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WO2025171248A1 - Système catalytique pour polyéthylène et procédé associé - Google Patents

Système catalytique pour polyéthylène et procédé associé

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Publication number
WO2025171248A1
WO2025171248A1 PCT/US2025/014993 US2025014993W WO2025171248A1 WO 2025171248 A1 WO2025171248 A1 WO 2025171248A1 US 2025014993 W US2025014993 W US 2025014993W WO 2025171248 A1 WO2025171248 A1 WO 2025171248A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
ethylene
catalyst system
butyl
olefin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2025/014993
Other languages
English (en)
Inventor
Angela I. Padilla-Acevedo
Chuan C. HE
Timothy R. Lynn
Roger L. Kuhlman
Rujul M. MEHTA
John F. Szul
Manjiri R. PARADKAR
Bo Liu
Eduardo Garcia
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
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Filing date
Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of WO2025171248A1 publication Critical patent/WO2025171248A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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

  • Gas-phase single reactor bimodal technologies provide for the synthesis of olefin terpolymers (and ethylene/a-olefin terpolymers in particular) polymerized with a high molecular weight component and a low molecular weight component.
  • utilization of a single polymerization reactor limits the comonomer distribution across the high molecular weight component (“HMW”) and the low molecular weight component (“LMW”) of the bimodal terpolymer.
  • Bimodal polymers with proportionally more comonomer content in the HMW component are known to exhibit an improved balance of various product properties, such as improved balance of slow crack growth resistance (SCGR) and long-term hydrostatic test performance (for pipes); improved balance of environmental stress cracking resistance (ESCR) and swell properties for (blow molded articles); and improved balance of ESCR and processability for wire and cable applications.
  • SCGR slow crack growth resistance
  • ESCR environmental stress cracking resistance
  • swell properties for (blow molded articles)
  • wire and cable applications are known to exhibit an improved balance of various product properties, such as improved balance of slow crack growth resistance (SCGR) and long-term hydrostatic test performance (for pipes); improved balance of environmental stress cracking resistance (ESCR) and swell properties for (blow molded articles); and improved balance of ESCR and processability for wire and cable applications.
  • the art recognizes the need for olefin-based polymer (and ethylene/a-olefin polymers in particular) synthesis performed in a single gas-phase reactor, the ethylene/a-olefin polymer having improved comonomer distribution across the HMW component and the LMW component.
  • the art further recognizes the need for improved catalyst lifetime as a function of residence time.
  • the present disclosure provides a catalyst system.
  • the catalyst system includes (A) a first catalyst and (B) a trim catalyst.
  • the trim catalyst includes a phenoxy imine catalyst selected from (i) bis(2,4-di-tert-butyl-6 isopropylamino phenoxy imine) zirconium dibenzyl and (ii) bis(2,4-di-tert-butyl-6 isopropylamino phenoxy imine) zirconium dichloride.
  • the catalyst system also includes (C) at least one spray-dried methylaluminoxane activator.
  • the process includes polymerizing ethylene with one or more olefins, under polymerization conditions, with a catalyst system.
  • the catalyst system includes (A) a first catalyst and (B) a trim catalyst.
  • the trim catalyst includes a phenoxy imine catalyst selected from (i) bis(2,4-di-tert-butyl-6 isopropylamino phenoxy imine) zirconium dibenzyl and (ii) bis(2,4-di-tert-butyl-6 isopropylamino phenoxy imine) zirconium dichloride.
  • the catalyst system also includes (C) at least one spray-dried methylaluminoxane activator.
  • the process includes forming a bimodal ethylene/olefin terpolymer composition.
  • the numerical ranges disclosed herein include all values from, and including, the lower and upper value.
  • explicit values e.g., 1 or 2; or 3 to 5; or 6; or 7
  • any subrange between any two explicit values is included (e.g., 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).
  • Bimodal refers to two, and only two, modalities, or modes.
  • a "bimodal catalyst system” is a catalyst system that contains two different catalysts for catalyzing the same polymerization process (e.g., olefin polymerization) and producing a bimodal polymer composition. Catalysts are different if they differ from each other in at least one of the following characteristics: (a) their catalytic metals are different (Ti versus Zr, Zr versus Hf, Ti versus Hf; not activator metals such as Al); (b) one catalyst has a functional ligand covalently bonded to its catalytic metal and the other catalysts are free of functional ligands bonded to its catalytic metal; (c) the catalysts have functional ligands covalently bonded to their catalytic metal and the structures of at least one of functional ligand of one of the catalysts is different than the structure of each of the functional ligand(s) of the other catalyst (e.g., cyclopentadienyl versus propylcyclopentadie
  • a "bimodal polymer composition” is a composition composed of (i) high molecular weight component (“HMW”), and (iii) low molecular weight component (LMW”), wherein the high molecular weight component consists of a first group of polymer macromolecules made by a first catalyst, and the low molecular weight component consists of a second group of polymer macromolecules made by a second catalyst, wherein at least one of the following differences are present: (a) the catalysts are different in catalytic metal and/or ligand composition; (b) the polymerization reaction making the higher molecular weight component is done at a different time than the polymerization reaction making the lower molecular weight component; (c) at least one of the first set of molecular weight-effective polymerization process conditions is different than one of the second set of molecular weight-effective polymerization process conditions.
  • HMW high molecular weight component
  • LMW low molecular weight component
  • Bimodal polymer compositions are in-reactor blends.
  • the bimodal polymer composition may be characterized by two peaks separated by a distinguishable local minimum therebetween in a plot of dW/dlog(MW) on the y-axis versus Log(MW) on the x-axis to give a Gel Permeation Chromatograph (GPC) chromatogram, wherein Log(MW) and dW/dlog(MW) are as defined herein and are measured by Gel Permeation Chromatograph (GPC) Test Method described herein.
  • GPC Gel Permeation Chromatograph
  • a "catalyst” is a material that enhances rate of a reaction (e.g., the polymerization of ethylene and a-olefin, for example) and is not completely consumed thereby.
  • a "catalyst system” is a combination of a catalyst per se and a companion material such as a modifier compound for attenuating reactivity of the catalyst, a support material on which the catalyst is disposed, a carrier material in which the catalyst is disposed, or a combination of any two or more thereof, or a reaction product of a reaction thereof.
  • compositions claimed through use of the term “comprising” may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary.
  • the term “consisting essentially of” excludes from the scope of any succeeding recitation any other component, step, or procedure, excepting those that are not essential to operability.
  • the term “consisting of” excludes any component, step, or procedure not specifically delineated or listed.
  • An "ethylene-based polymer” or “ethylene polymer” is a polymer that contains a majority amount, or greater than 50 mol%, of polymerized ethylene based on the weight of the polymer, and, optionally, may comprise at least one comonomer.
  • An "ethylene/a-olefin interpolymer” is an interpolymer that contains a majority amount of polymerized ethylene, based on the mole percent of the interpolymer, and at least one a-olefin.
  • a "feed” is a quantity of reactant or reagent that is added or “fed” into a reactor. In continuous polymerization operation, each feed independently may be continuous or intermittent. The quantities or “feeds” may be measured, e.g., by metering, to control amounts and relative amounts of the various reactants and reagents in the reactor at any given time.
  • a “feed line” is a pipe or conduit structure for transporting a feed.
  • a "hydrocarbon” is a compound that contains only hydrogen and carbon atoms.
  • interpolymer is a polymer prepared by the polymerization of at least two different types of monomers.
  • the generic term interpolymer thus includes copolymers (employed to refer to polymers prepared from two different types of monomers), terpolymers (employed to refer to polymers prepared from three different types of monomers), and polymers prepared from more than three different types of monomers.
  • a "metallocene catalyst” is a homogeneous or heterogeneous material that contains a cyclopentadienyl ligand-metal complex and enhances olefin polymerization reaction rates.
  • Each metal is a transition metal Ti, Zr, or Hf.
  • Each cyclopentadienyl ligand independently is an unsubstituted cyclopentadienyl group or a hydrocarbyl-substituted cyclopentadienyl group.
  • the metallocene catalyst has two cyclopentadienyl ligands, and at least one, alternatively both of the cyclopentenyl ligands independently is a hydrocarbyl-substituted cyclopentadienyl group.
  • Each hydrocarbyl-substituted cyclopentadienyl group may independently have 1, 2, 3, 4, or 5 hydrocarbyl substituents.
  • Each hydrocarbyl substituent may independently be a (Ci - C4) alkyl. Two or more substituents may be bonded together to form a divalent substituent, which with carbon atoms of the cyclopentadienyl group may form a ring.
  • an "olefin-based polymer” or “polyolefin” is a polymer that contains a majority amount, or greater than 50 mol%, of polymerized olefin monomer, for example, ethylene or propylene, (based on the weight of the polymer), and optionally, may contain at least one comonomer.
  • polymerized olefin monomer for example, ethylene or propylene, (based on the weight of the polymer), and optionally, may contain at least one comonomer.
  • Nonlimiting examples of an olefin-based polymer include an ethylene-based polymer and a propylene-based polymer.
  • a "polymer” is a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
  • the generic term polymer thus embraces the term “homopolymer” (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure), and the term “interpolymer.”
  • a "copolymer” is a polymer having two polymer units that are different from each other.
  • a “terpolymer” is a polymer having two or more polymer units that are different from each other. "Different" in reference to polymer units indicates that the polymer units differ from each other by at least one atom or are different isomerically.
  • a "polymerization process” is a process that is utilized to make a polymer.
  • the polymerization process can be a gas-phase or slurry-phase polymerization process.
  • the polymerization process consists of a gas-phase polymerization process.
  • the polymerization process consists of a slurryphase polymerization process.
  • Trace amounts of impurities, for example, catalyst residues, may be incorporated into and/or within the polymer. It also embraces all forms of copolymer, e.g., random, block, etc.
  • Nonlimiting examples of properties modified by the trim catalyst include density, melt index I2, flow index I21, melt flow ratio, molecular mass dispersity (M w /M n /M z ), and any combination thereof.
  • a "unimodal catalyst system” is a catalyst system that contains one catalyst for catalyzing a polymerization process (e.g., olefin polymerization) and producing a unimodal polymer composition. As described herein the catalyst of the unimodal catalyst system may be a trim catalyst that is introduced to an activator in the gas phase polymerization reactor.
  • the present disclosure provides a catalyst system.
  • the catalyst system includes (A) a first catalyst and (B) a trim catalyst.
  • the trim catalyst includes a phenoxy imine catalyst selected from (i) bis(2,4-di-tert-butyl-6 isopropylamino phenoxy imine) zirconium dibenzyl ("Fl-A") and/or (ii) bis(2,4-di-tert-butyl-6 isopropylamino phenoxy imine) zirconium dichloride (“Fl-B”).
  • the catalyst system also includes (C) at least one spray-dried methylaluminoxane activator.
  • the catalyst system includes the first catalyst.
  • the first catalyst is a nonmetallocene catalyst, a metallocene catalyst, and combinations thereof.
  • a "non-metallocene catalyst,” is a catalyst that is not a metallocene catalyst.
  • a non-metallocene catalyst is a catalyst that does not include a cyclopentadienyl ligand— metal complex.
  • a nonlimiting example for the non-metallocene catalyst includes bis (2- pentamethylphenylamido)ethyl)-amine zirconium dibenzyl).
  • Nonlimiting examples for the metallocene catalyst include methylcyclopentadienyl)(l,3-dimethyl-4,5,6,7-tetrahydroindenyl)zirconium dimethyl, 5- cyclopentadienyl)(/75-l,5-dimethylindenyl)di methylzirconium or (r 5-l,5- dimethylindenyl)dimethylzirconium, and bis(n-butylcyclopentadienyl)zirconium dimethyl.
  • the catalyst system includes the trim catalyst.
  • the trim catalyst in the inventive examples is a phenoxy imine catalyst.
  • the phenoxy imine catalyst is selected from (i) bis(2,4-di- tert-butyl-6 isopropylamino phenoxy imine) zirconium dibenzyl ("Fl-A") having the Formula I below and/or (ii) bis(2,4-di-tert-butyl-6 isopropylamino phenoxy imine) zirconium dichloride (“Fl- B”) having the Formula II below:
  • the catalyst system also includes an activator.
  • activator refers to any compound or combination of compounds, supported, or unsupported, which can activate a complex or a catalyst component, such as by creating a cationic species of the catalyst component. For example, this can include the abstraction of at least one leaving group, e.g., from the zirconium metal center of the complex/catalyst component, e.g., the metal complex of Formula I and/or Formula II.
  • leaving group refers to one or more chemical moieties bound to a metal atom and that can be abstracted by an activator, thus producing a species active towards olefin polymerization.
  • the activator can include a Lewis acid or a non-coordinating ionic activator or ionizing activator, or any other compound including Lewis bases, aluminum alkyls, and/or conventional-type co-catalysts.
  • illustrative activators can include, but are not limited to, aluminoxane or modified aluminoxane, and/or ionizing compounds, neutral or ionic, such as Dimethylanilinium tetrakis(pentafluorophenyl)borate, Triphenylcarbenium tetrakis(pentafluorophenyl)borate, Dimethylanilinium tetrakis(3,5-(CF3)2phenyl)borate, Triphenylcarbenium tetrakis(3,5-(CF3)2phenyl)borate, dimethylanilinium te
  • the activator is an aluminoxane.
  • An "aluminoxane” is an oligomeric aluminum compound having -AI(R)-0- subunits, where R is an alkyl group.
  • Aluminoxanes can be produced by the hydrolysis of the respective trialkylaluminum compound.
  • MMAO can be produced by the hydrolysis of trimethylaluminum and a higher trialkylaluminum, such as triisobutylaluminum.
  • the aluminoxane can include a modified methyl aluminoxane ("MMAO") type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylaluminoxane type 3A, discussed in U.S. Patent No. 5,041,584).
  • a source of MAO can be a solution having from about 1 wt. % to about a 50 wt. % MAO, for example.
  • Commercially available MAO solutions can include the 10 wt. % and 30 wt. % MAO solutions available from Albemarle Corporation, of Baton Rouge, LA.
  • One or more organo-aluminum compounds such as one or more alkylaluminum compound, can be used in conjunction with the aluminoxanes.
  • alkylaluminum compounds include, but are not limited to, diethylaluminum ethoxide, diethylaluminum chloride, diisobutylaluminum hydride, and combinations thereof.
  • alkylaluminum compounds e.g., trialkylaluminum compounds
  • examples of other alkylaluminum compounds include, but are not limited to, trimethylaluminum, triethylaluminum (“TEAL”), triisobutylaluminum (“TiBAI”), tri-n- hexylaluminum, tri-n-octylaluminum, tripropylaluminum, tributylaluminum, and combinations thereof.
  • the support may be a porous support material, for example, talc, an inorganic oxide, or an inorganic chloride.
  • Other support materials include resinous support materials, e.g., polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.
  • Support materials include inorganic oxides that include Group 2, 3, 4, 5, 13 or 14 metal oxides. Some preferred supports include silica, fumed silica, alumina, silica-alumina, and mixtures thereof. Some other supports include magnesia, titania, zirconia, magnesium chloride, montmorillonite, phyllosilicate, zeolites, talc, clays) and the like. Also, combinations of these support materials may be used, for example, silica-chromium, silica- alumina, silica-titania and the like. Additional support materials may include porous acrylic polymers, nanocomposites, aerogels, spherulites, and polymeric beads.
  • a nonlimiting example of a support is fumed silica available under the trade name CabosilTM TS- 610, or other TS- or TG-series support, available from Cabot Corporation.
  • Fumed silica is typically a silica with particles 7 to 30 nanometers in size that has been treated with dimethylsilyldichloride such that a majority of the surface hydroxyl groups are capped.
  • the support material has a surface area in the range from 10 to 700 m 2 /g, pore volume in the range from 0.1 to 4.0 g/cm 3 and an average particle size in the range from 5 to 500 microns. More preferably, the surface area of the support material is in the range from 50 to 500 m 2 /g, pore volume from 0.5 to 3.5 g/cm 3 and average particle size of from 10 to 200 microns. Most preferably the surface area of the support material is in the range from 100 to 400 m 2 /g, pore volume from 0.8 to 3.0 g/cm 3 and average particle size is from 5 to 100 microns.
  • the average pore size of the support material typically has pore size in the range of from 10 to 1000 Angstroms (A) or from 50 to 500A, or from 75 to 350A.
  • the solid support may be an uncalcined material or a calcined material prior to being contacted with the activator.
  • the solid support material may be a hydrophobic fumed silica (e.g., a fumed silica treated with dimethyldichlorosilane).
  • the activator spray-dried to the support may be in the form of a powdery, free-flowing particulate solid.
  • the activator is methylaluminoxane spray-dried to a hydrophobic fumed silica support.
  • the catalyst system includes (A) the first catalyst that is a metallocene catalyst, (B) the trim catalyst (Fl-A and/or Fl-B), and (C) methylaluminoxane activator spray-dried on a fumed silica support.
  • the metallocene catalyst include metallocene Y-123, H-15 and B.
  • the first catalyst is spray-dried to a support.
  • the support may be any support material as previously disclosed herein.
  • the support for the non- metallocene/metallocene catalyst is selected from silica, fumed silica, alumina, silica-alumina, and mixtures thereof.
  • Some other supports include magnesia, titania, zirconia, magnesium chloride, montmorillonite, phyllosilicate, zeolites, talc, clays) and the like.
  • combinations of these support materials may be used, for example, silica-chromium, silica- alumina, silica-titania and the like.
  • Additional support materials may include porous acrylic polymers, nanocomposites, aerogels, spherulites, and polymeric beads.
  • the support for first catalyst is fumed silica.
  • trim catalyst (the phenoxy imine catalyst) is dissolved in an alkane solvent (such as hexane for example) and/or mineral oil.
  • the phenoxy imine catalyst is present from 0.5 wt% to 4.0 wt%, or from 0.5 wt% to 1.5 wt%, or 1.0 wt% wherein weight percent is based on the total weight of the phenoxy imine catalyst and solvent.
  • the trim catalyst/solvent is injected into the polymerization reactor before, during, or after the introduction of the first catalyst and/or activator into the polymerization reactor.
  • the phenoxy imine catalyst is unsupported.
  • the trim catalyst is supported and is spray-dried to a fumed silica support.
  • the supported trim catalyst is introduced into the polymerization reactor before, during, or after the introduction of the first catalyst and/or activator into the polymerization reactor.
  • the present disclosure provides a process.
  • the process includes polymerizing ethylene with one or more olefins, under polymerization conditions, with a catalyst system composed of (A) the first catalyst, (B) the trim catalyst and (C) the activator.
  • the first catalyst is a non-metallocene catalyst or a metallocene catalyst as disclosed above.
  • the trim catalyst is a phenoxy imine catalyst selected from (i) bis(2,4-di-tert-butyl-6 isopropylamino phenoxy imine) zirconium dibenzyl and/or (ii) bis(2,4-di-tert-butyl-6 isopropylamino phenoxy imine) zirconium dichloride.
  • the catalyst system also includes at least one spray-dried methyl aluminoxane activator.
  • the process includes forming a bimodal ethylene/olefin terpolymer composition.
  • polymerization conditions refers to a combination of variables that may affect a polymerization reaction in a fluidized bed, gas-phase polymerization reactor ("FB-GPP reactor") reactor or a composition or property of a polymer composition product made thereby.
  • FB-GPP reactor gas-phase polymerization reactor
  • the variables may include reactor design and size, catalyst composition and amount; reactant composition and amount; molar ratio of different reactants; presence or absence of feed gases such as H2 and/or O2, molar ratio of feed gases versus reactants, absence or concentration of interfering materials (e.g., H2O), absence or presence of an induced condensing agent (ICA), average polymer residence time in the reactor, partial pressures of constituents, feed rates of monomers, reactor bed temperature (e.g., fluidized bed temperature), nature or sequence of process steps, time periods for transitioning between steps. Variables other than those being described or changed by the process may be kept constant.
  • the present polymerization conditions utilize a gas-phase polymerization (GPP) reactor, such as a stirred-bed gas phase polymerization reactor (SB-GPP reactor) or a fluid ized- bed gas- phase polymerization reactor (FB-GPP reactor), to make the polymer composition.
  • GPP gas-phase polymerization
  • SB-GPP reactor stirred-bed gas phase polymerization reactor
  • FB-GPP reactor fluid ized- bed gas- phase polymerization reactor
  • the FB-GPP reactor/method may be as described in US 3,709,853; US 4,003,712; US 4,01 1 ,382; US 4,302,566; US 4,543,399; US 4,882,400; US 5,352,749; US 5,541 ,270; EP-A-0802 202; and Belgian Patent No. 839,380.
  • SB-GPP and FB-GPP polymerization reactors and processes either mechanically agitate or fluidize by continuous flow of gaseous monomer and diluent the polymerization medium inside the reactor, respectively.
  • Other useful reactors/processes contemplated include series or multistage polymerization processes such as described in US 5,627,242; US 5,665,818; US 5,677,375; EP-A-0794 200; EP-B1 -0 649 992; EP- A-0802 202; and EP-B-634421.
  • the following variables can be adjusted and/or controlled in a GPP, SB-GPP, or FB-GPP.
  • Individual flow rates of ethylene (“Cz”), hydrogen (“Hz”) and olefin (such as 1 -hexene (“Cs”)) are controlled to maintain a fixed comonomer to ethylene monomer gas molar ratio (Ce/Cz) equal to a described value, a constant hydrogen to ethylene gas molar ratio (“Hz/Cz”) equal to a described value, and a constant ethylene (“Cz”) partial pressure equal to a described value.
  • Cz comonomer to ethylene monomer gas molar ratio
  • Hz/Cz constant hydrogen to ethylene gas molar ratio
  • Cz constant ethylene
  • Concentrations of gases are measured by an in-line gas chromatograph to maintain the composition in the recycle gas stream.
  • a reacting bed of growing polymer particles is maintained in a fluidized state by continuously flowing a make-up feed and recycle gas through the reaction zone.
  • the FB-GPP reactor is operated at a total pressure from 1861 kilopascals (kPa) to 2413 kPa (270 pounds per square inch-gauge (psig) to 350 psig) and at a described first reactor bed temperature RBT.
  • Start-up or restart of the GPP reactor may be illustrated with a fluidized bed, GPP reactor.
  • the start-up of a recommissioned FB-GPP reactor (cold start) or restart of a transitioning FB-GPP reactor (warm start) includes a time period that is prior to reaching steadystate polymerization conditions of step (a).
  • Start-up or restart may include the use of a polymer seedbed preloaded or loaded, respectively, into the fluidized bed reactor.
  • the polymer seedbed may be composed of powder of a polyethylene such as a polyethylene homopolymer or previously made batch of the bimodal polymer composition.
  • the FB-GPP reactor is a commercial scale reactor such as a UNIPOLTM reactor or UNIPOLTM II reactor, which are available from Univation Technologies, LLC, a subsidiary of The Dow Chemical Company, Midland, Michigan, USA.
  • the polymerization conditions may further include one or more additives such as a chain transfer agent or a promoter.
  • the chain transfer agent may be an alkyl metal such as diethyl zinc. Promoters are known such as in US 4,988,783 and may include chloroform, CFCI3, trichloroethane, and difluorotetrachloroethane.
  • a scavenging agent Prior to reactor start up, a scavenging agent may be used to react with moisture and during reactor transitions a scavenging agent may be used to react with excess activator. Scavenging agents may be a trialkylaluminum. Gas phase polymerizations may be operated free of (not deliberately added) scavenging agents.
  • the polymerization conditions for gas phase polymerization reactor/method may further include an amount (e.g., 0.5 to 200 ppm based on all feeds into reactor) of a static control agent and/or a continuity additive such as aluminum stearate or polyethyleneimine.
  • a static control agent may be added to the FB- GPP reactor to inhibit formation or buildup of static charge therein.
  • the process includes contacting the activator with the trim catalyst.
  • Each contacting step between activator and catalyst independently may be done either (a) in a separate vessel outside the GPP reactor (e.g., outside the FB-GPP reactor), (b) in a feed line to the GPP reactor, and/or (c) inside the GPP reactor (in situ).
  • the catalyst system once its catalysts are activated, may be fed into the GPP reactor as a dry powder, alternatively as a slurry in a non-polar, aprotic (hydrocarbon) solvent.
  • the catalyst system may be fed into the reactor prior to activation via a first feed line, the first activator may be fed into the reactor via a second feed line, the trim catalyst may be fed into the reactor via a third feed line, and the second activator may be feed into the reactor via a fourth feed line. Any two of the first to fourth feed lines may be the same or different.
  • the activator(s) may be fed into the reactor in "wet mode" in the form of a solution thereof in an inert liquid such as mineral oil or toluene, in slurry mode as a suspension, or in dry mode as a powder.
  • the process includes polymerizing, or otherwise contacting, ethylene with one or more olefins, under polymerization conditions, with the catalyst system.
  • an "olefin” refers to a linear, branched, or cyclic compound including carbon and hydrogen and having at least one double bond.
  • the olefin present in such polymeror copolymer is the polymerized form of the olefin.
  • a copolymer when a copolymer is said to have an ethylene content of 75 wt% to 85 wt%, it is understood that the polymer unit in the copolymer is derived from ethylene in the polymerization reaction and the derived units are present at 75 wt% to 85 wt%, based upon the total weight of the polymer.
  • a higher a-olefin refers to an a-olefin having 3 or more carbon atoms.
  • the one or more olefins include one or more a-olefins.
  • suitable a-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-l-pentene, 1-octene, 3,5,5-trimethyl-l-hexene, and any combination thereof.
  • the process includes forming a bimodal ethylene/olefin terpolymer composition.
  • bimodal ethylene/olefin terpolymers include bimodal ethylene-based polymers, having at least 50 wt % ethylene, including ethylene-l-butene, ethylene-l-hexene, and ethylene-l-octene copolymers, among others.
  • Other olefins that may be utilized include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins, for example.
  • Examples of the monomers may include, but are not limited to, norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutene, styrene, alkyl substituted styrene, ethylidene norbornene, dicyclopentadiene and cyclopentene.
  • a copolymer of ethylene can be produced, where with ethylene, a comonomer having at least one a-olefin having from 4 to 15 carbon atoms, or from 4 to 12 carbon atoms, or from 4 to 8 carbon atoms, is polymerized, e.g., in a gas-phase polymerization process.
  • ethylene and/or propylene can be polymerized with at least two different comonomers, optionally one of which may be a diene, to make a copolymer.
  • "Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
  • the bimodal ethylene/olefin terpolymer composition can include from 50 wt% to 99 wt%, or 50 wt% to 95 wt % units derived from ethylene and from 50 wt% to 1 wt%, or from 50 wt% to 5 wt% units derived from one or more olefins, or from 60 wt % to 90 wt%, of units derived from ethylene and 40 wt% to 10 wt% units derived from one or more olefins, or from 70 wt% to 85 wt% units derived from ethylene and from 30 wt% to 15 wt% units derived from one or more olefins, wherein weight percent is based on the total weight of the terpolymer.
  • the polymerization conditions include contacting a catalyst system with ethylene and a C4-C8 a-olefin comonomer, or hexene, under polymerization conditions the catalyst system including (A) a first catalyst that is a non-metallocene catalyst, (B) a trim catalyst and (C) an activator, and controlling, providing, or otherwise adjusting one, some, or all of the following variables:
  • reaction temperature from 75°C to 105°C, or from 90°C to less than 100°C, and/or
  • a reactor residence time from 1.0 hours to 4.5 hours, or from 1.0 hours to 3.0 hours or from 2.0 to 3.0 hours, and the process includes forming a bimodal ethylene/C4-C8 a-olefin copolymer (or a bimodal ethylene/hexene copolymer) having one, some, or all of the following properties:
  • v a weight-average molecular weight (Mw) from 100,000 g/mol to 400,000 g/mol, or from 200,000 g/mol to 350,000 g/mol; and/or
  • M n a number-average molecular weight from 10,000 g/mol to 30,000 g/mol, or from 15,000 g/mol to 25,000 g/mol;
  • a z-average molecular weight (Mz) from 1,500,000 g/mol to 4,000,000 g/mol, or from 2,000,000 g/mol to 3,000,000 g/mol; and/or (viii) a butyl branch frequency from 1.0 to 7.0 butyl branches per 1000 carbon atom, or from 1.0 to 1.5 butyl branches per 1000 carbon atom; and/or
  • (ix) a vinyl content from 0.5 per 1000 carbon atom to less than 1.0 per 1000 carbon atom, or from 0.5 per 1000 carbon atom to 0.8 per 1000 carbon atom.
  • the phenoxy imine olefin polymerization catalyst is particularly well adapted to help to provide bimodal polymers and particularly bimodal ethylene/olefin copolymer via a polymerization process in a gas-phase polymerization reactor independently or in combination with other polymerization catalysts.
  • the resultant bimodal ethylene/olefin copolymer can have an improved, i.e., higher, Mw/Mn as detailed herein, as compared to polymers made with other (non-inventive) polymerization catalysts at similar polymerization conditions. An increased Mw/Mn is desirable in some applications.
  • the resultant bimodal ethylene/olefin copolymer can have at least a high molecular weight polyethylene component and a low molecular weight polyethylene component, as detailed herein. Having a high molecular weight polyethylene component and a low molecular weight polyethylene component is desirable in some applications.
  • the polymerization conditions include a gas-phase polymerization reactor and the process includes contacting a catalyst system with ethylene and a C4-C8 a-olefin comonomer, or hexene, under polymerization conditions, the catalyst system including (A) a first catalyst that is a non-metallocene catalyst, (B) a trim catalyst Fl-A or Fl-B and (C) an activator, and controlling, providing, or otherwise adjusting one, some, or all of the following variables:
  • reaction temperature from 75°C to 1Q5°C, or from 90°C to 105°C, and/or
  • a reactor residence time from 1.5 hours to 4.5 hours, or from 1.5 hours to 3.0 hours, or from 2.0 to 3.0 hours, and the process includes forming a bimodal ethylene/Czi-Cs a-olefin copolymer (or a bimodal ethylene/hexene copolymer) having one, some or all of the following properties:
  • a HMW split greater than 50%, or from 51% to 75%, or from 51%, to 65%, or from 51% to 60%;
  • a molecular mass dispersity (M w /M n ) from 5.0 to 20.0, or from 10.0 to 18.0 or from 12.5 to 16.0; and or,
  • v a weight-average molecular weight (Mw) from 200,000 g/mol to 325,000 g/mol, or from 259,378 g/mol to 307,753 g/mol; and/or
  • M n a number-average molecular weight from 15,000 g/mol to 25,000 g/mol, or from 19,751 g/mol to 20,278 g/mol;
  • a z-average molecular weight (Mz) from 2,000,000 g/mol to 3,000,000 g/mol, or from 2,354,495 g/mol to 2,909,311 g/mol; and/or
  • a butyl branch frequency from 1.0 to 1.5 butyl branches per 1000 carbon atom, or from 1.29 to 1.35 butyl branches per 1000 carbon atom;
  • (ix) a vinyl content from 0.45 per 1000 carbon atom to 0.7 per 1000 carbon atom or from 0.6 per 1000 carbon atom to 0.7 per 1000 carbon.
  • the ethylene/olefin terpolymer can be utilized for a number of articles such as films, fibers, nonwoven and/or woven fabrics, extruded articles, and/or molded articles, among others.
  • Butyl Branch Frequency Comonomer content is determined using 13 C NMR analysis in accordance with techniques described, for example, in U.S. Patent No. 5,292,845 (Kawasaki, et al.) and by J. C. Randall in Rev. Macromol. Chem. Phys., C29, 201 -317, ranging from homopolymer zero short chain branches per 1,000 total carbon atoms (0 SCB/1000 total C) to 50 SCB/1000 total C, where total C is the sum of the carbons in polymer backbone plus the carbons in all polymer branches.
  • DSC Differential Scanning Calorimetry
  • Melt temperature can be determined via Differential Scanning Calorimetry according to ASTM C 3418-081. For instance, using a scan rate of 10° C./min on a sample of 10 mg and using the second heating cycle.
  • Density is measured according to ASTM D792-13, Standard Test Methods for Density and Specific Gravity (Relative Density) of Plastics by Displacement, Method B (fortesting solid plastics in liquids other than water, e.g., in liquid 2-propanol). Report results in units of grams per cubic centimeter (g/cc).
  • GPC Gel permeation chromatography
  • M w molecular weight
  • M n number-average molecular weight
  • M z average molecular weight
  • PDI M w /M n
  • Method uses a solvent composed of BHT-treated TCB at nominal flow rate of 1.0 milliliter per minute (mL/min.) and a nominal injection volume of 300 microliters (4).
  • Prepare the solvent by dissolving 6 grams of butylated hydroxytoluene (BHT, antioxidant) in 4 liters (L) of reagent grade 1,2,4-trichlorobenzene (TCB), and filtering the resulting solution through a 0.1 micrometer (pm) Teflon filterto give the solvent.
  • BHT butylated hydroxytoluene
  • TCB reagent grade 1,2,4-trichlorobenzene
  • Teflon filterto To give the solvent.
  • Degas the solvent with an inline degasser before it enters the HTGPC instrument. Calibrate the columns with a series of monodispersed polystyrene (PS) standards.
  • PS monodispersed polystyrene
  • test polymer dissolved in solvent by heating known amounts thereof in known volumes of solvent at 160 °C. with continuous shaking for 2 hours to give solutions. (Measure all quantities gravimetrically.)
  • Target solution concentrations, c of test polymer of from 0.5 to 2.0 milligrams polymer per milliliter solution (mg/mL), with lower concentrations, c, being used for higher molecular weight polymers.
  • DRI detector Prior to running each sample, purge the DRI detector. Then increase flow rate in the apparatus to 1.0 mL/min/ and allow the DRI detector to stabilize for 8 hours before injecting the first sample. Calculate M w and M n using universal calibration relationships with the column calibrations.
  • KDRI is a constant determined by calibrating the DRI
  • / denotes division
  • dn/dc is the refractive index increment for the polymer.
  • dn/dc 0.109.
  • Comonomer content may 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.
  • an infrared detector such as an IR5 detector in a gel permeation chromatography measurement
  • IR5 detector in a gel permeation chromatography measurement
  • Analytical Chemistry 201486 (17), 8649-8656 [0071] Melt Indices.
  • I2 For ethylene-based (co)polymer is measured according to ASTM D1238-13, using conditions of 190° C./2.16 kg.
  • Is Test Method: for ethylene-based (co)polymer is measured according to ASTM D1238-13, using conditions of 190° C./5.16 kg.
  • High Load Melt Index (“I21”) is measured according to ASTM D1238-13, using conditions of 190° C./21 .6 kilograms (kg). Report results in units of grams eluted per 10 minutes (g/10 min.).
  • 1 H nuclear magnetic resonance ( 1 H NMR) Test Method detects the following types of carbon- carbon double bonds ("unsaturation") in the polymer.
  • Polymer samples for 1 H NMR analysis were prepared by adding 130 mg of sample to 3.25 g of 50/50 by weight tetrachlorethane-d2/perchloroethylene with 0.001 M Cr(AcAc)s in a 10 mm NMR tube.
  • the samples were purged by bubbling N2 through the solvent via a pipette inserted into the tube for approximately 5 minutes to prevent oxidation, capped, sealed with Teflon tape.
  • the samples were heated and vortexed at 115°C to ensure homogeneity.
  • X H NMR was performed on a Bruker AVANCE 400/600 MHz spectrometer equipped with a Bruker high-temperature CryoProbe and a sample temperature of 120°C. Two experiments were run to obtain spectra, a control spectrum to quantify the total polymer protons, and a double presaturation experiment, which suppresses the intense polymer backbone peaks and enables high sensitivity spectra for quantitation of the end-groups.
  • the control was run with ZG pulse, 4 scans, SWH 10,000 Hz, AQ 1.64s, Di 14s.
  • the double presaturation experiment was run with a modified pulse sequence, Iclprf2.zzl, TD 32768, 100 scans, DS 4, SWH 10,000 Hz, AQ 1.64s, Di Is, D,3 13s.
  • Vinyl content is reported as the number of vinyl bonds per 1000 carbon atoms (1000C).
  • HMW Split Segment the chromatogram obtained using Gel permeation chromatography (GPC) Test into nine (9) Schulz-Flory molecular weight distributions. Such deconvolution method is described in US 6,534,604. Assign the lowest four MW distributions to the LMW polyethylene component and the five highest MW distributions to the HMW polyethylene component.
  • GPC Gel permeation chromatography
  • Oligomer content Volatile oligomers were determined in polyethylene (PE) using headspace gas chromatography with a flame ionization detector. An aliquot of the headspace vapors from a heated headspace vial containingthe sample is analyzed by headspace gas chromatography (HS/GC) with an Agilent model 8697 automated headspace analyzer and an Agilent model 8890 gas chromatograph with a flame ionization detector. About 1 g of resin was added to a headspace vial and sealed. One injection (extraction) is performed from each vial containing the resin after equilibrating for 30 min at 150 °C.
  • PE polyethylene
  • Calibration was performed using an external standard calibration procedure with liquid standards covering the volatile oligomer range from 1-hexene to hexadecane (Cg-Cie).
  • the liquid standard was spiked onto 1 g of a purged gas phase PE sample in a headspace vial.
  • the standard preparation corrects for partitioning of the components between the headspace and polymer. The data are reported as parts per million (ppm; pg/g).
  • Table 1 below provides catalysts, used to prepare the comparative samples (CS) and the Inventive Examples (IE).
  • a polymerization catalyst system was prepared by slurrying 1.5 kg of treated fumed silica (Cabosil TS-610) in 16.8 kg of toluene, followed by addition of a 10 % solution (11.1 kg) by weight of MAO in toluene and 54.5 g of bis(2-(pentamethylphenylamido)ethyl)amine zirconium dibenzyl (Formula III).
  • the resulting mixture was introduced into an atomizing device, producing droplets that were then contacted with a hot nitrogen gas stream to evaporate the liquid and form a powder.
  • the powder was separated from the gas mixture in a cyclone separator and discharged into a container.
  • the spray drier temperature was set at 160 °C and the outlet temperature at 70- 80 °C.
  • the product collected was a fine powder.
  • the resultant powder was then slurried to a final formulation of 16 wt % solids in 10 wt % n-hexane and 74 wt % Sonneborn Hydrobrite® 380 PO White mineral oil to give an activator formulation slurry form of a Catalyst System 1 ("AFS1").
  • AFS2 Preparation of Activator Formulation Slurry form of a Catalyst System 2
  • a spray-dried catalyst formulation was prepared from CabosilTM TS-610, methylaluminoxane, bis(2-(pentamethylphenylamido)ethyl)-amine zirconium dibenzyl (Formula III), and (methylcyclopentadienyl)(l,3-dimethyl-4,5,6,7-tetrahydroindenyl)zirconium dimethyl (Formula IV).
  • the mixture was introduced into an atomizing device of the spray dryer to produce droplets of the mixture, which were then contacted with a hot nitrogen gas stream to evaporate the liquid from the mixture to give a powder.
  • the powder was separated from the gas mixture in a cyclone separator and the separated powder was discharged into a container as a fine powder.
  • the resultant powder was slurried to give an activator formulation slurry form of a Catalyst System 4 ("AFS4") of 22 wt% solids in 10 wt% isoparaffin fluid and 68 wt% mineral oil.
  • AFS4 Catalyst System 4
  • TCS4 Trim Catalyst Solution 4
  • a trim solution of cyclopentadienyl(l,5-dimethylindenyl) zirconium dimethyl (Formula V) was prepared in n-hexane and isopentane.
  • (cyclopentadienyl)(l,5-dimethylindenyl)zirconium dimethyl (Formula V) and n- hexane were charged into a first cylinder.
  • the FB-GPP reactor had a 0.35 meter (m) internal diameter and 2.3 m bed height and a fluidized bed composed of polymer granules.
  • Fluidized gas flowed through a recycle gas loop comprising sequentially a recycle gas compressor and a shell-and-tube heat exchanger having a water side and a gas side.
  • the fluidization gas flowed through the compressor, then the water side of the shell-and-tube heat exchanger, then into the FB-GPP reactor below the distribution grid.
  • Fluidization gas velocity was about 0.55 to 0.61 meter per second (m/s, 1.8 to 2.0 feet per second).
  • the fluidization gas then exited the FB-GPP reactor through a nozzle in the top of the reactor and was recirculated continuously through the recycle gas loop.
  • a constant fluidized bed temperature was maintained by continuously adjusting the temperature of the water on the shell side of the shell-and-tube heat exchanger.
  • Feed streams of ethylene, nitrogen, and hydrogen were introduced together with the 1-hexene comonomer into the recycle gas line.
  • the FB-GPP reactor was operated at a total pressure of about 2420 kPa gauge, and vented reactor gases were flared to control the total pressure.
  • Individual flow rates of ethylene, nitrogen, hydrogen and the 1-hexene were adjusted to maintain their respective gas composition targets.
  • Ethylene partial pressure was set to 1.52 megapascal (MPa, 220 pounds per square inch (psi)), and set the Cg/C2 molar ratio and the H2/C2 molar ratio as specified.
  • Average copolymer residence time was from 1.9 to 4 hours. Concentrations of all gases were measured using an on-line gas chromatograph. The fluidized bed was maintained at constant height by withdrawing a portion of the bed at a rate equal to the rate of formation of particulate product bimodal ethylene/hexene copolymer. Product was removed semi-continuously via a series of valves into a fixed volume chamber. A nitrogen purge removed a significant portion of entrained and dissolved hydrocarbons in the fixed volume chamber.
  • the product was discharged from the fixed volume chamber into a fiber pack for collection.
  • the product was further treated with a small stream of humidified nitrogen to deactivate any trace quantities of residual catalyst and cocatalyst.
  • the ratio feed of trim catalyst solution was set to the feed of the Activator Formulation Slurry form of a Catalyst System to adjust the HLMI O21) of the produced bimodal ethylene/hexene copolymer in the reactor to achieve the
  • Inventive Examples 1 to 3 (IE1, IE2, IE3): synthesized a bimodal ethylene/hexene copolymer using the Polymerization Procedure described above, wherein 1-alkene comonomer was 1-hexene, and Activator Formulation Slurry form of Catalyst System 1 (AFS1) and Trim Catalyst Solution 1 (TCS1).
  • Comparative Sample 1 (CS1): synthesized a bimodal ethylene/hexene copolymer using the Polymerization Procedure described above, wherein 1-alkene comonomer was 1-hexene, and Activator Formulation Slurry form of Catalyst System 2 (AFS2) and Trim Catalyst Solution 2 (TCS2).
  • Comparative Sample 2 (CS2): synthesized a bimodal ethylene/hexene copolymer using the Polymerization Procedure described above, wherein 1-alkene comonomer was 1-hexene, and Activator Formulation Slurry form of Catalyst System 3 (AFS3) and Trim Catalyst Solution 3 (TCS3).
  • Comparative Sample 3 synthesized a bimodal ethylene/hexene copolymer using the Polymerization Procedure described above, wherein 1-alkene comonomer is 1-hexene, and Activator Formulation Slurry form of Catalyst System 4 (AFS4) and Trim Catalyst Solution 4 (TCS4).
  • AFS4 Catalyst System 4
  • TCS4 Trim Catalyst Solution 4
  • bimodal catalyst system of IE1, IE2, and IE3 with a phenoxy imine catalyst of Formula (I) or Formula (II) produces bimodal ethylene-based polymer, and bimodal ethylene/Czi-Cs a-olefin copolymer in particular, with high HMW split (greater than 50% HMW, or from 51% to 75% HMW) and low oligomer content less than 300 ppm, or less than 100 ppm, or 1- 50 ppm), at density greater than 0.940 g/cc, compared to CS1, CS2, and CS3.

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Abstract

La présente divulgation concerne un système catalytique. Dans un mode de réalisation, le système catalytique comprend (A) un premier catalyseur et (B) un catalyseur supplémentaire. Le catalyseur supplémentaire comprend un catalyseur phénoxy imine choisi parmi (i) le dibenzyle de bis(2,4-di-tert-butyl-6 isopropylamino phénoxy imine) zirconium et (ii) le dichlorure de bis (2,4-di-tert-butyl -6 isopropylamino phénoxy imine) zirconium. Le système catalytique comprend également (C) au moins un activateur de méthylaluminoxane séché par pulvérisation.
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