WO2020046406A1 - Procédés de polymérisation et polymères fabriqués au moyen de ces derniers - Google Patents

Procédés de polymérisation et polymères fabriqués au moyen de ces derniers Download PDF

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WO2020046406A1
WO2020046406A1 PCT/US2018/063121 US2018063121W WO2020046406A1 WO 2020046406 A1 WO2020046406 A1 WO 2020046406A1 US 2018063121 W US2018063121 W US 2018063121W WO 2020046406 A1 WO2020046406 A1 WO 2020046406A1
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catalyst
composition
mol
reactor
polymer
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PCT/US2018/063121
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English (en)
Inventor
Adriana S. Silva
Matthew W. Holtcamp
Ryan W. Impelman
Richard E. PEQUENO
Kevin A. STEVENS
Charles J. HARLAN
Xuan YE
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Exxonmobil Chemical Patents Inc.
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Priority claimed from US16/117,023 external-priority patent/US10808053B2/en
Priority claimed from US16/152,470 external-priority patent/US10927203B2/en
Priority claimed from US16/152,458 external-priority patent/US10927202B2/en
Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Publication of WO2020046406A1 publication Critical patent/WO2020046406A1/fr

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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/34—Polymerisation in gaseous state
    • 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
    • C08F4/65904—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with another component of C08F4/64

Definitions

  • BCD Broad Composition Distribution
  • PDI Polydispersity Index
  • BOCD behavior in a polymer composition has been associated with a good balance of mechanical and optical properties and has been an important goal in the development of new polymer products.
  • LLDPE Linear Low Density Polyethylene
  • sealing performance is also important. Sealing performance is affected mainly by density, it improves as density gets lower, but density has the opposite effect on stiffness. Therefore, to achieve a balanced performance, there is usually a trade-off between stiffness and sealing performance. Thus, to improve sealing performance while maintaining good stiffness remains a challenge.
  • polyethylene compositions that can exhibit, for example, BCD or BOCD behavior to produce LLDPE film products or other useful articles with a good balance of one or more of high stiffness, toughness and sealing performance, as well as good optical properties (e.g., haze and gloss).
  • the invention provides for a method for producing a polyolefin by contacting a first composition and a second composition in a line to form a third composition, which is fed to a gas-phase fluidized bed reactor, along with other feed components, including hydrogen, ethylene, and a one or more C3 to C12 alpha olefin comonomer(s).
  • the third composition and the other reactor feed components are then exposed to polymerization conditions in the gas-phase fluidized bed reactor in order to obtain a polyolefin.
  • the first composition is a slurry formed from the combination of a first bimetallic catalyst and a diluent.
  • the first bimetallic catalyst is the contact product of i) a hafnocene catalyst, ii) a zirconocene catalyst, iii) a support, and iv) an activator, wherein the mol ratio of hafnium to zirconium is from 95:5 to 70:30.
  • the second composition comprises a zirconocene catalyst, which may be the same or different from the zirconocene catalyst in the first bimetallic catalyst, and a solvent. This in the zirconocene catalyst is dissolved in the solvent to form a solution.
  • the third composition comprises a second bimetallic catalyst having mol ratio of hafnium to zirconium of from 85: 15 to 50:50. The third composition is formed by mixing the first composition and the second composition in a feed line.
  • the polymerization conditions in some embodiments include: a hydrogen concentration in the range of from 50 ppm to 2000 ppm, an ethylene concentration in the range of from 35 mol% to 95 mol%; a comonomer concentration in the range of from .2 mol% to 2 mol%; a reactor pressure in the range of from 200 psig to 500 psig; and a reactor temperature in the range of from l00°F to 250°F.
  • the invention provides for a method for producing a polyolefin by feeding a first bimetallic catalyst in diluent as a slurry to a gas-phase fluidized bed reactor, along with other feed components, including hydrogen, ethylene, a one or more C 3 to C12 alpha olefin comonomer(s), and a second bimetallic catalyst.
  • the first bimetallic catalyst in diluent as a slurry and the other reactor feed components are then exposed to polymerization conditions in the gas-phase fluidized bed reactor in order to obtain a polyolefin.
  • the first bimetallic catalyst and the second bimetallic catalyst are the same or different and are each the contact product of i) a hafnocene catalyst, ii) a zirconocene catalyst, iii) a support, and iv) an activator, wherein the mol ratio of hafnium to zirconium is from 95:5 to 70:30.
  • the polyolefin so produced is a polyethylene composition comprising at least 65 wt% ethylene derived units and from 0.1 to 35 wt% of C3-C12 olefin comonomer derived units, based upon the total weight of the polyethylene composition; wherein the polyethylene composition has:
  • an RCI,m 100 kg/mol or greater, such as 150 kg/mol or greater;
  • MI melt index
  • the invention provides for polymers made from the disclosed processes. BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 2 is a schematic of a nozzle, according to one embodiment.
  • the present disclosure is directed to catalyst systems and their use in polymerization processes to produce polyolefin polymers such as polyethylene polymers and polypropylene polymers.
  • the present disclosure is directed to polymerization processes to produce polyolefin polymers from catalyst systems comprising the product of the combination of one or more olefin polymerization catalysts, at least one activator, and at least one support.
  • the present disclosure is directed to a polymerization process to produce a polyethylene polymer, the process comprising contacting a catalyst system comprising the product of the combination of two or more metallocene catalysts, at least one activator, and at least one support, with ethylene and one or more C3-C10 alpha-olefin comonomers under polymerizable conditions.
  • the term“Cn” means hydrocarbon(s) having n carbon atom(s) per molecule, wherein n is a positive integer.
  • the term“hydrocarbon” means a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds having different values of n.
  • substituted means that a hydrogen group has been replaced with a heteroatom, or a heteroatom containing group (such as halogen (such as Br, Cl, F or I) or at least one functional group such as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SiR*3, GeR*3, SnR*3, PbR*3, and the like, or where at least one heteroatom has been inserted within a hydrocarbyl ring), or a hydrocarbyl group, except that substituted hydrocarbyl is a hydrocarbyl in which at least one hydrogen atom of the hydrocarbyl has been substituted with at least one heteroatom or heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2,
  • hydrocarbyl radical is defined to be Ci-Cioo radicals, that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic.
  • radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like including their substituted analogues.
  • alkyl refers to a saturated hydrocarbon radical having from 1 to 12 carbon atoms (i.e., C1-C12 alkyl), particularly from 1 to 8 carbon atoms (i.e.. C i-Cx alkyl), particularly from 1 to 6 carbon atoms (i.e.. Ci-Ce alkyl), and particularly from 1 to 4 carbon atoms (i.e.. C1-C4 alkyl).
  • alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, and so forth.
  • alkyl group may be linear, branched or cyclic. “Alkyl” is intended to embrace all structural isomeric forms of an alkyl group. For example, as used herein, propyl encompasses both n-propyl and isopropyl; butyl encompasses n-butyl, sec-butyl, isobutyl and tert-butyl and so forth.
  • “Ci alkyl” refers to methyl (-CEL)
  • “C2 alkyl” refers to ethyl (- CH2CH3)
  • “C3 alkyl” refers to propyl (-CH2CH2CH3)
  • “C4 alkyl” refers to butyl (e.g., - CH2CH2CH2CH3 ,-(CH 3 )CHCH 2 CH3, -CH 2 CH(CH 3 )2, etc ).
  • “Me” refers to methyl
  • “Et” refers to ethyl
  • “i-Pr” refers to isopropyl
  • “t-Bu” refers to tert-butyl
  • “Np” refers to neopentyl.
  • alkylene refers to a divalent alkyl moiety containing 1 to 12 carbon atoms (i.e.. C1-C12 alkylene) in length and meaning the alkylene moiety is attached to the rest of the molecule at both ends of the alkyl unit.
  • alkylenes include, but are not limited to, -CH2-, -CH2CH2-, - CH(CH3)CH2-, -CH2CH2CH2-, etc.
  • the alkylene group may be linear or branched.
  • alkenyl refers to an unsaturated hydrocarbon radical having from 2 to 12 carbon atoms (i.e., C2-C12 alkenyl), particularly from 2 to 8 carbon atoms (i.e.. C2-C8 alkenyl), particularly from 2 to 6 carbon atoms (i.e., C2-C6 alkenyl), and having one or more (e.g., 2, 3, etc.,) carbon-carbon double bonds.
  • the alkenyl group may be linear, branched or cyclic.
  • alkenyls include, but are not limited to ethenyl (vinyl), 2-propenyl, 3-propenyl, 1 ,4-pentadienyl, l,4-butadienyl, l-butenyl, 2-butenyl and 3-butenyl.
  • Alkenyl is intended to embrace all structural isomeric forms of an alkenyl. For example, butenyl encompasses l,4-butadienyl, l-butenyl, 2-butenyl and 3-butenyl, etc.
  • alkynyl refers to an unsaturated hydrocarbon radical having from 2 to 12 carbon atoms (i.e., C2-C12 alkynyl), particularly from 2 to 8 carbon atoms (i.e., C2-C8 alkynyl), particularly from 2 to 6 carbon atoms (i. e. , C2-C6 alkynyl), and having one or more (e.g. , 2, 3, etc.) carbon-carbon triple bonds.
  • the alkynyl group may be linear, branched or cyclic.
  • alkynyls include, but are not limited to ethynyl, l-propynyl, 2-butynyl, and l,3-butadiynyl.
  • Alkynyl is intended to embrace all structural isomeric forms of an alkynyl. For example, butynyl encompasses 2- butynyl, and l,3-butadiynyl and propynyl encompasses l-propynyl and 2-propynyl (propargyl).
  • alkoxy refers to— O— alkyl containing from 1 to about 10 carbon atoms.
  • the alkoxy may be straight-chain or branched-chain.
  • Non-limiting examples include methoxy, ethoxy, propoxy, butoxy, isobutoxy, tert-butoxy, pentoxy, and hexoxy.
  • “Ci alkoxy” refers to methoxy
  • “C2 alkoxy” refers to ethoxy
  • C3 alkoxy refers to propoxy
  • “C4 alkoxy” refers to butoxy.
  • OMe refers to methoxy and“OEt” refers to ethoxy.
  • continuous means a system that operates without interruption or cessation.
  • a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn.
  • A“catalyst composition” or“catalyst system” is the combination of at least two catalyst compounds, a support material, an optional activator, and an optional co-activator.
  • the ionic form of the component is the form that reacts with the monomers to produce polymers.
  • the transition metal compound may be neutral as in a precatalyst, or a charged species with a counter ion as in an activated catalyst system.
  • Coordination polymerization is an addition polymerization in which successive monomers are added to or at an organometallic active center to create and/or grow a polymer chain.
  • BOCD refers to a Broad Orthogonal Composition Distribution in which the comonomer of a copolymer is incorporated predominantly in the high molecular weight chains or species of a polyolefin polymer or composition.
  • the distribution of the short chain branches can be measured, for example, using Temperature Raising Elution Fractionation (TREF) in connection with a Light Scattering (LS) detector to determine the weight average molecular weight of the molecules eluted from the TREF column at a given temperature.
  • the combination of TREF and LS (TREF-LS) yields information about the breadth of the composition distribution and whether the comonomer content increases, decreases, or is uniform across the chains of different molecular weights of polymer chains.
  • BOCD has been described, for example, in U.S. Patent Nos. 8,378,043, Col. 3, line 34, bridging Col. 4, line 19, and 8,476,392, line 43, bridging Col. 16, line 54.
  • the breadth of the composition distribution is characterized by the T75- T25 value, wherein T25 is the temperature at which 25% of the eluted polymer is obtained and T75 is the temperature at which 75% of the eluted polymer is obtained in a TREF experiment as described herein.
  • the composition distribution is further characterized by the Fxo value, which is the fraction of polymer that elutes below 80°C in a TREF-LS experiment as described herein. A higher Fxo value indicates a higher fraction of comonomer in the polymer molecule.
  • An orthogonal composition distribution is defined by a M60/M90 value that is greater than 1, wherein Mbo is the molecular weight of the polymer fraction that elutes at 60°C in a TREF-LS experiment and M90 is the molecular weight of the polymer fraction that elutes at 90°C in a TREF-LS experiment as described herein.
  • the polymers as described herein may have a BOCD characterized in that the T75-T25 value is 1 or greater, 2.0 or greater, 2.5 or greater, 4.0 or greater, 5.0 or greater, 7.0 or greater, 10.0 or greater, 11.5 or greater, 15.0 or greater, 17.5 or greater, 20.0 or greater, 25.0 or greater, 30.0 or greater, 35.0 or greater, 40.0 or greater, or 45.0 or greater, wherein T25 is the temperature at which 25% of the eluted polymer is obtained and T75 is the temperature at which 75% of the eluted polymer is obtained in a TREF experiment as described herein.
  • the polymers as described herein may further have a BOCD characterized in that M60/M90 value is 1.5 or greater, 2.0 or greater, 2.25 or greater, 2.50 or greater, 3.0 or greater, 3.5 or greater, 4.0 or greater, 4.5 or greater, or 5.0 or greater, wherein Mbo is the molecular weight of the polymer fraction that elutes at 60° C in a TREF-LS experiment and M90 is the molecular weight of the polymer fraction that elutes at 90°C in a TREF-LS experiment as described herein.
  • Mbo is the molecular weight of the polymer fraction that elutes at 60° C in a TREF-LS experiment
  • M90 is the molecular weight of the polymer fraction that elutes at 90°C in a TREF-LS experiment as described herein.
  • the catalyst system useful herein is a mixed metallocene catalyst system comprising two or more different metallocene catalyst compounds, at least one activator, and at least one support.
  • a first metallocene catalyst compound is one or more hafhocene catalyst compounds represented by formula (Al) and/or formula (A2) below.
  • a second metallocene catalyst compound is one or more zirconocene catalyst compounds represented by formula (B) below.
  • each X 1 is, independently, a univalent anionic ligand, or two X 1 are joined and bound to the metal atom to form a metallocycle ring, or two X 1 are joined to form a chelating ligand, a diene ligand, or an alkybdene ligand (preferably each X 1 is independently, halogen or Ci to C12 alkyl or C5 to C12 aryl, such as Br, Cl, I, Me, Et, Pr, Bu, Ph);
  • each R" is independently hydrogen, or a substituted Ci to C12 hydrocarbyl group or an unsubstituted Ci to C12 hydrocarbyl group, preferably R" is a Ci to C20 substituted or unsubstituted hydrocarbyl, preferably a substituted Ci to C12 hydrocarbyl group or an unsubstituted Ci to C12 hydrocarbyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof.
  • R** is a C3 to C4 hydrocarbyl (preferably n- propyl or n-butyl).
  • each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, aryls, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof (two X’s may form a part of a fused ring or a ring system), preferably each X is independently selected from halides, aryls and Ci to Cs alkyl groups, preferably each X is a phenyl, methyl, ethyl, propyl, butyl, pentyl, bromo, or chloro group.
  • each X is, independently, a halide, a hydr
  • the first metallocene catalyst represented by the formula: (A) produces a polyolefin having a high comonomer content.
  • the first metallocene(s) are selected from the group consisting of:
  • one catalyst compound is considered different from another if they differ by at least one atom.
  • “bisindenyl zirconium dichloride” is different from“(indenyl)(2-methylindenyl) zirconium dichloride” which is different from “(indenyl)(2-methylindenyl) hafnium di chloride.”
  • Catalyst compounds that differ only by isomer are considered the same for purposes if this invention, e.g., rac-dimethylsilylbis(2- methyl 4-phenylindenyl)hafhium dimethyl is considered to be the same as meso- dimethylsilylbis(2-methyl 4-phenylindenyl)hafnium dimethyl.
  • the first metallocene catalyst compound is represented by the formula (A2):
  • each X is, independently, a univalent anionic ligand, or two X are j oined and bound to the metal atom to form a metallocycle ring, or two X are joined to form a chelating ligand, a diene ligand, or an alkybdene ligand (preferably halogen or Cl to C12 alkyl or aryl, such as Cl, Me, Et, Ph).
  • each R 1 , R 2 , and R 4 is independently hydrogen, or a substituted Ci to C12 hydrocarbyl group or an unsubstituted Ci to C12 hydrocarbyl group, preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof.
  • R 9 is -R 20 -SiR'3 or -R 20 -CR'3 where R 20 is a Ci to C4 hydrocarbyl (preferably methyl, ethyl, propyl, butyl), and R' is a Ci to C20 substituted or unsubstituted hydrocarbyl, preferably a substituted Ci to C12 hydrocarbyl group or an unsubstituted Ci to C12 hydrocarbyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof.
  • R 20 is a Ci to C4 hydrocarbyl (preferably methyl, ethyl, propyl, butyl)
  • R' is a Ci to C20 substituted or unsubstituted hydrocarbyl, preferably a substituted Ci to C12 hydrocarbyl group or an unsubstituted Ci to C12 hydrocarbyl group, preferably methyl, ethyl,
  • R 9 and optionally R 3 are, independently, -R 20 -CMe3, or -R 20 -SiMe3 where R 20 is a Ci to C4 hydrocarbyl (preferably methyl, ethyl, propyl, butyl), preferably -CH2- CMe 3 , or -CH 2 -SiMe3.
  • each X may be, independently, a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group.
  • each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, aryls, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof (two X’s may form a part of a fused ring or a ring system), preferably each X is independently selected from halides, aryls and Ci to C5 alkyl groups, preferably each X is a phenyl, methyl, ethyl, propyl, butyl, pentyl, bromo, or chloro group.
  • T is a bridging group containing at least one Group 13, 14, 15, or 16 element, in particular boron or a Group 14, 15 or 16 element.
  • Preferred examples for the bridging group T include CH2, CH2CH2, SiMe 2 , SiPh2, SiMePh, Si(CH 2 ) 3 , Si(CH 2 )4, O, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, Me2SiOSiMe2, and PBu.
  • T is represented by the formula R3 ⁇ 4J or (R3 ⁇ 4J)2, where J is C, Si, or Ge, and each Ra is, independently, hydrogen, halogen, Ci to C20 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a Ci to C20 substituted hydrocarbyl, and two Ra can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system.
  • Ci to C20 hydrocarbyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl
  • two Ra can form a cyclic structure including aromatic, partially saturated, or saturated cycl
  • T is a bridging group comprising carbon or silica, such as dialkylsilyl
  • T is selected from CEE, CH2CH2, C(CEh)2, SiMe 2 , SiPh2, SiMePh, silylcyclobutyl (Si(CH2) 3 ), (Ph)2C, (p-(Et) 3 SiPh)2C, Me2SiOSiMe2, and cyclopentasilylene (Si(CH2)4).
  • the catalyst comprises greater than 55 mol% of the racemic isomer, or greater than 60 mol% of the racemic isomer, or greater than 65 mol% of the racemic isomer, or greater than 70 mol% of the racemic isomer, or greater than 75 mol% of the racemic isomer, or greater than 80 mol% of the racemic isomer, or greater than 85 mol% of the racemic isomer, or greater than 90 mol% of the racemic isomer, or greater than 92 mol% of the racemic isomer, or greater than 95 mol% of the racemic isomer, or greater than 97 mol% of the racemic isomer, based on the total amount of the racemic and meso isomer, if any, formed.
  • the metallocene transition metal compound formed consists essentially of the racemic isomer.
  • Amounts of rac and meso isomers are determined by proton NMR. 1H NMR data are collected at 23°C in a 5 mm probe using a 400 MHz Bruker spectrometer with deuterated methylene chloride. (Note that some of the examples herein may use deuterated benzene, but for purposes of the claims, methylene chloride shall be used.) Data is recorded using a maximum pulse width of 45°, 5 seconds between pulses and signal averaging 16 transients. The spectrum is normalized to protonated methylene chloride in the deuterated methylene chloride, which is expected to show a peak at 5.32 ppm.
  • Catalyst compounds that are particularly useful in this invention include one or more of: rac/meso Me2Si(Me3SiCH2Cp)2Hf e2; racMe2Si(Me3SiCH2Cp)2Hf e2; rac/meso Ph2Si(Me3SiCH2Cp)2Hf e2; rac/meso (CH2)3Si(Me3SiCH2Cp)2HfMe2; rac/meso (CH2)4Si(Me3SiCH2Cp)2HfMe2; rac/meso (C6F5)2Si(Me3SiCH2Cp)2Hf e2; rac/meso
  • Metallocene catalyst compounds useful herein are compounds different from compounds represented by formulas Al and A2 and are compounds represented by the formula (B):
  • T is a bridging group
  • y is 0 or 1
  • X 5 is a leaving group (such as a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group);
  • n 0, 1, 2 or 3
  • q 0, 1, 2, or 3
  • Preferred examples for the bridging group T include CH2, CH2CH2, SiMe2, SiPh2, SiMePh, Si(CH 2 ) 3 , Si(CH 2 )4, O, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, Me2SiOSiMe2, and PBu.
  • T is represented by the formula R3 ⁇ 4J or (R3 ⁇ 4J)2, where J is C, Si, or Ge, and each R a is, independently, hydrogen, halogen, Ci to C20 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a Ci to C20 substituted hydrocarbyl, and two R a can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system.
  • Ci to C20 hydrocarbyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl
  • two R a can form a cyclic structure including aromatic, partially
  • G is an alkyl amido group, preferably t-butyl amido or do-decyl amido.
  • each X 5 is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, aryls, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof (two X 5 ’s may form a part of a fused ring or a ring system), preferably each X 5 is independently selected from halides, aryls and Ci to Cri alkyl groups, preferably each X 5 is a phenyl, methyl, ethyl, propyl, butyl, pentyl, bromo, or chloro group.
  • each X 5 is, independently, a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group.
  • each Cp is independently an indene, which may be substituted or unsubstituted
  • each M 6 is zirconium
  • each X 5 is, independently, a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group.
  • y may be 1, m may be one, n may be 1, J may be N, and R* may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl or an isomer thereof.
  • the one or more second metallocene polymerization catalysts may comprise one or more metallocene catalysts of: bis(tetrahydroindenyl)Hf Me2; (dimethylsilyl)20 bis(indenyl)ZrCl2; dimethylsilylbis(tetrahydroindenyl)ZrCl2; dimethylsilyl- (3-phenyl-indenyl)(tetramethylcyclopentadienyl)ZrCl2; tetramethyldisilylene bis(4-(3,5-di- tert-butylphenyl)-indenyl)ZrCl2; bis(indenyl)zirconium dichloride; bis(indenyl)zirconium dimethyl; bis(tetrahydro-l-indenyl)zirconium di chloride; bis(tetrahydro-l-indenyl)zirconium dimethyl; dimethyls
  • the second metallocene catalysts may comprise bis(indenyl)zirconium di chloride, bis(indenyl)zirconium dimethyl, bis(tetrahydro-l- indenyl)zirconium dichloride, bis(tetrahydro-l-indenyl)zirconium dimethyl, rac/meso-bis(l- ethylindenyl)zirconium dichloride, rac/meso-bis(l-ethylindenyl)zirconium dimethyl, rac/meso-bis(l-methylindenyl)zirconium dichloride, rac/meso-bis(l-methylindenyl)zirconium dimethyl, rac/meso-bis(l-propylindenyl)zirconium dichloride, rac/meso-bis(l-propylindenyl)zirconium dichloride, rac/meso-bis(l-propylindenyl)zirconium
  • the one or more metallocene catalyst may comprise rac/meso-bis(l-ethylindenyl)zirconium dichloride, rac/meso-bis(l- ethylindenyl)zirconium dimethyl, rac/meso-bis(l-methylindenyl)zirconium dichloride, rac/meso-bis(l -methylindenyl)zirconium dimethyl, rac/meso-bis(l -propylindenyl)zirconium dichloride, rac/meso-bis(l-propylindenyl)zirconium dimethyl, rac/meso-bis(l-butylindenyl)zirconium dichloride, rac/meso-bis(l-butylindenyl)zirconium dimethyl, meso- bis(l-ethylindenyl) zirconium dichloride, meso-bis(lethy
  • catalyst combinations such as bis(l-ethyl-indenyl) zirconium dimethyl and bis(n-propyl-cyclopentadienyl) hafnium dimethyl, may be used in a catalyst system or a mixed catalyst system, sometimes also referred to as a dual catalyst system if only two catalysts are used.
  • Particularly preferred catalyst systems comprise bis(l-ethyl-indenyl) zirconium dimethyl, bis(n-propyl-cyclopentadienyl) hafnium dimethyl, a support such as silica, and an activator such as an alumoxane (i.e., methylalumoxane).
  • the two transition metal compounds may be used in any ratio.
  • Preferred molar ratios of all compounds represented by the formula (A) to all compounds represented by the formula (B) fall within the range of (A:B) 1 : 1000 to 1000: 1, alternatively 1: 100 to 500: 1, alternatively 1: 10 to 200: 1, alternatively 1: 1 to 100: 1, and alternatively 1 : 1 to 75: 1, and alternatively 5: 1 to 50: 1.
  • the particular ratio chosen will depend on the exact catalysts chosen, the method of activation, and the end product desired.
  • useful mole percents are 10 to 99.9% A to 0.1 to 90% B, alternatively 25 to 99% A to 0.5 to 50% B, alternatively 50 to 99% A to 1 to 25% B, and alternatively 75 to 99% A to 1 to 10% B.
  • the catalyst compositions may be combined with activators in any manner in the art including by supporting them for use in slurry or gas phase polymerization.
  • Activators are generally compounds that can activate any one of the catalyst compounds described above by converting the neutral metal compound to a catalytically active metal compound cation.
  • Non- limiting activators include alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and conventional-type cocatalysts.
  • Preferred activators typically include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract a reactive, s-bound, metal ligand making the metal compound cationic and providing a charge-balancing non-coordinating or weakly coordinating anion.
  • Alumoxane activators are utilized as activators in the catalyst compositions described herein.
  • Alumoxanes are generally oligomeric compounds containing -A ⁇ R ⁇ -O- sub-units, where R 1 is an alkyl group.
  • Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane.
  • Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is an alkyl, halide, alkoxide or amide.
  • alumoxanes Mixtures of different alumoxanes and modified alumoxanes may also be used. It may be preferable to use a visually clear methylalumoxane.
  • a cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution.
  • a useful alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, covered under patent number U.S. Patent No. 5,041,584).
  • MMAO modified methyl alumoxane
  • the activator is an alumoxane (modified or unmodified)
  • some embodiments select the maximum amount of activator typically at up to a 5000-fold molar excess Al/M over the catalyst compound (per metal catalytic site).
  • the minimum activator-to-catalyst-compound is a 1 : 1 molar ratio. Alternate preferred ranges include from 1 :1 to 500: 1 , alternately from 1 : 1 to 200: 1, alternately from 1 : 1 to 100: 1, or alternately from 1: 1 to 50: 1.
  • alumoxane In a class of embodiments, little or no (zero %) alumoxane is used in the polymerization processes described herein.
  • the alumoxane is present at a molar ratio of aluminum to catalyst compound transition metal less than 500: 1, preferably less than 300: 1, preferably less than 100:1, and preferably less than 1: 1.
  • the at least one activator comprises aluminum and the aluminum to transition metal, for example, hafnium or zirconium, ratio is at least 150 to 1; the at least one activator comprises aluminum and the aluminum to transition metal, for example, hafnium or zirconium, ratio is at least 250 to 1 ; or the at least one activator comprises aluminum and the aluminum to transition metal, for example, hafnium or zirconium, ratio is at least 1,000 to 1.
  • non-coordinating anion means an anion which either does not coordinate to a cation or which is only weakly coordinated to a cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base.
  • “Compatible” non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral transition metal compound and a neutral by-product from the anion.
  • Non-coordinating anions useful in accordance with this invention are those that are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge at +1, and yet retain sufficient lability to permit displacement during polymerization.
  • Ionizing activators useful herein typically comprise an NCA, particularly a compatible NCA.
  • an ionizing activator such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, a tris perfluorophenyl boron metalloid precursor or a tris perfluoronaphthyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid (US 5,942,459), or combination thereof. It is also within the scope of this invention to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators.
  • Preferred activators include N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, trimethylammonium tetrakis(perfluorfluor
  • the activator comprises a triaryl carbonium (such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).
  • a triaryl carbonium such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetra
  • the activator comprises one or more of trialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-dialkylanilinium tetrakis- (2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate, N,N- dialkylanilinium tetrakis(perfluoronaphthyl)borate, trialkylammonium tetrakis(perfluorobiphen
  • the typical activator-to-catalyst ratio e.g., all NCA activators-to-catalyst ratio is about a 1: 1 molar ratio.
  • Alternate preferred ranges include from 0.1: 1 to 100: 1, alternately from 0.5 : 1 to 200: 1 , alternately from 1 : 1 to 500: 1 alternately from 1 : 1 to 1000: 1.
  • a particularly useful range is from 0.5: 1 to 10: 1, preferably 1 : 1 to 5: 1.
  • the catalyst composition comprises at least one“support” or sometimes also referred to as a“carrier”.
  • Suitable supports include but are not limited to silica, alumina, silica-alumina, zirconia, titania, silica-alumina, cerium oxide, magnesium oxide, or combinations thereof.
  • the catalyst may optionally comprise a support or be disposed on at least one support.
  • Suitable supports include but are not limited to, active and inactive materials, synthetic or naturally occurring zeolites, as well as inorganic materials such as clays and/or oxides such as silica, alumina, zirconia, titania, silica-alumina, cerium oxide, magnesium oxide, or combinations thereof.
  • the support may be silica-alumina, alumina and/or a zeolite, particularly alumina.
  • Silica- alumina may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides.
  • the at least one support may comprise an organosilica material.
  • the organosilica material supports may be a polymer formed of at least one monomer.
  • the organosilica material may be a polymer formed of multiple distinct monomers. Methods and materials for producing the organosilica materials as well as a characterization description may be found in, for example, WO 2016/094770 and WO 2016 094774.
  • the support material is an inorganic oxide in a finely divided form.
  • Suitable inorganic oxide materials for use in catalyst systems herein include Groups 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof.
  • Other inorganic oxides that may be employed either alone or in combination with the silica, or alumina are magnesia, titania, zirconia, and the like.
  • suitable support materials can be employed, for example, finely divided functionalized polyolefins, such as finely divided polyethylene.
  • Particularly useful supports include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, and the like.
  • Aluminum alkyl compounds which may be utilized as scavengers or co-activators include, for example, one or more of those represented by the formula AIR3, where each R is, independently, a Ci- C8 aliphatic radical, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl octyl or an isomer thereof), especially trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n- hexylaluminum, tri-n-octylaluminum or mixtures thereof.
  • the solution employed should be liquid under the conditions of polymerization and relatively inert.
  • the liquid utilized in the catalyst compound solution is different from the diluent used in the catalyst component slurry. In another embodiment, the liquid utilized in the catalyst compound solution is the same as the diluent used in the catalyst component solution.
  • the ratio of metal in the activator to metal in the catalyst compound in the solution may be 1000: 1 to 0.5: 1, 300: 1 to 1 : 1, or 150: 1 to 1 : 1.
  • the activator and catalyst compound are present in the solution at up to about 90 wt%, at up to about 50 wt%, at up to about 20 wt%, preferably at up to about 10 wt%, at up to about 5 wt%, at less than 1 wt%, or between 100 ppm and 1 wt%, based upon the weight of the solvent and the activator or catalyst compound.
  • the catalyst component solution can include any one of the catalyst compound(s) of the present disclosure. As the catalyst is dissolved in the solution, a higher solubility is desirable. Accordingly, the catalyst compound in the catalyst component solution may often include a metallocene, which may have higher solubility than other catalysts.
  • any of the above described catalyst component containing solutions may be combined with any of the catalyst component containing slurry/slurries described above.
  • more than one catalyst component solution may be utilized.
  • a static control agent is a chemical composition which, when introduced into a fluidized bed reactor, may influence or drive the static charge (negatively, positively, or to zero) in the fluidized bed.
  • the specific static control agent used may depend upon the nature of the static charge, and the choice of static control agent may vary dependent upon the polymer being produced and the single site catalyst compounds being used.
  • Control agents such as aluminum stearate may be employed.
  • the static control agent used may be selected for its ability to receive the static charge in the fluidized bed without adversely affecting productivity.
  • Other suitable static control agents may also include aluminum distearate, ethoxylated amines, and anti-static compositions such as those provided by Innospec Inc. under the trade name OCTASTAT.
  • OCTASTAT 2000 is a mixture of a polysulfone copolymer, a polymeric polyamine, and oil soluble sulfonic acid.
  • control agents may be employed either alone or in combination as a control agent.
  • the carboxylate metal salt may be combined with an amine containing control agent (e.g., a carboxylate metal salt with any family member belonging to the KEMAMINE(R) (available from Crompton Corporation) or ATMER(R) (available from ICI Americas Inc.) family of products).
  • an amine containing control agent e.g., a carboxylate metal salt with any family member belonging to the KEMAMINE(R) (available from Crompton Corporation) or ATMER(R) (available from ICI Americas Inc.) family of products).
  • FIG. 1 is a schematic of a gas-phase reactor system 100, showing the addition of at least two catalysts, at least one of which is added as a trim catalyst.
  • the catalyst component slurry in diluent such as a mineral oil slurry, including at least one support and at least one activator, and at least one catalyst compound (such as two different catalyst compounds) may be placed in a vessel or catalyst pot (cat pot) 102.
  • the slurry diluent can further include a wax, which can provide increased viscosity to the mineral oil slurry, which provides for use of a slurry roller of conventional trim processes to be merely optional. Lower viscosity slurries of conventional trim processes involve rolling the slurry cylinders immediately prior to use.
  • a slurry roller can provide reduced or eliminated foam when the slurry is transferred down in pressure to the slurry vessel (e.g., cat pot 102).
  • the viscosity of a mineral oil slurry comprising a wax is such that the time scale of settling of suspended solids in the slurry is longer than the time scale of use of the slurry in a polymerization process. As such, agitation of the slurry (e.g., cat pot 102) can be limited or unnecessary.
  • a mineral oil slurry has 5 wt% or greater of wax, such as 10 wt% or greater, such as 25 wt% or greater, such as 40 wt% or greater, such as 50 wt% or greater, such as 60 wt% or greater, such as 70 wt% or greater.
  • a mineral oil slurry can have 70 wt% mineral oil, 10 wt% wax, and 20 wt% supported dual catalyst. It has been discovered that the increased viscosity provided by including a wax in the mineral oil slurry provides reduced settling of supported dual catalyst in a vessel or catalyst pot. It has further been discovered that using an increased viscosity mineral oil slurry does not inhibit trim efficiency.
  • maintaining cat pot 102 at an elevated temperature can also reduce or eliminates foaming, in particular when a wax is present in the mineral oil slurry.
  • a synergy provided by increased viscosity of the slurry provided by the wax and decreased viscosity provided by elevated temperature of the slurry can provide the reduced or eliminated foam formation in a cat pot vessel.
  • Maintaining cat pot 102 at an elevated temperature can further reduce or eliminate solid residue formation on vessel walls which could otherwise slide off of the walls and cause plugging in downstream delivery lines.
  • cat pot 102 has a volume of from about 300 gallons to 2,000 gallons, such as from 400 gallons to 1,500 gallons, such as from 500 gallons to 1,000 gallons, such as from 500 gallons to 800 gallons, for example about 500 gallons.
  • cat pot 102 is also maintained at pressure of 25 psig or greater, such as from 25 psig to 75 psig, such as from 30 psig to 60 psig, for example about 50 psig.
  • Conventional trim processes involve slurry cylinders rolled at 25 psig, and foam is created when transferred down in pressure to the slurry vessel. It has been discovered that operating a slurry vessel (e.g., cat pot 102) at higher pressures can reduce or prevent foam.
  • piping 130 and piping 140 of gas-phase reactor system 100 is maintained at an elevated temperature, such as from 30°C to 75°C, such as from 40°C to 45°C, for example about 43°C or about 60°C. Elevated temperature can be obtained by electrically heat tracing piping 130 and or piping 140 using, for example, a heating blanket. Maintaining piping 130 and or piping 140 at an elevated temperature can provide the same or similar benefits as described for an elevated temperature of cat pot 102.
  • a catalyst component solution prepared by mixing a solvent and at least one catalyst compound and/or activator, is placed in another vessel, such as a trim pot 104.
  • Trim pot 104 can have a volume of from about 100 gallons to 2,000 gallons, such as from 100 gallons to 1,500 gallons, such as from 200 gallons to 1,000 gallons, such as from 200 gallons to 500 gallons, for example about 300 gallons.
  • Trim pot 104 can be maintained at an elevated temperature, such as from 30°C to 75°C, such as from 40°C to 45°C, for example about 43°C or about 60°C. Elevated temperature can be obtained by electrically heat tracing trim pot 104 using, for example, a heating blanket.
  • the catalyst component slurry includes a wax
  • a diluent of the catalyst component solution have a viscosity that is greater than the viscosity of an alkane solvent, such as isopentane (iC5) or isohexane (iC6).
  • iC5 or iC6 as a diluent in a trim pot can promote catalyst settling and static mixer plugging.
  • the catalyst component slurry of cat pot 102 includes a wax, as described above
  • the catalyst component solution of trim pot 104 includes a diluent that is mineral oil.
  • trim efficiency is maintained or improved using wax in the catalyst component slurry and mineral oil in the catalyst component solution. Furthermore, use of wax and mineral oil reduces or eliminates the amount of iC5 and iC6 used in a trim process, which can reduce or eliminate emissions of volatile material (such as iC5 and iC6).
  • Mineral oil can have a density of from 0.85 g/cm 3 to 0.9 g/cm 3 at 25°C according to ASTM D4052, such as from 0.86 g/cm 3 to 0.88 g/cm 3 .
  • the catalyst component slurry and solution can be mixed in-line.
  • the solution and slurry may be mixed by utilizing a static mixer 108 or an agitating vessel.
  • the mixing of the catalyst component slurry and the catalyst component solution should be long enough to allow the catalyst compound in the catalyst component solution to disperse in the catalyst component slurry such that the catalyst component, originally in the solution, migrates to the supported activator originally present in the slurry.
  • the combination forms a uniform dispersion of catalyst compounds on the supported activator forming the catalyst composition.
  • the length of time that the slurry and the solution are contacted is typically up to about 220 minutes, such as about 1 to about 60 minutes, about 2 to about 20 minutes, or about 3 to about 10 minutes.
  • static mixer 108 of gas-phase reactor system 100 is maintained at an elevated temperature, such as from 30°C to 75°C, such as from 40°C to 45°C, for example about 43°C or about 60°C. Elevated temperature can be obtained by electrically heat tracing static mixer 108 using, for example, a heating blanket. Maintaining static mixer 108 at an elevated temperature can provide reduced or eliminated foaming in static mixer 108 and can promote mixing of the catalyst component slurry and catalyst solution (as compared to lower temperatures) which reduces run times in the static mixer and for the overall polymerization process.
  • the combination can yield a new polymerization catalyst in less than 1 h, less than 30 min, or less than 15 min. Shorter times are more effective, as the new catalyst is ready before being introduced into the reactor, which can provide faster flow rates.
  • an aluminum alkyl, an ethoxy lated aluminum alkyl, an aluminoxane, an anti-static agent or a borate activator such as a Ci to C15 alkyl aluminum (for example tri-isobutyl aluminum, trimethyl aluminum or the like), a Ci to C15 ethoxylated alkyl aluminum or methyl aluminoxane, ethyl aluminoxane, isobutylaluminoxane, modified aluminoxane or the like are added to the mixture of the slurry and the solution in line.
  • a carrier gas 114 such as nitrogen, argon, ethane, propane, and the like, may be added in-line to the mixture of the slurry and the solution.
  • the carrier gas may be added at the rate of about 1 to about 100 lb/hr (0.4 to 45 kg/hr), or about 1 to about 50 lb/hr (5 to 23 kg/hr), or about 1 to about 33 lb/hr (0.4 to 15 kg/hr).
  • a condensing agent can alter the concentration of comonomer present at a catalyst active site during polymerization, thus affecting comonomer incorporation (and Mw, MI, MWD and MIR), but without affecting the density of the polymer product.
  • a molar ratio of first catalyst to second catalyst can be from about 1:99 to 99: 1, such as from 85: 15 to 50:50, such as from 80:20 to 50:50, such as from 70:30 to 50:50.
  • the feed lines 240A, 242A, 244A can be any conduit capable of transporting a fluid therein. Suitable conduits can include tubing, flex hose, and pipe.
  • a condensing agent can be injected into first conduit 240, second conduit 220, and/or support member 128 via respective feed lines 240A, 242A, and/or 244A, alone or in combination with the other components moving through the conduits, support member, and/or feed lines.
  • a three way valve 215 can be used to introduce and control the flow of the fluids (i.e. catalyst slurry, purge gas and monomer) to the injection nozzle 300. Any suitable commercially available three way valve can be used.
  • a nozzle is a conventional“slurry” nozzle having a first conduit that is conventional tubing and typically protrudes farther into the reactor than a second conduit.
  • a carrier gas flow rate is from 1 kg/hr to 50 kg/hr, such as from 1 kg/hr to 25 kg/hr, such as from 2 kg/hr to 20 kg/hr, such as from 2.5 kg/hr to 15 kg/hr.
  • a carrier fluid flow rate is from 1 kg/hr to 100 kg/hr, such as from 2 kg/hr to 50 kg/hr, such as from 2 kg/hr to 30 kg/hr, such as from 3 kg/hr to 25 kg/hr, for example about 15 kg/hr.
  • oxygen or fluorobenzene can be added to the reactor 122 directly or to the gas stream 126 to control the polymerization rate.
  • a metallocene catalyst which is sensitive to oxygen or fluorobenzene
  • oxygen can be used to modify the metallocene polymerization rate relative to the polymerization rate of the other catalyst.
  • An example of such a catalyst combination is bis(n-propylcyclopentadienyl) zirconium dichloride and [(2,4,6-Me3C6H2)NCH2CH2)]2NHZrBn2, where Me is methyl or bis(indenyl)zirconium dichloride and IG h- e G.FhiNCFLCFhfyNHHfB . where Me is methyl.
  • WO 1996/009328 discloses the addition of water or carbon dioxide to gas phase polymerization reactors, for example, for similar purposes.
  • a slurry can be combined with two or more solutions having the same or different catalyst compounds and or activators.
  • the solution may be combined with two or more slurries each having the same or different supports, and the same or different catalyst compounds and or activators.
  • two or more slurries combined with two or more solutions, preferably in-line where the slurries each comprise the same or different supports and may comprise the same or different catalyst compounds and or activators and the solutions comprise the same or different catalyst compounds and or activators.
  • the slurry may contain a supported activator and two different catalyst compounds, and two solutions, each containing one of the catalysts in the slurry, and each are independently combined, in-line, with the slurry.
  • the properties of the product polymer may be controlled by adjusting the timing, temperature, concentrations, and sequence of the mixing of the solution, the slurry and any optional added materials (condensing agent, nucleating agents, catalyst compounds, activators, etc.) described above.
  • the MWD, MI, density, MIR, relative amount of polymer produced by each catalyst, and other properties of the polymer produced may also be changed by manipulating process parameters. Any number of process parameters may be adjusted, including manipulating hydrogen concentration in the polymerization system, changing the amount of the first catalyst in the polymerization system, or changing the amount of the second catalyst in the polymerization system.
  • Time dependent parameters may be adjusted such as changing the relative feed rates of the slurry or solution, changing the mixing time, the temperature and or degree of mixing of the slurry and the solution in-line, adding different types of activator compounds to the polymerization process, and adding oxygen or fluorobenzene or other catalyst poison to the polymerization process. Any combinations of these adjustments may be used to control the properties of the final polymer product.
  • the MWD of the polymer product is measured at regular intervals and one of the above process parameters, such as temperature, catalyst compound feed rate, the ratios of the two or more catalysts to each other, the ratio of comonomer to monomer, the monomer partial pressure, and or hydrogen concentration, is altered to bring the composition to the desired level, if necessary.
  • the MWD may be measured by size exclusion chromatography (SEC), e.g., gel permeation chromatography (GPC), among other techniques.
  • a polymer product property is measured in-line and in response the ratio of the catalysts being combined is altered.
  • the molar ratio of the catalyst compound in the catalyst component slurry to the catalyst compound in the catalyst component solution, after the slurry and solution have been mixed to form the final catalyst composition is 500: 1 to 1 :500, or 100: 1 to 1: 100, or 50: 1 to 1:50 or 40: 1 to 1 : 10.
  • the molar ratio of a Group 15 catalyst compound in the slurry to a metallocene catalyst compound in the solution, after the slurry and solution have been mixed to form the catalyst composition is 500: 1, 100: 1, 50: 1, 10: 1, or 5: 1.
  • the product property measured can include the dynamic shear viscosity, flow index, melt index, density, MWD, comonomer content, and combinations thereof.
  • the introduction rate of the catalyst composition to the reactor, or other process parameters is altered to maintain a desired production rate.
  • the catalyst system can be used to polymerize one or more olefins to provide one or more polymer products therefrom.
  • Any suitable polymerization process can be used, including, but not limited to, high pressure, solution, slurry, and/or gas phase polymerization processes.
  • modifications to a catalyst addition system that are similar to those discussed with respect to FIG. 1 and or FIG. 2 can be used.
  • a trim system may be used to feed catalyst to a loop slurry reactor for polyethylene copolymer production.
  • polyethylene and“polyethylene copolymer” refer to a polymer having at least 50 wt% ethylene derived units.
  • the polyethylene can have at least 70 wt% ethylene-derived units, at least 80 wt% ethylene-derived units, at least 90 wt% ethylene-derived units, or at least 95 wt% ethylene-derived units.
  • the polyethylene polymers described herein are generally copolymer, but may also include terpolymers, having one or more other monomeric units.
  • a polyethylene can include, for example, at least one or more other olefins or comonomers.
  • the polymerization conditions in some embodiments include: a hydrogen concentration in the range of from 50 ppm to 2000 ppm, or from 150 ppm to 600 ppm, or from 300 ppm to 450 ppm; an ethylene concentration in the range of from 35 mol% to 95 mol%, or from 45 mol% to 85 mol%, or from 55 mol% to 75 mol%; a comonomer concentration in the range offrom .2 mol% to 2 mol%, or from .7 mol% to 1.5 mol%, or from .9 mol% to 1.3 mol%; a reactor pressure in the range of from 200 psig to 500 psig, or from 270 psig to 320 psig, or from 280 psig to 305 psig; and a reactor temperature in the range of from l00°F to 250°F, or from l60°F to 205°F, or from l75°F to l90°F. Other ranges are disclosed
  • the monomer comprises ethylene and optional comonomers comprising one or more C3 to C40 olefins, preferably C4 to C20 olefins, or preferably Ce to C 12 olefins.
  • the C3 to C40 olefin monomers may be linear, branched, or cyclic.
  • the C3 to C40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.
  • one or more dienes are present in the polymer produced herein at up to 10 wt%, preferably at 0.00001 to 1.0 wt%, preferably 0.002 to 0.5 wt%, even more preferably 0.003 to 0.2 wt%, based upon the total weight of the composition.
  • 500 ppm or less of diene is added to the polymerization, preferably 400 ppm or less, preferably or 300 ppm or less.
  • at least 50 ppm of diene is added to the polymerization, or 100 ppm or more, or 150 ppm or more.
  • Diolefin monomers useful in this invention include any hydrocarbon structure, preferably C4 to C30, having at least two unsaturated bonds, wherein at least two of the unsaturated bonds are readily incorporated into a polymer by either a stereospecific or a non- stereospecific catalyst(s). It is further preferred that the diolefin monomers be selected from alpha, omega-diene monomers (i.e., di -vinyl monomers). More preferably, the diolefin monomers are linear di-vinyl monomers, most preferably those containing from 4 to 30 carbon atoms.
  • Suitable diluents/solvents for polymerization include non-coordinating, inert liquids.
  • examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (IsoparTM); perhalogenated hydrocarbons, such as perfluorinated C4-10 alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene.
  • straight and branched-chain hydrocarbons such as isobutane
  • hydrogen is present in the polymerization reactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa), preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7 to 70 kPa).
  • the polymerization is performed in the slurry phase.
  • a slurry polymerization process generally operates between 1 to about 50 atmosphere pressure range (15 psi to 735 psi, 103 kPa to 5068 kPa) or even greater and temperatures as described above.
  • a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which monomer and comonomers, along with catalysts, are added.
  • the suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor.
  • the liquid diluent employed in the polymerization medium is typically an alkane having from 3 to 7 carbon atoms, preferably a branched alkane.
  • the medium employed should be liquid under the conditions of polymerization and relatively inert. When a propane medium is used, the process is typically operated above the reaction diluent critical temperature and pressure. Often, a hexane or an isobutane medium is employed.
  • reaction heat is removed through the loop wall since much of the reactor is in the form of a double-jacketed pipe.
  • the slurry is allowed to exit the reactor at regular intervals or continuously to a heated low pressure flash vessel, rotary dryer and a nitrogen purge column in sequence for removal of the isobutane diluent and all unreacted monomer and comonomers.
  • the resulting hydrocarbon free powder is then compounded for use in various applications.
  • an aliphatic hydrocarbon solvent such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; preferably where aromatics are preferably present in the solvent at less than 1 wt%, preferably less than 0.5 wt%, preferably at 0 wt% based upon the weight of the solvents);
  • the catalyst system used in the polymerization preferably comprises bis(l-ethyl-indenyl) zirconium dimethyl, bis(n-propyl-cyclopentadienyl) hafnium dimethyl, a support such as silica, and an activator (such as methylalumoxane, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, or N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate);
  • an activator such as methylalumoxane, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, or N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate
  • the polyethylene composition may comprise from 99.0 to about 80.0 wt%, 99.0 to 85.0 wt%, 99.0 to 87.5 wt%, 99.0 to 90.0 wt%, 99.0 to 92.5 wt%, 99.0 to 95.0 wt%, or 99.0 to 97.0 wt%, of polymer units derived from ethylene and about 1.0 to about 20.0 wt%, 1.0 to 15.0 wt%, 0.5 to 12.5 wt%, 1.0 to 10.0 wt%, 1.0 to 7.5 wt%, 1.0 to 5.0 wt%, or 1.0 to 3.0 wt% of polymer units derived from one or more C3 to C20 a-olefin comonomers, preferably C3 to C 10 a-olefins, and more preferably C4 to Cx a-olefins, such as hexene and octene.
  • the a-olef
  • the polyethylene composition may have a melt index, I2.16, according to the test method listed below, of > about 0.10 g/lO min, e.g., > about 0.15 g/lO min, > about 0.18 g/lO min, > about 0.20 g/lO min, > about 0.22 g/lO min, > about 0.25 g/lO min, > about 0.28 g/lO min, or > about 0.30 g/lO min and, also, a melt index (I2.16) ⁇ about 3.00 g/lO min, e.g., ⁇ about 2.00 g/lO min, ⁇ about 1.00 g/lO min, ⁇ about 0.70 g/lO min, ⁇ about 0.50 g/lO min, ⁇ about 0.40 g/lO min, or ⁇ about 0.30 g/lO min.
  • a melt index I2.16, according to the test method listed below, of > about 0.10 g/lO min, e.g.
  • the polyethylene composition may have a density ⁇ about 0.945 g/cm 3 , e.g., ⁇ about 0.940 g/cm 3 , ⁇ about 0.937 g/cm 3 , ⁇ about 0.935 g/cm 3 , ⁇ about 0.933 g/cm 3 , or ⁇ about 0.930 g/cm 3 .
  • MI melt index
  • figures 6-11 illustrate representative non-bimodal molecular weight distribution curves. These include unimodal molecular weight distributions as well as distribution curves containing two peaks that cannot be easily distinguished, separated, or deconvoluted.
  • the polyethylene composition may have an internal unsaturation as measured by 'H NMR (see below for the test method) of more than 0.2 total internal unsaturations per thousand carbon atoms, alternatively, more than 0.3 total internal unsaturations per thousand carbon atoms, alternatively, more than 0.32 total internal unsaturations per thousand carbon atoms, alternatively, more than 0.38 total internal unsaturations per thousand carbon atoms, and alternatively, more than 0.4 total internal unsaturations per thousand carbon atoms.
  • the polymer (preferably the polyethylene or polypropylene) or polyethylene composition produced herein is combined with one or more additional polymers in a blend prior to being formed into a film, molded part, or other article.
  • a“blend” may refer to a dry or extruder blend of two or more different polymers, and in-reactor blends, including blends arising from the use of multi or mixed catalyst systems in a single reactor zone, and blends that result from the use of one or more catalysts in one or more reactors under the same or different conditions (e.g., a blend resulting from in series reactors (the same or different) each running under different conditions and/or with different catalysts).
  • Useful additional polymers include other polyethylenes, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene, and/or butene, and/or hexene, poly butene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene-l, isotactic polybutene, ABS resins, ethylene- propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic block copolymers, polyamides, polycarbonates, PET resins, cross linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as
  • End uses include polymer products and products having specific end-uses.
  • Exemplary end uses are films, film-based products, diaper backsheets, housewrap, wire and cable coating compositions, articles formed by molding techniques, e.g., injection or blow molding, extrusion coating, foaming, casting, and combinations thereof.
  • End uses also include products made from films, e.g., bags, packaging, and personal care films, pouches, medical products, such as for example, medical films and intravenous (IV) bags.
  • Films include monolayer or multilayer films. Films include those film structures and film applications known to those skilled in the art. Specific end use films include, for example, blown films, cast films, stretch films, stretch/cast films, stretch cling films, stretch handwrap films, machine stretch wrap, shrink films, shrink wrap films, green house films, laminates, and laminate films. Exemplary films are prepared by any conventional technique known to those skilled in the art, such as for example, techniques utilized to prepare blown, extruded, and/or cast stretch and/or shrink films (including shrink-on-shrink applications).
  • multilayer films or multiple-layer films may be formed by methods well known in the art.
  • the total thickness of multilayer films may vary based upon the application desired. A total film thickness of about 5-100 pm, more typically about 10-50 pm, is suitable for most applications.
  • the materials forming each layer may be coextruded through a coextrusion feedblock and die assembly to yield a film with two or more layers adhered together but differing in composition. Coextrusion can be adapted for use in both cast film or blown film processes.
  • Exemplary multilayer films have at least two, at least three, or at least four layers. In one embodiment the multilayer films are composed of five to ten layers. [00199] To facilitate discussion of different film structures, the following notation is used herein. Each layer of a film is denoted "A" or "B". Where a film includes more than one A layer or more than one B layer, one or more prime symbols (', ", etc.) are appended to the A or B symbol to indicate layers of the same type that can be the same or can differ in one or more properties, such as chemical composition, density, melt index, thickness, etc. Finally, the symbols for adjacent layers are separated by a slash (/).
  • A/B/A' a three-layer film having an inner layer disposed between two outer layers
  • A/B/A' a five-layer film of alternating layers
  • A/B/A'/B'/A a five-layer film of alternating layers
  • the left-to-right or right-to-left order of layers does not matter, nor does the order of prime symbols; e.g., an A/B film is equivalent to a B/A film, and an A/A'/B/A" film is equivalent to an A/B/A'/A" film, for purposes described herein.
  • each film layer is similarly denoted, with the thickness of each layer relative to a total film thickness of 100 (dimensionless) indicated numerically and separated by slashes; e.g., the relative thickness of an A/B/A film having A and A' layers of 10 pm each and a B layer of 30 pm is denoted as 20/60/20.
  • each layer of the film, and of the overall film is not particularly limited, but is determined according to the desired properties of the film.
  • Typical film layers have a thickness of from about 1 to about 1000 pm, more typically from about 5 to about 100 pm, and typical films have an overall thickness of from about 10 to about 100 pm.
  • the films can further be embossed, or produced or processed according to other known film processes.
  • the films can be tailored to specific applications by adjusting the thickness, materials and order of the various layers, as well as the additives in or modifiers applied to each layer.
  • the articles (preferably films) produced herein have a dart drop impact resistance of 600 g/mil or greater.
  • Films may be used in“shrink-on-shrink” applications.“Shrink-on-shrink,” as used herein, refers to the process of applying an outer shrink wrap layer around one or more items that have already been individually shrink wrapped (herein, the“inner layer” of wrapping). In these processes, it is desired that the films used for wrapping the individual items have a higher melting (or shrinking) point than the film used for the outside layer. When such a configuration is used, it is possible to achieve the desired level of shrinking in the outer layer, while preventing the inner layer from melting, further shrinking, or otherwise distorting during shrinking of the outer layer. Some films described herein have been observed to have a sharp shrinking point when subjected to heat from a heat gun at a high heat setting, which indicates that they may be especially suited for use as the inner layer in a variety of shrink-on-shrink applications.
  • Packaging includes those packaging structures and packaging applications known to those skilled in the art.
  • Exemplary packaging includes flexible packaging, food packaging, e.g., fresh cut produce packaging, frozen food packaging, bundling, packaging and unitizing a variety of products.
  • Applications for such packaging include various foodstuffs, rolls of carpet, liquid containers, and various like goods normally containerized and/or palletized for shipping, storage, and/or display.
  • a parison is formed between mold halves and the mold is closed around the parison, sealing one end of the parison and closing the parison around a mandrel at the other end. Air is then blown through the mandrel (or through a needle) to inflate the parison inside the mold. The mold is then cooled and the part formed inside the mold is solidified. Finally, the mold is opened and the molded part is ejected.
  • the process lends itself to any design having a hollow shape, including but not limited to bottles, tanks, toys, household goods, automobile parts, and other hollow containers and/or parts.
  • Injection molding is a process commonly known in the art, and is a process that usually occurs in a cyclical fashion. Cycle times generally range from 10 to 100 seconds and are controlled by the cooling time of the polymer or polymer blend used.
  • Extrusion coating materials are typically used in food and non-food packaging, pharmaceutical packaging, and manufacturing of goods for the construction (insulation elements) and photographic industries (paper).
  • Electrical devices described herein can be formed by methods well known in the art, such as by one or more extrusion coating steps in a reactor/extruder equipped with a cable die.
  • Such cable extrusion apparatus and processes are well known.
  • an optionally heated conducting core is pulled through a heated extrusion die, typically a cross-head die, in which a layer of melted polymer composition is applied.
  • Multiple layers can be applied by consecutive extrusion steps in which additional layers are added, or, with the proper type of die, multiple layers can be added simultaneously.
  • the cable can be placed in a moisture curing environment, or allowed to cure under ambient conditions.
  • TREF -LS data reported herein were measured using an analytical size TREF instrument (Polymerchar, Spain), with a column of the following dimension: inner diameter (ID) 7.8 mm and outer diameter (OD) 9.53 mm and a column length of 150 mm.
  • the column was filled with steel beads.
  • 0.5 mL of a 6.4% (w/v) polymer solution in orthodichlorobenzene (ODCB) containing 6 g BHT/4 L were charged onto the column and cooled from l40°C to 25°C at a constant cooling rate of l.0°C/min.
  • a small volume (0.5 ml) of the solution was introduced into a TREF column (stainless steel; o.d., 3/8"; length, 15 cm; packing, non-porous stainless steel micro-balls) at l50°C, and the column temperature was stabilized for 30 min at a temperature (l20-l25°C) approximately 20°C higher than the highest-temperature fraction for which the GPC analysis was included in obtaining the final bivariate distribution.
  • the sample volume was then allowed to crystallize in the column by reducing the temperature to an appropriate low temperature (30, 0, or -l5°C) at a cooling rate of 0.2°C/min.

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Abstract

La présente invention concerne des procédés de polymérisation d'oléfine(s). Les procédés peuvent comprendre la mise en contact d'une première composition et d'une deuxième composition dans une conduite pour former une troisième composition. La première composition peut comprendre un produit de contact d'un premier catalyseur, d'un second catalyseur, d'un support, d'un premier activateur, d'une huile minérale. La deuxième composition peut comprendre un produit de contact d'un activateur, d'un diluant, et le premier catalyseur ou le second catalyseur. Les procédés peuvent comprendre l'introduction de la troisième composition provenant de la conduite dans un réacteur à lit fluidisé en phase gazeuse, l'introduction d'un agent de compensation dans la conduite et/ou le réacteur, l'exposition de la troisième composition à des conditions de polymérisation, et/ou l'obtention d'une polyoléfine. L'invention concerne des compositions de polyéthylène comprenant au moins 65 % en poids de motifs dérivés de l'éthylène rapporté au poids total de la composition de polyéthylène.
PCT/US2018/063121 2018-08-30 2018-11-29 Procédés de polymérisation et polymères fabriqués au moyen de ces derniers WO2020046406A1 (fr)

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US16/117,023 US10808053B2 (en) 2017-10-23 2018-08-30 Polyethylene compositions and articles made therefrom
US16/117,023 2018-08-30
US16/117,008 US10822434B2 (en) 2017-10-23 2018-08-30 Catalyst systems and polymerization processes for using the same
US16/117,008 2018-08-30
US16/152,458 2018-10-05
US16/152,470 US10927203B2 (en) 2017-11-13 2018-10-05 Polyethylene compositions and articles made therefrom
US16/152,470 2018-10-05
US16/152,458 US10927202B2 (en) 2017-11-13 2018-10-05 Polyethylene compositions and articles made therefrom
US201862754231P 2018-11-01 2018-11-01
US201862754217P 2018-11-01 2018-11-01
US201862754248P 2018-11-01 2018-11-01
US201862754237P 2018-11-01 2018-11-01
US201862754241P 2018-11-01 2018-11-01
US201862754224P 2018-11-01 2018-11-01
US62/754,217 2018-11-01
US62/754,248 2018-11-01
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