zr, each X is benzyl, and subscript n is 2; and
  • Precatalyst 6 a precatalyst of formula (II) wherein R 1 , R 2 , and R 5 to R 9 are H, R 3 and R 4 are each triethylmethyl, each R 10 is tertiary- butyl, M is Hf, each X is benzyl, and subscript n is 2
  • the thiophene ligand was azeotropically dried using PhMe (4 x 10 mL) prior to use.
  • Examples 41 and 42 synthesis of Precatalyst 7: a precatalyst of formula (II) wherein R 1 , R 2 , and R 5 to R 9 are H, R 3 and R 4 are each 3,5-di-(t-butyl)phenyl, each R 10 is tertiary-
  • Precatalyst 8 a precatalyst of formula are each 3,5-di-(t-butyl)phenyl, each R 10 is tertiary-butyl, M is Hf, each X is benzyl, and subscript n is 2.
  • Examples 43 and 44 synthesis of Precatalyst 9: a precatalyst of formula (II) wherein R 1 , R 2 , and R 5 to R 9 are H, R 3 and R 4 are each CH 3 (CH 2 ) 7 ,(CH 3 ) 2 Si- (octyl-dimethyl-silyl), each R 10 is tertiary-butyl, M is Zr, each X is benzyl, and subscript n is 2; and Precatalyst 10: a precatalyst of formula (II) wherein R 1 , R 2 , and R 5 to R 9 are H, R 3 and R 4 are each Hf, each X is
  • the thiophene ligand was azeotropically dried using PhMe (4 x 10 mL) prior to use.
  • PhMe x 10 mL
  • Examples 45 and 46 synthesis of Precatalyst 11: a precatalyst of formula (II) wherein R 1 , R 2 , and R 5 to R 9 are H, R 3 and R 4 are each 4-(triethylmethyl)phenyl (4-Et 3 C-Ph), each is tertiary-butyl, M is Zr, each X is benzyl, and subscript n is 2; and Precatalyst 12: a precatalyst of formula (II) wherein R 1 , R 2 , and R 5 to R 9 are H, R 3 and R 4 are each 4- (triethylmethyl)phenyl (4-Et 3 C-Ph), each R 10 is tertiary-butyl, M is Hf, each X is benzyl, and subscript n is 2.
  • the thiophene ligand was azeotropically dried using PhMe (4 x 10 mL) prior to use.
  • PhMe x 10 mL
  • Examples 47 synthesis of Precatalyst 13: a precatalyst of formula (II) wherein R 1 , R 5 R 9 R 3 R 4 R 10
  • a clear colorless solution of the thiophene (53.6 mg, 0.04337 mmol, 1.00 eq) in PhMe (20.1 mL) in a continuous purge, nitrogen filled glovebox at 23 °C was added a solution of ZrBn2Cl2 (20.0 mg, 0.04771 mmol, 1.10 eq) in PhMe (1.60 mL) in a dropwise manner.
  • Examples 48 to 60 spray-drying precatalysts to make spray-dried supported catalyst systems.
  • Supported catalyst systems described in TABLE 3 above were made and spray-dried in a nitrogen-purged glove box.
  • CabosilTM TS-610 fumed silica was slurried in toluene until well dispersed, then a 10 % solution by weight of MAO in toluene was added. The mixture was stirred magnetically 15 minutes, then the metal-ligand complex was added to the resulting slurry, and the mixture was stirred for 30 to 60 minutes.
  • TABLE 4 contains the amounts of the metal-ligand complex, fumed silica, 10% MAO solution, and toluene used to make each of the spray-dried supported catalyst systems 1 to 13. Quantities of reagents used are listed below in TABLE 4. [00284] TABLE 4: Precatalyst Fumed 10% MAO Weight, Silica, solution, Toluene, Spray- Actual Actual Actual Ex.
  • the spray dried catalysts described in TABLE 4 were used to catalyze gas phase polymerizations of ethylene monomer and 1-hexene comonomer to give ethylene/1-hexene copolymers (also called poly(ethylene-co-1-hexene) copolymers).
  • the gas phase polymerizations conducted in a 2 liter (L), semi-batch, stainless steel autoclave gas phase polymerization reactor equipped with a mechanical agitator. For each polymerization run, the reactor was first dried (“baked out”) for 1 hour by charging the reactor with 200 grams (g) of NaCl, and heating the reactor contents at 100 °C under dry nitrogen for 30 minutes.
  • the reactor temperature was brought to a predetermined polymerization temperature, typically 90° C. or 100° C. is used for these experiments, but any temperature from 75° to 115° C. may be used, and maintained at this polymerization temperature while keeping the ethylene, 1-hexene, and hydrogen feed ratios consistent for 1 hour.
  • a predetermined polymerization temperature typically 90° C. or 100° C. is used for these experiments, but any temperature from 75° to 115° C. may be used, and maintained at this polymerization temperature while keeping the ethylene, 1-hexene, and hydrogen feed ratios consistent for 1 hour.
  • the feeds of hydrogen, 1-hexene, and ethylene were stopped, the reactor was cooled down, vented and opened.
  • the resulting product mixture was washed with water and methanol, then dried to give the ethylene/1-hexene copolymer. The weight of the copolymer was recorded.
  • Catalyst productivity (grams copolymer/gram catalyst-hour) and catalyst efficiency (grams copolymer/gram catalyst metal (Zr or Hf)) were determined to compare the amount of copolymer produced, based on ethylene and hexene uptake/consumption, relative to the amount of supported catalyst system added to the reactor.
  • the copolymer samples were characterized by DSC and melt flow.
  • the polymerization run conditions and results are listed in the following TABLES. [00287] TABLE 5.
  • the inventive catalysts can produce polyethylene copolymers with medium-to-ultra-high weight average molecular weight (Mw up to 1,300,000 g/mol), high Mz (up to 3,981,900 g/mol), broad molecular weight distribution (MWD) or polydispersity index (PDI), up to 10, broad Mw/Mz, up to 10.8, and high comonomer incorporation (up to 11 wt%).
  • Mw medium-to-ultra-high weight average molecular weight
  • Mz up to 3,981,900 g/mol
  • MWD broad molecular weight distribution
  • PDI polydispersity index
  • up to 10 broad Mw/Mz up to 10.8, and high comonomer incorporation (up to 11 wt%).
  • Mw and Mz may be lowered by increasing the temperature as well as the H2/C2 and/or C6/C2 ratio used in the reactor.
  • LCBf is a measurement, or quantification, of the number of long-chain branches per 1000 carbon atoms (LCB/1000C) based on analysis of Mark-Houwink plots as shown in Figures 5 to 15, where the higher the LCBf, the higher the amount of long- chain branching.
  • a model fit for LCBf was calculated using Microsoft Solver using Equation 1 below to fit a model curve to the experimental data, where the Log(IV) is calculated at a given log(Mw) (a) of a sample with an LCBf (b), weight percent comonomer (c) and number of carbons in comonomer (d). Equation 1 (Eq.
  • a precatalyst of formula (II) is provided either in neat form, or as a solution thereof dissolved in toluene, or as a solid form wherein the precatalyst is already supported on spray-dried activator/hydrophobic fumed silica solids, wherein the activator is methylaluminoxane.
  • This supported activator is called “SMAO” herein and is white in color.
  • Unsupported precatalysts are diluted to 4.21 millimolar (mM) concentration in anhydrous deoxygenated toluene, and pipetted into oven-dried 4 mL or 8 mL scintillation vials containing a pre-weighed amount of the SMAO such that the resultant slurry has a catalyst formulation of 45 micromoles ( ⁇ mol) Zr atom or Hf atom, as the case may be, per 1.0 grams (g) SMAO, unless otherwise noted.
  • the slurry is stirred at 300 rotations per minute (rpm) and heated to 50 °C for 30 minutes, then returned to room temperature to give a slurry of an undried supported catalyst system (“ud-SCS”) in toluene.
  • rpm rotations per minute
  • ud-SCS undried supported catalyst system
  • the prepared reactor cells were partially filled (to an appropriate solvent level) with an isoparaffin hydrocarbon (“solvent”, Isopar-E from ExxonMobil), and olefin comonomer (for these experiments 1-hexene) using a robotic needle to later give a final total volume of 5 mL in each reactor cell (once all of the reagent solutions are added later).
  • solvent isoparaffin hydrocarbon
  • the reactor cells were heated to a target starting-the-polymerization temperature (in these experiments, 100 °C) and the stirring rate was increased.
  • the reactor cells When the temperature of the reactor cells reached the starting-the polymerization temperature, which required about 10-30 minutes of heating, the reactor cells were pressurized to a target starting the polymerization pressure with either pure ethylene, or a gas mixture of ethylene and hydrogen from a gas accumulator, and until the solvent was saturated with the pure ethylene or the gas mixture, respectively, (as observed by the gas uptake). If the gas mixture of ethylene and hydrogen was used, once the solvent was saturated in all cells, the gas feed line was switched from the accumulator to pure ethylene for the remainder of the polymerization run.
  • the desired pressure (within approximately 2-6 psig) was maintained by adding supplemental amount of ethylene gas by opening the valve at the target pressure minus 2 psi and closing the valve when the pressure reached 2 psi above target pressure. All drops in reactor cell pressure were cumulatively recorded as uptake of ethylene for the duration of the run.
  • the slurry phase polymerization reactions proceeded for 90 minutes or to an ethylene uptake of 90 psi, whichever occurred first, and then were quenched by adding a 60 psi overpressure of 10% (v/v) CO 2 in argon. Data collection of each cell continued for 5 minutes after the quench. After the last cell finished quenching, any potential gas leaks were identified from the cell pressure and ethylene uptake curves were noted.
  • HT-HT-GPC High Throughput High Temperature Gel Permeation Chromatography
  • Decane (10 ⁇ L) was added to each sample for use as an internal flow marker.
  • Samples were first diluted in 1,2,4- trichlorobenzene (TCB) stabilized with 300ppm butylated hydroxyl toluene (BHT) at a concentration of 10mg/mL and dissolved by stirring at 160°C for 120 minutes. Prior to injection samples were further diluted with TCB stabilized with BHT to a concentration of 2 mg/mL.
  • TCB 1,2,4- trichlorobenzene
  • BHT butylated hydroxyl toluene
  • ud-SCS undried supported catalyst system, which is prepared according to the procedure of Synthesis of Undried Supported Catalyst Systems for slurry phase polymerization.
  • the quench time is the time it takes to consume 90 psi of ethylene during the experiment, where the faster the time, the more active the catalyst.
  • SCS 1, SCS 2, and SCS 3 each exhibit significantly high activity in slurry polymerization process as indicated by the low catalyst loading (10 - 25 nmol) combined with the fast quench time (143 – 1,103 s) in the slurry polymerization process.
  • inventive supported catalysts can produce ethylene/hexene copolymers with high Mw (> 100,000 g/mol under these conditions for PPR process), high Mz, copolymers with broad PDI ( ⁇ 4.0 for PPR process) as well as Mz/Mw, and high 1-hexene incorporation ( ⁇ 3.0 wt% under these conditions for slurry PPR process).

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Abstract

Sont divulgués un système de catalyseur supporté comprenant un composé de 2-hydroxythiophène substitué et un matériau de support ; et un procédé de fabrication du système de catalyseur supporté ; sont divulgués également un procédé de polymérisation en phase gazeuse ou en suspension épaisse utilisant le système de catalyseur supporté ; et une polyoléfine fabriquée par le procédé de polymérisation en phase gazeuse ou en phase de suspension épaisse. Sont divulgués en outre, un composé 2-hydroxythiophène substitué et un précatalyseur comprenant le composé 2-hydroxythiophène substitué, un atome métallique et un groupe partant. Sont divulgués par ailleurs, des procédés de fabrication du précatalyseur et du composé 2-hydroxythiophène substitué.
PCT/US2024/030820 2023-06-08 2024-05-23 Catalyseurs de polymérisation d'oléfines supportés comprenant des composés 2-hydroxythiophène substitués WO2024253863A1 (fr)

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