WO2020167824A1 - B!s(aryl phenolate) lewis base catalysts and methods thereof - Google Patents

B!s(aryl phenolate) lewis base catalysts and methods thereof Download PDF

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WO2020167824A1
WO2020167824A1 PCT/US2020/017740 US2020017740W WO2020167824A1 WO 2020167824 A1 WO2020167824 A1 WO 2020167824A1 US 2020017740 W US2020017740 W US 2020017740W WO 2020167824 A1 WO2020167824 A1 WO 2020167824A1
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borate
tetrakis
catalyst
hydrocarbyl
rings
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PCT/US2020/017740
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English (en)
French (fr)
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Georgy P. GORYUNOV
Vladislav A. POPOV
Dmitry V UBORSKY
Alexander Z. Voskoboynikov
John R. Hagadorn
Irene C. CAI
Hua Zhou
Jo Ann M. Canich
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Exxonmobil Chemical Patents Inc.
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Priority to CN202080013654.1A priority Critical patent/CN113423742B/zh
Priority to SG11202107809TA priority patent/SG11202107809TA/en
Priority to EP20756711.6A priority patent/EP3924395A4/en
Publication of WO2020167824A1 publication Critical patent/WO2020167824A1/en

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    • 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

Definitions

  • the present disclosure relates to bis(aryl phenolate) Lewis base transition metal complexes, catalyst systems including bis(aryl phenolate) Lewis base 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
  • a comonomer such as hexene
  • 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 aZiegler-Natta catalyst, a chromium 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.
  • Plefins Angew. Chem. Int. Ed., v.53, pp. 9722-9744; KR 2018/022137; WO 2016/172110.
  • This invention relates to a transition metal compound comprising a tridentate dianionic ligand chelated to a group 4 transition metal, wherein the tridentate ligand coordinates to the metal with two anionic oxygen donors and one neutral heterocyclic nitrogen donor to form a pair of eight-membered metallocycle rings.
  • M is a group 3, 4, or 5 metal
  • a 1 and A 2 are independently an aromatic group
  • J is a heterocyclic Lewis base, preferably having six ring atoms
  • L is a Lewis base
  • X is an anionic ligand
  • n 1, 2 or 3;
  • n 0, 1, or 2;
  • n+m is not greater than 4.
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 is independently hydrogen, C 1-C40 hydrocarbyl, C 1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , or R 7 and R 8 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and where substitutions on the ring can join to form additional rings;
  • any two L groups 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; and any two X groups may be joined together to form a dianionic ligand group.
  • the present disclosure provides a catalyst system comprising an activator and a catalyst of the present disclosure.
  • the present disclosure provides a polymerization process comprising a) contacting one or more olefin monomers with a catalyst system comprising: i) an activator and ii) a catalyst 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 provides for a process for the production of an ethylene alpha-olefin copolymer comprising polymerizing ethylene and at least one C3-C20 alpha-olefin by contacting the ethylene and the at least one C3-C20 alpha- olefin with a catalyst system in at least one continuous stirred tank reactor or loop reactor.
  • the present disclosure provides for a process for the production of a propylene alpha-olefin copolymer comprising polymerizing propylene and at least one ethylene and/or C4-C20 alpha-olefin by contacting the propylene and the at least one ethylene and/or at least one C4-C20 alpha-olefin with a catalyst system in at least one continuous stirred tank reactor or loop reactor.
  • the catalyst compounds represented by Formula (I) feature two eight-membered metallocycle rings.
  • the first of these eight-membered metallocycle rings contains the atoms from the metal M, a phenolate oxygen, two carbons of the phenolate aryl group, two atoms of the aryl group A 1 , and two atoms from the bridging
  • Lewis base group J The second of these eight-membered metallocycle rings contains the atoms from the metal M, a phenolate oxygen, two carbons of the phenolate aryl group, two atoms of the aryl group A 2 , and two atoms from the bridging Lewis base group J.
  • the present disclosure provides catalyst compounds including a bis(aryl phenolate) Lewis base tridentate ligand which coordinates to a transition metal center, forming two eight- membered rings, catalyst systems including such catalyst compounds, and uses thereof.
  • Catalyst compounds of the present disclosure can be zirconium or hafnium-containing compounds having one or more aryl and/or heteroaryl ligand(s) substituted and linked with bis(aryl phenolate) Lewis base.
  • the present disclosure is directed to polymerization processes to produce polyolefin polymers from catalyst systems including one or more olefin polymerization catalysts, at least one activator, and an optional support.
  • Polyolefin polymers can be polyethylene polymers or polypropylene polymers.
  • the bis(aryl phenolate) Lewis base tridentate ligand is a class of tridentate ligands that may use heterocycles such as a pyridine group.
  • This class of ligands can include bis(aryl phenolate)heterocycles or bis(aryl phenolate) heterocyclic ligands. These ligands coordinate to a transition metal in a“tridentate” fashion, which means that the ligand forms three different bonds to the metal center.
  • a feature of the bis(aryl phenolate)heterocycle complexes, for example, is that the ligand binds in a tridentate fashion with the formation of two eight- membered metallocycle rings.
  • the complex is thought to be chiral (i.e. lacking a mirror plane of symmetry).
  • these complexes are useful as catalyst components for the production of polypropylene and other polymers of C3 and higher alpha olefins because chirality is advantageous for the production of poly(alpha olefins) of high isotacticity.
  • Catalysts, catalyst systems, and processes of the present disclosure can provide high temperature ethylene polymerization, propylene polymerization, ethylene alpha-olefin (e.g., ethylene- 1-octene) copolymerization, or propylene alpha-olefin copolymerization as the bis(aryl phenolate) Lewis Base catalysts are stable at high polymerization temperatures and have good activity at the high polymerization temperatures. The stable catalysts with good activity 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, because polymerizations in general occur at a higher rate at higher temperatures.
  • ethylene alpha-olefin e.g., ethylene- 1-octene
  • propylene alpha-olefin copolymerization e.g., ethylene- 1-octene
  • propylene alpha-olefin copolymerization e.g.,
  • a“group 4 metal” is an element from group 4 of the Periodic Table, e.g., Hf, Ti, or Zr.
  • Me is methyl
  • Et is ethyl
  • Ph is phenyl
  • tBu is tertiary butyl
  • MAO is methylalumoxane
  • NMR nuclear magnetic resonance
  • t time
  • s is second
  • h hour
  • psi pounds per square inch
  • psig pounds per square inch gauge
  • equiv equivalent
  • RPM rotation per minute
  • the specification describes transition metal complexes.
  • the term complex is used to describe molecules in which an ancillary ligand is coordinated to a central transition metal atom.
  • the ligand is bulky and stably bonded to the transition metal so as to maintain its influence during use of the catalyst, such as polymerization.
  • the ligand may be coordinated to the transition metal by covalent bond and/or electron donation coordination or intermediate bonds.
  • the transition metal complexes are generally subjected to activation to perform their polymerization or oligomerization function using an activator which, without being bound by theory, is believed to create a cation as a result of the removal of an anionic group, often referred to as a leaving group, from the transition metal.
  • olefin polymerization catalyst(s) refers to any catalyst, such as an organometallic complex or compound that is capable of coordination polymerization addition where successive monomers are added in a monomer chain at the organometallic active center.
  • 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 grams of product polymer (P) produced per millimole of catalyst (cat) used per hour (gP.mmolcar' .h 1 ).
  • heteroatom refers to any 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, BEE, SiFB, OH, NH, NH2, etc.
  • substituted heteroatom describes a heteroatom that has one or more of these hydrogen atoms replaced by a hydrocarbyl or substituted hydrocarbyl group(s).
  • An“olefin,” alternatively referred to as“alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • the 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 “terpoly mer” is a polymer having three mer units that are different from each other.“Different” is used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically. Accordingly, the definition of copolymer, as used herein, includes terpolymers.
  • 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.
  • 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 wherein R 1 is hydrogen, and R 2 is hydrogen or a linear alkyl group.
  • ethylene shall be considered an alpha- olefin.
  • the term“Cn” means hydrocarbon(s) having n carbon atom(s) per molecule, wherein n is a positive integer.
  • the term“hydrocarbon” means a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds having different values of n.
  • a“C m -C y ” group or compound refers to a group or compound comprising carbon atoms at a total number thereof in the range from m to y.
  • a C1-C50 alkyl group refers to an alkyl group comprising carbon atoms at a total number thereof in the range from 1 to 50.
  • the term“substituted” means that at least one hydrogen atom has been replaced with at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, where q is 1 to 10 and each R* is independently a
  • substituted hydrocarbyl means a hydrocarbyl radical in which at least one hydrogen atom of the hydrocarbyl radical has been substituted with at least one heteroatom (such as halogen, e.g., Br, Cl, F or I) or heteroatom-containing group (such as a functional group, e.g., -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2,
  • heteroatom such as halogen, e.g., Br, Cl, F or I
  • heteroatom-containing group such as a functional group, e.g., -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2,
  • hydrocarbyl substituted phenyl means a phenyl group having 1, 2, 3, 4 or 5 hydrogen groups replaced by a hydrocarbyl or substituted hydrocarbyl group.
  • the "hydrocarbyl substituted phenyl” group can be represented by the formula:
  • each of R a , R b , R c , R d , and R e can be independently selected from hydrogen, C1-C40 hydrocarbyl or C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group (provided that at least one of R a , R b , R c , R d , and R e is not H), or two or more of R a , R b , R c , R d , and R e can be joined together to form a C4-C62 cyclic or polycyclic hydrocarbyl ring structure, or a combination thereof.
  • substituted aromatic means an aromatic group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group.
  • substituted phenyl mean a phenyl group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group.
  • substituted carbazole means a carbazolyl group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group.
  • substituted naphthyl means a naphthyl group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group.
  • substituted anthracenyl means an anthracenyl group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group.
  • substituted fluorenyl means a fluorenyl group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group.
  • substituted benzyl means a benzyl group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group, such as a substituted benzyl group is represented by the formula:
  • each of R a , R b , R c , R d , and R e and Z is independently selected from hydrogen, C1-C40 hydrocarbyl or Ci-C4o substituted hydrocarbyl, aheteroatom or a heteroatom-containing group (provided that at least one of R a , R b , R c , R d , and R e and Z is not H), or two or more of R a , R b , R c , R d , and R e and Z are joined together to form a C4-C62 cyclic or polycyclic ring structure, or a combination thereof.
  • alkoxy and“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 C10 hydrocarbyl.
  • the alkyl group may be straight chain, branched, or cyclic.
  • the alkyl group may be saturated or unsaturated.
  • suitable alkoxy radicals can include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, phenoxyl.
  • 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 can include ethenyl, propentyl, allyl, 1 ,4-butadienyl cyclopropentyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloctenyl, including their substituted analogues.
  • alkyl radical is defined to be Ci-Cioo alkyls that 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, including their substituted analogues.
  • Substituted alkyl radicals are radicals in which at least one hydrogen atom of the alkyl radical has been substituted with at least a non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, and each R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted completely saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within a hydrocarbyl
  • 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; likewise the term aromatic also refers to substituted aromatics.
  • 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.
  • an arylalkyl group is a substituent on another group, it is bound to that group via the aryl.
  • Formula (AI) the aryl portion is bound to E.
  • 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.
  • an alkylaryl group is a substituent on another group, it is bound to that group via the alkyl.
  • Formula (AI) the alkyl portion is bound to E.
  • 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).
  • ring atom means an atom that is part of a cyclic ring structure.
  • a benzyl group has six ring atoms and tetrahydrofuran has 5 ring atoms.
  • 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.
  • Other examples of heterocycles may include pyridine, imidazole, and thiazole.
  • hydrocarbyl radical “hydrocarbyl group,” or“hydrocarbyl” may be used interchangeably and are defined to mean a group consisting of hydrogen and carbon atoms only.
  • a hydrocarbyl can be a Ci-Cioo radical that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic.
  • radicals may include, but are not limited to, alkyl groups such as methyl, ethyl, propyl (such as n-propyl, isopropyl, cyclopropyl), butyl (such as n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), pentyl (such as iso-amyl, cyclopentyl) hexyl (such as cyclohexyl), octyl (such as cyclooctyl), nonyl, decyl (such as adamantyl), undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl,
  • “low comonomer content” is defined as a polyolefin having less than 8 wt% of comonomer based upon the total weight of the polyolefin.
  • “high comonomer content” is defined as a polyolefin having greater than or equal to 8 wt% of comonomer based upon the total weight of the polyolefin.
  • 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
  • “high molecular weight” is defined as a number average molecular weight (Mn) value of 100,000 g/mol or more. “Low molecular weight” is defined as an Mn value of less than 100,000 g/mol.
  • melting points are differential scanning calorimetry (DSC) second melt.
  • A“catalyst system” is a combination of at least one catalyst compound, at least one activator, an optional coactivator, and an optional support material.
  • the terms“catalyst compound”,“catalyst complex”,“transition metal complex”,“transition metal compound”, “precatalyst compound”, and“precatalyst complex” are used interchangeably.
  • Catalyst system When “catalyst system” is used to describe such a pair before activation, it means the unactivated catalyst complex (precatalyst) together with an activator and, optionally, a coactivator. When it is used to describe such a pair after activation, it means the activated complex and the activator or other charge-balancing moiety.
  • the transition metal compound may be neutral as in a precatalyst, or a charged species with a counter ion as in an activated catalyst system.
  • a precatalyst or a charged species with a counter ion as in an activated catalyst system.
  • the ionic form of the component is the form that reacts with the monomers to produce polymers.
  • a polymerization catalyst system is a catalyst system that can polymerize monomers to polymer.
  • catalyst compounds and activators represented by formulae herein are intended to embrace both neutral and ionic forms of the catalyst compounds and activators.
  • 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 pairs of 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.
  • Lewis bases include ethylether, trimethylamine, pyridine, tetrahydrofuran, dimethylsulfide, and triphenylphosphine.
  • heterocyclic Lewis base refers to Lewis bases that are also heterocycles. Examples of heterocyclic Lewis bases include pyridine, imidazole, thiazole, and furan.
  • the bis(aryl phenolate) Lewis base ligands are tridentate ligands that bind to the metal via two anionic donors (phenolates) and one heterocyclic Lewis base donor (e.g., pyridinyl group).
  • the bis(aryl phenolate)heterocycle ligands are tridentate ligands that bind to the metal via two anionic donors (phenolates) and one heterocyclic Lewis base donor.
  • 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.
  • 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.
  • 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 non-coordinating 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.
  • 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 Oliveira, J. V. et al. (2000) Ind. Eng. Chem. Res., 2000, 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%.
  • the present disclosure relates to novel catalyst compounds having a bis(aryl phenolate) Lewis base tridentate ligand which coordinates to a group 3, 4, or 5 transition metal center, forming two eight-membered rings.
  • a catalyst compound can be represented by Formula (I):
  • M is a group 3, 4, or 5 metal
  • a 1 and A 2 are independently an aromatic group, such as an aromatic hydrocarbyl group; J is a heterocyclic Lewis base, preferably having six ring atoms;
  • L is a Lewis base
  • X is an anionic ligand
  • n 1, 2 or 3;
  • n 0, 1, or 2;
  • n+m is not greater than 4.
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 is independently hydrogen, C 1-C40 hydrocarbyl, C1-C40 substituted hydrocarbyl, or a heteroatom or a heteroatom-containing group, or one or more of R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , or R 7 and R 8 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and where substitutions on the ring can join to form additional rings;
  • any two L groups 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; and any two X groups may be joined together to form a dianionic ligand.
  • a 1 is represented by the formula: where indicates a connection to the catalyst compound, and each of R 9 , R 10 , R 11 , and R 12 is independently hydrogen, C1-C40 hydrocarbyl, C 1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 9 and R 10 , R 10 and R 11 , or R 11 and R 12 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms.
  • each of R 9 , R 10 , R 11 , and R 12 is independently hydrogen or a C1-C40 hydrocarbyl.
  • a 2 is represented by the formula:
  • each of R 13 , R 14 , R 15 , and R 16 is independently hydrogen, C 1-C40 hydrocarbyl, C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 13 and R 14 , R 14 and R 15 , or R 15 and R 16 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms.
  • each of R 13 , R 14 , R 15 , and R 16 is independently hydrogen or a C1-C40 hydrocarbyl.
  • R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 is independently hydrogen or a C1-C40 hydrocarbyl, such as a C2 to C20 hydrocarbyl.
  • J is cyclic with 6 ring atoms one of which is a heteroatom.
  • J is represented by the formula: where indicates a connection to the catalyst compound, and each of R 17 , R 18 , and R 19 is independently hydrogen, C1-C40 hydrocarbyl, C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 17 and R 18 , R 18 and R 19 , or R 17 and R 19 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atom.
  • R 17 , R 18 , and R 19 can be hydrogen.
  • the catalyst compound represented by Formula (I) is represented by Formula (II):
  • M is a group 3, 4, or 5 metal
  • L is a Lewis base
  • X is an anionic ligand
  • n 1, 2, or 3;
  • n 0, 1, or 2;
  • n+m is not greater than 4.
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 is independently hydrogen, C1-C40 hydrocarbyl, C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , or R 7 and R 8 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms;
  • each of R 9 , R 10 , R 11 , and R 12 is independently hydrogen, C1-C40 hydrocarbyl, C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 9 and R 10 , R 10 and R 11 , or R 11 and R 12 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms;
  • each of R 13 , R 14 , R 15 , and R 16 is independently hydrogen, C1-C40 hydrocarbyl, C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 13 and R 14 , R 14 and R 15 , or R 15 and R 16 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms;
  • each of R 17 , R 18 , and R 19 is independently hydrogen, C1-C40 hydrocarbyl, C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 17 and R 18 , R 18 and R 19 , or R 17 and R 19 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms;
  • any two L groups 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; and any two X groups may be joined together to form a dianionic ligand group.
  • M of Formula (I) or Formula (II) can be a group 3, 4 or 5 metal, such as M can be a group 4 metal.
  • Group 4 metals may include zirconium, titanium, and hafnium. In at least one embodiment, M is zirconium or hafnium.
  • Each L of Formula (I) or Formula (II) can be independently selected from ethers, amines, phosphines, thioethers, esters, Et20, MeOtBu, Et3N, PhNMe2, MePh2N, tetrahydrofuran, and dimethylsulfide, and each X can be independently selected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, trifluoromethanesulfonate, dimethylamido, diethylamido, dipropylamido, and diisopropylamido.
  • n of Formula (I) or Formula (II) is 2 and each X is independently chloro or methyl.
  • the Lewis base (J) of Formula (I) can be selected from cyclic Lewis bases.
  • the Lewis base J is a divalent group that bridges the A 1 and A 2 groups and is coordinated to the metal center M as a neutral 2-electron donor.
  • the Lewis base J may be an aromatic or non aromatic heterocyclic.
  • the Lewis base J may be a heterocyclic Lewis base having 5 or 6 ring atoms.
  • J is a group 15-containing heterocycle, or a group 16-containing heterocycle, such as J is a nitrogen-containing heterocycle, an oxygen- containing heterocycle, a phosphorus-containing heterocycle, or a sulfur-containing heterocycle, for example.
  • 5-membered heterocyclic Lewis bases may include thiazoles, isothiazoles, 1, 2, 4-thi diazoles, 1,2,5-thidiazoles, 1, 3, 4-thi diazoles, thiophenes, oxazoles, isoxazoles, oxazolines (e.g., 2-oxazoline, 3-oxazoline, 4-oxazoline), oxazolidines, imidazoles, furans, thiofurans, pyrroles, pyrazoles, 1,2, 3 -triazoles, 1,2,4-triazoles, boroles, phospholes, azaphospholes, or isomers thereof, substituted or unsubstituted.
  • thiazoles e.g., 2-oxazoline, 3-oxazoline, 4-oxazoline
  • oxazolidines imidazoles, furans, thiofurans, pyrroles, pyrazoles, 1,2, 3 -triazoles, 1,2,4-triazoles
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 of Formula (I) or Formula (II) can be independently selected from hydrogen, C 1-C40 hydrocarbyl, C 1-C40 substituted hydrocarbyl, alkoxy, silyl, amino, aryloxy, halogen, or phosphino, or one or more of R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , or R 7 and R 8 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms.
  • one or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 of Formula (I) or Formula (II) is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, phenyl, substituted phenyl, biphenyl or an isomer thereof, which may be halogenated (such as perfluoropropyl, perfluorobutyl, perfluoroethyl, perfluoromethyl), substituted hydrocarbyl radicals and all isomers of substituted hydrocarbyl radicals including trimethylsilylpropyl, trimethylsilylmethyl, trimethylsilylethyl, phenyl, or all isomers of hydrocarbyl substituted phenyl including
  • R 4 and R 5 of Formula (I) or Formula (II) can be independently
  • R 4 and R 5 can be tert-butyl.
  • R 4 and R 5 are independently selected from unsubstituted phenyl, substituted phenyl, unsubstituted carbazole, substituted carbazole, unsubstituted naphthyl, substituted naphthyl, unsubstituted anthracenyl, substituted anthracenyl, unsubstituted fluorenyl, or substituted fluorenyl, a heteroatom or a heteroatom-containing group, such as R 4 and R 5 can be independently unsubstituted phenyl or
  • R 4 can be C1-C10 alkyl (e.g., R 4 can be tert- butyl) and R 5 can be an aryl
  • R 5 can be C1-C10 alkyl (e.g., R 5 can be tert-butyl) and R 4 can be an aryl
  • R 4 and/or R 5 can be independently a heteroatom, such as R 4 and
  • R 5 can be a halogen atom (such as Br, Cl, F, or I).
  • R 4 and/or R 5 can be independently a silyl group, such as R 4 and R 5 can be a trialkylsilyl or triarylsilyl group, where the alkyl is a Ci to C30 alkyl (such methyl, ethyl, propyl (such as n-propyl, isopropyl, cyclopropyl), butyl (such as n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), pentyl (such as iso-amyl, cyclopentyl) hexyl (such as cyclohexyl), octyl (such as cyclooctyl), nonyl, decyl (such as adamantyl), undecyl, dodecyl, tridecyl, t
  • R 4 and R 5 can be triethylsilyl.
  • the identity of R 4 and R 5 can be used to control the molecular weight of the polymer products.
  • the catalyst compound may provide high molecular weight polymers.
  • the catalyst compound may provide low molecular weight polymers.
  • each R 2 and R 7 of Formula (I) or Formula (II) is independently C1-C10 alkyl, such as R 2 and R 7 are independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dimethyl-pentyl, tert-butyl, isopropyl, or isomers thereof.
  • R 1 , R 3 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 of Formula (II) can be independently hydrogen or C1-C10 alkyl, such as R 1 , R 3 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 can be independently hydrogen, methyl, ethyl, propyl, or isopropyl.
  • R 1 , R 3 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 are hydrogen.
  • each of R 1 , R 3 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 of Formula (II) can be independently hydrogen, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy, or trimethylsilyl.
  • the catalyst compound is one or more of:
  • the catalyst compound represented by Formula (I) is selected from:
  • one or more different catalyst compounds are present in a catalyst system.
  • One or more different catalyst compounds can be present in the reaction zone where the process(es) described herein occur.
  • 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.
  • the two transition metal compounds may be used in any ratio.
  • Molar ratios of (A) transition metal compound to (B) transition metal compound can be a range of
  • the particular ratio chosen will depend on the exact pre-catalysts chosen, the method of activation, and the end product desired.
  • mole percentages when using the two pre-catalysts, where both are activated with the same activator, can be from 10% to 99.9% A to 0.1% to 90% B, alternatively 25% to 99% A to 0.5% to 75% B, alternatively 50% to 99% A to 1% to 50% B, and alternatively 75% to 99% A to 1% to 10% B.
  • the catalyst systems described herein may comprise a catalyst complex as described above and an activator such as alumoxane or a non-coordinating anion and may be formed by combining the catalyst components described herein with activators in any manner known from the literature including combining them with 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 one or more activators and one, two or more catalyst components.
  • Activators are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral metal compound to a catalytically active metal compound cation.
  • Non-limiting activators may include alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and conventional-type cocatalysts.
  • Suitable activators may include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract a reactive, s-bound, metal ligand making the metal compound cationic and providing a charge-balancing non-coordinating or weakly coordinating anion, e.g., a non-coordinating anion.
  • the catalyst system includes an activator and the catalyst compound of Formula (I) or Formula (II).
  • Alumoxane activators are utilized as activators in the catalyst systems described herein.
  • Alumoxanes are generally oligomeric compounds containing -Al(R a )-0- sub-units, where R a is an alkyl group.
  • Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane.
  • Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is an alkyl, halide, alkoxide or amide. Mixtures of different alumoxanes and modified alumoxanes may also be used. It may be suitable to use a visually clear methylalumoxane. A cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution.
  • a useful alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc.
  • MMAO modified methyl alumoxane
  • the activator is an alumoxane (modified or unmodified)
  • at least one embodiment select the maximum amount of activator 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 can be a 1: 1 molar ratio. Alternate ranges may 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 can be present at zero mol%, alternately the alumoxane can be 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. Ionizing/Non-Coordinating Anion Activators
  • non-coordinating anion means an anion which either does not coordinate to a cation or which is only weakly coordinated to a cation thereby remaining sufficiently labile to be displaced by a Lewis base.
  • “Compatible” non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral transition metal compound and a neutral by-product from the anion.
  • Non-coordinating anions useful in accordance with the 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.
  • Ionizing activators useful herein typically comprise an NCA, particularly a compatible NCA.
  • the catalyst systems of the present disclosure can include at least one non coordinating anion (NCA) activator.
  • NCA 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 Lewis base
  • H is hydrogen
  • (L-H) is a
  • a ⁇ - is a boron containing non-coordinating anion having the charge d-; d is 1, 2, or 3.
  • the cation component, Z ⁇ + 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 bulky ligand transition metal catalyst precursor, resulting in a cationic transition metal species.
  • the activating cation Z d + may also be a moiety such as silver, tropybum, carbeniums, ferroceniums and mixtures, such as carbeniums and ferroceniums.
  • Z d + can be triphenyl carbenium.
  • Reducible Lewis acids can be a triaryl carbenium (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 Ci to C40 hydrocarbyl, or a substituted Ci to C40 hydrocarbyl), such as the reducible Lewis acids "Z" may include those represented by the formula: (Ph 3 C), where Ph is a substituted or unsubstituted phenyl, such as substituted with Ci to C40 hydrocarbyls or substituted a Ci to C40 hydrocarbyls, such as Ci to C20 alkyls or aromatics or substituted Ci to C20 alkyls or aromatics, such as Z is a triphenylcarbenium.
  • 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 triethylphosphine, triphenylphosphine, and diphenylphosphine, oxoniums from ethers such as dimethyl
  • Each Q can be a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, such as each Q is a fluorinated aryl group, and such as each Q is a pentafluoryl aryl group.
  • - 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.
  • + (A cl_ ) can be one or more of N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, dioctadecylmethylammonium tetrakis(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5- bis(trifluoro
  • the activator compounds are represented by Formula (AI):
  • E is nitrogen or phosphorous, preferably nitrogen
  • each of R 1 , R 2 , and R 3 is independently H, optionally substituted C1-C40 alkyl (such as branched or linear alkyl), or optionally substituted Cs-Cso-aryl (alternately each of R 1 , R 2 , and R 3 is independently unsubstituted or substituted with at least one of halide, C5-C50 aryl, C6-C35 arylalkyl, C6-C35 alkylaryl and, in the case of the Cs-Cso-aryl, C1-C50 alkyl); wherein R 1 , R 2 , and R 3 together comprise 15 or more carbon atoms (such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 37 or more carbon atoms, such as 40 or more carbon atoms, such as
  • M is an element selected from group 13 of the Periodic Table of the Elements, preferably B or Al, preferably B;
  • each Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical, preferably a fluorinated aryl group, such fluoro-phenyl or fluoro-naphthyl, more preferably perfluorophenyl or perfluoronaphthyl.
  • each of R 1 , R 2 and R 3 may independently be selected from:
  • linear alkyls such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, n-henicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl,
  • arylalkyls such as (methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, tridecylphenyl, tetradecylphenyl, pentadecylphenyl, hexadecylphenyl, heptadecylphenyl, octadecylphenyl, nonadecylphenyl, icosylphenyl, henicosylphenyl, docosylphenyl, tricosylphenyl, tetracosylphenyl, pentacosylphenyl, hexacosylphenyl, hepta
  • optionally substituted silyl groups such as a trialkylsilyl group, where each alkyl is independently an optionally substituted Ci to C20 alkyl (such as trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triheptylsilyl, trioctylsilyl, trinonylsilyl, tridecylsilyl, triundecylsilyl, tridodecylsilyl, tri-tridecylsilyl, tri-tetradecylsilyl, tri-pentadecylsilyl, tri-hexadecylsilyl, tri-heptadecylsilyl, tri-octadecylsilyl, tri-nonadecylsilyl, tri-icosylsilyl);
  • Ci to C20 alkyl such as trimethylsilyl
  • optionally substituted alkoxy groups such as -OR*, where R* is an optionally substituted Ci to C20 alkyl or aryl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, phenyl, alkylphenyl (such as methyl phenyl, propyl phenyl, etc.), naphthyl, or anthracenyl);
  • R* is an optionally substituted Ci to C20 alkyl or aryl (such as methyl, ethyl, propyl, butyl, pentyl,
  • halogen containing groups such as bromomethyl, bromophenyl, and the like.
  • activators represented by Formula (IA) that are useful herein please see US2019-0330139 and US2019-0330139, which are incorporated by reference herein.
  • Useful activators include iV-methyl-4-nonadecyl-N- octadecylanilinium tetrakis(perfluoronaphthalen-2-yl)borate, and iV-methyl-4-nonadecyl-N- octadecylanilinium tetrakis(perfluorophenyl)borate.
  • each R A is independently a halide, such as a fluoride
  • Ar is substituted or unsubstituted aryl group (such as a substituted or unsubstituted phenyl), such as substituted with Ci to C40 hydrocarbyls, such as Ci to C20 alkyls or aromatics; each R B is independently a halide, a Ce to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula -0-Si-R D , where R D is a Ci to C20 hydrocarbyl or hydrocarbylsilyl group (such as R B is a fluoride or a perfluorinated phenyl group);
  • each R c is a halide, Ce to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula -0-Si-R D , where R D is a Ci to C20 hydrocarbyl or hydrocarbylsilyl group (such as R D is a fluoride or a Ce perfluorinated aromatic hydrocarbyl group); where R B and R c can form one or more saturated or unsaturated, substituted or unsubstituted rings (such as R B and R c form a perfluorinated phenyl ring);
  • L is a Lewis base
  • (L-H) + is a Bronsted acid
  • d is 1, 2, or 3;
  • anion has a molecular weight of greater than 1,020 g/mol
  • (Ar 3 C) cj + can be (Ph 3 C) c
  • Ph is a substituted or unsubstituted phenyl, such as substituted with Ci to C40 hydrocarbyls or substituted Ci to C40 hydrocarbyls, such as Ci to C20 alkyls or aromatics or substituted Ci to C20 alkyls or aromatics.
  • 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. [0102] 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, v.71(ll), November 1994, pp.
  • one or more of the NCA activators is chosen from the activators described in US 6,211,105.
  • the activator is selected from one or more of 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-
  • the activator is selected from 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 tetrakis-(
  • Suitable activator-to-catalyst ratio may be about a 1 : 1 molar ratio. Alternate 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, such as 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 1994/007928; and WO 1995/014044 which discuss the use of an alumoxane in combination with an ionizing activator).
  • Useful chain transfer agents can be hydrogen, alkylalumoxanes, a compound represented by the formula AIR3, ZnR.2 (where each R is, independently, a C i-Cx 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.
  • a catalyst system of the present disclosure may include a metal hydrocarbenyl chain transfer agent represented by the formula:
  • each R 1 can be independently a C 1-C30 hydrocarbyl group, and/or each R", can be independently a C4-C20 hydrocarbenyl group having an end-vinyl group; and v can be from 0.1 to 3.
  • the activators described herein have a solubility of more than 10 mM (or more than 20 mM, or more than 50 mM) at 25°C (stirred 2 hours) in methylcyclohexane and/or a solubility of more than 1 mM (or more than 10 mM, or more than 20 mM) at 25°C (stirred 2 hours) in isohexane.
  • the present disclosure relates to a catalyst system comprising a metallocene transition metal compound and an activator compound represented by Formula (IA), to the use of such activator compounds for activating a transition metal compound in a catalyst system for polymerizing olefins, and to processes for polymerizing olefins, the process comprising contacting under polymerization conditions one or more olefins with a catalyst system comprising a metallocene transition metal compound and such activator compounds, where aromatic solvents, such as toluene, are absent (e.g. present at zero mol%, alternately present at less than 1 mol%, preferably the catalyst system, the polymerization reaction and/or the polymer produced are free of detectable aromatic hydrocarbon solvent, such as toluene.
  • aromatic solvents such as toluene
  • the poly alpha-olefins produced herein preferably contain 0 ppm (alternately less than 1 ppm, alternately less than 5 ppm, alternately less than 10 ppm) of aromatic hydrocarbon.
  • the polyalpha-olefms produced herein contain 0 ppm (alternately less than 1 ppm, alternately less than 5 ppm, alternately less than 10 ppm) of toluene.
  • the catalyst systems used herein preferably contain 0 ppm (alternately less than 1 ppm, alternately less than 5 ppm, alternately less than 10 ppm) of aromatic hydrocarbon.
  • the catalyst systems used herein contain 0 ppm (alternately less than 1 ppm, alternately less than 5 ppm, alternately less than 10 ppm) of toluene.
  • Aluminum alkyl or alumoxane compounds which may be utilized as scavengers or coactivators may include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n- hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, methylalumoxane (MAO), modified methylalumoxane (MMAO), MMAO-3A, and diethyl zinc.
  • MAO methylalumoxane
  • MMAO modified methylalumoxane
  • MMAO-3A diethyl zinc
  • the catalyst system may include an inert support material.
  • the supported material can be a porous support material, for example, talc, and inorganic oxides.
  • Other support materials include zeolites, clays, organoclays, or another organic or inorganic support material, or mixtures thereof.
  • the support material can be an inorganic oxide in a finely divided form.
  • Suitable inorganic oxide materials for use in catalyst systems herein 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 can be magnesia, titania, zirconia.
  • Other suitable support materials can be employed, for example, finely divided functionalized polyolefins, such as finely divided polyethylene.
  • suitable supports may include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays.
  • combinations of these support materials may be used, for example, silica- chromium, silica-alumina, silica-titania.
  • the support material is selected from AI2O3, Zr02, S1O2, S1O2/AI2O3, Si02/Ti02, silica clay, silicon oxide/clay, or mixtures thereof.
  • the support material such as an inorganic oxide, can have a surface area in the range of from about 10 m 2 /g to about 700 m 2 /g, pore volume in the range of from about 0.1 cm 3 /g to about 4.0 cm 3 /g and average particle size in the range of from about 5 pm to about 500 pm.
  • the surface area of the support material can be in the range of from about 50 m 2 /g to about 500 m 2 /g, pore volume of from about 0.5 cm 3 /g to about 3.5 cm 3 /g and average particle size of from about 10 pm to about 200 pm.
  • the surface area of the support material is in the range is from about 100 m 2 /g to about 400 m 2 /g, pore volume from about 0.8 cm 3 /g to about 3.0 cm 3 /g and average particle size is from about 5 pm to about 100 pm.
  • the average pore size of the support material useful in the present disclosure is in the range of from 10 A to 1000 A, such as 50 A to about 500 A, and such as 75 A to about 350 A.
  • suitable silicas can be the silicas 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, for example (such as at 875°C).
  • the support material should be dry, that is, free of absorbed water. Drying of the 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. When the support material is silica, it is heated to at least 200°C, such as about 200°C to about 850°C, and 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 supported catalyst systems of the present disclosure.
  • the calcined support material is then contacted with at least one polymerization catalyst comprising at least one catalyst compound and an activator.
  • the support material having reactive surface groups, such as 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 support material is first contacted with the activator for a period of time in the range of from about 0.5 hour 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 support material is first contacted with the catalyst compound for a period of time in the range of from about 0.5 hour 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 and support is heated from about 0°C to about 70°C, such as from about 23°C to about 60°C, such as at room temperature.
  • Contact times can be from about 0.5 hours to about 24 hours, such as 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 used herein, e.g., the activator and the catalyst compound, are at least partially soluble and which are liquid at reaction temperatures.
  • Non-polar solvents can be 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 (e.g., ethylene; propylene), and optionally comonomer, are contacted with a catalyst system including an activator and at least one catalyst compound, as described above.
  • the catalyst compound and activator may be combined in any order.
  • the catalyst compound and activator may be combined prior to contacting with the monomer.
  • the catalyst compound and activator may be introduced into the polymerization reactor separately, wherein they subsequently react to form the active catalyst.
  • Monomers include substituted or unsubstituted C2 to C40 alpha olefins, such as C2 to C20 alpha olefins, such as C2 to C12 alpha olefins, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof.
  • the monomer includes ethylene and an optional comonomer comprising one or more C3 to C40 olefins, such as C4 to C20 olefins, such as Ce to C12 olefins.
  • the C3 to C40 olefin monomers may be linear, branched, or cyclic.
  • the C3 to C40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.
  • the monomer includes propylene and an optional comonomer comprising one or more ethylene or C4 to C40 olefins, such as C4 to C20 olefins, such as Ce to C12 olefins.
  • the C4 to C40 olefin monomers may be linear, branched, or cyclic.
  • the C4 to C20 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.
  • Exemplary C2 to C40 olefin monomers and optional comonomers may include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbomene, ethylidenenorbomene, vinylnorbomene, norbomadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbomadiene, substituted derivatives thereof, and isomers thereof, such as hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, l-hydroxy
  • Polymerization processes of the present disclosure can be carried out in any suitable manner. Any suitable suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization process can be used. Such processes can be run in a batch, semi-batch, or continuous mode. Homogeneous polymerization processes and slurry processes can be used. A bulk homogeneous process can be used. Alternately, 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 found with the monomer; e.g., propane in propylene). In another embodiment, the process is a slurry process.
  • slurry polymerization process means a polymerization process performed in a hydrocarbon solvent where a supported catalyst is employed and monomers are polymerized on the supported catalyst particles at a temperature that is below the melting point of the polymer produced. 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 may include non-coordinating, inert liquids.
  • diluents/solvents for polymerization may include straight and branched- chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (IsoparTM); perhalogenated hydrocarbons, such as perfluorinated C4 to C10 alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene
  • Suitable solvents may 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-l-pentene, 1-octene,
  • 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 run in a bulk process.
  • Polymerizations can be run at any temperature and/or pressure suitable to obtain the desired polymers.
  • Typical temperatures and/or pressures include a temperature in the range 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 160°C, such as from about 80°C to about 160°C, such as from about 90°C to about 140°C; and at a pressure in the range of from about 0.1 MPa to about 25 MPa, such as from about 0.45 MPa to about 6 MPa, or from about 0.5 MPa to about 4 MPa.
  • the run time of the reaction is up to 300 minutes, such as from about 5 minutes to 250 minutes, such as from about 10 minutes to 120 minutes, such as from about 20 minutes to 90 minutes, such as from about 30 minutes to 60 minutes.
  • 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 psig to 50 psig (0.007 kPa to 345 kPa), such as from 0.01 psig to 25 psig (0.07 kPa to 172 kPa), such as from 0.1 psig to 10 psig (0.7 kPa to 70 kPa).
  • alumoxane can be present at zero mol%, alternately the alumoxane can be present at a molar ratio of aluminum to transition metal less than 500: 1, such as less than 300: 1, such as less than 100: 1, such as less than 1 : 1.
  • the polymerization: 1) is conducted at temperatures of
  • 0°C to 300°C (such as 25°C to 250°C, such as 80°C to 160°C, such as 100°C to 140°C);
  • the catalyst system used in the polymerization comprises less than 0.5 mol%, such as 0 mol% alumoxane, alternately the alumoxane is present at a molar ratio of aluminum to transition metal less than 500: 1, such as less than 300: 1, such as less than 100: 1, such as less than 1 : 1; 5) the polymerization occurs in one reaction zone; 6) optionally scavengers (such as trialkyl aluminum compounds) 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, such as less than 50: 1, such as less than 15: 1, such as less than 10: 1); and 7) optionally hydrogen is present in the polymerization reactor at a partial pressure of 0.001 psig to 50 psig (0.007 kPa to 345 kPa) (such as from 0.01 psig to 25 psig (0.07 k
  • 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 stirred-tank reactor or a loop reactor. When multiple reactors are used in a continuous polymerization process, each reactor is considered as a separate polymerization zone. For a multi-stage polymerization in a batch polymerization process, each polymerization stage is considered as a separate polymerization zone. In at least one embodiment, the polymerization occurs in one reaction zone. Room temperature is 23°C unless otherwise noted.
  • the present disclosure provides a process for the production of an ethylene based polymer comprising: polymerizing ethylene by contacting the ethylene with the catalyst system of the present disclosure described above in one or more continuous stirred tank reactors or loop reactors, in series or in parallel, at a reactor pressure of from 0.05 MPa to 1,500 MPa and a reactor temperature of from 30°C to 230°C to form an ethylene based polymer.
  • hydrogen is present in the polymerization reactor at a partial pressure of from about 5 psig to about 300 psig, such as from about 10 psig to about 250 psig, such as from about 30 psig to about 200 psig, such as from about 20 psig to about 150 psig, such as from about 50 psig to about 100 psig (e.g., 75 psig).
  • the activity of the catalyst is at least 5,000 gP.mmolcat fh 1 , such as from about 5,000 gP.mmolcat fh 1 to 1,000,000 gP.mmolcat fh 1 , such as from about 7,500 gP.mmolcat fh 1 to 900,000 gP.mmolcat fh 1 , such as from about 10,000 gP.mmolcat fh 1 to 750,000 gP.mmolcat fh 1 , such as from about 12,500 gP.mmolcat fh 1 to 600,000 gP.mmolcat fh 1 .
  • the present disclosure provides a process for the production of propylene based polymer comprising: polymerizing propylene by contacting the propylene with the catalyst system of the present disclosure described above in one or more continuous stirred tank reactors or loop reactors, in series or in parallel, at a reactor pressure of from 0.5
  • hydrogen is present in the polymerization reactor at a partial pressure from about 10 psig to about 300 psig, such as from about 20 psig to about 250 psig, such as from about 30 psig to about 200 psig, such as from about 40 psig to about 150 psig, such as from about 50 psig to about 100 psig (e.g., 75 psig).
  • the activity of the catalyst is at least 100 gP.mmolcat fh 1 , such as from 100 gP.mmolcat 1 .
  • h 1 to 6,000,000 gP.mmolcat 1 . h 1 such as from 200 gP.mmolcat fh Ho 5,000,000 gP.mmolcat 1 . h x , alternatively from 300 gP.mmolcat fh Ho 1,500,000 gP.mmolcat 1 . h 1 .
  • the present disclosure provides a process for the production of an ethylene alpha-olefin copolymer comprising: polymerizing ethylene and at least one C3- C20 alpha-olefin by contacting the ethylene and the at least one C3-C20 alpha-olefin with a catalyst system described above in one or more continuous stirred tank reactors or loop reactors, in series or in parallel, at a reactor pressure of from 0.05 MPa to 1,500 MPa and a reactor temperature of from 30°C to 230°C to form an ethylene alpha-olefin copolymer.
  • hydrogen is present in the polymerization reactor at a partial pressure of from about 10 psig to about 300 psig, such as from about 20 psig to about 250 psig, such as from about 30 psig to about 200 psig, such as from about 40 psig to about 150 psig, such as from about 50 psig to about 100 psig (e.g., 75 psig), alternatively from about 150 psig to about 300 psig (e.g., 200 psig).
  • the activity of the catalyst is at least 1,000 gP.mmolcat 1 . h 1 , such as from about 1,000 gP.mmolcaffh 1 to about 10,000,000 gP.mmolcat 1 .
  • h 1 such as from about 1,500 gP.mmolcat 1 . h 1 to about 8,000,000 gP.mmolcat fh 1 , such as from about 1,800 gP.mmolcat 1 . h 1 to about 1,000,000 gP.mmolcat 1 . h 1 , alternatively from about 10,000 gP.mmolcat 1 . h 1 to about 8,000,000 gP.mmolcat 1 . h 1 .
  • the present disclosure provides a process for the production of an propylene alpha-olefin copolymer comprising: polymerizing propylene and at least one ethylene and or at least one C4-C20 alpha-olefin by contacting the propylene and the at least one ethylene and or at least one C3-C20 alpha-olefin with a catalyst system described above in one or more continuous stirred tank reactors or loop reactors, in series or in parallel, at a reactor pressure of from 0.05 MPa to 1,500 MPa and a reactor temperature of from 30°C to 230°C to form an ethylene alpha-olefin copolymer.
  • hydrogen is present in the polymerization reactor at a partial pressure of from about 10 psig to about 300 psig, such as from about 20 psig to about 250 psig, such as from about 30 psig to about 200 psig, such as from about 40 psig to about 150 psig, such as from about 50 psig to about 100 psig (e.g., 75 psig), alternatively from about 150 psig to about 300 psig (e.g., 200 psig).
  • the activity of the catalyst is at least 1,000 gP.mmolcat fh 1 , such as from about 1,000 gP.mmolcat fh 1 to about 10,000,000 gP.mmolcat fh 1 , such as from about 1,500 gP.mmolcat fh 1 to about 8,000,000 gP.mmolcat fh 1 , such as from about 1,800 gP.mmolcaffh 1 to about 1,000,000 gP.mmolcat fh 1 , alternatively from about 10,000 gP.mmolcat fh 1 to about 500,000 gP.mmolcat fh 1 .
  • 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.
  • alumoxane is present at zero mol%, alternately the alumoxane is present at a molar ratio of aluminum to transition metal less than 500: 1, such as less than 300: 1, such as less than 100: 1, such as less than 1 : 1.
  • little or no scavenger is used in the process to produce the ethylene polymer.
  • 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, such as less than 50:1, such as less than 15: 1, such as less than 10: 1.
  • additives may also be used in the polymerization, as desired, such as one or more scavengers, hydrogen, aluminum alkyls, 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 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,
  • the polymerization process with catalyst compounds of the present disclosure is a solution polymerization process.
  • a solution polymerization is 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.
  • Solution polymerization may involve polymerization in a continuous reactor in which the polymer formed, the starting monomer and catalyst materials supplied are agitated to reduce or avoid concentration gradients and in which the monomer acts as a diluent or solvent or in which a hydrocarbon is used as a diluent or solvent.
  • Suitable processes can operate at temperatures from about 0°C to about 250°C, such as from about 50°C to about 170°C, such as from about 80°C to about 150°C, such as from about 100°C to about 140°C, and/or at pressures of about 0.1 MPa or more, such as 2 MPa or more.
  • the upper pressure limit is not critically constrained but can be about 200 MPa or less, such as 120 MPa or less, such as 30 MPa or less.
  • Temperature control in the reactor can generally be obtained by balancing the heat of polymerization and with reactor cooling by reactor jackets or cooling coils to cool the contents of the reactor, auto refrigeration, pre-chilled feeds, vaporization of liquid medium (diluent, monomers or solvent) or combinations of all three. Adiabatic reactors with pre-chilled feeds can also be used.
  • the purity, type, and amount of solvent can be optimized for the maximum catalyst productivity for a particular type of polymerization.
  • the solvent can be also introduced as a catalyst carrier.
  • the solvent can be introduced as a gas phase or as a liquid phase depending on the pressure and temperature.
  • the solvent can be kept in the liquid phase and introduced as a liquid.
  • Solvent can be introduced in the feed to the polymerization reactors.
  • a process described herein can be a solution polymerization process that may be performed in a batchwise fashion (e.g., batch; semi-batch) or in a continuous process.
  • Suitable reactors may include tank, loop, and tube designs.
  • the process is performed in a continuous fashion and dual loop reactors in a series configuration are used.
  • the process is performed in a continuous fashion and dual continuous stirred-tank reactors (CSTRs) in a series configuration are used.
  • CSTRs continuous stirred-tank reactors
  • the process can be performed in a continuous fashion and a tube reactor can be used.
  • the process is performed in a continuous fashion and one loop reactor and one CSTR are used in a series configuration.
  • the process can also be performed in a batchwise fashion and a single stirred tank reactor can be used.
  • compositions of matter produced by the methods described herein relate to compositions of matter produced by the methods described herein.
  • a process described herein produces C2 to C20 olefin homopolymers (e.g., polyethylene; polypropylene), or C2 to C20 olefin copolymers (e.g., ethylene-octene, ethylene-propylene) and/or propylene-alpha-olefin copolymers, such as C3 to C20 copolymers (such as propylene-hexene copolymers or propylene-octene copolymers).
  • C2 to C20 olefin homopolymers e.g., polyethylene; polypropylene
  • C2 to C20 olefin copolymers e.g., ethylene-octene, ethylene-propylene
  • propylene-alpha-olefin copolymers such as C3 to C20 copolymers (such as propylene-hexene copolymers or propylene-octene copolymers).
  • a process described herein produces C3 to C20 isotactic olefin homopolymers, such as isotactic polypropylene, such as highly isotactic polypropylene.
  • the term“isotactic” is defined as having at least 20% or more isotactic pentads according to analysis by 13 C NMR.
  • the term“highly isotactic” is defined as having 50% or more isotactic pentads according to analysis by 13 C NMR.
  • an ethylene or propylene based polymer has one or more of: an Mw value of 1,000 g/mol or greater, such as from about 1,000 g/mol to about 3,000,000 g/mol, such as from about 25,000 g/mol to about 2,000,000 g/mol, alternately from about 3,000,000 g/mol to about 10,000,000 g/mol, such as from about 5,000,000 g/mol to about 7,500,000 g/mol; an Mn value of 1,000 g/mol or greater, such as from about 1,000 g/mol to about 2,000,000 g/mol, such as from about 100,000 g/mol to about 1,200,000 g/mol, alternately from about 2,000,000 g/mol to about 10,000,000 g/mol, such as from about 5,000,000 g/mol to about 7,500,000 g/mol; an Mz value of 5,000 g/mol or greater, such as from about 1,000 g/mol to about 10,000,000 g/mol, such as from about 100,000 to about 6,000,000 g/mol,
  • the ethylene or propylene based polymer has an Mw/Mn (PDI) value of from 1 to 20, such as from 5 to 20, such as from 10 to 20, alternatively from 1 to 5, such as from 1.5 to about 3.
  • PDI Mw/Mn
  • 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 ethylene or propylene based polymer has a melting point (Tm) of less than 100°C, such as from about 30°C to about 80°C, such as from about 40°C to about 70°C.
  • Tm melting point
  • a propylene based polymer has one or more of: an Mw value of about 500 g/mol or greater, such as from about 500 g/mol to about 200,000 g/mol, such as from about 2,000 g/mol to about 100,000 g/mol, alternately such as from about 1,000 g/mol to about 400,000 g/mol; an Mn value of 500 g/mol or greater, such as from about 500 g/mol to about 250,000 g/mol, such as from about 10,000 g/mol to about 100,000, alternately 1,000 g/mol to 500,000; an Mz value of 2,000 g/mol or greater, such as from about 2,000 g/mol to about 400,000 g/mol, such as from about 10,000 g/mol to about 200,000 g/mol, alternately from about 1,000 g/mol to about 750,000 g/mol.
  • an Mw value of about 500 g/mol or greater such as from about 500 g/mol to about 200,000 g/mol, such as from about 2,000 g/mol to about
  • a propylene based polymer has an Mw/Mn (PDI) value of from 1 to 3, such as from 1 to 2.5.
  • a propylene based polymer has a melting point (Tm) of at least 50°C, such as from 100°C to 170°C, such as from 120°C to 150°C.
  • Tm melting point
  • an ethylene or propylene based polymer is an ethylene alpha-olefin copolymer or propylene alpha-olefin copolymer having one or more of: an Mw value of 1,000 g/mol or greater, such as from about 1,000 g/mol to about 1,500,000 g/mol, such as from about 15,000 g/mol to about 750,000 g/mol, alternately from about 500,000 g/mol to about 10,000,000 g/mol, such as from about 3,500,000 g/mol to about 7,500,000 g/mol; an Mn value of 2,000 g/mol or greater, such as from about 2,000 g/mol to about 1,000,000 g/mol, such as from about 50,000 g/mol to about 750,000 g/mol,
  • the ethylene alpha-olefin copolymer or propylene alpha-olefin copolymer has a comonomer content of from 0.1 wt% to 99 wt%, such as from 1 wt% to 40 wt%, such as from 40 wt% to 95 wt%, such as from 20 wt% to 50 wt%, such as from 15 wt% to 30 wt%.
  • the ethylene alpha-olefin copolymer or propylene alpha-olefin copolymer has an Mw/Mn (PDI) value of from about 1 to about 40, such as from about 1 to about 30, such as from about 1 to about 20, such as from about 1 to about 10, such as from about 1 to about 5, alternatively from 20 to 40.
  • PDI Mw/Mn
  • the ethylene alpha-olefin copolymer or propylene alpha-olefin copolymer has a melting point (Tm) of at least 40°C, such as from about 40°C to about 140°C, such as from about 90°C to about 120°C.
  • the distribution and the moments of molecular weight (Mw, Mn, Mz, Mw/Mn, etc.), the comonomer content and the branching index (g 1 ) 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.
  • Three Agilent PLgel 10-pm Mixed-B LS columns are used to provide polymer separation.
  • Reagent grade 1, 2, 4-tri chlorobenzene (TCB) (from Sigma- Aldrich) comprising -300 ppm antioxidant BHT can be used as the mobile phase at a nominal flow rate of -1.0 mL/min and a nominal injection volume of -200 pL.
  • the whole system including transfer lines, columns, and detectors can be contained in an oven maintained at ⁇ 145°C.
  • a given amount of sample can be weighed and sealed in a standard vial with ⁇ 10 pL flow marker (heptane) added thereto. After loading the vial in the auto-sampler, the oligomer or polymer may automatically be dissolved in the instrument with ⁇ 8 mL added TCB solvent at ⁇ 160°C with continuous shaking.
  • the sample solution concentration can be from -0.2 to -2.0 mg/ml, with lower concentrations used for higher molecular weight samples.
  • concentration, c. at each point in the chromatogram can be calculated from the baseline-subtracted IR5 broadband signal, /, using the equation: c al. where a is the mass constant determined with polyethylene or polypropylene standards.
  • 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 lOM gm/mole.
  • PS monodispersed polystyrene
  • the comonomer composition is determined by the ratio of the IR5 detector intensity corresponding to CEE and CEE 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 (CH3/IOOOTC) as a function of molecular weight.
  • the short-chain branch (SCB) content per lOOOTC (SCB/1000TC) is then computed as a function of molecular weight by applying a chain-end correction to the CH3/IOOOTC 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 C3, C4, Ce, Ce, and so on co-monomers, respectively:
  • bulk SCB/1000TC bulk CH3/1000TC - bulk CH3end/1000TC and 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
  • 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.):
  • AR(0) is the measured excess Rayleigh scattering intensity at scattering angle Q
  • c is the polymer concentration determined from the IR5 analysis
  • a 2 is the second virial coefficient
  • R(q) 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 8 for the solution flowing through the viscometer is calculated from their outputs.
  • the intrinsic viscosity, [h] q s /c, where c is concentration and is determined from the IR5 broadband channel output.
  • the branching index (g'vis) is calculated using the output of the GPC-IR5-LS-VIS method as follows.
  • av g. of the sample is calculated by:
  • the branching index g' vis is defined as g' v s where M v is the viscosity-average
  • the polymer (such as the polyethylene or polypropylene) 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, poly butene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene-1, isotactic poly butene, ABS resins, ethylene- propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic block cop
  • the polymer (such as the polyethylene or polypropylene ) is present in the above blends, at from 10 wt% to 99 wt%, based upon the weight of the polymers in the blend, such as 20 wt% to 95 wt%, such as at least 30 wt% to 90 wt%, such as at least 40 wt% to 90 wt%, such as at least 50 wt% to 90 wt%, such as at least 60 wt% 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-Geigy
  • any of the foregoing polymers such as the foregoing polypropylenes or blends thereof, 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 can be oriented in the Machine Direction (MD) at a ratio of up to 15, such as from about 5 to about 7, and in the Transverse Direction (TD) at a ratio of up to 15, such as from about 7 to about 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 pm to 50 pm can be suitable. Films intended for packaging can be from 10 pm to 50 pm thick. The thickness of the sealing layer can be from 0.2 pm to 50 mih. 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.
  • M is a group 3, 4, or 5 metal
  • a 1 and A 2 are independently an aromatic group, such as an aromatic hydrocarbyl group;
  • J is a heterocyclic Lewis base, such as a 6 membered heterocyclic ring;
  • L is a Lewis base
  • X is an anionic ligand
  • n 1, 2 or 3;
  • n 0, 1, or 2;
  • n+m is not greater than 4.
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 is independently hydrogen, C 1-C40 hydrocarbyl, C 1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , or R 7 and R 8 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and where substitutions on the ring can join to form additional rings;
  • any two L groups 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; and any two X groups may be joined together to form a dianionic ligand group.
  • each of R 9 , R 10 , R 11 , and R 12 is independently hydrogen, C1-C40 hydrocarbyl, C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 9 and R 10 , R 10 and R 11 , or R 11 and R 12 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms.
  • each of R 13 , R 14 , R 15 , and R 16 is independently hydrogen, C1-C40 hydrocarbyl, C 1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 13 and R 14 , R 14 and R 15 , or R 15 and R 16 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms.
  • Clause 4 The catalyst compound of any of Clauses 1 to 3, wherein J is selected from a pyridine, a thiazole, an oxazole, an oxazoline, an imidazole, a furan, or a thiofuran.
  • each of R 17 , R 18 , and R 19 is independently hydrogen, C1-C40 hydrocarbyl, C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 17 and R 18 , R 18 and R 19 , or R 17 and R 19 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms.
  • R 17 , R 18 , and R 19 are hydrogen.
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 is independently hydrogen, C 1-C40 hydrocarbyl, C 1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , or R 7 and R 8 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms; each of R 9 , R 10 , R 11 , and R 12 is independently hydrogen, C1-C40 hydrocarbyl, C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 9 and R 10 , R 10 and R 11 , or R 11 and
  • each of R 13 , R 14 , R 15 , and R 16 is independently hydrogen, C1-C40 hydrocarbyl, C 1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 13 and R 14 , R 14 and R 15 , or R 15 and R 16 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms; and
  • each of R 17 , R 18 , and R 19 is independently hydrogen, C1-C40 hydrocarbyl, C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 17 and R 18 , R 18 and R 19 , or R 17 and R 19 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms.
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are independently selected from hydrogen, C1-C40 hydrocarbyl, C1-C40 substituted hydrocarbyl, alkoxy, silyl, amino, aryloxy, halogen, phosphino, or one or more of R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , or R 7 and R 8 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms.
  • Clause 11 The catalyst compound of any of clauses 1-10, wherein R 4 and R 5 are independently C1-C10 alkyl.
  • Clause 13 The catalyst compound of any of clauses 1-10, wherein R 4 and R 5 are aryl. Clause 14. The catalyst compound of clause 13, wherein R 4 and R 5 are phenyl or carbazole. Clause 15. The catalyst compound of clause 13, wherein R 4 and R 5 are Et3Si.
  • Clause 16 The catalyst compound of clause 13, wherein R 4 and R 5 are 3.5-di-/e/V- butylbenzyl. Clause 17. The catalyst compound of any of clauses 1-10, wherein R 2 and R 7 are independently Ci-Cio alkyl.
  • Clause 18 The catalyst compound of any of clauses 1-10, wherein R 2 and R 7 are methyl.
  • each of R 1 , R 3 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 is independently hydrogen, methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy, or trimethylsilyl.
  • Clause 26 A catalyst system comprising an activator and the catalyst compound of any of clauses 1 to 25.
  • Clause 27 The catalyst system of clause 26, further comprising a support material.
  • Clause 28 The catalyst system of clauses 26 or 27, wherein the support material is selected from AI2O3, ZrC , S1O2, S1O2/AI2O3, SiC /TiCh, silica clay, silicon oxide/clay, or mixtures thereof.
  • Clause 29 The catalyst system of any of clauses 26 to 28, wherein the activator comprises a non-coordinating anion activator.
  • Z is (L-H) or a reducible Lewis Acid
  • L is an Lewis base
  • H is hydrogen
  • (L-H) + is a Bronsted acid
  • - is a non-coordinating anion having the charge d-
  • d is an integer from 1 to 3.
  • E is nitrogen or phosphorous, preferably nitrogen
  • each of R 1 , R 2 , and R 3 is independently H, optionally substituted C1-C40 alkyl (such as branched or linear alkyl), or optionally substituted Cs-Cso-aryl (alternately each of R 1 , R 2 , and R 3 is independently unsubstituted or substituted with at least one of halide, C5-C50 aryl, C6-C35 arylalkyl, C6-C35 alkylaryl and, in the case of the Cs-Cso-aryl, C1-C50 alkyl); wherein R 1 , R 2 , and R 3 together comprise 15 or more carbon atoms (such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 37 or more carbon atoms, such as 40 or more carbon atoms, such as
  • each Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical, preferably a fluorinated aryl group, such fluoro-phenyl or fluoro-naphthyl, more preferably perfluorophenyl or perfluoronaphthyl.
  • Clause 32 The catalyst system of any of clauses 26 to 31, wherein the activator is one or more of:
  • each R 1 independently is a C1-C30 hydrocarbyl group; each R", independently, is a C4- C20 hydrocarbenyl group having an end-vinyl group; and v is from 0.1 to 3.
  • Clause 34 The catalyst system of any of clauses 26 to 33, wherein the activator comprises an alkylalumoxane.
  • Clause 35 The catalyst system of any of clauses 26 to 34, wherein the alumoxane is present at a molar ratio of aluminum to catalyst compound transition metal of 100: 1 or more.
  • Clause 36 A process for the production of an ethylene based polymer comprising: polymerizing ethylene by contacting the ethylene with a catalyst system of any of clauses 26 to 35, in one or more continuous stirred tank reactors or loop reactors, in series or in parallel, at a reactor pressure of from 0.05 MPa to 1,500 MPa and a reactor temperature of from 30°C to 230°C.
  • Clause 37 The process of clause 36, wherein the catalyst has an activity from 5,000 gP.mmolcat fh 1 to 1,000,000 gP.mmolcat fh 1 .
  • Clause 38 The process of clauses 36 or 37, wherein the ethylene based polymer has an Mw value of from 1,000 to 3,000,000, Mn value of from 1,000 to 2,000,000, Mz value of from 1,000 to 10,000,000, and a PDI of from 1 to 20.
  • Clause 40 The process of any of clauses 36 to 39, wherein the ethylene based polymer has a PDI of from 10 to 20.
  • Clause 41 The process of any of clauses 36 to 40, wherein the ethylene based polymer has a melting point of from 100°C to 150°C.
  • a process for the production of a propylene based polymer comprising: polymerizing propylene by contacting the propylene with a catalyst system of any of clauses 26 to 35, in one or more continuous stirred tank reactors or loop reactors, in series or in parallel, at a reactor pressure of from 0.05 MPa to 1,500 MPa and a reactor temperature of from 30°C to 230°C to form a propylene based polymer.
  • Clause 43 The process of clause 42, wherein the catalyst has an activity from 100 gP.mmolcat fh ⁇ to 6,000,000 gP.mmolcat fh 1 .
  • Clause 44 The process of clauses 42 or 43, wherein the propylene based polymer has an Mw value of from 500 to 150,000, Mn value of from 500 to 100,000, Mz value of from 2,000 to 400,000, and a PDI of from 1 to 3.
  • Clause 45 The process of any of clauses 42 to 44, wherein the propylene based polymer has a melting point of from 50°C to 170°C.
  • a process for the production of an ethylene alpha-olefin copolymer comprising: polymerizing ethylene and at least one C3-C20 alpha-olefin by contacting the ethylene and the at least one C3-C20 alpha-olefin with a catalyst system of any of clauses 25 to 34, in one or more continuous stirred tank reactors or loop reactors, in series or in parallel, at a reactor pressure of from 0.05 MPa to 1,500 MPa and a reactor temperature of from 30°C to 230°C to form an ethylene alpha-olefin copolymer.
  • Clause 47 The process of clause 46, wherein the catalyst has an activity from 1,000 gP.mmolcat fh ⁇ to 10,000,000 gP.mmolcat fh 1 .
  • Clause 48 The process of clauses 46 or 47, wherein the ethylene alpha-olefin copolymer has an Mw value of from 5,000 to 1,500,000, and Mz value of from 5,000 to 10,000,000, an Mn value of from 2,000 to 400,000, and a PDI of from 1 to 40.
  • Clause 50 The process of any of clauses 46 to 48, wherein the ethylene alpha-olefin copolymer has a PDI of from 20 to 40.
  • Clause 51 The process of any of clauses 46 to 50, wherein the ethylene alpha-olefin copolymer has a melting point of from 40°C to 140°C.
  • Clause 53 The transition metal compound of clause 52, wherein the bis(aryl phenolate) heterocyclic ligand is coordinated to the metal center with the formation of a pair of eight- membered metallocycle rings.
  • Clause 54 The catalyst compound of clause 1 formed by chelation of a tridentate dianionic ligand to a group 4 transition metal, where the tridentate ligand coordinates to the metal to form a pair of eight-membered metallocycle rings.
  • 3 ⁇ 4 NMR spectroscopic data were acquired at 250 MHz, 400 MHz, or 500 MHz using solutions prepared by dissolving approximately 10 mg of a sample in either C6D6, CD2CI2, CDCh, Dx-toluene. or other deuterated solvent.
  • the chemical shifts (d) presented are relative to the residual protium in the deuterated solvent at 7.15 ppm, 5.32 ppm, 7.24 ppm, and 2.09 ppm for C6D6, CD2CI2, CDCh, D8-toluene, respectively.
  • the obtained mixture was extracted with dichloromethane (3 x 50 mL), and the combined organic extract was dried over Na2SC>4 and then evaporated to dryness.
  • To the resulting oil were added 50 mL of THF, 50 mL of methanol and 1 mL of 12 N hydrochloric acid. The reaction mixture was stirred overnight at 60°C and then poured into 200 mL of water.
  • the obtained mixture was extracted with dichloromethane (3 x 50 mL), and the combined organic extract was dried over Na2SC>4 and then evaporated to dryness.
  • the obtained mixture was extracted with dichloromethane (3 x 50 mL).
  • the combined organic extract was dried over Na2SC>4 and then evaporated to dryness.
  • To the resulting oil were added 50 mL of THF, 50 mL of methanol and 1 mL of 12 N hydrochloric acid.
  • the reaction mixture was stirred overnight at 60°C and then poured into 200 mL of water.
  • the obtained mixture was extracted with dichloromethane (3 x 50 mL).
  • the combined organic extract was dried over Na2SC>4 and then evaporated to dryness.
  • Tetrahydrofuran (15 mL) was added to ZnCh (0.481 g, 3.53 mmol) and the mixture was stirred to form a clear colorless solution.
  • ZnCh 0.481 g, 3.53 mmol
  • -20°C solid (2'-(methoxymethoxy)-3',5'-di-tert-pentyl- [l,l'-biphenyl]-2-yl)lithium (1.16 g, 3.21 mmol) and a little tetrahydrofuran (2 mL) were added to the solution. The solution was allowed to warm to ambient temperature and was stirred for 2 hours.
  • Chlorotriethylsilane (1.885 g, 12.5 mmol) was added to 11.9 mmol of (5-methyl-2- ((tetrahydro-2H-pyran-2-yl)oxy)phenyl)lithium in 50 mL of THF. The reaction was stirred overnight at 40°C. The reaction was concentrated to remove the THF. The resulting mixture was extracted with pentane and filtered to remove all solids. The crude product was purified by chromatography on silica gel, eluted with 10-15% dichloromethane in pentane. Yield: 3.20 g (88%).
  • Pentane was added to the resulting residue and subsequently removed under vacuum.
  • the resulting solid was extracted with toluene.
  • the combined extracts were filtered through a glass fiber plug.
  • the filtrate was concentrated under vacuum; pentane was added to the resulting residue and subsequently removed under vacuum to give an off-white solid. Yield 40 mg (62%).
  • Pentane was added to the resulting residue and subsequently removed under vacuum.
  • the resulting solid was extracted with toluene.
  • the combined extracts were filtered through a glass fiber plug.
  • the filtrate was concentrated under vacuum; pentane was added to the resulting residue and subsequently removed under vacuum to give a tan solid. Yield 29 mg (49%).
  • alkyllithiums, Grignard reagents, organoaluminums, organozincs may also be used as the transition metal reagent to form an active catalyst mixture by reaction with a bis(phenol) ligand.
  • Bis(phenol) ligands that feature a neutral Lewis base donor that bridges a pair of phenol groups may be suitable for the formation of active polymerization catalyst by reaction with transition metal reagents.
  • Solvents, polymerization grade toluene and/or isohexanes were supplied by ExxonMobil Chemical Co. and were purified by passing through a series of columns: two 500 cm 3 Oxyclear cylinders in series from Labclear (Oakland, California), followed by two 500 cm 3 columns in series packed with dried 3 A molecular sieves (8 mesh - 12 mesh; Aldrich Chemical Company), and two 500 cm 3 columns in series packed with dried 5 A molecular sieves (8-12 mesh; Aldrich Chemical Company).
  • 1-Octene (98%) (Aldrich Chemical Company) was dried by stirring over Na-K alloy overnight followed by filtration through basic alumina (Aldrich Chemical Company, Brockman Basic 1).
  • Tri-(n-octyl)aluminum (TNOA) was purchased from either Aldrich Chemical Company or Akzo Nobel and used as received.
  • Polymerization grade ethylene was further purified by passing it through a series of columns: 500 cm 3 Oxyclear cylinder from Labclear (Oakland, California) followed by a 500 cm 3 column packed with dried 3 A molecular sieves (8 mesh - 12 mesh; Aldrich Chemical Company), and a 500 cm 3 column packed with dried 5 A molecular sieves (8 mesh - 12 mesh; Aldrich Chemical Company).
  • Polymerization grade propylene was further purified by passing it through a series of columns: 2250 cm 3 Oxyclear cylinder from Labclear followed by a 2250 cm 3 column packed with 3 A molecular sieves (8 mesh - 12 mesh; Aldrich Chemical Company), then two 500 cm 3 columns in series packed with 5 A molecular sieves (8 mesh - 12 mesh; Aldrich Chemical Company), a 500 cm 3 column packed with Selexsorb CD (BASF), and finally a 500 cm 3 column packed with Selexsorb COS (BASF).
  • 2250 cm 3 Oxyclear cylinder from Labclear followed by a 2250 cm 3 column packed with 3 A molecular sieves (8 mesh - 12 mesh; Aldrich Chemical Company), then two 500 cm 3 columns in series packed with 5 A molecular sieves (8 mesh - 12 mesh; Aldrich Chemical Company), a 500 cm 3 column packed with Selexsorb CD (BASF), and finally a 500 cm 3 column packed with Selexsorb COS (BASF).
  • Methylalumoxane (MAO) was purchased from Albemarle Corporation as a 10 wt% in toluene.
  • N,N-Dimethyanilinium tetrakis(pentafluorophenyl)borate was purchased from Albemarle Corporation. All complexes and the activators were added to the reactor as dilute solutions in toluene. The concentrations of the solutions of activator, scavenger, and complexes that were added to the reactor were chosen so that between 40 microliters - 200 microliters of the solution were added to the reactor to ensure accurate delivery.
  • N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate) solution (in toluene) was added via syringe to the reactor at process conditions, followed by a pre-catalyst (i.e., complex or catalyst) solution (in toluene) via syringe to the reactor at process conditions.
  • Ethylene was allowed to enter (through the use of computer controlled solenoid valves) the autoclaves during polymerization to maintain reactor gauge pressure (+/-2 psi). Reactor temperature was monitored and typically maintained within +/-1°C.
  • Polymerizations were halted by addition of approximately 50 psi Ch/Ar (5 mol% Ch) gas mixture to the autoclaves for approximately 30 seconds. The polymerizations were quenched after a predetermined cumulative amount of ethylene had been added or for a maximum of 30 minutes polymerization time. The reactors were cooled and vented. The polymer was isolated after the solvent was removed in-vacuo. 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).
  • scavenger solution e.g., TNOA in isohexane
  • optional scavenger solution e.g., TNOA in isohexane
  • optional non-coordinating activator e.g., TNOA in isohexane
  • N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate) solution (in toluene) was then added via syringe to the reactor at process conditions, followed by a pre-catalyst (i.e., complex or catalyst) solution (in toluene) via syringe to the reactor at process conditions.
  • Reactor temperature was monitored and typically maintained within +/-1°C.
  • Polymerizations were halted by addition of approximately 50 psi Ch/Ar (5 mol% Ch) gas mixture to the autoclaves for approximately 30 seconds. The polymerizations were quenched based on a predetermined pressure loss of approximately 8 psi or for a maximum of 30 minutes polymerization time.
  • the reactors were cooled and vented.
  • the polymer was isolated after the solvent was removed in- vacuo. Yields reported include total weight of polymer and residual catalyst. Catalyst activities are typically reported as grams of polymer per mmol transition metal compound per hour of reaction time (g/mmol/hr).
  • polymer sample solutions were prepared by dissolving the polymer in 1 ,2, 4-tri chlorobenzene (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.
  • DSC Differential Scanning Calorimetry
  • the wt% copolymer was determined via measurement of the methyl deformation band at -1,375 cm 1 .
  • the peak height of this band was normalized by the combination and overtone band at -4,321 cm 1 , which corrects for path length differences.
  • the normalized peak height was correlated to individual calibration curves from 'H NMR data to predict the wt% copolymer content within a concentration range of -2 wt% to 35 wt% for octene. Typically, R2 correlations of 0.98 or greater were achieved. Reported values below 4.1 wt% are outside the calibration range.
  • Tables 1 to 6 illustrate results obtained for Catalysts 1, 2, 3, 4, 5, 6, and 7. All catalysts were found to be active catalysts for olefin polymerization upon activation with N,N- dimethylanilinium tetrakis(pentafluorophenyl)borate or MAO, respectively.
  • Table 1 illustrates ethylene polymerization results obtained using Catalysts 1, 2, 3, 4, and 5.
  • catalyst complex 25 nmol
  • N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate activator 1.1 equiv
  • Al(n-octyl)3 500 nmol
  • temperature 80°C
  • total volume 5 mL.
  • narrow PDI was obtained (from 1.6 to 3.4).
  • Catalysts 1 and 4 were found to be the most active catalysts for olefin polymerization upon activation with N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, with Catalysts 1 and 4 only differing from their metal groups, Hf and Zr, respectively.
  • the polymerization process was performed using 25 nmol of the catalyst with 1.1 equivalents of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate in the presence of 500 nmol TNOA as a scavenger.
  • Catalyst 5 exhibited the highest catalyst activity (Run 16, 573,257 gP.mmolcat fh 1 )
  • both Catalysts 1 and 4 provided polyethylenes with the highest Mw (up to 1,630,381 g/mol), Mn (up to 482,351 g/mol), and Mz (up to 5,817,836).
  • the highest melting points for polyethylenes were obtained when Catalyst 1 or Catalyst 4 were employed (e.g., Tm of from 135°C to 136°C), whereas the lowest melting point for polyethylene was obtained when Catalyst 3 was employed (e.g., Tm of 107°C).
  • Catalyst 3 was the least active (Run 8, 13,083 gP.mmolcat fh 1 ).
  • Catalyst 3 exhibited in general the lowest catalyst activity (Runs 7 through 9, from 15,671 gP.mmolcar'.h 1 to 20,566 gP.mmolcat fh 1 ), Catalyst 3 also provided the highest molecular weight polymers (e.g., Run 8), with the highest melting point (Tm of 136°C), and anarrow PDI (1.8 to 1.9).
  • Catalyst 1 exhibited similar results as Catalyst 3. However, Mn values of polyethylenes formed by Catalyst 1 were lower (from 223,959 g/mol to 366,904 g/mol) than polyethylenes formed by Catalyst 3.
  • Catalyst 2 exhibited similar results as Catalyst 3 as well. However, PDI values of polyethylenes formed by Catalyst 2 were the highest observed, from 11.3 to 15.2. When Catalyst 5 was employed (Runs 13 through 15), polyethylenes were obtained with the lowest Mn, Mw, Mz, PDI and Tm, even though Catalyst 5 exhibited the highest catalyst activity observed.
  • Table 3 illustrates ethylene-octene copolymerization results obtained using
  • catalyst complex 25 nmol
  • N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate activator 27.5 nmol
  • Al(n-octyl)3 500 nmol
  • temperature 80°C
  • total volume 5 mL.
  • melting points of the ethylene-octene copolymers from 45°C to 120°C were lower than that of the polyethylene homopolymers.
  • the lowest melting points were obtained for the copolymers produced using catalysts including aryl substituents (such as Catalysts 2, 3, and 5) at the positions adj acent to the phenolate oxygens, and the highest melting points were obtained with Catalysts 1 and 4, with Catalyst 4 exhibiting the highest Mn, Mw and Mz (Runs 18 through 23).
  • Table 4 illustrates ethylene-octene copolymerization results obtained for Catalysts 1, 2, 3, 4, and 5.
  • catalyst complex 25 nmol
  • MAO activator 500 equiv
  • Catalyst 3 provided the ethylene-octene copolymer with the highest Mw, Mz, and PDI, as well as a melting point of 122°C, while exhibiting the lowest catalyst activity values observed (Runs 12 through 17).
  • Catalysts 1 and 4 exhibited similar results even though the catalyst activity of Catalyst 4 was about 8 to 10 fold higher than the catalyst activity of Catalyst 1.
  • Copolymers produced using Catalysts 1, 4, and 5 were obtained with narrow PDIs, whereas the copolymers produced using Catalysts 2 and 3 were obtained with PDI values of from 16.6 to 34.7.
  • Table 5 illustrates propylene polymerization results obtained for Catalysts 1, 2, 3, 4, 5, 6, and 7.
  • catalyst complex 25 nmol
  • N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate activator 27.5 nmol
  • propylene 1 mL
  • Al(n-octyl)3 500 nmol
  • total volume 5 mL.
  • narrow PDI was obtained (from 1.6 to 2.2).
  • Catalysts 1 and 4 were found to be the most active catalysts observed for olefin polymerization upon activation with N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate.
  • the highest melting points for polypropylenes were obtained when Catalyst 1 or Catalyst 4 were employed (e.g., Tm of from 149°C to 151°C), whereas the lowest melting points for polyethylenes were obtained when Catalysts 3 or Catalyst 5 were employed (e.g., Tm of from 52°C to 55°C).
  • Catalyst 3 was the least active (Run 15, 288 gP.mmolcat fh 1 ) catalyst tested.
  • Catalyst 4 exhibited the highest catalyst activity (Run 19, 4,350,000 gP.mmolcat fh 1 ) observed.
  • Table 6 illustrates propylene polymerization results obtained for Catalysts 1, 2, 3, 4, and 5.
  • catalyst complex 40 nmol
  • MAO activator 500 equiv
  • propylene 1 mL
  • total volume 5 mL.
  • Catalysts 1 and 4 were found to be the most active catalysts tested for olefin polymerization upon activation with MAO.
  • the highest melting points for polypropylene polymers were obtained when Catalyst 1 or Catalyst 4 were employed (e.g., Tm of from 133°C to 149°C), with Catalyst 4 exhibiting the highest catalyst activity (Run 20, 1,088,156 gP.mmolcat fh 1 ) observed.
  • Table 7 illustrates ethylene polymerization results obtained using Catalysts 8 through 14.
  • catalyst complex 25 nmol
  • N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate activator 1.1 equiv
  • 75 psig ethylene 1.1 equiv
  • Al(n-octyl)3 500 nmol
  • temperature 80°C
  • total volume 5 mL
  • solvent toluene.
  • Table 8 illustrates an ethylene polymerization results obtained using Catalyst 11.
  • catalyst complex 25 nmol
  • MAO activator 500 equiv
  • 75 psig ethylene 75 psig ethylene
  • temperature 80°C
  • total volume 5 mL
  • solvent toluene.
  • Table 9 illustrates ethylene-octene copolymerization results obtained using
  • Table 10 illustrates ethylene-octene copolymerization results obtained for Catalyst 11.
  • catalyst complex 25 nmol
  • MAO activator 500 equiv
  • 0.1 mL octene 0.1 mL
  • temperature 80°C
  • total volume 5 mL
  • solvent toluene.
  • Table 11 illustrates propylene polymerization results obtained for Catalysts 8 through 14.
  • catalyst complex 25 nmol
  • N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate activator 27.5 nmol
  • propylene 1 mL
  • Al(n-octyl)3 500 nmol
  • total volume 5 mL
  • solvent isohexane.
  • Table 12 illustrates ethylene polymerization results obtained using Catalysts 16 and 17.
  • catalyst complex 25 nmol
  • N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate activator 1.1 equiv
  • temperature 80°C
  • total volume 5 mL
  • solvent toluene.
  • Table 13 illustrates ethylene-octene copolymerization results obtained using Catalysts 16 and 17.
  • catalyst complex 25 nmol
  • N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate activator 27.5 nmol
  • Al(n-octyl)3 500 nmol
  • temperature 80°C
  • total volume 5 mL
  • solvent toluene.
  • catalysts, catalyst systems, and processes of the present disclosure can provide high temperature ethylene polymerization, propylene polymerization, or copolymerization as the bis(aryl phenolate)Lewis base catalysts are stable at high polymerization temperatures and have good activity at the high polymerization temperatures.
  • the stable catalysts with good activity 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.
  • the present disclosure demonstrates highly active catalysts capable of operating at high reactor temperatures while producing polymers with controlled molecular weights and/or robust isotacticity.
  • 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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CN112358498B (zh) * 2020-10-27 2023-03-03 万华化学集团股份有限公司 一种四芳氧基ivb族双核金属配合物及其制备和应用
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WO2020167799A1 (en) 2020-08-20
EP3924394A1 (en) 2021-12-22
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JP2022520575A (ja) 2022-03-31
KR20210118204A (ko) 2021-09-29
CN113423742B (zh) 2023-05-05
JP7242879B2 (ja) 2023-03-20
EP3924395A1 (en) 2021-12-22
CN113614123B (zh) 2024-01-23
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