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WO2020214288A1 - Systèmes catalytiques amido-benzoquinone et procédés associés - Google Patents

Systèmes catalytiques amido-benzoquinone et procédés associés Download PDF

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Publication number
WO2020214288A1
WO2020214288A1 PCT/US2020/022244 US2020022244W WO2020214288A1 WO 2020214288 A1 WO2020214288 A1 WO 2020214288A1 US 2020022244 W US2020022244 W US 2020022244W WO 2020214288 A1 WO2020214288 A1 WO 2020214288A1
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Prior art keywords
catalyst system
catalyst
halogen
ethylene
hydrocarbyl
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Inventor
Tzu-Pin Lin
Lubin Luo
Alex E. Carpenter
Gursu CULCU
Catherine A. Faler
Irene C. Cai
John R. Hagadorn
Jo Ann M. Canich
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon 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
    • 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61908—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • the present disclosure relates to amido-benzoquinone transition metal complexes, catalyst systems including amido-benzoquinone transition metal complexes, and polymerization processes to produce polyolefin polymers such as polyethylene -based polymers and polypropylene-based polymers.
  • Olefin polymerization catalysts are of great use in industry and polyolefins are widely used commercially because of their robust physical properties. Hence, there is interest in finding new catalyst systems that increase the marketing value of the catalyst and allow the production of polymers having improved properties.
  • Polyolefins such as polyethylene, often have a comonomer, such as hexene, incorporated into the polyethylene backbone. These copolymers provide varying physical properties compared to polyethylene alone and are typically produced in a low pressure reactor, utilizing, for example, solution, slurry, or gas phase polymerization processes. Polymerization may take place in the presence of catalyst systems such as those using a Ziegler-Natta catalyst, a transition metal based catalyst, or a metallocene catalyst.
  • catalyst systems such as those using a Ziegler-Natta catalyst, a transition metal based catalyst, or a metallocene catalyst.
  • pre-catalysts should be thermally stable at and above ambient temperature, as they are often stored for weeks before being used.
  • the performance of a given catalyst is closely influenced by the reaction conditions, such as the monomer concentrations and temperature.
  • the solution process which benefits from being run at temperatures above 120°C, is particularly challenging for catalyst development. At such high reactor temperatures, it is often difficult to maintain high catalyst activity and high molecular weight capability as both attributes quite consistently decline with an increase of reactor temperature.
  • References of interest include: CN107641164A; CN107955088A;
  • the present disclosure relates to catalyst systems including a catalyst compound and an activator, where the catalyst compound is represented by Formula (I):
  • M is a group 8, 9, or 10 transition metal
  • L is a Lewis base
  • j 0, 1, or 2;
  • X is an anionic ligand
  • k 0, 1, or 2;
  • R 1 , R 2 , R 3 , and R 4 are independently selected from hydrogen, substituted or unsubstituted C1-C30 hydrocarbyl, -CN, -NR' 2 , -OR' , halogen, -NO 2 , -SiR 3', five-, six-, or seven- membered heterocyclyl (where each R is independently hydrogen, C 1 -C 30 hydrocarbyl, and R is optionally substituted by halogen, or two R ’ radicals optionally bond to form a five- or six- membered ring), or -SiR " 3 , -SiR " 2 (OR ), -SiR" (OR “ ) 2 , or -Si(OR )3 (where each R " and R ” is independently hydrogen, C 1 -C 30 hydrocarbyl, or two R" radicals optionally bond to form a five- or six-membered ring);
  • R 1 , R 2 , R 3 , and R 4 are optionally substituted by halogen, -NO 2 , -CN, -CF 3 , - CF 2 CF 3 , -CH 2 CF 3 , -NR 2 , -OR, -OSi(OR) 3 , where each R is independently hydrogen, C 1 -C 30 hydrocarbyl, and R ’ is optionally substituted by halogen, or two R ’ radicals optionally bond to form a five- or six-membered ring, or -SiR 3 where each R " is independently hydrogen, C 1 -C 30 hydrocarbyl, or two R radicals optionally bond to form a five- or six-membered ring; and the activator is represented by Formula (II):
  • M’ is selected from boron, aluminum, or gallium
  • E 1 , E 2 , and E 3 are independently selected from oxygen, nitrogen, phosphorus, sulfur or halogen;
  • R a , R b , and R c are independently selected from a C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 30 carbon atoms, alkylaryl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 30 carbon atoms, a support material, or two or more of R a , R b , and R c are optionally bonded to form a five-, six- or seven-membered carbocyclic or heterocyclic ring, the heterocyclic ring comprising at least one atom from the group consisting of N, P, O and S;
  • R a , R b , and R c are optionally substituted by halogen, -NO 2 , -CF 3 , -CF 2 CF 3 ,
  • each R is independently hydrogen, C 1 -C 22 -hydrocarbyl, and R is optionally substituted by halogen, or two R’ radicals optionally bond to form a five- or six- membered ring
  • -SiR 3 where each R" is independently hydrogen, C 1 -C 22 -hydrocarbyl, or two R radicals optionally bond to form a five- or six-membered ring
  • w is 0 if E 1 is a halogen, y is 0 if E 2 is a halogen, and z is 0 if E 3 is a halogen;
  • w is 1 if E 1 is oxygen or sulfur and w is 2 if E 1 is nitrogen or phosphorus;
  • y is 1 if E 2 is oxygen or sulfur and y is 2 if E 2 is nitrogen or phosphorus; and z is 1 if E 3 is oxygen or sulfur and z is 2 if E 3 is nitrogen or phosphorus.
  • the present disclosure provides a catalyst system including an activator, a catalyst support, and a catalyst of the present disclosure.
  • a polymerization process including contacting one or more olefin monomers with a catalyst system of the present disclosure.
  • the present disclosure provides a polyolefin formed by a catalyst system and or method of the present disclosure.
  • the present disclosure relates to amido-benzoquinone transition metal catalyst systems for polymerization of olefins.
  • the catalyst systems include an amido-benzoquinone transition metal catalyst compound and an activator, and may be supported. It has been discovered that catalyst systems including a group 8, 9, or 10 transition metal and an aryloxymetal activator may have higher activity in the polymerization of ethylene and reduced activator usage when compared to other late transition metal catalyst systems.
  • Catalyst systems and methods of the present disclosure can provide formation of polymers having high molecular weights and the ability to make an increased amount of polymer in a given reactor, as compared to conventional catalysts.
  • Catalyst systems and methods of the present disclosure can provide highly active catalysts capable of operating at high reactor temperatures with reduced quantities of activator while producing polymers with controlled molecular weights.
  • a“group 8 metal” is an element from group 8 of the Periodic Table, e.g. Fe, Ru, or Os.
  • Catalyst productivity is a measure of how many grams of polymer (P) are produced using a polymerization catalyst including W mmol 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 gP mmolcat -1 hr -1 .
  • Conversion is the amount of monomer that is converted to polymer product, and is reported as mol% and is calculated based on the polymer yield and the amount of monomer fed into the reactor.
  • An“olefin” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • olefin present in such polymer or copolymer is the polymerized form of the olefin.
  • 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.
  • copolymer includes terpolymers. “Different” as used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically.
  • An "ethylene polymer” or “ethylene copolymer” is a polymer or copolymer including at least 50 mol% ethylene derived units
  • a "propylene polymer” or “propylene copolymer” is a polymer or copolymer including at least 50 mol% propylene derived units, and so on.
  • A“linear alpha-olefin” is an alpha-olefin defined in this paragraph where R 1 is hydrogen, and R 2 is hydrogen or a linear alkyl group.
  • ethylene shall be considered an a-olefin.
  • C n means hydrocarbon(s) having n carbon atom(s) per molecule, where n is a positive integer.
  • 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.
  • a“Cn-Cm” group or compound refers to a group or compound including carbon atoms at a total number thereof in the range from n to m.
  • a C1-C50 hydrocarbyl group refers to a hydrocarbyl group including carbon atoms at a total number thereof in the range from 1 to 50 and a C1-C50 alkyl group refers to an alkyl group including carbon atoms at a total number thereof in the range from 1 to 50.
  • hydrocarbyl radical “hydrocarbyl group,” or“hydrocarbyl” may be used interchangeably and are defined to mean a group consisting of hydrogen and carbon atoms.
  • Suitable hydrocarbyls are C1-C100 radicals that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic.
  • radicals include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, tert- butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and aryl groups, such as phenyl, benzyl, and naphthyl.
  • alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, tert- butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopen
  • heteroatom refers to a group 13-17 element, excluding carbon.
  • a heteroatom may include B, Si, Ge, Sn, N, P, As, O, S, Se, Te, F, Cl, Br, and I.
  • heteroatom may include the aforementioned elements with hydrogens attached, such as BH, B3 ⁇ 4, S1H 2 , OH, NH, NH 2 , etc.
  • substituted heteroatom describes a heteroatom that has one or more of these hydrogen atoms replaced by a hydrocarbyl or substituted hydrocarbyl group(s).
  • Halocarbyl radicals are radicals in which one or more hydrocarbyl hydrogen atoms have been substituted with at least one halogen (e.g. F, Cl, Br, I) or halogen-containing group (e.g. CF 3 ).
  • halogen e.g. F, Cl, Br, I
  • halogen-containing group e.g. CF 3
  • substituted aromatic means an aromatic group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group.
  • alkoxide mean an alkyl or aryl group bound to an oxygen atom, such as an alkyl ether or aryl ether group/radical connected to an oxygen atom and can include those where the alkyl/aryl group is a Ci to Cio hydrocarbyl.
  • the alkyl group may be straight chain, branched, or cyclic.
  • the alkyl group may be saturated or unsaturated. Examples of suitable alkoxide substituents can include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso- butoxy, sec-butoxy, tert-butoxy, phenoxy.
  • alkyl radical is defined to be Ci-Cioo alkyls, which may be linear, branched, or cyclic.
  • radicals can include 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.
  • aryl or "aryl group” means an aromatic ring and the substituted variants thereof, such as phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl.
  • heteroaryl means an aryl group where a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, such as N, O, or S.
  • aromatic also refers to pseudoaromatic heterocycles which are heterocyclic substituents that have similar properties and structures (nearly planar) to aromatic heterocyclic ligands, but are not by definition aromatic.
  • arylalkyl means an aryl group where a hydrogen has been replaced with an alkyl or substituted alkyl group.
  • 3,5'-di-tert-butyl-phenyl indenyl is an indene substituted with an arylalkyl group.
  • alkylaryl means an alkyl group where a hydrogen has been replaced with an aryl or substituted aryl group.
  • phenethyl indenyl is an indene substituted with an ethyl group bound to a benzene group.
  • a heterocyclic ring is a ring having a heteroatom in the ring structure as opposed to a heteroatom substituted ring where a hydrogen on a ring atom is replaced with a heteroatom.
  • tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatom substituted ring.
  • Mn is number average molecular weight
  • Mw is weight average molecular weight
  • Mz is z average molecular weight
  • wt% is weight percent
  • mol% is mole percent.
  • Molecular weight distribution also referred to as polydispersity index (PDI)
  • PDI polydispersity index
  • melting points are differential scanning calorimetry (DSC) second melt.
  • MAO is methylalumoxane
  • THF is tetrahydrofuran
  • RT room temperature (and is 23 °C unless otherwise indicated).
  • A“catalyst system” is a mixture or reaction product of at least one catalyst compound, at least one activator, an optional co-activator, and an optional support material.
  • Catalyst system means the unactivated catalyst complex (pre-catalyst) together with an activator and, optionally, a co- activator.
  • it means the activated complex and the activator or other charge-balancing moiety.
  • the transition metal compound may be neutral as in a pre-catalyst, or a charged species with a counter ion as in an activated catalyst system.
  • a polymerization catalyst system is a catalyst system that can polymerize monomers to polymer.
  • the catalyst may be described as a catalyst, a catalyst precursor, a pre-catalyst compound, catalyst compound or a transition metal compound, and these terms are used interchangeably.
  • An“anionic ligand” is a negatively charged ligand which donates one or more electrons to a metal ion.
  • A“Lewis base” is a neutrally charged ligand which donates one or more pairs of electrons to a metal ion.
  • a scavenger is a compound that can be added to facilitate polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as coactivators. A coactivator, that is not a scavenger, may also be used in conjunction with an activator in order to form an active catalyst. In at least one embodiment, a coactivator can be pre-mixed with the transition metal compound to form an alkylated transition metal compound.
  • 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 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 can be homogeneous.
  • a homogeneous polymerization is one where the polymer product is dissolved in the polymerization medium. Suitable systems may be not turbid as described in J. Vladimir Oliveira, C. Dariva and J. C. Pinto (2000) Ind. Eng. Chem. Res., v.29, p. 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, such as less than 10 wt%, such as less than 1 wt%, such as 0 wt%.
  • This present disclosure relates to a novel group of amido-benzoquinone catalyst compounds and activators, said catalyst having a metal atom attached to Lewis base ligands.
  • this present disclosure related to a catalyst compound, and catalyst systems including such compounds, represented by Formula (I):
  • M is a group 8, 9, or 10 transition metal
  • L is a Lewis base
  • j 0, 1, or 2;
  • X is an anionic ligand
  • k 0, 1, or 2;
  • R 1 , R 2 , R 3 , and R 4 are independently selected from hydrogen, substituted or unsubstituted C 1 -C 30 hydrocarbyl, -CN, -NR 2 , -OR , halogen, -NO 2 , -SiR 3 , five-, six-, or seven- membered heterocyclyl (where each R is independently hydrogen, C 1 -C 30 hydrocarbyl, and R is optionally substituted by halogen, or two R ’ radicals optionally bond to form a five- or six- membered ring), or -SiR 3 , -SiR " 2 (OR “ , -SiR " OR “ 2 , or -Si(OR ) 3 (where each R “ and R ” is independently hydrogen, C 1 -C 30 hydrocarbyl, or two R radicals optionally bond to form a five- or six- membered ring);
  • R 1 , R 2 , R 3 , and R 4 are optionally substituted by halogen, -NO 2 , -CN, -CF 3 ,
  • M of Formula (I) is a metal selected from Ru, Rh, Pd, Fe, Co, or Ni. In some embodiments, M is a metal selected from Fe, Co, or Ni. In at least one embodiment M is Ni. Preferably M is Ni.
  • Each L, if any, of Formula (I) can be independently selected from ethers, amines, imines, phosphines, nitriles, carbenes, thioethers, esters, THF, and dimethylsulfide.
  • L is selected from an imine, an amine, a phosphine, a nitrile, an ether, a thioether, a sulfoxide, or a carbene.
  • L is a phosphine, such as triphenylphosphine.
  • L may be absent, present, or present in multiples such that j can be 0, 1, or 2. If j is 2, then two L’s may combine to form part of a fused ring or ring system.
  • j is 1. In at least one embodiment] is 1 and L is a phosphine.
  • Each X, if any, of Formula (I) can be independently selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, and a combination(s) thereof, such as each X is independently selected from halides and C 1 to C 7 hydrocarbyl groups, such as X is an alkyl, aryl group, an arylakyl group, or an alkylaryl group, such as each X is a halogen, methyl, ethyl, propyl, benzyl, phenyl, or naphthyl, such as X is phenyl.
  • X may be absent, present, or present in multiples such that k can be 0, 1, or 2. If k is 2, then two X’s may form part of a fused ring or ring system. In some embodiments k is 1. In at least one embodiment, k is 1 , and X is a phenyl group.
  • two L groups of Formula (I) may be joined together to form a bidentate Lewis base; an X group may be joined to an L group to form a monoanionic bidentate group; or any two X groups may be joined together to form a dianionic ligand group.
  • R 3 and R 4 of Formula (I) bond together to form a substituted or unsubstituted aryl group.
  • R 3 and R 4 bond together to form an aromatic ring incorporating the carbon atoms to which R 3 and R 4 are attached.
  • R 3 and R 4 bond to form a 5 or 6 membered carbocyclic or heterocyclic ring, such as a C 6 carbocyclic ring.
  • R 3 and R 4 bond to form a C 6 aromatic ring.
  • R 1 of Formula (I) is selected from an aryl, an arylalkyl, an alkylaryl, or an alkyl.
  • R 1 is a 2,6-substituted aryl, such as
  • R 1 is a 2,4,6-substituted aryl, such as 2-chloro-4,6-dimethylphenyl, or 2,6-(diphenylmethyl)-4-methylphenyl. In at least one embodiment, R 1 is 2,6-(diphenylmethyl)-4-methylphenyl.
  • R 2 of Formula (I) is selected from hydrogen, halogen, or alkyl, for example, R 2 may be a hydrogen, methyl, ethyl, propyl, fluoro, chloro, bromo, or iodo. In some embodiments, R 2 is selected from hydrogen, methyl, fluoro, or chloro. In at least one embodiment, R 2 is hydrogen.
  • the catalyst compound represented by Formula (I) is represented by Formula (la):
  • M is a group 8, 9, orlO transition metal
  • L is a Lewis base
  • j 0, 1, or 2;
  • X is an anionic ligand
  • k 0, 1, or 2;
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 is independently selected from hydrogen, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, alkylaryl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, -NR 2 , -OR , halogen, -NO 2 , -SiR' 3 , five- , six-, or seven-membered heterocyclyl (where each R is independently hydrogen, C 1 -C 22 - alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl where alkyl has from 1 to 10 carbon
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are optionally substituted by halogen, -NO 2 , -CF3, -CF 2 CF 3 , -CH 2 CF 3 , -NR' -OR (where each R is independently hydrogen, C1-C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, and R’ is optionally substituted by halogen, or two R’ radicals optionally bond to form a five- or six-membered ring), or -SiR 3 (where each R" is independently hydrogen, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalky
  • M of Formula (la) is a metal selected from Ru, Rh, Pd, Fe, Co, or Ni. In some embodiments, M is a metal selected from Fe, Co, or Ni. In at least one embodiment M is Ni. Preferably M is Ni.
  • Each L, if any, of Formula (la) can be independently selected from ethers, amines, imines, phosphines, nitriles, carbenes, thioethers, esters, THF, and dimethylsulfide.
  • L is selected from an imine, an amine, a phosphine, a nitrile, an ether, a thioether, a sulfoxide, or a carbene.
  • L is a phosphine, such as triphenylphosphine.
  • L may be absent, present, or present in multiples such that j can be 0, 1, or 2. If j is 2, then two L’s may combine to form part of a fused ring or ring system.
  • j is 1. In at least one embodiment] is 1 and L is a phosphine.
  • Each X, if any, of Formula (la) can be independently selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, and a combination(s) thereof, such as each X is independently selected from halides and C 1 to C 7 hydrocarbyl groups, such as X is an alkyl, aryl group, an arylakyl group, or an alkylaryl group, such as each X is methyl, ethyl, propyl, benzyl, phenyl, or naphthyl, such as X is phenyl.
  • X may be absent, present, or present in multiples such that k can be 0, 1, or 2. If k is 2, then two X’s may form part of a fused ring or ring system. In some embodiments k is 1. In at least one embodiment, k is 1 , and X is a phenyl group.
  • two L groups of Formula (la) may be joined together to form a bidentate Lewis base; an X group may be joined to an L group to form a monoanionic bidentate group; or any two X groups may be joined together to form a dianionic ligand group.
  • R 5 of Formula (la) is selected from hydrogen, halogen, or alkyl, for example, R 5 may be a hydrogen, methyl, ethyl, propyl, fluoro, chloro, bromo, or iodo. In some embodiments, R 5 is selected from hydrogen, methyl, fluoro, or chloro. In at least one embodiment, R 5 is hydrogen.
  • each of R 1 , R 2 , R 3 , and R 4 of Formula (la) is independently selected from hydrogen, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, and alkylaryl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms.
  • each of R 1 , R 2 , R 3 , and R 4 is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, or hexyl. In at least one embodiment, each of R 1 , R 2 , R 3 , and R 4 is hydrogen.
  • each of R 6 , R 7 , R 8 , R 9 , and R 10 of Formula (la) is independently selected from hydrogen, halogen, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, and alkylaryl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms.
  • each of R 6 , R 7 , R 8 , R 9 , and R 10 is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, chloro, fluoro, bromo, or iodo.
  • R 6 and R 10 are independently selected from hydrogen, methyl, ethyl, propyl, phenyl, benzyl, chloro, and fluoro and each of R 7 , R 8 , and R 9 is independently selected from hydrogen, methyl, ethyl, propyl, and phenyl.
  • R 6 and R 10 are independently selected from hydrogen, methyl, ethyl, propyl, phenyl, benzyl, chloro, and fluoro, and each of R 7 , R 8 , and R 9 is independently selected from hydrogen, methyl, or phenyl.
  • Formula (la) is selected from:
  • Formula (la) is selected from:
  • 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.
  • two or more different catalyst compounds are present in the catalyst system described herein. In at least one embodiment, two or more different catalyst compounds are present in the reaction zone where the process(es) described herein occur.
  • the two transition metal compounds can be chosen such that the two are compatible.
  • a simple screening method such as by 1 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.
  • the same activator can be used 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 X ligand which is not a hydride, hydrocarbyl, or substituted hydrocarbyl
  • the transition metal compound(s) may be contacted with an alkylating compound (such as alumoxane) prior to addition of the non coordinating anion activator.
  • the two transition metal compounds may be used in any suitable ratio.
  • Suitable molar ratios of (A) transition metal compound to (B) transition metal compound (A:B) may be 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 pre-catalysts chosen, the method of activation, and the end product desired.
  • useful mole percent of A and B 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.
  • a potassium salt of an amido-benzoquinone is suspended in solvent.
  • a solution of transition metal M with at least one of L and X attached is added.
  • the mixture is warmed, stirred, and solvent removed. The residue can be washed with hydrocarbon solvent and recrystallized.
  • M’ is selected from boron, aluminum, or gallium
  • E 1 , E 2 , and E 3 are independently selected from oxygen, nitrogen, phosphorus, sulfur or halogen;
  • R a , R b , and R c are independently selected from a C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 - aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 30 carbon atoms, alkylaryl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 30 carbon atoms, a support material, or two or more of R a , R b , and R c are optionally bonded to form a five-, six- or seven-membered carbocyclic or heterocyclic ring, the heterocyclic ring comprising at least one atom from the group consisting of N, P, O and S;
  • R a , R b , and R c are optionally substituted by halogen, -NO 2 , -CF 3 , -CF 2C F 3 , - CH 2 CF 3 , -NR 2 , -OR (where each R ’ is independently hydrogen, C 1 -C 22 -hydrocarbyl, and R ’ is optionally substituted by halogen, or two R ’ radicals optionally bond to form a five- or six- membered ring), or -SiR 3 (where each R is independently hydrogen, C 1 -C 22 -hydrocarbyl, or two R radicals optionally bond to form a five- or six-membered ring);
  • w is 0 if E 1 is a halogen, y is 0 if E 2 is a halogen, and z is 0 if E 3 is a halogen;
  • w is 1 if E 1 is oxygen or sulfur and w is 2 if E 1 is nitrogen or phosphorus;
  • y is 1 if E 2 is oxygen or sulfur and y is 2 if E 2 is nitrogen or phosphorus; and z is 1 if E 3 is oxygen or sulfur and z is 2 if E 3 is nitrogen or phosphorus.
  • M’ is aluminum.
  • M is Al.
  • w, y, and z are 1.
  • E 1 , E 2 , and E 3 are oxygen.
  • w, y, and z are 2.
  • E 1 , E 2 , and E 3 are nitrogen.
  • w, y, and z are 1 and E 1 , E 2 , and E 3 are oxygen.
  • R a , R b , and R c are independently selected from aryl, arylalkyl, or alkyl. In some embodiments, R a , R b , and R c have the same chemical structure. In some embodiments, R a , R b , and R c have the same chemical structure selected from aryl, arylalkyl, or alkyl, such as phenyl, 2,3,4,5,6-pentamethylphenyl, perfluorophenyl, perchlorophenyl, -CF 3 , -CF2CF 3 , or - CH 2 CF 3 . In at least one embodiment, R a , R b , and R c are perfluorophenyl.
  • R a , R b , and R c is selected from a support.
  • Suitable supports may be an inorganic oxide, such as Groups 2, 4, 13, and 14 metal oxides, such as silica, alumina, magnesia, titania, zirconia and mixtures thereof.
  • Other suitable support materials may include, for example, functionalized polyolefins, such as finely divided polyethylene or polystyrene.
  • Particularly useful supports include silica, alumina, magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, and mixture(s) thereof.
  • R a , R b , and R c is selected from silica, alumina, or a mixture thereof.
  • the remaining R groups maybe independently selected from aryl, arylalkyl, or alkyl, for example, if R a is silica then R b and/or R c may be selected from phenyl, 2,3,4,5,6-pentamethylphenyl, perfluorophenyl, perchlorophenyl, -CF 3 , -CF 2 CF 3 , or -CH 2 CF 3 .
  • the catalyst systems described herein typically include a catalyst compound as described above and an activator as described above and may be formed by combining the catalyst compound described herein with activators in any suitable manner including combining them with physical supports, such as silica.
  • the catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in the monomer).
  • Catalyst systems of the present disclosure may have additional activators and one, two or more catalyst compounds.
  • Activators are defined to be a compound which can activate one of the catalyst compounds described above by converting the neutral metal compound to a catalytically active metal compound cation.
  • Example activators may include:
  • Alumoxane activators may be utilized as additional activators in the catalyst systems described herein.
  • Alumoxanes are generally oligomeric compounds containing -A1(R 1 )-0- sub-units, where R 1 is an alkyl group.
  • Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MM AO), ethylalumoxane and isobutylalumoxane.
  • Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is an alkyl, halide, alkoxide or amide.
  • a visually clear methylalumoxane can be used.
  • 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).
  • Another useful alumoxane is solid polymethylaluminoxane as described in US 9,340,630; US 8,404,880; and US 8,975,209.
  • the additional activator is an alumoxane (modified or unmodified)
  • at least one embodiment select the maximum amount of additional activator typically at up to a 5,000-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 suitable 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 is present at zero mole %, alternately the alumoxane is present at a molar ratio of aluminum to catalyst compound transition metal less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.
  • NCA non-coordinating anion
  • the term “non-coordinating anion” 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, preferably remaining sufficiently labile to be displaced by a neutral Lewis base.
  • NCA is also defined to include multicomponent NCA-containing activators, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, that contain an acidic cationic group and the non-coordinating anion.
  • NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, that can react with a catalyst to form an activated species by abstraction of an anionic group.
  • a Lewis acid is defined to be a compound or element that can react with an electron donor to form a bond.
  • An NCA coordinates weakly enough that a Lewis base, such as an olefin 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. "Compatible" non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes.
  • Non- coordinating anions useful in accordance with this present disclosure 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.
  • Additional activators useful herein may include an NCA, particularly a compatible NCA.
  • NCA alone or in combination with alumoxane or modified alumoxane as additional activators.
  • additional activators please see US 8,658,556 and US 6,211,105.
  • Suitable non-coordinating 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,
  • an additional activator includes a triaryl carbenium (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 carbenium such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3
  • an additional activator includes one or more of trialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(perfluoronaphthyl)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 t
  • an additional activator is represented by Formula (III):
  • Z is (L-H) or a reducible Lewis Acid
  • L is an neutral Lewis base
  • H is hydrogen
  • (L-H) + is a Brpnsted acid
  • a d- is a non-coordinating anion having the charge d-
  • d is an integer from 1 to 3, such as Z is (Ar3C + ), where Ar is aryl or aryl substituted with a heteroatom, a C 1 to C 40 hydrocarbyl, or a substituted C 1 to C 40 hydrocarbyl.
  • Z d + is the activating cation (L-H) d + , it can be 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, such as ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, dioctadecylmethylamine, phosphoniums from trie thy lphosphine, triphenylphosphine, and diphenylphosphine, oxoniums from ethers such as di
  • NCA activator is represented by the formula:
  • Z is (L-H) or a reducible Lewis Acid
  • L is an neutral Lewis base
  • H is hydrogen
  • (L-H) + is a Bronsted acid
  • a d- is a non-coordinating anion having the charge d-
  • d is an integer from 1 to 3, preferably Z is (Ar3C + ), where Ar is aryl or aryl substituted with a heteroatom, a C 1 to C 40 hydrocarbyl, or a substituted C 1 to C 40 hydrocarbyl.
  • 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 or perfluoronaphthyl group.
  • suitable A d_ also include diboron compounds as disclosed in U.S. Patent No. 5,447,895, which is fully incorporated herein by reference.
  • Suitable activator-to-catalyst ratio e.g., all activators-to-catalyst ratio can be about a 1: 1 molar ratio.
  • suitable ranges may 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.
  • suitable ranges can be from 0.5:1 to 10:1, such as 1: 1 to 5:1.
  • the catalyst compounds can be combined with combinations of the activator and additional activators including alumoxanes and NCA's (see for example, US 5,153,157; US 5,453,410; EP 0 573 120 Bl; WO 1994/007928; and WO 1995/014044 (the disclosures of which are incorporated by reference) which discuss the use of an alumoxane in combination with an ionizing activator).
  • additional activators including alumoxanes and NCA's (see for example, US 5,153,157; US 5,453,410; EP 0 573 120 Bl; WO 1994/007928; and WO 1995/014044 (the disclosures of which are incorporated by reference) which discuss the use of an alumoxane in combination with an ionizing activator).
  • Optional Scavengers Co- Activators. Chain Transfer Agents
  • scavengers or co-activators may be used.
  • 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.
  • Chain transfer agents may be used in the catalyst systems and or processes described herein.
  • Useful chain transfer agents are typically alkylalumoxanes, a compound represented by the formula AIR 3 , ZnR 2 (where each R is, independently, a C 1 -C 8 aliphatic radical, such as 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.
  • the catalyst system may include an inert physical support material.
  • the physical support material can be a porous support material, for example, talc, and inorganic oxides.
  • Other physical support materials include zeolites, clays, organoclays, or any other suitable organic or inorganic support material, or mixtures thereof.
  • the physical support material can be an inorganic oxide in a finely divided form.
  • Suitable inorganic oxide materials for use in catalyst systems may 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, or zirconia.
  • Other suitable physical support materials can be employed, for example, finely divided functionalized polyolefins, such as finely divided polyethylene or polystyrene.
  • Particularly useful supports include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, and clays. Also, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, or silica-titania. Suitable support materials include A1 2 O 3 , ZrO 2 , SiO 2 , and combinations thereof, such as SiO 2 , A1 2 O 3 , or SiO 2 /Al 2 O 3 .
  • the physical support material such as an inorganic oxide, can have a surface area of from about 10 to about 700 m 2 /g, pore volume of from about 0.1 to about 4 cc/g and average particle size of from about 5 to about 500 mm.
  • the surface area of the physical support material can be, for example, from about 50 m 2 /g to about 500 m 2 /g
  • the pore volume can be from about 0.5 cc/g to about 3.5 cc/g
  • the average particle size can be from about 10 mm to about 200 mm.
  • the surface area of the physical support material can further be from about 100 m 2 /g to about 400 m 2 /g, pore volume from about 0.8 cc/g to about 3 cc/g and average particle size from about 5 mm to about 100 pm.
  • the average pore size of the physical support material can be from 10 A to 1000 A, such as 50 A to about 500 A, such as 75 A to about 350 A.
  • Suitable silicas are marketed under the tradenames of DAVISONTM 952 or DAVISONTM 955 by the Davison Chemical Division of W.R. Grace and Company. In other embodiments DAVISONTM 948 is used.
  • a silica can be ES-70TM silica (PQ Corporation, Malvern, Pennsylvania) that has been calcined (such as at 875 °C), for example.
  • the physical support material should be dry, that is, free of absorbed water. Drying of the physical support material can be effected by heating or calcining at about 100°C to about 1,000°C, such as at least about 600°C.
  • the physical support material is silica
  • it is heated to at least 200°C, such as about 200°C to about 850°C, such as at about 600°C; and for a time of about 1 minute to about 100 hours, from about 12 hours to about 72 hours, or from about 24 hours to about 60 hours.
  • the calcined support material must have at least some reactive hydroxyl (OH) groups to produce physically supported catalyst systems of this present disclosure.
  • the calcined support material is then contacted with at least one polymerization catalyst including at least one catalyst compound and an activator.
  • the physical support material having reactive surface groups, typically hydroxyl groups, is slurried in a non-polar solvent and the resulting slurry is contacted with a solution of a catalyst compound and an activator.
  • the slurry of the physical support material is first contacted with the activator for a period of time from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.
  • the solution of the catalyst compound is then contacted with the isolated support/activator.
  • the supported catalyst system is generated in situ.
  • the slurry of the physical support material is first contacted with the catalyst compound for a period of time from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.
  • the slurry of the supported catalyst compound is then contacted with the activator solution.
  • the mixture of the catalyst, activator(s) and support is heated to about 0°C to about 70°C, such as about 23 °C to about 60°C, such as at room temperature.
  • Contact times typically range from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.
  • Suitable non-polar solvents are materials in which all of the reactants, i.e., the activator, and the catalyst compound, are at least partially soluble and which are liquid at reaction temperatures.
  • Suitable non-polar solvents are alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, although a variety of other materials including cycloalkanes, such as cyclohexane, aromatics, such as benzene, toluene, and ethylbenzene, may also be employed.
  • the present disclosure relates to polymerization processes where monomer (such as ethylene), and optionally comonomer, are contacted with a catalyst system including an activator, at least one catalyst compound, and optionally additional activators, as described above.
  • the catalyst compound and activator may be combined in any suitable order, and are combined typically prior to contacting with the monomer.
  • Monomers suitable for use may include substituted or unsubstituted C 2 to C 40 alpha olefins, such as C 2 to C 20 alpha olefins, such as C 2 to C 12 alpha olefins, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof.
  • C 2 to C 40 alpha olefins such as C 2 to C 20 alpha olefins, such as C 2 to C 12 alpha olefins, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof.
  • the monomer includes propylene and an optional comonomers including one or more ethylene or C 4 to C 40 olefins, such as C 4 to C 20 olefins, such as C 6 to C 12 olefins.
  • the C 4 to C 40 olefin monomers may be linear, branched, or cyclic.
  • the C 4 to C 40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.
  • the monomer includes ethylene and an optional comonomers including one or more C 3 to C 40 olefins, such as C 4 to C 20 olefins, such as C 6 to C 12 olefins.
  • the C 3 to C 40 olefin monomers may be linear, branched, or cyclic.
  • the C 3 to C 40 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 40 olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbomadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, such as 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 at up to 10 weight %, such as at 0.00001 to 1 weight %, such as 0.002 to 0.5 weight %, such as 0.003 to 0.2 weight %, based upon the total weight of the composition.
  • 500 ppm or less of diene is added to the polymerization, such as 400 ppm or less, such as 300 ppm or less.
  • at least 50 ppm of diene is added to the polymerization, or 100 ppm or more, or 150 ppm or more.
  • Suitable diolefin monomers useful in this present disclosure include hydrocarbon stmcture(s), such as C 4 to C 30 , having at least two unsaturated bonds, where at least two of the unsaturated bonds are readily incorporated into a polymer by either a stereospecific or a non- stereospecific catalyst(s).
  • the diolefin monomers can be selected from alpha, omega-diene monomers (i.e. di-vinyl monomers).
  • the diolefin monomers can be linear di- vinyl monomers, such as those containing from 4 to 30 carbon atoms.
  • dienes examples include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, such as dienes include 1,6-heptadiene, 1,7-octadiene, 1,8- nonadiene, 1,9-decadiene, 1,
  • Suitable cyclic dienes include cyclopentadiene, vinylnorbomene, norbomadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene or higher ring containing diolefins with or without substituents at various ring positions.
  • Polymerization processes of this present disclosure can be carried out in any suitable manner known in the art including: suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization processes. Such processes can be run in a batch, semi-batch, or continuous mode. Homogeneous polymerization processes and slurry processes can be employed. (A homogeneous polymerization process is preferably a process where at least 90 wt% of the product is soluble in the reaction media.) A homogeneous polymerization process can be a bulk homogeneous process.
  • a bulk process is preferably a process where monomer concentration in all feeds to the reactor is 70 volume % or more.
  • no solvent or diluent is present or added in the reaction medium, (except for the small amounts used as the carrier for the catalyst system or other additives, or amounts typically found with the monomer; e.g., propane in propylene).
  • the process is a slurry process.
  • the term“slurry polymerization process” means a polymerization process where a supported catalyst is employed and monomers are polymerized on the supported catalyst particles. At least 95 wt% of polymer products derived from the supported catalyst are in granular form as solid particles (not dissolved in the diluent).
  • Suitable diluents/solvents for polymerization include non-coordinating, inert liquids.
  • examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (IsoparTM fluids); 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 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, such as aromatics are present in the solvent at less than 1 wt%, such as less than 0.5 wt%, such as less than 0 wt% based upon the weight of the solvents.
  • the feed concentration of the monomers and comonomers for the polymerization is 60 vol% solvent or less, such as 40 vol% or less, such as 20 vol% or less, based on the total volume of the feedstream.
  • the polymerization is ran in a bulk process.
  • Suitable polymerizations can be run at temperatures and/or pressures suitable to obtain the desired ethylene polymers.
  • Suitable temperatures and/or pressures may include a temperature of from about 0°C to about 300°C, such as about 20°C to about 200°C, such as about 35°C to about 150°C, such as from about 40°C to about 120°C, such as from about 70°C to about 100°C; and at a pressure of from about 0.35 MPa to about 10 MPa, such as from about 0.45 MPa to about 6 MPa, such as from about 0.5 MPa to about 4 MPa.
  • the run time of the reaction can be up to 300 minutes, such as from about 5 to 250 minutes, such as from about 10 to 120 minutes. In a continuous process the run time may be the average residence time of the reactor.
  • hydrogen is present in the polymerization reactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa), such as from 0.01 to 25 psig (0.07 to 172 kPa), such as 0.1 to 10 psig (0.7 to 70 kPa).
  • the activity of the catalyst is at least 10,000 kg/mol/hour, such as 50,000 or more kg/mol/hour, such as 100,000 or more kg/mol/hr, such as 150,000 or more kg/mol/hr.
  • the conversion of olefin monomer is at least 10%, based upon polymer yield and the weight of the monomer entering the reaction zone, such as 20% or more, such as 30% or more, such as 50% or more, such as 80% or more.
  • scavenger such as tri alkyl aluminum
  • the scavenger can be present at zero mol%, alternately the scavenger can be present at a molar ratio of scavenger metal to transition metal of less than 100: 1, such as less than 50:1, such as less than 15:1, such as less than 10:1.
  • the polymerization 1) is conducted at temperatures of 0°C to 300°C (such as 25°C to 150°C, such as 40°C to 120°C, such as 45°C to 80°C); 2) is conducted at a pressure of atmospheric pressure to 10 MPa (such as 0.35 to 10 MPa, such as from 0.45 to 6 MPa, such as from 0.5 to 4 MPa); 3) is conducted in an aliphatic hydrocarbon solvent (such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; such as where aromatics can be present in the solvent at less than 1 wt%, such as less than
  • the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, such as less than 50:1, such as less than 15: 1, such as less than 10:1); 8) optionally hydrogen is present in the polymerization reactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa) (such as from 0.01 to 25 psig (0.07 to 172 kPa), such as 0.1 to 10 psig (0.7 to 70 kPa)); and 9) where the catalyst system used in the polymerization includes co-activator at less than 0.5 mol%, preferably 0%.
  • the catalyst system used in the polymerization includes no more than one catalyst compound.
  • a "reaction zone” also referred to as a "polymerization zone” is a vessel where polymerization takes place, for example a batch reactor. When multiple reactors are used in either series or parallel configuration, each reactor is considered as a separate polymerization zone. For a multi-stage polymerization in both a batch reactor and a continuous reactor, each polymerization stage is considered as a separate polymerization zone. In at least one embodiment, 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, reducing agents, oxidizing agents, hydrogen, aluminum alkyls, silanes, or chain transfer agents (such as alkylalumoxanes, a compound represented by the formula AIR3 or ZnR 2 (where each R is, independently, a Ci-Cs aliphatic radical, such as 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).
  • scavengers such as methyl, ethyl, propyl, butyl, pentyl, hexyl octyl or an isomer thereof
  • This present disclosure also relates to compositions of matter produced by methods described.
  • Processes of this present disclosure may produce olefin polymers, such as polyethylene and polypropylene homopolymers and copolymers.
  • the polymers produced are homopolymers of ethylene or propylene, are copolymers of ethylene having, for example, from 0 to 25 mol% (alternately from 0.5 to 20 mol%, alternately from 1 to 15 mol%, such as from 3 to 10 mol%) of one or more C 3 to C 20 olefin comonomer (such as C 3 to C 1 2 alpha-olefin, such as propylene, butene, hexene, octene, decene, dodecene, such as propylene, butene, hexene, octene), or are copolymers of propylene having from 0 to 25 mol% (alternately from 0.5 to 20 mol%, alternately from 1 to 15 mol%, such as from 3
  • the monomer is ethylene and the comonomer is hexene, such as from 1 to 15 mol% hexene, alternately 1 to 10 mol%.
  • the polymers produced have an Mw of 5,000 to 5,000,000 g/mol (such as 5,000 to 3,000,000 g/mol, such as 10,000 to 2,000,000 g/mol, such as 25,000 to 750,000 g/mol, such as 50,000 to 500,000 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 polymers produced have a high weight average molecular weight (Mw) of 100,000 g/mol or more, such as 500,000 g/mol or more, such as 1,000,000 g/mol or more, such as 1,500,000 g/mol or more, such as 2,000,000 g/mol or more, such as 2,500,000 g/mol or more, such as 3,000,000 g/mol or more.
  • Mw weight average molecular weight
  • the polymers produced have a high number average molecular weight (Mn) of 100,000 g/mol or more, such as 500,000 g/mol or more, such as 1,000,000 g/mol or more, such as 1,500,000 g/mol or more, such as 2,000,000 g/mol or more.
  • Mn number average molecular weight
  • the polymers produced have an Mw/Mn of greater than 1 to 10 (alternately 1.2 to 8, alternately 1.3 to 7, alternately 1.4 to 6, 1.5 to 4, alternately 1.5 to 3).
  • a polymer of the present disclosure has an Mn from about 100,000 g/mol to about 3,000,000, such as from about 175,000 g/mol to about 2,000,000 g/mol, such as from about 250,000 g/mol to about 1,250,000 g/mol, such as from about 350,000 g/mol to about 1,000,000 g/mol.
  • the ethylene or propylene based polymer has a melting point (Tm) of at least 100°C, such as from about 100°C to about 150°C, such as from about 100°C to about 140°C.
  • the polymer produced has a unimodal or multimodal molecular weight distribution as determined by Gel Permeation Chromatography (GPC).
  • GPC Gel Permeation Chromatography
  • unimodal is meant that the GPC trace has one peak or inflection point.
  • multimodal is meant that the GPC trace has at least two peaks or inflection points.
  • An inflection point is that point where the second derivative of the curve changes in sign (e.g., from negative to positive or vice versus).
  • GPC 4-D For purposes of the claims, and unless otherwise indicated, the distribution and the moments of molecular weight (Mw, Mn, Mz, Mw/Mn, etc.), the comonomer content and the branching index (g') are determined by using a high temperature Gel Permeation Chromatography (Polymer Char GPC-IR) equipped with a multiple-channel band-filter based infrared detector IR5 with a multiple-channel band filter based infrared detector ensemble IR5 with band region covering from about 2,700 cm -1 to about 3,000 cm -1 (representing saturated C-H stretching vibration), an 18-angle light scattering detector and a viscometer.
  • Polymer Char GPC-IR Polymer Char GPC-IR
  • the oligomer or polymer is automatically dissolved in the instrument with -8 mL added TCB solvent at ⁇ 160°C with continuous shaking.
  • the sample solution concentration is from ⁇ 0.2 to ⁇ 2 mg/ml, with lower concentrations used for higher molecular weight samples.
  • the mass recovery can be calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume.
  • the conventional molecular weight (IR MW) is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to 10M gm/mole.
  • PS monodispersed polystyrene
  • the comonomer composition is determined by the ratio of the IR5 detector intensity corresponding to CH 2 and CH 3 channel calibrated with a series of PE and PP homo/copolymer standards whose nominal value are predetermined by NMR or FTIR. In particular, this provides the methyls per 1,000 total carbons (CH 3 /1000TC) as a function of molecular weight.
  • the short-chain branch (SCB) content per 1000TC (SCB/1000TC) is then computed as a function of molecular weight by applying a chain-end correction to the CH 3 /1000TC function, assuming each chain to be linear and terminated by a methyl group at each end.
  • the weight % comonomer is then obtained from the following expression in which / is 0.3, 0.4, 0.6, 0.8, and so on for C 3 , C 4 , C 6 , C 8 , and so on co-monomers, respectively:
  • bulk SCB/1000TC bulk CH3/1000TC - bulk CH3end/1000TC where bulk SCB/1000TC is converted to bulk w2 in the same manner as described above.
  • the LS detector is the 18-angle Wyatt Technology High Temperature DAWN HELEOSII.
  • the LS molecular weight ( M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering ( Light Scattering from Polymer Solutions; Huglin, M. B., Ed.; Academic Press, 1972.):
  • DR(0) is the measured excess Rayleigh scattering intensity at scattering angle ⁇
  • c is the polymer concentration determined from the IR5 analysis
  • a 2 is the second virial coefficient
  • P( ⁇ ) is the form factor for a monodisperse random coil
  • K 0 is the optical constant for the system:
  • N A is Avogadro’s number
  • (dn/dc) is the refractive index increment for the system.
  • a high temperature Agilent (or Viscotek Corporation) viscometer which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity.
  • One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure.
  • the specific viscosity, h s for the solution flowing through the viscometer 2019EM128-PCT
  • the average intrinsic viscosity, [h] avg of the sample is calculated by: [ ] ⁇ c i [ h ]
  • v is a , where M v is the viscosity-average v
  • the polymer produced has a composition distribution 25 breadth index (CDBI) of 50% or more, such as 60% or more, such as 70% or more.
  • CDBI is a measure of the composition distribution of monomer within the polymer chains and is measured by the procedure described in PCT publication WO 1993/003093, published February 18, 1993, specifically columns 7 and 8 as well as in Wild et al. (1982) J. Poly. Sci., Poly. Phys. Ed., v.20, p.441, and U.S. Patent No.5,008,204, including that fractions having a 30 weight average molecular weight (Mw) below 15,000 g/mol are ignored when determining
  • Mw weight average molecular weight
  • the polymer (such as the polyethylene or polypropylene) produced 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 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, styrenic block copo
  • the polymer (such as the polyethylene or polypropylene) is present in the above blends, at from 10 to 99 wt%, based upon the weight of the polymers in the blend, such as 20 to 95 wt%, v at least 30 to 90 wt%, such as at least 40 to 90 wt%, such as at least 50 to 90 wt%, such as at least 60 to 90 wt%, such as at least 70 to 90 wt%.
  • the blends described above may be produced by mixing the polymers of the present disclosure with one or more polymers (as described above), by connecting reactors together in series to make reactor blends or by using more than one catalyst in the same reactor to produce multiple species of polymer.
  • the polymers can be mixed together prior to being put into the extruder or may be mixed in an extruder.
  • the blends may be formed using conventional equipment and methods, such as by dry blending the individual components and subsequently melt mixing in a mixer, or by mixing the components together directly in a mixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin-screw extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization process, which may include blending powders or pellets of the resins at the hopper of the film extruder. Additionally, additives may be included in the blend, in one or more components of the blend, and/or in a product formed from the blend, such as a film, as desired.
  • a mixer such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin-screw extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization
  • additives are well known in the art, and can include, for example: fillers; antioxidants (e.g., hindered phenolics such as IRGANOXTM 1010 or IRGANOXTM 1076 available from Ciba-Geigy); phosphites (e.g., IRGAFOSTM 168 available from Ciba-Geigy); anti-cling additives; tackifiers, such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosins; UV stabilizers; heat stabilizers; anti -blocking agents; release agents; anti-static agents; pigments; colorants; dyes; waxes; silica; fillers; talc. Films; antioxidants (e.g., hindered phenolics such as IRGANOXTM 1010 or IRGANOXTM 1076 available from Ciba-Geig
  • One or more of the foregoing polymers may be used in a variety of end-use applications. Such applications include, for example, mono- or multi-layer blown, extruded, and/or shrink films. These films may be formed by any number of well-known extrusion or coextrusion techniques, such as a blown bubble film processing technique, wherein the composition can be extruded in a molten state through an annular die and then expanded to form a uni-axial or biaxial orientation melt prior to being cooled to form a tubular, blown film, which can then be axially slit and unfolded to form a flat film.
  • extrusion or coextrusion techniques such as a blown bubble film processing technique
  • Films may be subsequently unoriented, uniaxially oriented, or biaxially oriented to the same or different extents.
  • One or more of the layers of the film may be oriented in the transverse and/or longitudinal directions to the same or different extents.
  • the uniaxially orientation can be accomplished using typical cold drawing or hot drawing methods.
  • Biaxial orientation can be accomplished using tenter frame equipment or a double bubble processes and may occur before or after the individual layers are brought together.
  • a polyethylene layer can be extrusion coated or laminated onto an oriented polypropylene layer or the polyethylene and polypropylene can be coextruded together into a film then oriented.
  • oriented polypropylene could be laminated to oriented polyethylene or oriented polyethylene could be coated onto polypropylene then optionally the combination could be oriented even further.
  • the films are oriented in the Machine Direction (MD) at a ratio of up to 15, such as between 5 and 7, and in the Transverse Direction (TD) at a ratio of up to 15, such as 7 to 9.
  • MD Machine Direction
  • TD Transverse Direction
  • the film is oriented to the same extent in both the MD and TD directions.
  • the films may vary in thickness depending on the intended application; however, films of a thickness from 1 to 50 mm are usually suitable. Films intended for packaging are usually from 10 to 50 mm thick. The thickness of the sealing layer is typically 0.2 to 50 mm. There may be a sealing layer on both the inner and outer surfaces of the film or the sealing layer may be present on only the inner or the outer surface.
  • one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwave.
  • one or both of the surface layers is modified by corona treatment.
  • This invention also relates to:
  • a catalyst system comprising a catalyst compound and an activator, wherein the catalyst compound is represented by Formula (I):
  • M is a group 8, 9, or 10 transition metal
  • L is a Lewis base
  • j 0, 1, or 2;
  • X is an anionic ligand
  • k 0, 1, or 2;
  • R 1 , R 2 , R 3 , and R 4 are independently selected from hydrogen, substituted or unsubstituted C 1 -C 30 hydrocarbyl, -CN, -NR 2 , -OR , halogen, -NO 2 , -SiR 3 , five-, six-, or seven- membered heterocyclyl (where each R is independently hydrogen, C 1 -C 30 hydrocarbyl, and R is optionally substituted by halogen, or two R radicals optionally bond to form a five- or six- membered ring), or -SiR 3 , -SiR 2(OR ), -SiR (OR )2, or -Si(OR ) 3 (where each R " and R ” is independently hydrogen, C 1 -C 30 hydrocarbyl, or two R " radicals optionally bond to form a five- or six-membered ring);
  • R 1 , R 2 , R 3 , and R 4 are optionally substituted by halogen, -NO 2 , -CN, -CF 3 , -CF 2 CF 3 , -CH 2 CF 3 , -NR 2 , -OR , -OSi(OR) 3 , where each R ’ is independently hydrogen, C 1 -C 30 hydrocarbyl, and R ’ is optionally substituted by halogen, or two R ’ radicals optionally bond to form a five- or six-membered ring, or -SiR 3 where each R " is independently hydrogen, C 1 -C 30 hydrocarbyl, or two R radicals optionally bond to form a five- or six-membered ring; and the activator is represented by the Formula (II):
  • M’ is selected from boron, aluminum, or gallium
  • E 1 , E 2 , and E 3 are independently selected from oxygen, nitrogen, phosphorus, sulfur or halogen;
  • R a , R b , and R c are independently selected from a C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 - aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 30 carbon atoms, alkylaryl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 30 carbon atoms, a support material, or two or more of R a , R b , and R c are optionally bonded to form a five-, six- or seven-membered carbocyclic or heterocyclic ring, the heterocyclic ring comprising at least one atom from the group consisting of N, P, O and S;
  • R a , R b , and R c are optionally substituted by halogen, -NO 2 , -CF 3 , -CF2CF 3 , -CH 2 CF 3 , -NR 2 , -OR (where each R is independently hydrogen, C 1 -C 22 -hydrocarbyl, and R is optionally substituted by halogen, or two R radicals optionally bond to form a five- or six- membered ring), or -SiR 3 (where each R " is independently hydrogen, C 1 -C 22 -hydrocarbyl, or two R " radicals optionally bond to form a five- or six- membered ring);
  • w is 0 if E 1 is a halogen, y is 0 if E 2 is a halogen, and z is 0 if E 3 is a halogen;
  • w is 1 if E 1 is oxygen or sulfur and w is 2 if E 1 is nitrogen or phosphorus;
  • y is 1 if E 2 is oxygen or sulfur and y is 2 if E 2 is nitrogen or phosphorus; and z is 1 if E 3 is oxygen or sulfur and z is 2 if E 3 is nitrogen or phosphorus.
  • a process for the production of an ethylene alpha-olefin copolymer comprising: polymerizing ethylene and at least one C 3 -C 20 alpha-olefin by contacting the ethylene and the at least one C 3 -C 20 alpha-olefin with a catalyst system of any of paragraphs 1 to 25 in at least one gas phase reactor at a reactor pressure of from 0.7 to 70 bar and a reactor temperature of from 20 °C to 150°C to form an ethylene alpha-olefin copolymer.
  • a process for the production of an ethylene polymer comprising: polymerizing ethylene and optionally at least one C 3 -C 20 alpha-olefin by contacting the ethylene and the optional C 3 -C 20 alpha-olefin with the catalyst system of paragraph 1 in a gas phase reactor at a reactor pressure of from 0.7 to 70 bar and a reactor temperature of from 20°C to 150°C to form an ethylene polymer.
  • reagents for catalyst synthesis were purchased from commercial vendors (Sigma Aldrich) and used as received unless otherwise noted. Solvents were sparged with N2 and dried over 3 A molecular sieves. All chemical manipulations were performed in a nitrogen environment unless otherwise stated. Flash column chromatography was carried out with Sigma Aldrich silica gel 60 A (70 Mesh - 230 Mesh) using solvent systems specified. All anhydrous solvents were purchased from Fisher Chemical and were degassed and dried over molecular sieves prior to use. Deuterated solvents were purchased from Cambridge Isotope Laboratories and were degassed and dried over molecular sieves prior to use.
  • Ni4 is represented by the formula:
  • Al2 is tris((perfluoronaphthalen-2-yl)oxy)aluminum.
  • Al3 is tris((perfluoro-[1,1’-biphenyl]-4-yl)oxy)aluminum.
  • B1 is tris(perfluorophenyl)boron (B1) and was purchased from Boulder Scientific Company.
  • Ni1, Ni2, Ni3, and Ni5 were prepared in a similar fashion to Ni4 above.
  • Solvents, polymerization-grade toluene, and isohexane were supplied by 20 ExxonMobil Chemical Company and purified by passing through a series of columns: two 500 cc Oxyclear cylinders in series from Labclear (Oakland, Calif.), followed by two 500 cc columns in series packed with dried 3 ⁇ mole sieves (8-12 mesh; Aldrich Chemical Company), and two 500 cc columns in series packed with dried 5 ⁇ mole sieves (8-12 mesh; Aldrich Chemical Company).
  • 1-octene (C8) and 1-hexene (C6) (98%, Aldrich Chemical Company) 25 were dried by stirring over NaK overnight followed by filtration through basic alumina (Aldrich Chemical Company, Brockman Basic 1).
  • the autoclaves were prepared by purging with dry nitrogen at 110°C or 115°C for 5 hours and then at 25 °C for 5 hours.
  • Solutions of the metal complexes and activators were prepared in a drybox using toluene (ExxonMobil Chemical Company; anhydrous, stored under nitrogen; 98%). Concentrations are typically 0.2 mmol/L for the metal complexes, 0.2 mmol/L for Activators, and 0.5 % w/w for methyl alumoxane (MAO) purchased from Albemarle, if MAO was used.
  • MAO methyl alumoxane
  • a pre-weighed glass vial insert and disposable stirring paddle were fitted to each reaction vessel within the reactor. The reactor was then closed and each vessel was individually heated to the desired temperature and pressurized to 120 psi. The contents of the vessel were then stirred at 800 rpm.
  • reaction was then allowed to proceed until either 30 psi of pressure had been taken up by the polymerization or a set amount of ethylene had been taken up by the reaction (ethylene pressure was maintained in each reaction vessel at the pre-set level by computer control; in the event the uptake is less than 30 psi, the reaction is quenched at 1,200 or 1,800 seconds). At this point, the reaction was quenched by pressurizing the vessel with compressed air. After the polymerization reaction, the glass vial insert containing the polymer product and solvent was removed from the pressure cell and the inert atmosphere glove box, and the volatile components were removed using a Genevac HT-12 centrifuge and Genevac VC3000D vacuum evaporator operating at elevated temperature and reduced pressure.
  • the vial was then weighed to determine the yield of the polymer product.
  • the resultant polymer was analyzed by Rapid GPC (described below) to determine the molecular weight and Differential Scanning Calorimetry (described below) to determine melting point.
  • Rapid GPC described below
  • Differential Scanning Calorimetry described below
  • the results demonstrate that Catalyst systems and methods of the present disclosure can provide highly active catalysts capable of operating at high reactor temperatures (100°C demonstrated) with reduced quantities of activator (as low as 1.1 equivalents) while producing polymers with controlled molecular weights (high Mw's, such as greater than 1 million, and narrow Mw/Mn).
  • Yields reported include total weight of polymer and residual catalyst.
  • Catalyst activity is reported as grams of polymer per mmol transition metal compound per hour of reaction time (g/mmol/hr).
  • Table 1 illustrates ethylene polymerization results obtained using a catalyst Ni4:
  • polymer sample solutions were prepared by dissolving the polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity from Sigma- Aldrich) containing 2,6-di- tert-butyl-4-methylphenol (BHT, 99% from Aldrich) at 165°C in a shaker oven for approximately 3 hours.
  • the typical concentration of polymer in solution was between 0.1 to 0.9 mg/mL with a BHT concentration of 1.25 mg BHT/mL of TCB. Samples were cooled to 135°C for testing.
  • High temperature size exclusion chromatography was performed using an automated "Rapid GPC" system as described in US Patent Nos. 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388; each of which is incorporated by reference.
  • PDI polydispersity
  • DSC Differential Scanning Calorimetry
  • melt points decrease with increasing amounts of 1 -hexene, in line with incorporation of 1 -hexene.
  • catalyst systems and processes of the present disclosure can provide high temperature ethylene polymerization, propylene polymerization, or copolymerization with good activity. It has been discovered that amido-benzoquinone late transition metal compounds (groups 8-10) activated with Lewis acids can polymerize olefins with improved activity over previous polymerization reactions using late transition metals. Furthermore, the catalyst systems described may involve less activator (e.g., a Lewis Acid) than previous late transition metal catalyst systems. The catalyst systems can provide formation of polymers having high molecular weights and the ability to make an increased amount of polymer in a given reactor, as compared to conventional catalysts. Hence, the present disclosure demonstrates highly active catalysts capable of operating at high reactor temperatures with reduced quantities of activator while producing polymers with controlled molecular weights. Furthermore, in the presence of Lewis acids, catalysts of the present disclosure may produce polymers with lower melting points.
  • ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
  • ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
  • within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.
  • compositions, an element or a group of elements are preceded with the transitional phrase “comprising”, it is understood that we also contemplate the same composition or group of elements with transitional phrases“consisting essentially of,”“consisting of’, selected from the group of“consisting of’ or“is” preceding the recitation of the composition, element, or elements and vice versa.

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Abstract

La présente invention concerne des complexes de métal de transition amido-benzoquinone, des systèmes de catalyseur comprenant des complexes de métal de transition amido-benzoquinone, et des procédés de polymérisation pour produire des polymères de polyoléfine tels que des polymères à base de polyéthylène et des polymères à base de polypropylène.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0474391A2 (fr) * 1990-08-21 1992-03-11 Nippon Oil Co. Ltd. Polyoléfines
JPH06306121A (ja) * 1993-04-21 1994-11-01 Dow Chem Co:The 弾性で実質的に線状であるオレフィンポリマー
CN107955088A (zh) * 2017-09-28 2018-04-24 东华大学 一种催化剂、其制备方法、由其制得的组合物及应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
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