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WO2018182860A1 - Procédé de préparation de copolymères d'éthylène en solution - Google Patents

Procédé de préparation de copolymères d'éthylène en solution Download PDF

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Publication number
WO2018182860A1
WO2018182860A1 PCT/US2018/017752 US2018017752W WO2018182860A1 WO 2018182860 A1 WO2018182860 A1 WO 2018182860A1 US 2018017752 W US2018017752 W US 2018017752W WO 2018182860 A1 WO2018182860 A1 WO 2018182860A1
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Prior art keywords
borate
tetrakis
hydrocarbyl
substituted
phenyl
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PCT/US2018/017752
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English (en)
Inventor
Donna J. Crowther
Hua Zhou
Jacqueline A. LOVELL
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Exxonmobil Chemical Patents Inc.
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Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Priority to US16/492,736 priority Critical patent/US11028192B2/en
Publication of WO2018182860A1 publication Critical patent/WO2018182860A1/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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/10—Heteroatom-substituted bridge, i.e. Cp or analog where the bridge linking the two Cps or analogs is substituted by at least one group that contains a heteroatom
    • 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
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+

Definitions

  • This invention relates to process to make ethylene copolymers using cyclopentadienyl- fluorenyl transition metal compounds.
  • Olefin polymers are of great use in industry. Hence there is interest in finding new processes that increase the commercial usefulness of catalysts to make olefin polymers and enhance the production of polymers having improved properties.
  • EP 1 052 263 A2 US 2005/131171; US 2003/162651; US 2002/086958; US 2005/148460; US 2004/192866; US 2007/255021; US 2005/288178; US 5,756,607; EP 1 086 146 Al; US 8,129,473; US 2002/103313; US 6,914,027; US 6,559,089; US 6,897,273; EP 1 727 841 Bl; US 7,393,907; US 6,383,969; US 2003/162651 Al; J. Am. Chem. Soc. 2004, 126, 16716-16717; US 2006/251835 and US 9,150,676.
  • This invention relates to a method to polymerize olefins comprising contacting, in solution phase at a temperature of 60°C to 200°C, ethylene and at least one olefin comonomer with a catalyst system comprising a non-coordinating anion activator and a metallocene catalyst compound represented by the formula:
  • M is Hf or Zr
  • each R 3 is independently an anionic group
  • each R 2 is independently H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl;
  • R 4 is a hydrocarbyl radical having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof;
  • R * is phenyl or a substituted phenyl;
  • each R 5 , R 6 , R 7 , and R 8 is independently H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl;
  • the polymer comprises ethylene, diene, and optional C3 to C20 olefin comonomer.
  • This invention relates to a method to polymerize olefins comprising contacting, in solution phase at a temperature of 60°C to 200°C, ethylene, at least one diene comonomer, and optionally a C3 to C20 alpha olefin with a catalyst system comprising a non-coordinating anion activator and a metallocene catalyst compound represented by the formula:
  • M is Hf or Zr
  • each R 3 is independently an anionic group
  • each R 2 is independently H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl;
  • R 4 is a hydrocarbyl radical having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof;
  • R * is phenyl or a substituted phenyl;
  • each R 5 , R 6 , R 7 , and R 8 is independently H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl;
  • Figure 1 is a graph showing relative activities from ethylene octene copolymerizations at 110°C.
  • Figure 2 is a graph showing a comparison of Mn (g/mol) to comonomer content
  • Figure 3 is a graph showing a comparison of Mn (g/mol) to comonomer content (wt%) at 85 °C.
  • Figure 4 is a graph showing a comparison of Mn (g/mol) to comonomer content (wt%) at ll5°C.
  • Figure 5 is graph showing relative activities from ethylene octene copolymers at 65°C, 85°C, and ll5°C.
  • Figure 6 is a graph showing melting point of ethylene norbornene copolymers.
  • Figure 7 is a graph showing activities of ethylene norbornene copolymerizations.
  • Figure 8 is a graph showing melting point of ethylene norbornene copolymers.
  • Figure 9 is a graph showing activities of ethylene norbornene copolymerizations.
  • a "group 4 metal” is an element from group 4 of the Periodic Table, e.g. Hf, Ti, or Zr.
  • catalyst productivity is a measure of how many grams of polymer (P) are produced using a polymerization catalyst comprising W g of catalyst (cat), over a period of time of T hours; and may be expressed by the following formula: P/(T x W) and expressed in units of gPgcaHhr 1 . Conversion is the amount of monomer that is converted to polymer product, and is reported as mol% and is calculated based on the polymer yield and the amount of monomer fed into the reactor.
  • catalyst activity is a measure of how active the catalyst is and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kgP/molcat).
  • an “olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • alkene is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • a copolymer when a copolymer is said to have an "ethylene" content of 35 wt% to 55 wt%, it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer.
  • a "polymer” has two or more of the same or different mer units.
  • a “homopolymer” is a polymer having mer units that are the same.
  • a “copolymer” is a polymer having two or more mer units that are different from each other.
  • a “terpolymer” is a polymer having three mer units that are different from each other.
  • ethylene polymer or "ethylene copolymer” is a polymer or copolymer comprising at least 50 mol% ethylene derived units
  • ethylene copolymer is a polymer or copolymer comprising at least 50 mol% propylene derived units
  • ethylene shall be considered an a-olefin.
  • substituted means that a hydrogen group has been replaced with a heteroatom, or a heteroatom containing group.
  • a “substituted hydrocarbyl” is a radical made of carbon and hydrogen where at least one hydrogen is replaced by a heteroatom or heteroatom containing group.
  • substituted means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom, or a heteroatom containing group.
  • methyl cyclopentadiene (Cp) is a Cp group substituted with a methyl group.
  • Mn is number average molecular weight
  • Mw is weight average molecular weight
  • Mz is z average molecular weight
  • wt% is weight percent
  • mol% is mole percent.
  • Molecular weight distribution also referred to as polydispersity, is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units (e.g., Mw, Mn, Mz) are g/mol.
  • Me is methyl
  • Et is ethyl
  • Pr is propyl
  • cPR is cyclopropyl
  • nPr is n-propyl
  • iPr is isopropyl
  • Bu is butyl
  • nBu is normal butyl
  • iBu is isobutyl
  • sBu is sec-butyl
  • tBu is tert-butyl
  • Oct octyl
  • Ph is phenyl
  • Bn or Bz is benzyl
  • TMS is trimethylsilyl
  • TIBAL is triisobutylaluminum
  • TNOAL is tri(n- octyl) aluminum
  • THF also referred to as thf
  • RT room temperature (and is 23°C unless otherwise indicated)
  • tol is toluene
  • EtOAc is ethyl acetate
  • Cy is cyclohexyl
  • MAO is cyclo
  • a “catalyst system” is combination of at least one catalyst compound, at least one activator, an optional co-activator, and an optional support material.
  • catalyst systems are described as comprising neutral stable forms of the components, it is well understood by one of ordinary skill in the art, that the ionic form of the component is the form that reacts with the monomers to produce polymers.
  • the catalyst may be described as a catalyst precursor, a pre- catalyst compound, catalyst compound or a transition metal compound, and these terms are used interchangeably.
  • a polymerization catalyst system is a catalyst system that can polymerize monomers to polymer.
  • An "anionic ligand” is a negatively charged ligand which donates one or more pairs of electrons to a metal ion.
  • alkoxides include those where the alkyl group is a Q to C 10 hydrocarbyl.
  • the alkyl group may be straight chain, branched, or cyclic.
  • the alkyl group may be saturated or unsaturated. In some embodiments, the alkyl group may comprise at least one aromatic group.
  • hydrocarbyl radical is defined to be a C r C 100 radical, that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic.
  • radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like including their substituted analogues.
  • Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom of the hydrocarbyl radical has been substituted with a heteroatom or heteroatom containing group, preferably the hydrocarbyl has been substituted with at least one halogen (such as Br, CI, 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 , where R* is a Ci to C20 hydrocarbyl and the like, or where at least one heteroatom has been inserted within a hydrocarbyl ring.
  • halogen such as Br, CI, F or I
  • functional group such as NR* 2 , OR*, SeR*, TeR*, PR* 2 , AsR* 2 , SbR* 2 , SR*,
  • alkenyl means a straight-chain, branched-chain, or cyclic hydrocarbon radical having one or more double bonds. These alkenyl radicals may be optionally substituted. Examples of suitable alkenyl radicals include, but are not limited to, ethenyl, propenyl, allyl, 1 ,4-butadienyl cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl and the like including their substituted analogues.
  • aryl or "aryl group” means a six carbon aromatic ring and the substituted variants thereof, including but not limited to, phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl.
  • heteroaryl means an aryl group where a ring carbon atom (or two or thee ring carbon atoms) has been replaced with a heteroatom, preferably N, O, or S.
  • aromatic also refers to pseudoaromatic heterocycles which are heterocyclic substituents that have similar properties and structures (nearly planar) to aromatic heterocyclic ligands, but are not by definition aromatic; likewise the term aromatic also refers to substituted aromatics.
  • isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl) reference to one member of the group (e.g., n-butyl) shall expressly disclose the remaining isomers (e.g., iso-butyl, sec -butyl, and tert-butyl) in the family.
  • alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer (e.g., butyl) expressly discloses all isomers (e.g., n-butyl, iso-butyl, sec- butyl, and tert-butyl).
  • Complex as used herein, is also often referred to as catalyst precursor, precatalyst, catalyst, catalyst compound, transition metal compound, or transition metal complex. These words are used interchangeably. Activator and cocatalyst are also used interchangeably.
  • a scavenger is a compound that is typically added to facilitate polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. A co-activator, that is not a scavenger, may also be used in conjunction with an activator in order to form an active catalyst. In some embodiments a co-activator can be pre- mixed with the transition metal compound to form an alkylated transition metal compound.
  • the catalyst may be described as a catalyst precursor, a precatalyst compound, catalyst compound or a transition metal compound, and these terms are used interchangeably.
  • a polymerization catalyst system is a catalyst system that can polymerize monomers to polymer.
  • 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.
  • This invention relates to a method to polymerize olefins comprising contacting, in solution phase at a temperature of 60°C to 200°C, ethylene and at least olefin comonomer (preferably C3 to C20 olefin, preferably propylene, hexene, octene, norbornene or diene) with a catalyst system comprising a non-coordinating anion activator, preferably a bulky activator as defined below, and a metallocene catalyst compound described herein.
  • olefin comonomer preferably C3 to C20 olefin, preferably propylene, hexene, octene, norbornene or diene
  • This invention also relates to a method to polymerize olefins comprising contacting, in solution phase at a temperature of 60°C to 200°C, ethylene and at least one diene comonomer and, optionally, an olefin comonomer (preferably C3 to C20 olefin, preferably propylene, hexene, octene, or norbornene) with a catalyst system comprising a non- coordinating anion activator, preferably a bulky activator as defined below and a metallocene catalyst compound represented by the catalyst compounds described herein.
  • a catalyst system comprising a non- coordinating anion activator, preferably a bulky activator as defined below and a metallocene catalyst compound represented by the catalyst compounds described herein.
  • This invention relates to a method to polymerize olefins comprising contacting, in solution phase at a temperature of 60°C to 200°C, ethylene and at least one olefin comonomer with a catalyst system comprising a non-coordinating anion activator and a metallocene catalyst compound represented by the formula:
  • M is Hf or Zr
  • each R 3 is independently an anionic group
  • each R 2 is independently H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl;
  • R 4 is a hydrocarbyl radical having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, preferably R 4 is H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl, preferably
  • R 4 is a Ci to C20 alkyl, such as butyl, t-butyl, phenyl, or substituted phenyl);
  • R * is phenyl or a substituted phenyl (such as an alkoxy substituted phenyl, where the alkyl in the alkoxy is a Ci to C20 alkyl);
  • each R 5 is independently H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl
  • each R 6 is independently H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl (preferably methyl, ethyl, propyl, butyl, including t-butyl, pentyl, heptyl, octyl, nonyl, decyl, undecyl, or docecyl);
  • each R 7 is independently H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl (preferably methyl, ethyl, propyl, butyl, including t-butyl, pentyl, heptyl, octyl, nonyl, decyl, undecyl, or docecyl);
  • each R 8 is independently H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl (preferably methyl, ethyl, propyl, butyl, including t-butyl, pentyl, heptyl, octyl, nonyl, decyl, undecyl, or docecyl);
  • the polymer comprises ethylene, diene, and optional C3 to C20 olefin comonomer.
  • This invention relates to a method to polymerize olefins comprising contacting, in solution phase at a temperature of 60°C to 200°C, ethylene, at least one diene comonomer, and optionally a C3 to C20 alpha olefin with a catalyst system comprising a non-coordinating anion activator and a metallocene catalyst compound represented by the formula:
  • M is Hf or Zr
  • each R 3 is independently an anionic group
  • each R 2 is independently H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl;
  • R 4 is H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl (preferably a Ci to C20 alkyl, such as butyl, t-butyl, phenyl, or substituted phenyl);
  • R * is phenyl or a substituted phenyl (such as an alkoxy substituted phenyl, where the alkyl in the alkoxy is a Ci to C20 alkyl);
  • each R 5 is independently H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl (preferably methyl, ethyl, propyl, butyl, including t-butyl, pentyl, heptyl, octyl, nonyl, decyl, undecyl, or docecyl); each R 6 is independently H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl (preferably methyl, ethyl, propyl, butyl, including t-butyl, pentyl, heptyl, octyl, nonyl, decyl, undecyl, or docecyl);
  • each R 7 is independently H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl (preferably methyl, ethyl, propyl, butyl, including t-butyl, pentyl, heptyl, octyl, nonyl, decyl, undecyl, or docecyl);
  • each R 8 is independently H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl (preferably methyl, ethyl, propyl, butyl, including t-butyl, pentyl, heptyl, octyl, nonyl, decyl, undecyl, or docecyl);
  • this invention relates to catalyst compounds, and catalyst systems comprising such compounds, represented by the formula:
  • M is Hf or Zr
  • each R 3 is independently an anionic group
  • each R 2 is independently H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl;
  • R 4 is H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl (preferably a Ci to C20 alkyl, such as butyl, t-butyl, phenyl, or substituted phenyl);
  • R * is phenyl or a substituted phenyl (such as an alkoxy substituted phenyl, where the alkyl of the alkoxy is a Ci to C20 alkyl);
  • each R 5 is independently H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl (preferably methyl, ethyl, propyl, butyl, including t-butyl, pentyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, or an isomer thereof);
  • each R 6 is independently H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl (preferably methyl, ethyl, propyl, butyl, including t-butyl, pentyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, or an isomer thereof);
  • each R 7 is independently H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl (preferably methyl, ethyl, propyl, butyl, including t-butyl, pentyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, or an isomer thereof);
  • each R 8 is independently H or a Ci to C20 hydrocarbyl or Ci to C20 substituted hydrocarbyl (preferably methyl, ethyl, propyl, butyl, including t-butyl, pentyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, or an isomer thereof); and
  • R 2 , R 5 , R 6 , R 7 and/or R 8 is independently methyl, ethyl, or propyl.
  • the catalyst compound is represented by the formula:
  • the catalyst compounds described herein may be prepared according to the general procedures described in US 6,693,153. Synthesis of Catalysts A and B is described below in the Experimental section.
  • one catalyst compound is used, e.g., the catalyst compounds are not different.
  • 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 dichloride.”
  • two or more different catalyst compounds are present in the catalyst system used herein. In some embodiments, two or more different catalyst compounds are present in the reaction zone where the process(es) described herein occur.
  • the two transition metal compounds are preferably chosen such that the two are compatible.
  • a simple screening method such as by l H or 13 C NMR, known to those of ordinary skill in the art, can be used to determine which transition metal compounds are compatible. It is preferable to use the same activator for the transition metal compounds, however, two different activators, such as a non-coordinating anion activator and an alumoxane, can be used in combination.
  • transition metal compounds contain an R 4 or R* ligand which is not a hydride, hydrocarbyl, or substituted hydrocarbyl, then the alumoxane is typically contacted with the transition metal compounds prior to addition of the non- coordinating anion activator.
  • the two transition metal compounds may be used in any ratio.
  • Preferred molar ratios of (A) transition metal compound to (B) transition metal compound 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, alternatively 1: 1 to 75:1, and alternatively 5:1 to 50:1.
  • the particular ratio chosen will depend on the exact pre-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.
  • catalyst and “activator” are used herein interchangeably and are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral catalyst compound to a catalytically active catalyst compound cation.
  • catalyst systems may be formed by combining them with activators in any manner known from the literature including by supporting them for use in slurry or gas phase polymerization.
  • the catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in the monomer).
  • the catalyst system typically comprise a complex as described above and an activator such as a non-coordinating anion.
  • Non-limiting activators include ionizing activators, which may be neutral or ionic.
  • Preferred activators typically include ionizing anion precursor compounds that abstract a reactive, ⁇ -bound, metal ligand making the metal complex cationic and providing a charge-balancing noncoordinating or weakly coordinating anion.
  • 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.
  • alumoxane is present at zero mol%, alternately 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, preferably less than 1:1.
  • NCA noncoordinating anion
  • NCA is defined to mean an anion either that does not coordinate to the catalyst metal cation or that does coordinate to the metal cation, but only weakly.
  • NCA is also defined to include multicomponent NCA-containing activators, such as ⁇ , ⁇ -dimethylanilinium tetrakis(pentafluorophenyl)borate, that contain an acidic cationic group and the non-coordinating anion.
  • NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, that can react with a catalyst to form an activated species by abstraction of an anionic group.
  • NCA coordinates weakly enough that a neutral Lewis base, such as an olefinically or acetylenically unsaturated monomer can displace it from the catalyst center.
  • a neutral Lewis base such as an olefinically or acetylenically unsaturated monomer can displace it from the catalyst center.
  • Any metal or metalloid that can form a compatible, weakly coordinating complex may be used or contained in the noncoordinating anion. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus, and silicon.
  • An activator can be either neutral or ionic.
  • non-coordinating anion includes neutral activators, ionic activators, and Lewis acid activators.
  • 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.
  • an ionizing or stoichiometric 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.
  • the catalyst systems of this invention can include at least one non-coordinating anion
  • boron containing NCA activators represented by the formula below can be used:
  • Z is (L-H) or a reducible Lewis acid
  • L is a neutral Lewis base
  • H is hydrogen
  • a d_ is a boron containing non-coordinating anion having the charge d-; d is 1, 2, or 3.
  • the cation component, Z d + may include Bronsted acids such as protons or protonated Lewis bases or reducible Lewis acids capable of protonating or abstracting a moiety, such as an alkyl or aryl, from the transition metal catalyst precursor, resulting in a cationic transition metal species.
  • the activating cation Z d + may also be a moiety such as silver, tropylium, carboniums, ferroceniums and mixtures, preferably carboniums and ferroceniums. Most preferably Z d + is triphenyl carbonium.
  • Preferred reducible Lewis acids can be any triaryl carbonium (where the aryl can be substituted or unsubstituted, such as those represented by the formula: (Ar 3 C+), where Ar is aryl or aryl substituted with a heteroatom, a Q to C 40 hydrocarbyl, or a substituted Ci to C 4 o hydrocarbyl), preferably the reducible Lewis acids in formula (14) above as "Z" include those represented by the formula: (Ph 3 C), where Ph is a substituted or unsubstituted phenyl, preferably substituted with Q to C 40 hydrocarbyls or substituted a Q to C 40 hydrocarbyls, preferably C 1 to C 2 o alkyls or aromatics or substituted C 1 to C 20 alkyls or aromatics, preferably Z is a triphenylcarbonium.
  • Z d + is the activating cation (L-H) d +, it is preferably a Bronsted acid, capable of donating a proton to the transition metal catalytic precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof, preferably ammoniums of methylamine, aniline, dimethylamine, diethylamine, N- methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo ⁇ , ⁇ -dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxoniums from ethers such as dimethyl ether diethyl ether, tetrahydro
  • each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a pentafluoryl aryl group.
  • suitable A d ⁇ also include diboron compounds as disclosed in US 5,447,895, which is fully incorporated herein by reference.
  • boron compounds which may be used as an activating cocatalyst are the compounds described as (and particularly those specifically listed as) activators in US 8,658,556, which is incorporated by reference herein.
  • the ionic stoichiometric activator Z d + (A d ⁇ ) is one or more of N,N- dimethylanilinium tetra(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, ⁇ , ⁇ -dimethylanilinium tetrakis(perfluorobiphenyl)borate, ⁇ , ⁇ -dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbenium tetra(perfluoropheny
  • each R x is, independently, a halide, preferably a fluoride;
  • Ar is substituted or unsubstituted aryl group (preferably a substituted or unsubstituted phenyl), preferably substituted with Q to C 40 hydrocarbyls, preferably Q to C 2 o alkyls or aromatics;
  • each R 2 is, independently, a halide, a C 6 to C 20 substituted aromatic hydrocarbyl group or a siloxy group of the formula -0-Si-R a , where R a is a Q to C 20 hydrocarbyl or hydrocarbylsilyl group (preferably R 2 is a fluoride or a perfluorinated phenyl group);
  • each R 3 is a halide, C 6 to C 20 substituted aromatic hydrocarbyl group or a siloxy group of the formula -0-Si-R a , where R a is a Q to C 20 hydrocarbyl or hydrocarbylsilyl group (preferably R 3 is a fluoride or a C 6 perfluorinated aromatic hydrocarbyl group); wherein R 2 and R 3 can form one or more saturated or unsaturated, substituted or unsubstituted rings (preferably R 2 and R 3 form a perfluorinated phenyl ring);
  • L is a neutral Lewis base; (L-H)+is a Bronsted acid; d is 1, 2, or 3;
  • the anion has a molecular weight of greater than 1020 g/mol
  • (Ar 3 C) d + is (Ph 3 C) d + , where Ph is a substituted or unsubstituted phenyl, preferably substituted with C 1 to C 40 hydrocarbyls or substituted C 1 to C 40 hydrocarbyls, preferably C 1 to C 20 alkyls or aromatics or substituted C 1 to C 20 alkyls or aromatics and d is 1, 2, or 3.
  • Molecular volume is used herein as an approximation of spatial steric bulk of an activator molecule in solution. Comparison of substituents with differing molecular volumes allows the substituent with the smaller molecular volume to be considered “less bulky” in comparison to the substituent with the larger molecular volume. Conversely, a substituent with a larger molecular volume may be considered “more bulky” than a substituent with a smaller molecular volume.
  • Molecular volume may be calculated as reported in "A Simple 'Back of the Envelope' Method for Estimating the Densities and Molecular Volumes of Liquids and Solids," Journal of Chemical Education, Vol. 71, No. 11, November 1994, pp. 962-964.
  • V s is the sum of the relative volumes of the constituent atoms, and is calculated from the molecular formula of the substituent using the following table of relative volumes. For fused rings, the V s is decreased by 7.5% per fused ring.
  • one or more of the NCA activators is chosen from the activators described in US 6,211,105.
  • Preferred activators include ⁇ , ⁇ -dimethylanilinium tetrakis(perfluoronaphthyl)borate, ⁇ , ⁇ -dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, ⁇ , ⁇ -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, [Ph 3 C + ][B(C 6 F
  • 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,
  • the activator comprises one or more of trialkylammonium tetrakis(pentafluorophenyl)borate, ⁇ , ⁇ -dialkylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dia]kylanilinium tetrakis- (2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate, N,N- dialkylanilinium tetrakis(perfluoronaphthyl)borate, trialkylammonium tetrakis(perfluorobiphen
  • the activator is one or more of: ⁇ , ⁇ -dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammonium tetrakis(perfluoronaphthyl)borate, tripropylammonium tetrakis(perfluoronaphthyl)borate, tri(n-butyl) ammonium tetrakis(perfluoronaphthyl)borate, tri(t-butyl) ammonium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate
  • 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 compounds can be combined with combinations of alumoxanes and NCA's (see for example, US 5,153,157; US 5,453,410; EP 0 573 120 Bl; WO 94/07928; and WO 95/14044 which discuss the use of an alumoxane in combination with an ionizing activator).
  • Chain transfer agents may also be used in the polymerizations described herein.
  • Useful chain transfer agents are typically alkylalumoxanes, a compound represented by the formula AIR3, ZnR2 (where each R is, independently, a Ci-Cs aliphatic radical, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof.
  • Aluminum alkyl or organoaluminum compounds which may be utilized as scavengers or co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethyl zinc.
  • the invention relates to polymerization processes where monomer (such as ethylene), and optionally comonomer, are contacted with a catalyst system comprising an activator and at least one catalyst compound, as described above.
  • the catalyst compound and activator may be combined in any order, and are combined typically prior to contacting with the monomer.
  • Monomers useful herein include substituted or unsubstituted C2 to C40 alpha olefins, preferably C2 to C20 alpha olefins, preferably C2 to C12 alpha olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, and isomers thereof.
  • the monomer comprises propylene and an optional comonomers comprising one or more ethylene or C 4 to C 40 olefins, preferably C 4 to C 2 o olefins, or preferably C 6 to C 12 olefins.
  • the C 4 to C 40 olefin monomers may be linear, branched, or cyclic.
  • the C to C 0 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.
  • the monomer comprises ethylene and an optional comonomers comprising one or more C 3 to C 0 olefins, preferably C to C 20 olefins, or preferably C 6 to C 12 olefins.
  • the C 3 to C 0 olefin monomers may be linear, branched, or cyclic.
  • the C 3 to C 0 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.
  • Exemplary C 2 to C 0 olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5 -cyclooctadiene, l-hydroxy-4-cyclooctene, l-acetoxy-4- cyclooctene,
  • 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.
  • Preferred diolefin monomers useful in this invention include any hydrocarbon structure, preferably C 4 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.
  • Examples of preferred dienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, particularly preferred dienes include 1,6-heptadiene, 1,7-octadiene, 1,8- nonadiene, 1 ,9-decad
  • Preferred cyclic dienes include cyclopentadiene, vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene or higher ring containing diolefins with or without substituents at various ring positions.
  • a solution polymerization means a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert solvent or monomer(s) or their blends.
  • a solution polymerization is typically homogeneous.
  • a homogeneous polymerization is one where the polymer product is dissolved in the polymerization medium.
  • Such systems are preferably not turbid as described in J. Vladimir Oliveira, C. Dariva and J. C. Pinto, Ind. Eng. Chem. Res. 29, 2000, 4627.
  • a bulk polymerization means a polymerization process in which the monomers and/or comonomers being polymerized are used as a solvent or diluent using little or no inert solvent as a solvent or diluent.
  • a small fraction of inert solvent might be used as a carrier for catalyst and scavenger.
  • a bulk polymerization system contains less than 25 wt% of inert solvent or diluent, preferably less than 10 wt%, preferably less than 1 wt%, preferably 0 wt%.
  • Polymerization processes of this invention can be carried out in any manner known in the art. Any suspension, homogeneous, bulk, or solution, polymerization process known in the art can be used. Such processes can be run in a batch, semi-batch, or continuous mode. Homogeneous polymerization processes are preferred. (Preferred homogeneous polymerization processes are those where at least 90 wt% of the product is soluble in the reaction media.) A bulk homogeneous process is particularly preferred, especially one where monomer concentration in all feeds to the reactor is 70 vol% or more.
  • the process is a solution process.
  • 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 C 4 _ 10 alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene.
  • straight and branched-chain hydrocarbons such as isobut
  • Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3 -methyl- 1- pentene, 4-methyl- 1-pentene, 1-octene, 1-decene, and mixtures thereof.
  • aliphatic hydrocarbon solvents are used as the solvent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof.
  • the solvent is not aromatic, preferably aromatics are present in the solvent at less than 1 wt%, preferably less than 0.5 wt%, preferably less than 0 wt% based upon the weight of the solvents.
  • the feed concentration of the monomers and comonomers for the polymerization is 60 vol% solvent or less, preferably 40 vol% or less, or preferably 20 vol% or less, based on the total volume of the feedstream.
  • the polymerization is run in a bulk process.
  • Preferred polymerizations can be run at any temperature and/or pressure suitable to obtain the desired ethylene polymers.
  • Typical temperatures and/or pressures include a temperature in the range of from about 60°C to about 200°C, preferably about 70°C to about 200°C, preferably about 80°C to about 175°C, preferably from about 85°C to about 160°C; and optionally at a pressure in the range of from about 0.35 MPa to about 10 MPa, preferably from about 0.45 MPa to about 6 MPa, or preferably from about 0.5 MPa to about 4 MPa.
  • the run time of the reaction is up to 300 minutes, preferably in the range of from about 5 to 250 minutes, or preferably from about 10 to 120 minutes.
  • 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).
  • alumoxane is present at zero mol%, alternately the alumoxane is present at a molar ratio of aluminum to transition metal less than 500: 1, preferably less than 300:1, preferably less than 100:1, preferably less than 1:1.
  • scavenger such as tri-alkyl aluminum
  • the scavenger is present at zero mol%, alternately the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, preferably less than 50:1, preferably less than 15:1, preferably less than 10:1.
  • the polymerization :
  • an aliphatic hydrocarbon solvent such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; preferably where aromatics are 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 comprises less than 0.5 mol%, preferably 0 mol% alumoxane, alternately the alumoxane is present at a molar ratio of aluminum to transition metal less than 500:1, preferably less than 300:1, preferably less than 100:1, preferably less than 1:1;
  • the polymerization preferably occurs in one reaction zone
  • the productivity of the catalyst compound is at least 80,000 g/mmol/hr (preferably at least 150,000 g/mmol/hr, preferably at least 200,000 g/mmol/hr, preferably at least 250,000 g/mmol/hr, preferably at least 300,000 g/mmol/hr);
  • scavengers such as trialkyl aluminum compounds
  • scavengers are absent (e.g., present at zero mol%, alternately the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, preferably less than 50: 1, preferably less than 15:1, preferably less than 10: 1); and
  • the catalyst system used in the polymerization comprises no more than one catalyst compound.
  • a "reaction zone” also referred to as a "polymerization zone” is a vessel where polymerization takes place, for example a batch reactor. When multiple reactors are used in either series or parallel configuration, each reactor is considered as a separate polymerization zone. For a multi-stage polymerization in both a batch reactor and a continuous reactor, each polymerization stage is considered as a separate polymerization zone.
  • the polymerization occurs in one reaction zone.
  • additives may also be used in the polymerization, as desired, such as one or more scavengers, promoters, modifiers, chain transfer agents (such as diethyl zinc), reducing agents, oxidizing agents, hydrogen, aluminum alkyls, or silanes.
  • Useful chain transfer agents are typically alkylalumoxanes, a compound represented by the formula AIR3, ZnR2 (where each R is, independently, a Ci-C 8 aliphatic radical, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof.
  • This invention also relates to compositions of matter produced by the methods described herein.
  • the process described herein produces olefin polymers, preferably polyethylene and polypropylene homopolymers and copolymers.
  • the polymers produced herein are homopolymers of ethylene or propylene, are copolymers of ethylene preferably having from 0 to 45 mol% (alternately from 0.5 to 35 mol%, alternately from 1 to 25 mol%, preferably from 3 to 10 mol%) of one or more C3 to C20 olefin comonomer (preferably norbornene and or C3 to C12 alpha-olefin, preferably propylene, butene, hexene, octene, decene, dodecene, norbornene preferably propylene, butene, hexene, octene, norbornene), or are copolymers of propylene preferably having from 0 to 45 mol% (alternately from 0.1 to 25 mol%, alternately from 0.5 to 20 mol%, alternately from 1 to 15 mol%, alternately from 3 to 10 mol%) of one or more of C2 or C
  • the monomer is ethylene and the comonomer is hexene, preferably from 1 to 15 mol% hexene, alternately 1 to 10 mol%.
  • the monomer is ethylene and the comonomer is octene, preferably from 1 to 15 mol% octene, alternately 1 to 10 mol%.
  • the monomer is ethylene and the comonomer is norbornene, preferably from 1 to 40 mol% norbornene, alternately 1 to 10 mol%.
  • the polymers produced herein are copolymers of ethylene preferably having from 0 to 25 mol% (alternately from 0.5 to 20 mol%, alternately from 1 to 15 mol%, preferably from 3 to 10 mol%) of one or more C3 to C20 olefin comonomers (preferably C3 to C12 alpha-olefin, preferably propylene, butene, hexene, octene, decene, dodecene, norbornene, preferably propylene, butene, hexene, octene), and from 0.1 to 25 mol% of a diene (alternately from 0.5 to 20 mol%, alternately from 1 to 15 mol%, preferably from 3 to 10 mol%), preferably the diene comprises one or more of butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene
  • the polymers produced herein are copolymers of ethylene preferably having from 0 to 25 mol% (alternately from 0.5 to 20 mol%, alternately from 1 to 15 mol%, preferably from 3 to 10 mol%) of one or more C3 to C20 olefin comonomers (preferably C3 to C12 alpha-olefin, preferably propylene, butene, hexene, octene, decene, dodecene, norbornene, preferably propylene, butene, hexene, octene, norbornene), and from 0.1 to 25 wt% of a diene (alternately from 0.5 to 20 mol%, alternately from 1 to 15 mol%, preferably from 3 to 10 mol%), preferably vinylnorbornene, norbornadiene, ethylidene norbornene, or a mixture thereof (such as vinylnorbornene and
  • the polymers produced herein have an Mw of 100,000 to 1,000,000 g/mol (preferably 125,000 to 850,000 g/mol, preferably 150,000 to 750,000 g/mol), and/or an Mw/Mn of greater than 1 to 40 (alternately 1.2 to 20, alternately 1.3 to 10, alternately 1.4 to 5, 1.5 to 4, alternately 1.5 to 3).
  • the polymer produced herein has a unimodal or multimodal molecular weight distribution as determined by Gel Permeation Chromatography (GPC).
  • GPC Gel Permeation Chromatography
  • unimodal is meant that the GPC trace has two peaks or inflection points.
  • multimodal is meant that the GPC trace has at least three peaks or inflection points.
  • An inflection point is that point where the second derivative of the curve changes in sign (e.g., from negative to positive or vice versus).
  • Mw, Mn, MWD are determined by GPC as described in US 2006/0173123, pages 24-25, paragraphs [0334] to [0341].
  • the polymer produced herein has a composition distribution breadth index (CDBI) of 50% or more, preferably 60% or more, preferably 70% or more.
  • CDBI is a measure of the composition distribution of monomer within the polymer chains and is measured by the procedure described in PCT publication WO 93/03093, published February 18, 1993, specifically columns 7 and 8 as well as in Wild et al, J. Poly. Sci., Poly. Phys. Ed., Vol. 20, p. 441 (1982) and US 5,008,204, including that fractions having a weight average molecular weight (Mw) below 15,000 are ignored when determining CDBI.
  • Mw weight average molecular weight
  • the polymer (preferably the polyethylene, polypropylene or ethylene propylene diene monomer polymer) produced herein is combined with one or more additional polymers prior to being formed into a film, molded part or other article.
  • additional polymers include polyethylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene, and/or butene, and/or hexene, polybutene, 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-1, isotactic polybutene, ABS resins, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer,
  • the polymer (preferably the polyethylene, polypropylene or EPDM) is present in the above blends, at from 10 to 99 wt%, based upon the weight of the polymers in the blend, preferably 20 to 95 wt%, even more preferably at least 30 to 90 wt%, even more preferably at least 40 to 90 wt%, even more preferably at least 50 to 90 wt%, even more preferably at least 60 to 90 wt%, even more preferably at least 70 to 90 wt%.
  • the polymer preferably the polyethylene, polypropylene or EPDM
  • the blends described above may be produced by mixing the polymers of the invention with one or more polymers (as described above), by connecting reactors together in series to make reactor blends or by using more than one catalyst in the same reactor to produce multiple species of polymer.
  • the polymers can be mixed together prior to being put into the extruder or may be mixed in an extruder.
  • the blends may be formed using conventional equipment and methods, such as by dry blending the individual components and subsequently melt mixing in a mixer, or by mixing the components together directly in a mixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin-screw extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization process, which may include blending powders or pellets of the resins at the hopper of the film extruder. Additionally, additives may be included in the blend, in one or more components of the blend, and/or in a product formed from the blend, such as a film, as desired.
  • a mixer such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin-screw extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization
  • additives are well known in the art, and can include, for example: fillers; antioxidants (e.g., hindered phenolics such as IRGANOXTM 1010 or IRGANOXTM 1076 available from Ciba- Geigy); phosphites (e.g., IRGAFOSTM 168 available from Ciba-Geigy); anti-cling additives; tackifiers, such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosins; UV stabilizers; heat stabilizers; anti-blocking agents; release agents; anti- static agents; pigments; colorants; dyes; waxes; silica; fillers; talc; and the like.
  • antioxidants e.g., hindered phenolics such as IRGANOXTM 1010 or IRGANOXTM 1076 available from Ciba- Geig
  • Catalyst A Catalyst B
  • Catalysts A and B were made according to the procedures described below.
  • Catalyst C is (o-SiEt 3 -Ph) 2 C(Cp)(3,7 di-t-Bu-Flu)HfMe 2 .
  • Catalyst D is Ph 2 C(Cp)(3,7 di-Ph-Flu)HfMe 2 .
  • Catalyst E is Ph 2 C(Cp)(3,7 di-t-Bu-Flu)HfMe 2 .
  • Crystallization temperature (T c ) and melting temperature (or melting point, T m ) are measured using Differential Scanning Calorimetry (DSC) on a commercially available instrument (e.g., TA Instruments 2920 DSC).
  • DSC Differential Scanning Calorimetry
  • 6 to 10 mg of molded polymer or plasticized polymer are sealed in an aluminum pan and loaded into the instrument at room temperature.
  • Melting data (first heat) is acquired by heating the sample to at least 30°C above its melting temperature, typically 220°C for polypropylene, at a heating rate of 10°C/min. The sample is held for at least 5 minutes at this temperature to destroy its thermal history.
  • Crystallization data are acquired by cooling the sample from the melt to at least 50°C below the crystallization temperature, typically -50°C for polypropylene, at a cooling rate of 20°C/min. The sample is held at this temperature for at least 5 minutes, and finally heated at 10°C/min to acquire additional melting data (second heat).
  • the endothermic melting transition (first and second heat) and exothermic crystallization transition are analyzed according to standard procedures. The melting temperatures reported are the peak melting temperatures from the second heat unless otherwise specified.
  • the melting temperature is defined to be the peak melting temperature from the melting trace associated with the largest endothermic calorimetric response (as opposed to the peak occurring at the highest temperature).
  • the crystallization temperature is defined to be the peak crystallization temperature from the crystallization trace associated with the largest exothermic calorimetric response (as opposed to the peak occurring at the highest temperature).
  • Areas under the DSC curve are used to determine the heat of transition (heat of fusion, Hf, upon melting or heat of crystallization, H c , upon crystallization), which can be used to calculate the degree of crystallinity (also called the percent crystallinity).
  • the percent crystallinity (X%) is calculated using the formula: [area under the curve (in J/g) / H° (in J/g)] * 100, where H° is the ideal heat of fusion for a perfect crystal of the homopolymer of the major monomer component.
  • Ph2CCp(C2Me 4 (CH2)2)2FlLi (1.6 g, 2.6 mmol) was isolated by filtration and washed by hexane. It was then dissolved in THF (50 ml) and KH (0.4g, 10.4 mmol) was added in one portion. The reaction was stirred at room temperature for 3 days. Crude l H NMR showed that the reaction was complete. Excess KH was removed by filtration. All volatiles were removed under vacuo. The product (1.25 g) was isolated as a dark purple solid.
  • the solid Li/K salt (1.25 g, 1.78 mmol) was slurried in Et20 (10 ml) and toluene (20 ml) mixture and reacted with ZrCl 4 (0.415 g, 1.78 mmol). The reaction was stirred at room temperature for 6 hours. Crude l H NMR showed that the reaction was complete. MeMgl (1.4 ml, 3 M in Et20) was then added and the reaction was stirred at 48°C for 16 hours. Crude l H NMR showed that reaction is complete. The reaction was cooled to room temperature and 1, 4 dioxane (0.6 ml) was added.
  • the solid dilithio salt (1.0 g) was slurried in Et20 (50 ml) and reacted with HfCl 4 (0.4 g). The reaction was stirred at room temperature for 30 min. Crude l H NMR showed that the reaction was complete. MeMgl (1.0 g, 3 M in Et20) was then added and the reaction was stirred at 70°C for 1 hours. Crude 3 ⁇ 4 NMR showed that reaction is complete. The reaction was cooled to room temperature and 1, 4 dioxane (2 ml) was added. The mixture was stirred for 15 min and solids were removed by filtration on celite. All volatiles were then removed under vacuo.
  • Typical solution polymerizations were carried out in using high throughput robotic system manufactured by Symyx Technologies (Santa Clara, CA). The experimental details were developed using Library Studio version 7.1.9. The reactions were carried out in parallel with robotic control and typically take less than 2 hrs for completion. Individual reaction wells were lined with disposable glass inserts and were equipped with Teflon stirring paddles. Stock solutions of metallocene and activator in toluene were added separately to an isohexane reaction solvent containing a specific amount of scavenger, Al(CsHi7)3. Monomers were then added and the reactions controlled either by time or in some cases by a pre-specified pressure drop. The total volume of monomers, solvent, metallocene, activator and scavenger was maintained at 5.4 ml. The reactions were quenched with CO2 addition and the volatiles were removed under reduced pressure.
  • the ethylene pressure was maintained at 125 psi and 50 microliters of octene was used per run.
  • the reaction temperature was 110°C.
  • the amount of activator (N,N- dimethylanilinium tetrakis(pentafluorophenyl)borate) was 0.022 micromol and that of the catalyst compound (A, C, D, or E) was 0.020 micromol per experiment.
  • the scavenger used was tri-n-octylaluminum in the amount of 0.45 micromol per experiment.
  • the reaction was quenched after 20 psi ethylene was consumed. Relative activities are reported in Figure 1.
  • Catalyst compounds A, C and D were run at 3 different temperatures (65 °C, 85 °C, and 115°C) using 60 microliters of octene. All other variables were the same as above.
  • Figures 2, 3, and 4 show comparisons of molecular weight and octene comonomer content.
  • Figure 5 shows the relative activities of Catalyst compounds A, C, and D at 65°C, 85°C, and 115°C. The data in the figures are the average of 4 runs each and show that catalyst compound A produces the highest Mn at any temperature but is superior at 115°C.
  • Catalyst compounds A, C, D, and E were run according to the procedure above with ethylene and propylene at 110°C. Ethylene pressure was 125 psi. Propylene was present at 75, 150, or 250 microliters. Propylene comonomer wt% incorporation Mw and Mn are listed in the table below. Note that Mw's are higher for inventive Catalyst A at same level of propylene incorporation as compared with benchmark Catalyst C.
  • Tri-n-octylaluminum was used as a scavenger in the amount of 0.450 micromol. The reaction was quenched when 40 psi of ethylene was consumed. The data are reported in Figures 6 and 7 (data points in figure 6 are average of at least 5 replicates and at least 6 replicates in Figure 7). The procedure above was followed for additional ethylene-norbornene copolymerizations using activator N,N-dimethylanilinium tetrakis(pentafluoronaphthnyl)borate. Norbornene was added as a solution of 85 wt% norbornene in toluene. To each cell, 42 microliters of the NB solution was added.
  • the ethylene pressure was maintained at 125 psi throughout the reaction.
  • the reaction temperature was 110°C.
  • the catalyst compound amount for each cell was 0.02 micromol and the amount of activator was 0.022 micromol.
  • Tri-n-octylaluminum was used as a scavenger in the amount of 0.450 micromol.
  • the reaction was quenched when 40 psi of ethylene was consumed.
  • the data are reported in figures 8 and 9 (data points in figure 8 are average of at least 4 replicates and at least 6 replicates in Figure 9).
  • compositions, an element or a group of elements are preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” or “selected from the group of consisting of,” preceding the recitation of the composition, element, or elements and vice versa.

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Abstract

La présente invention concerne un procédé de polymérisation d'oléfines comprenant la mise en contact, en phase en solution à une température de 60 °C à 200 °C, d'éthylène, et d'au moins un comonomère d'oléfine avec un système de catalyseur comprenant un activateur d'anions non coordonnateur et un composé de catalyseur de métallocène, de préférence représenté par la formule : et 2) l'obtention d'un polymère d'éthylène ayant un Mw supérieur à 100 000 g/mol, de préférence supérieur à 400 000 g/mol.
PCT/US2018/017752 2017-03-27 2018-02-12 Procédé de préparation de copolymères d'éthylène en solution WO2018182860A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020219050A1 (fr) * 2019-04-25 2020-10-29 Exxonmobil Chemical Patents Inc. Activateurs de benzimidazolium de type anion non coordonnants
WO2021101153A1 (fr) * 2019-11-18 2021-05-27 한화솔루션 주식회사 Polymère oléfinique et son procédé de préparation
US11059791B2 (en) 2019-04-25 2021-07-13 Exxonmobil Chemical Patents Inc. Non-coordinating anion type benzimidazolium activators

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JP2004051676A (ja) * 2002-07-16 2004-02-19 Mitsui Chemicals Inc エチレン系共重合体の製造方法
US20060270812A1 (en) * 2004-03-31 2006-11-30 Mitsui Chemicals, Inc. Process for producing olefin polymers
WO2013161833A1 (fr) * 2012-04-26 2013-10-31 三井化学株式会社 Procédé de production de polymère d'oléfine
WO2015122414A1 (fr) * 2014-02-13 2015-08-20 三井化学株式会社 Procédé de production d'un copolymère éthylène/alpha-oléfine
EP3106481A1 (fr) * 2014-02-14 2016-12-21 Mitsui Chemicals, Inc. Copolymère d'éthylène/alpha-oléfine/polyène non-conjugué, son procédé de production, et utilisation associée

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004051676A (ja) * 2002-07-16 2004-02-19 Mitsui Chemicals Inc エチレン系共重合体の製造方法
US20060270812A1 (en) * 2004-03-31 2006-11-30 Mitsui Chemicals, Inc. Process for producing olefin polymers
WO2013161833A1 (fr) * 2012-04-26 2013-10-31 三井化学株式会社 Procédé de production de polymère d'oléfine
WO2015122414A1 (fr) * 2014-02-13 2015-08-20 三井化学株式会社 Procédé de production d'un copolymère éthylène/alpha-oléfine
EP3106481A1 (fr) * 2014-02-14 2016-12-21 Mitsui Chemicals, Inc. Copolymère d'éthylène/alpha-oléfine/polyène non-conjugué, son procédé de production, et utilisation associée

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020219050A1 (fr) * 2019-04-25 2020-10-29 Exxonmobil Chemical Patents Inc. Activateurs de benzimidazolium de type anion non coordonnants
US11059791B2 (en) 2019-04-25 2021-07-13 Exxonmobil Chemical Patents Inc. Non-coordinating anion type benzimidazolium activators
WO2021101153A1 (fr) * 2019-11-18 2021-05-27 한화솔루션 주식회사 Polymère oléfinique et son procédé de préparation

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