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WO2021188337A1 - Complexes de métaux de transition du groupe 6 de type dimérique pentavalent et leurs procédés d'utilisation - Google Patents

Complexes de métaux de transition du groupe 6 de type dimérique pentavalent et leurs procédés d'utilisation Download PDF

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Publication number
WO2021188337A1
WO2021188337A1 PCT/US2021/021694 US2021021694W WO2021188337A1 WO 2021188337 A1 WO2021188337 A1 WO 2021188337A1 US 2021021694 W US2021021694 W US 2021021694W WO 2021188337 A1 WO2021188337 A1 WO 2021188337A1
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group
independently
transition metal
substituted
composition
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Alexander V. Zabula
Carlos Lopez-Barron
Gursu CULCU
David A. Cano
Lubin Luo
Yong Yang
Alan A. Galuska
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/11—Homopolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/21—Stereochemical aspects
    • C08G2261/216—Cis-trans isomerism
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/22—Molecular weight
    • C08G2261/222—Molecular weight monodisperse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/22—Molecular weight
    • C08G2261/228—Polymers, i.e. more than 10 repeat units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3321—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from cyclopentene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]

Definitions

  • the present disclosure relates to ring-opening metathesis polymerization.
  • a number of catalysts have been developed for synthesizing polyolefins.
  • the choice of catalyst may allow tailoring of various polyolefin properties, such as molecular weight, branching, tacticity, crystallinity, melt index, and similar features.
  • activators such as alkyl aluminum compounds, alumoxanes and non-coordinating anion activators are commonly used as co- catalysts for various types of transition metal complexes.
  • ROMP ring opening metathesis polymerization
  • a chain-growth process takes place to convert a cyclic olefin into a polymeric material.
  • ROMP has become an effective method for preparing a wide range of polymers, particularly linear polymers.
  • Such catalyst system have presented many disadvantages, such as, a) the highly oxidizing nature of Group 6 metals in their highest chemically accessible oxidation state (i.e., +6), thus limiting the range of ligands compatible with the conditions used for forming the catalyst; b) undefined or multiple active site structures, thereby resulting in an uncontrollable reaction environment; c) generation of corrosive gases (e.g., HC1 and Cl 2 ) during catalyst formation, which can also promote catalyst deactivation; and d) instability when the catalysts are contacted with air or water, which may require special anaerobic precautions during transport, handling, and polymerization.
  • a) the highly oxidizing nature of Group 6 metals in their highest chemically accessible oxidation state (i.e., +6) thus limiting the range of ligands compatible with the conditions used for forming the catalyst
  • homogeneous Ziegler-Natta polymerizations often require the addition of a diluent quench, often ethanol, to stop the polymerization reaction, precipitate the product, and separate it from catalyst residue, which can result in a colored, sometimes unusable, product. Recovery and recycling of monomer and catalyst are therefore difficult.
  • the foregoing factors collectively have a negative impact on the yield, stereo-selectivity (trans:cis ratio), molecular weight, molecular weight distribution, and cost of ROMP-produced polypentenamers and similar polymers produced through ring opening. Consequently, commercial scaling of cyclic olefin polymerization has been very challenging.
  • references of interest include US patent numbers: US 3,598,796, US 3,631,010, US 3,707,520, US 3,778,420, US 3,941,757, US 4,002,815, US 4,239,484, US 5,218,065, US 5,753,721, US 5,962,364, US 6,093,779, US 8,889,786; US patent publication numbers: US 2010/0113719, US 2014/0309466, US 2016/0289352, US 2017/0247479; Canadian patent number: CA 1,074,949; Chinese Pat. Pub. No.
  • This invention relates to a composition
  • a composition comprising: at least 1 wt%, based upon the weight of composition, of a transition metal complex comprising a pentavalent transition metal and represented by the Formula (1): wherein: each M is independently tungsten or molybdenum; each L is independently a monodentate anionic organic ligand; and each X is independently a halide.
  • This invention also relates to a composition
  • a composition comprising: 2 wt% (alternately 5 wt%, alternately 10 wt%, alternately 15 wt%, alternately 20 wt%, alternately 25 wt%, alternately 30 wt%, alternately 40 wt%, alternately 50 wt%, alternately 60 wt%, alternately 70 wt%, alternately 80 wt%, alternately 85 wt%, alternately 90 wt%, alternately 95 wt%) or more based upon the weight of composition, of a transition metal complex comprising a pentavalent transition metal and represented by the Formula (1) described herein.
  • FIG. 1A shows a representation of the molecular structure of
  • Figure 1B shows a representation of the molecular structure of C 1 2 W(4-C 6 H 5 CH 2 C 6 H 4 O) ⁇ (p-C1 2 )W(4-C 6 H 5 CH 2 C 6 H 4 O) 2 C1 2 in the solid state (X-ray diffraction study (50% thermal ellipsoid plot)).
  • FIG. 1C shows a representation of the molecular structure of C 1 2 W ( 2-C1C 6 ,H4O) 2 ( ⁇ -C1 2 ) W ( 2-C1C 6 ,H4O ) 2 C1 2 in the solid state (X-ray diffraction study (50% thermal ellipsoid plot)).
  • the present disclosure generally relates to ring-opening metathesis polymerization (ROMP) and, more specifically, pentavalent dimeric Group 6 transition metal complexes effective for conducting ROMP.
  • ROMP ring-opening metathesis polymerization
  • a “Group 6 metal” is an element from Group 6 of the Periodic Table.
  • the groups (columns) are numbered sequentially from left to right from 1 through 18, excluding the f-block elements (lanthanides and actinides).
  • the term “transition metal” refers to any atom from groups 3 to 12 of the Periodic Table, inclusive of the lanthanides and actinide elements.
  • W and Mo are Group 6 transition metals.
  • 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
  • percent refers to percent by weight, expressed as “wt%.”
  • an “olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • alkene is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • 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 “terpolymer” is a polymer having three mer units that are different from each other.
  • An "ethylene polymer” or “ethylene copolymer” is a polymer or copolymer comprising at least 50 mol% ethylene derived units
  • a "propylene polymer” or “propylene copolymer” is a polymer or copolymer comprising at least 50 mol% propylene derived units, and so on.
  • hydrocarbon refers to a class of compounds having 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 numbers of carbon atoms.
  • C n refers to hydrocarbon(s) having n carbon atom(s) per molecule or group, wherein n is a positive integer.
  • Such hydrocarbon compounds may be one or more of linear, branched, cyclic, acyclic, saturated, unsaturated, aliphatic, or aromatic, with optional substitution being present in some cases.
  • hydrocarbyl radical hydrocarbyl group
  • hydrocarbyl may be used interchangeably and are defined to mean a group consisting of hydrogen and carbon atoms only and bearing at least one unfilled valence position when removed from a parent compound.
  • Preferred hydrocarbyls are Ci-Cioo radicals that may be linear or branched. Examples of such radicals include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl.
  • hydrocarbyl group having 1 to about 100 carbon atoms refers to a moiety selected from a linear, cyclic or branched Ci-Cioo hydrocarbyl group.
  • the hydrocarbyl radical is independently selected from methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl,
  • examples include phenyl, methylphenyl, benzyl, methylbenzyl, naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and the like.
  • a radical when listed, it indicates that radical type and all other radicals formed when that radical type is subjected to the substitutions defined above.
  • Alkyl, alkenyl, and alkynyl radicals listed include all isomers including, where appropriate, cyclic isomers, for example, butyl includes n-butyl, 2-methylpropyl, 1-methylpropyl, tert- butyl, and cyclobutyl (and analogous alkyl substituted cyclopropyls); pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, and neopentyl (and analogous alkyl substituted cyclobutyls and cyclopropyls); butenyl includes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-l-propenyl, 1 -methyl-2 -propenyl, 2-methyl- 1-propenyl, and 2-methyl-2-propenyl (and cyclobutenyls and cycl
  • Cyclic compounds having substitutions include all isomer forms.
  • methylphenyl includes ortho-methylphenyl, meta-methyl phenyl and para- methylphenyl; and dimethylphenyl includes 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, and 3,5-dimethylphenyl.
  • 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 functional group.
  • Heteroatoms may include, but are not limited to, B, O, N, S, P, F, Cl, Br, I, Si, Pb, Ge, Sn, As, Sb, Se, and Te.
  • R is a hydrocarbyl group or H.
  • Suitable hydrocarbyl R groups may include alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, and the like, any of which may be optionally substituted.
  • Preferred heteroatom functional groups include groups such as -NR* 2, -OR*, -SeR*, -TeR*, -PR* 2 , -AsR* 2 , -SbR* 2 , -SR*, -BR* 2 , -SiR* 3 , -GeR* 3 , -SnR* 3 , -PbR* 3 , -(CH 2 )q-SiR* 3 , and the like, where q is 1 to 10 and each R* is independently hydrogen, 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). Substituted also includes replacement of a carbon atom with a heteroatom, or a heteroatom functional group.
  • any of the hydrocarbyl groups herein may be optionally substituted.
  • optionally substituted means that a group may be unsubstituted or substituted. Unless otherwise specified, any of the hydrocarbyl groups herein may be optionally substituted.
  • optionally substituted means that a group may be unsubstituted or substituted. Unless otherwise specified, any of the hydrocarbyl groups herein may be optionally substituted.
  • Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom has been substituted with a heteroatom or heteroatom containing group, preferably with at least one functional group, such as halogen (Cl, Br, I, F), NR* 2 , OR*, SeR*, TeR*, PR* 2 , AsR* 2 , SbR* 2 , SR*, BR* 2 , SiR* 3 , GeR* 3 , SnR* 3 , PbR* 3 , and the like or where at least one heteroatom has been inserted within the hydrocarbyl radical, where R* is, independently, hydrogen or a hydrocarbyl.
  • halogen Cl, Br, I, F
  • NR* 2 OR*, SeR*, TeR*, PR* 2 , AsR* 2 , SbR* 2 , SR*, BR* 2 , SiR* 3 , GeR* 3 , SnR* 3 , PbR* 3
  • alkyl refers to a hydrocarbyl group having no unsaturated carbon-carbon bonds.
  • substituted alkyl refers to an alkyl group where at least one hydrogen atom or carbon atom of alkyl group has been replaced with a heteroatom or heteroatom functional group.
  • aromatic or “aromatic hydrocarbon” refer to a hydrocarbon or hydrocarbyl group having a cyclic arrangement of conjugated pi-electrons that satisfies the Hiickel rule.
  • aryl is equivalent to the term “aromatic” as defined herein.
  • aryl refers to both aromatic compounds and heteroaromatic compounds. Both mononuclear and polynuclear aromatic compounds are encompassed by these terms.
  • substituted aryl or substituted aromatic refers to an aryl group where one or more hydrogen groups have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom functional group.
  • heteroaryl and “heteroaromatic” refer to an aromatic ring containing a heteroatom and which satisfies the Hiickel rule.
  • substituted heteroaryl or “substituted heteroaromatic” refers to a heteroaryl or heteroaromatic group where one or more hydrogen groups have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom functional group.
  • arylalkyl refers to an aryl group where one or more hydrogen groups has been replaced with an alkyl group or substituted alkyl group.
  • substituted arylalkyl refers to an alkylaryl group where one or more hydrogen groups from the aryl moiety are replaced by a hydrocarbyl (other than the alkyl groups), substituted hydrocarbyl, heteroatom or heteroatom functional group and or where one or more hydrogen groups from the alkyl moiety are replaced by a heteroatom or heteroatom functional group.
  • alkylaryl refers to an alkyl group where a hydrogen has been replaced with an aryl group or substituted aryl group.
  • a benzyl group is an example of an alkylaryl group.
  • substituted alkylaryl refers to an alkylaryl group where one or more hydrogen groups from the aryl moiety are replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom functional group and or where one or more hydrogen groups from the alkyl moiety are replaced by a heteroatom or heteroatom functional group.
  • Silylcarbyl radicals are radicals in which one or more hydrocarbyl hydrogen atoms have been substituted with at least one SiR* 3 containing group or where at least one -Si(R*) 2 - has been inserted within the hydrocarbyl radical where R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.
  • Silylcarbyl radicals may be bonded via a silicon atom or a carbon atom.
  • Halocarbyl radicals are radicals in which one or more hydrocarbyl hydrogen atoms have been substituted with at least one halogen (e.g . , F, Cl, Br, I) or halogen-containing group (e.g. , CF 3 ).
  • linear or “linear hydrocarbon” refer to a hydrocarbon or hydrocarbyl group having a continuous carbon chain without side chain branching, in which the continuous carbon chain may be optionally substituted.
  • cyclic or “cyclic hydrocarbon” refer to a hydrocarbon or hydrocarbyl group having a closed carbon ring, which may be optionally substituted.
  • carbocyclic may also synonymously refer to such a hydrocarbon or hydrocarbyl group.
  • branched or “branched hydrocarbon” refer to a hydrocarbon or hydrocarbyl group having a linear carbon chain or a closed carbon ring, in which a hydrocarbyl side chain extends from the linear carbon chain or the closed carbon ring. Optional substitution may be present in the linear carbon chain, the closed carbon ring, and/or the hydrocarbyl side chain.
  • saturated or “saturated hydrocarbon” refer to a hydrocarbon or hydrocarbyl group in which all carbon atoms are bonded to four other atoms, with the exception of an unfilled valence position being present upon carbon in a hydrocarbyl group.
  • unsaturated or “unsaturated hydrocarbon” refer to a hydrocarbon or hydrocarbyl group in which one or more carbon atoms are bonded to less than four other atoms, exclusive of an open valence position upon carbon being present. That is, the term “unsaturated” refers to a hydrocarbon or hydrocarbyl group bearing one or more double and/or triple bonds, with the double and/or triple bonds being between two carbon atoms and/or between a carbon atom and a heteroatom.
  • independently when referenced to selection of multiple items from within a given Markush group, means that the selected choice for a first item does not necessarily influence the choice of any second or subsequent item. That is, independent selection of multiple items within a given Markush group means that the individual items may be the same or different from one another.
  • saturated hydrocarbyl groups include, but are not limited to, methyl, ethyl, n-propyl. isopropyl, n-butyl, isobutyl, sec-butyl. tert-butyl, pentyl, iso-amyl (isopentyl), neopentyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, including their substituted analogues.
  • unsaturated hydrocarbyl groups include, but are not limited to, ethenyl, propenyl, allyl, 1,4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl and the like, including their substituted analogues.
  • aromatic hydrocarbyl groups include, but are not limited to, phenyl, tolyl, xylyl, naphthyl, and the like.
  • Heteroaryl and polynuclear heteroaryl groups may include, but are not limited to, pyridyl, quinolinyl, isoquinolinyl, pyrimidinyl, quinazolinyl, acridinyl, pyrazinyl, quinoxalinyl, imidazolyl, benzimidazolyl, pyrazolyl, benzopyrazolyl, oxazolyl, benzoxazolyl, isoxazolyl, benzisoxazolyl, imidazolinyl, thiophenyl, benzothiophenyl, furanyl and benzofuranyl.
  • Polynuclear aryl groups may include, but are not limited to, naphthalenyl, anthracenyl, indanyl, in
  • C n group or compound refers to a group or a compound comprising carbon atoms at total number thereof of n, etc.
  • a “C m -C n ” group or compound refers to a group or compound comprising carbon atoms at a total number thereof in the range from m to n.
  • a C 1 -C 50 alkyl group refers to an alkyl group comprising carbon atoms at a total number thereof in the range from 1 to 50.
  • alkene and “olefin” are used synonymously herein.
  • alkenic and “olefmic” are used synonymously herein. Unless otherwise noted, all possible geometric isomers are encompassed by these terms.
  • alkene alternatively termed “alkene,” refers to an unsaturated hydrocarbon compound having a hydrocarbon chain containing at least one carbon-to-carbon double bond in the structure thereof, wherein the carbon-to-carbon double bond does not constitute a part of an aromatic ring.
  • the olefin may be linear, branched, or cyclic.
  • cyclic olefin refers to any cyclic species comprising at least one ethylenic double bond in a ring.
  • the atoms of the ring may be optionally substituted.
  • the ring may comprise any number of carbon atoms and/or heteroatoms. In some cases, the cyclic olefin may comprise more than one ring.
  • a ring may comprise at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, or more, atoms.
  • Non-limiting examples of cyclic olefins include cyclobutene, cyclopentene, cyclohexene, cyclooctene, norbomene, dicyclopentadiene (DCPD), bicyclo compounds having at least one olefmic group, oxabicyclo compounds having at least one olefmic group, and the like, all optionally substituted.
  • Bicyclo compounds are a class of compounds consisting of two rings only and having two or more atoms in common.
  • the term “substantially free of’ with respect to a particular component means the concentration of that component in the relevant composition is no greater than 10 mol% (such as no greater than 5 mol%, no greater than 3 mol%, no greater than 1 mol%, or 0%, within the bounds of the relevant measurement framework), based on the total quantity of the relevant composition.
  • catalyst refers to mean a compound capable of initiating catalysis and/or of facilitating a chemical reaction without being substantially consumed.
  • the catalyst may be described as a catalyst precursor, a pre-catalyst compound, or a transition metal compound, with these terms being used interchangeably.
  • a catalyst compound may be used by itself to promote a reaction or may be used in combination with an activator to promote a reaction. When the catalyst compound is combined with an activator to promote a reaction, the catalyst compound is often referred to as a pre-catalyst or catalyst precursor.
  • catalyst system refers to the combination of a transition metal complex (i.e., a catalyst compound) and at least one activator.
  • a transition metal complex i.e., a catalyst compound
  • activator i.e., a catalyst compound
  • catalyst system is understood to mean the unactivated transition metal complex (precatalyst) together with the activator and, optionally, a coactivator.
  • catalyst system is understood to mean the activated complex and the activator or other charge-balancing moiety.
  • the term “pentavalent” refers to a transition metal having an oxidation state of +5 within the complex.
  • hexavalent refers to a transition metal having an oxidation state of +6 within the complex.
  • isolated refers to the condition of a substance being obtained in a state substantially free of solvent and/or precursors to the given substance.
  • ROMP ring opening metathesis
  • Me is methyl
  • Et is ethyl
  • Pr is propyl
  • iPr is isopropyl
  • Bu is butyl
  • tBu is tert-butyl
  • Ph is phenyl
  • Ts is Tosyl
  • DCPD is dicyclopentadiene
  • RT room temperature (i.e., approximately 23°C)
  • equiv equivalent
  • tol is toluene
  • ppm is parts per million
  • s is second.
  • compositions comprising the pentavalent dimeric transition metal complexes of the present disclosure may be substantially free of hexavalent transition metals, such as WC 1 6 .
  • the pentavalent dimeric transition metal complexes disclosed herein may afford high polymer molecular weights and avoid generation of HC1 and Ch during polymerization, the latter resulting from substantial absence of hexavalent transition metals.
  • the pentavalent dimeric transition metal complexes disclosed herein may also lead to active catalysts having a well-defined active site, which may afford narrow polymer molecular weight distributions, in contrast to the behavior of in situ- formed Ziegler-Natta catalysts.
  • the pentavalent dimeric transition metal complexes of the present disclosure are substantially air- and water-stable, thereby minimizing the need to exclude air and water during polymerization processes.
  • the air- and water stability represents a distinct advantage over compositions comprising hexavalent transition metals.
  • compositions and catalyst systems of the present disclosure are substantially free of a hexavalent transition metal, specifically a Group 6 hexavalent transition metal.
  • a hexavalent transition metal may be used to form the transition metal complexes described herein, and the transition metal complexes may be subsequently isolated in pure or near-pure form, such that the complexes are substantially free of any residual hexavalent transition metal.
  • compositions comprising at least 1 wt%, based upon the weight of thee composition, of one or more pentavalent dimeric transition metal complexes represented by Formula 1:
  • each M is independently a Group 6 transition metal, preferably tungsten (W), molybdenum (Mo), or a combination thereof, more preferably both M are tungsten; each L is independently a monodentate anionic organic ligand; and each X independently is a halide, preferably Cl.
  • the catalyst compositions are substantially free of hexavalent transition metals, particularly hexavalent Group 6 transition metals.
  • the catalyst composition may comprise: 2 wt% (alternately 5 wt%, alternately 10 wt%, alternately 15 wt%, alternately 20 wt%, alternately 25 wt%, alternately 30 wt%, alternately 40 wt%, alternately 50 wt%, alternately 60 wt%, alternately 70 wt%, alternately 80 wt%, alternately 85 wt%, alternately 90 wt%, alternately 95 wt%) or more, based upon the weight of composition, of a transition metal complex comprising a pentavalent transition metal and represented by the Formula (I) described herein.
  • Suitable monodentate anionic organic ligands that may be present in the transition metal complexes disclosed herein include, for example, an alkoxide, an aryloxide, an alkyl thiolate, or an aryl thiolate.
  • the alkyl in the alkoxide or alkyl thiolate is a C 1 to C 30 alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, tert- butyl, isopentyl, neopentyl, or an isomer thereof, any of which may be optionally substituted.
  • alkyl in the alkoxide or alkyl thiolate is a C 1 to C 30 alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, tert- butyl, isopentyl, neopentyl, or an iso
  • the aryl in the aryloxide or aryl thiolate is a C 5 to C 30 aryl, such as phenyl, substituted phenyl, naphthyl, substituted naphthyl, anthracenyl, and substituted anthracenyl.
  • each L in Formula 1 may be the same or different.
  • each L is the same. More preferably, each L is an aryloxide or aryl thiolate. Still more preferably, each L is an aryloxide (preferably the alkyloxide is a C 1 to C 30 alkyloxide, such as methoxide, ethoxide, propoxide, butoxide, pentoxide, hexoxide, heptoxide, octoxide, nonoxide, decoxide, isopropoxide, isobutoxide, tert-but oxide, isopentoxide, neopentoxide, or an isomer thereof, any of which may be optionally substituted.).
  • the alkyloxide is a C 1 to C 30 alkyloxide, such as methoxide, ethoxide, propoxide, butoxide, pentoxide, hexoxide, heptoxide, octoxide, nonoxide,
  • transition metal complexes of the present disclosure may be represented by Formula 2:
  • M is a Group 6 transition metal, preferably tungsten (W), molybdenum (Mo), or a combination thereof, more preferably both M are tungsten;
  • X is a halide, preferably chloride
  • Z is oxygen or sulfur, preferably oxygen; each Q is independently a hydrocarbyl, a substituted hydrocarbyl, a heteroatom or a heteroatom functional group; and n is 0, 1, 2, 3, 4, or 5.
  • Q may be present upon the aromatic ring (i.e., n is 1, 2, 3, 4, or 5, wherein n represents the number of Q substituents) and present in any open valence position upon the aromatic ring.
  • Suitable hydrocarbyl groups useful as Q include, for example, any C 1 -C 30 hydrocarbyl group or substituted C 1 -C 30 hydrocarbyl group, which may be linear, branched or cyclic, saturated or unsaturated, and/or aromatic or aliphatic.
  • Suitable heteroatom substituents useful as Q may include any heteroatom or heteroatom-containing functional group such as, for example, halogen, phenol, alkoxy, aryloxy, thio, thioether, amino, substituted amino, silyl, carboxylic acid, carboxamide, carboxylic ester, nitrile, or the like.
  • Two or more optional substitutions Q when located upon adjacent carbon atoms, may be joined to form a ring in certain embodiments, wherein the ring may be aromatic, aliphatic, and/or heterocyclic, mono- nuclear or multi-nuclear. Any carbon atoms upon the aromatic ring that lack an optional substitution Q are bound to a hydrogen atom.
  • transition metal complexes of the present disclosure may be represented by Formula 3:
  • each M is independently a Group 6 transition metal, preferably tungsten (W), molybdenum (Mo), or a combination thereof, more preferably both M are tungsten;
  • X is a halide, preferably Cl, Br, F or I, preferably C1;
  • each of R 1 , R 2 , R 3 , R 4 and R 5 is independently hydrogen, C 1 -C 30 alkyl group, preferably a C 1 -C 20 alkyl group, which may be optionally substituted, or a C 7 -C 30 alkylaryl group, preferably benzyl, which may be optionally substituted.
  • each of R 1 , R 2 , R 3 , R 4 and R 5 independently may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, tert- butyl, isopentyl, neopentyl, or an isomer thereof, any of which may be optionally substituted.
  • the optionally substituted alkyl group may be linear, branched or cyclic, saturated or unsaturated, and/or aromatic or aliphatic and may contain 1 to about 30 carbon atoms.
  • at least one of R 1 , R 2 , R 3 , R 4 and R 5 is methyl and/or -(CH 2 )Ph (benzyl).
  • each R 3 is independently hydrogen, is a C 1 -C 30 alkyl group, preferably a C 1 -C 20 alkyl group, which may be optionally substituted, or R 3 is a C 7 -C 30 alkylaryl group, preferably benzyl, which may be optionally substituted.
  • R 3 may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, t-butyl, isopentyl, neopentyl, or an isomer thereof, any of which may be optionally substituted.
  • the optionally substituted alkyl group may be linear, branched or cyclic, saturated or unsaturated, and/or aromatic or aliphatic and may contain 1 to about 30 carbon atoms.
  • R 3 is methyl.
  • R 3 is -(CH2)Ph (benzyl).
  • each of R 1 , R 2 , R 3 , R 4 and R 5 is independently hydrogen, heteroatom-containing functional group (such as halogen, preferably chlorine), C 1 -C 30 alkyl group (preferably a C 1 -C 20 alkyl group), which may be optionally substituted, or a C 7 -C 30 alkylaryl group (preferably benzyl, which may be optionally substituted).
  • heteroatom-containing functional group such as halogen, preferably chlorine
  • C 1 -C 30 alkyl group preferably a C 1 -C 20 alkyl group
  • C 7 -C 30 alkylaryl group preferably benzyl, which may be optionally substituted
  • each of R 1 , R 2 , R 3 , R 4 and R 5 independently may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, tert- butyl, isopentyl, neopentyl, chlorine, trifluoromethyl, or an isomer thereof, any of which may be optionally substituted.
  • the optionally substituted alkyl group may be linear, branched or cyclic, saturated or unsaturated, and/or aromatic or aliphatic and may contain 1 to about 30 carbon atoms.
  • at least one of R 1 , R 2 , R 3 , R 4 and R 5 is halogen, such as chlorine.
  • At least one of R 1 and R 5 is halogen, such as chlorine.
  • at least one of R 1 , R 2 , R 3 , R 4 and R 5 is not hydrogen.
  • R 3 is not hydrogen.
  • R 3 is a C 1 -C 30 alkyl group (preferably a C 1 -C 20 alkyl group), such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, t-butyl, isopentyl, neopentyl, or an isomer thereof.
  • R 3 is a C 7 -C 30 alkylaryl group (preferably benzyl), or a substituted C7-C40 alkylaryl group.
  • each X is chloride.
  • each M is tungsten.
  • each halide X can be F, Cl, or Br, preferably
  • each X is the same.
  • More specific examples of transition metal complexes of the present disclosure include those represented by Formulas 4, 5 and 6 below.
  • the transition metal complex is one or more of Formula 4 or 5 or 6:
  • the transition metal complexes of the present disclosure may be synthesized in a single step by reacting an aluminum bis or tris alkoxide, aryloxide, alkyl thiolate, or aryl thiolate (where the alkyl is preferably a Ci to C30 alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, t-butyl, isopentyl, neopentyl, or an isomer thereof, any of which may be optionally substituted, and the aryl is a C 5 to C 30 aryl, such as phenyl, naphthyl, anthracenyl, any of which may be optionally substituted) with a Group 6 metal halide, preferably a hexavalent Group 6 metal halide, as
  • the transition metal complexes of the present disclosure may be formed by contacting two equivalents or more of an aluminum bis aryloxide monohalide or bis arylthiolate monohalide with a Group 6 metal halide (e.g, WC1 6 ) to form the dimeric transition metal complex via an oxidative coupling reaction, as shown in Scheme 1 below.
  • M is a Group 6 transition metal, preferably Mo or W, which undergoes reduction from a hexavalent state to a pentavalent state when forming the dimeric transition metal complexes.
  • the dimeric transition metal complex may be readily isolated by crystallization to afford separation from residual quantities of MXr,.
  • An alternative general synthetic route to form the transition metal complexes of the present disclosure includes contacting an aluminum tris aryloxide or tris arylthiolate with a Group 6 metal halide (e.g ., WC1 6 ) to promote an oxidative coupling reaction as shown in Scheme 2 below.
  • M is a Group 6 transition metal, preferably Mo or W, which undergoes reduction from a hexavalent state to a pentavalent state when forming the dimeric transition metal complexes.
  • substituted or/and functionalized biphenyls produced by oxidative coupling
  • HC1 and AIC 1 3 are formed as co- products when forming the pentavalent dimeric transition metal complex in this manner.
  • an aluminum bis aryloxide can be prepared by reacting an aluminum bis alkyl monohalide (Alkyl ⁇ AlX (e.g., Me2AlCl or Et2AlCl) with 2 equivalents of a phenol in a hydrocarbon solvent (e.g., toluene and/or isohexane) by slow addition of the phenol to the aluminum bis alkyl monohalide at ambient temperature (e.g., about 25°C).
  • Alkyl ⁇ AlX e.g., Me2AlCl or Et2AlCl
  • a hydrocarbon solvent e.g., toluene and/or isohexane
  • an aluminum tris aryloxide can be prepared by reacting an aluminum tris alkoxide (AlkylO)3Al with 3 equivalents of a phenol in a hydrocarbon solvent (e.g. , toluene and/or isohexane) by slow addition at ambient temperature.
  • the aluminum tris aryloxide may form as a precipitate and be obtained as a crystalline solid after heating at a temperature of about 50°C to about 120°C (e.g., 80°C).
  • Catalyst systems comprising the transition metal complexes are also described in various embodiments of the present disclosure. Any of the pentavalent dimeric transition metal complexes described herein may be suitably present in the catalyst systems.
  • the catalyst systems comprise the pentavalent dimeric transition metal complex in combination with at least one activator, wherein the at least one activator leads to formation of a reactive species that is effective for promoting olefin polymerization.
  • Suitable activators may include, for example, organoaluminum compounds and alumoxanes.
  • W and Mo may be especially effective for promoting olefin polymerization through olefin metathesis, more preferably W.
  • suitable activators for the transition metal complexes of the present disclosure may comprise an organoaluminum compound, preferably a trialkylaluminum compound.
  • organoaluminum compound may lead to formation of an activated carbene species, as specified in Formulas 7 A and 7B below.
  • Suitable organoaluminum compounds for use in the catalyst systems of the present disclosure are not considered to be especially limited, provided that they allow a polymerization reaction to occur upon contacting a polymerizable monomer, such as one or more olefinic monomers, as described herein, preferably one or more cyclic olefins.
  • Organoaluminum compounds which may be utilized as an activator include, but are not limited to, trialkylaluminum compounds, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri -n-octyl al umin um. and the like, Triethylaluminum may be an especially suitable organoaluminum compound for use in combination with the transition metal complexes disclosed herein.
  • organoaluminum compounds are represented by the formula Al(Rri). where each R’ is independently a hydrogen atom, or a substituted, or unsubstituted alkyl group, and/or a substituted or unsubstituted aryl group, provided that at least one R 1 is not H.
  • organoaluminum compounds suitable for use in the present disclosure are organoaluminum compounds.
  • one or more R’ groups may be an alkyl group containing 1 to 30 carbon atoms, alternately 2 to 20 carbon atoms. In further embodiments of the present disclosure, one, two, or three R’ groups are not H.
  • one, two, or three R’ groups are not methyl. In another embodiment of the present disclosure, one or two groups are H. In further embodiment of the present disclosure, one, two, or three R’ groups are independently a C 1 -C 30 alkyl group, alternately a C 2 -C 20 alkyl group. Suitable R’ groups include, but are not limited to, methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, aryl, and all isomers thereof.
  • the activator may be an alumoxane.
  • Alumoxanes are generally oligomeric compounds containing -A1(R 1 )-O- sub-units, where R 1 is an alkyl group.
  • Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane.
  • Alkyl alumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is an alkyl, halide, alkoxide or amide.
  • Alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, covered under patent number U.S. PatentNo. 5,041,584).
  • MMAO modified methyl alumoxane
  • Another useful alumoxane is solid polymethylaluminoxane as described in US 9,340,630; US 8,404,880; and US 8,975,209.
  • the catalyst systems of the present disclosure comprise at least one activator and a dimeric transition metal complex of the present disclosure, wherein the variables associated with the dimeric transition metal complex are described in more detail above.
  • the at least one activator may react with the transition metal complexes during a polymerization process to replace at least two of the halide ligands, preferably two of the halide ligands, more preferably four of the halide ligands, thus forming at least one short-lived intermediate metal alkyl species (e.g ., compounds having structures represented by Formulas 7A and 7B).
  • the intermediate metal alkyl species may then undergo spontaneous reductive elimination to afford one or more active metal carbene species (e.g., compounds having structures represented by Formulas 8A and 8B).
  • active metal carbene species e.g., compounds having structures represented by Formulas 8A and 8B.
  • the stability of the active transition metal carbene species may be result from intramolecular ⁇ - ⁇ stacking interactions in the transition metal complexes.
  • transition metal complexes of the present disclosure may be converted into an intermediate metal alkyl species having a structure represented by Formula 7A or Formula 7B:
  • Formula 7A Formula 7B wherein R”’ is an alkyl group and M, X, L are as defined above.
  • the non-bridging halide atoms such as chloride, may be displaced with an alkyl group transferred from the alkyl aluminum compound, such as trimethylaluminum or triethylaluminum.
  • the bridging halide atoms are not believed to be displaced in this process.
  • the intermediate transition metal species having structures represented by Formulas 7A and 7B may undergo spontaneous reductive elimination to afford one or more metal carbene species having structures represented by Formulas 8 A and 8B
  • Formula 8A Formula 8B wherein R”” is an alkyl group having one less carbon atom than R’” and M, L and X are defined as above.
  • the amount of activator combined with the dimeric transition metal complex in the catalyst systems of the present disclosure can widely vary.
  • the molar amount of the activator to the transition metal complex can range from about 1:1 to about 10,000: 1.
  • the ratio of activator to transition metal complex can range from about 2:1, such as about 5:1, such as about 10:1, such as about 25:1, such as about 50:1, or about 100:1, up to about 10:1, up to about 500:1, up to about 1000:1, up to about 5,000:1, or up to about 10,000:1, all on a molar basis.
  • Some embodiments select the maximum amount of activator typically at up to a 5000-fold molar excess Al/M over the catalyst compound (per metal catalytic site).
  • the minimum activator-to-catalyst-compound is a 1:1 molar ratio. Alternate preferred ranges include from 1:1 to 500:1, alternately from 1:1 to 200:1, alternately from 1:1 to 100:1, or alternately from 1:1 to 50:1.
  • a [2+2] cycloaddition reaction upon undergoing activation, can undergo between the active transition metal carbene species and a cyclic olefin monomer (e.g., C 4 -C 20 cyclic olefin), thus forming a four-membered metallacyclobutane intermediate, as shown in Scheme 3 below.
  • a cyclic olefin monomer e.g., C 4 -C 20 cyclic olefin
  • the resulting olefin remains attached to the transition metal as part of an alkylidene-bound polymer chain, which may propagate through repetition of the chain propagation steps.
  • m is an integer ranging from 0 to 16.
  • catalyst systems suitable for use in the disclosure herein may be disposed on a solid support.
  • the solid support may allow a catalytic reaction, such as polymerization of an olefinic feed, to be conducted under heterogeneous conditions.
  • the solid support may be silica.
  • Other suitable solid supports may include, but are not limited to, alumina, magnesium chloride, talc, inorganic oxides, or chlorides including one or more metals from Groups 2, 3, 4, 5, 13, or 14 of the Periodic Table, and polymers such as polystyrene, or functionalized and/or cross-linked polymers.
  • inorganic oxides that may suitably function as solid supports include, for example, titania, zirconia, boron oxide, zinc oxide, magnesia, or any combination thereof. Combinations of inorganic oxides may be suitably used as solid supports as well. Illustrative combinations of suitable inorganic oxides include, but are not limited to, silica-alumina, silica-titania, silica- zirconia, silica-boron oxide, and the like. [0094] Suitable activators may be disposed on silica or another suitable solid support before being combined with the dimeric transition metal complexes disclosed herein. The transition metal complexes disclosed herein may be disposed upon silica or another suitable support before being combined with an activator.
  • the resulting catalyst system may become disposed upon the solid support.
  • Catalyst systems having different catalytic properties may be obtained depending upon whether the transition metal complex or the activator are supported on the solid support first.
  • the activator such as triethylaluminum
  • an inert solvent such as toluene
  • a solid support such as silica.
  • the activator deposition upon the solid support may occur at a temperature from about 60°C to 120°C, or about 80°C to 120°C, or about 100°C to 120°C. Deposition occurring below 60°C, including room temperature deposition, may also be effective.
  • Solid supports suitable for use in the disclosure herein may have a surface area ranging from about 1 m 2 /g to about 1000 m 2 /g, about 5 m 2 /g to about 900 m 2 /g, about 50 m 2 /g to about 500 m 2 /g, or about 100 m 2 /g to about 400 m 2 /g.
  • a solid support may have a pore volume ranging from about 0.01 cm 3 /g to about 4 cm 3 /g, about 0.1 cm 3 /g to about 3 cm 3 /g, about 0.8 cmVg to about 3 cm 3 /g, or about 1 cmVg to about 2.5 cm 3 /g.
  • a solid support may have an average particle size ranging from about 0.1 ⁇ m low of about 500 ⁇ m, such as from about 0.3 ⁇ m to about 400 ⁇ m, such as from about 0.5 ⁇ m to about 250 ⁇ m, such as from about 1 ⁇ m to about 200 ⁇ m, such as from about 5 ⁇ m to about 150 ⁇ m, or about 10 ⁇ m to about 100 ⁇ m.
  • polymerization methods are also described herein.
  • the polymerization methods of the present disclosure may comprise providing an olefmic feed, which may comprise one or more olefmic monomers, such as comprising at least one C 4 -C 20 cyclic olefin, and contacting a catalyst system, as specified herein, with the olefmic feed under polymerization reaction conditions.
  • the present disclosure may include methods comprising: contacting a catalyst system with an olefmic feed comprising at least one C 4 -C 20 cyclic olefin under polymerization reaction conditions, wherein the catalyst system comprises at least one activator and a transition metal complex described herein, such as a complex represented by Formula 1, 2, or 3.
  • the catalyst systems are substantially free of hexavalent transition metals.
  • cyclic olefin polymerization processes may comprise contacting a transition metal complex having a structure represented by Formula 1, 2, or 3, with at least one C 4 -C 20 cyclic olefin monomer in a polymerization reactor under conditions sufficient to form a reaction mixture comprising a polymer, unreacted monomer, transition metal complex, and optionally a solvent; and recovering the polymer from the reaction mixture.
  • the process further comprises separating the cyclic olefin monomer from the reaction mixture and recycling the cyclic olefin monomer to the polymerization reactor; contacting recovered catalyst with an activator prior to recycling to the polymerization reactor; or a combination thereof.
  • the polymerization may be terminated by addition of active protons, such as by adding methanol or butylated hydroxy toluene (BHT).
  • active protons such as by adding methanol or butylated hydroxy toluene (BHT).
  • polymerization reaction conditions and reactants may be selected to alter the Mw and/or the trans:cis ratio of the polymers produced.
  • the supported transition metal complex when the transition metal complex is supported, can be employed in a reactor comprising a filtration element that retains the supported catalyst but which allows a solution of resulting polymer to pass through such that the polymer is effectively separated from the supported catalyst as part of a continuous process.
  • small scale polymerization conversion rates may be monitored and estimated with a 'H NMR method using a Bruker 400 MHz instrument, as indicated.
  • CDC 1 3 was the lock solvent.
  • the chemical shift of cyclopentene monomer double bond protons was measured to be about 5.75 ppm and the chemical shift of polypentenamer double bond protons was experimentally determined to be about 5.53 ppm. Integration from 5.45 ppm to 6.00 ppm (Im+p) was used to cover the two chemical shifts, which was then set to 100% to represent total cyclopentene.
  • the temperature of the polymerization reaction conditions may be selected within a range from about -35°C to 300°C, depending on the monomers used and the desired properties of the polymer.
  • Suitable temperatures and/or pressures may also include a temperature in the range of about -20°C to about 200°C, such as about -10°C to about 150°C, such as about -5°C to about 100°C, such as from about 40°C to about 120°C, such as from about 45°C to about 80°C.
  • Suitable pressures may include a pressure in the range of about 0.35 MPa to about 10 MPa, such as from about 0.45 MPa to about 6 MPa, such as from about 0.5 MPa to about 4 MPa.
  • the run time of the polymerization process may be up to 300 minutes, such as in the range of from about 5 minutes to 250 minutes, such as from about 10 minutes to 120 minutes. For continuous polymerization processes, the run time may correspond to a residence time in the reactor.
  • the polymerization may be performed in anaerobic or substantially anaerobic conditions.
  • the cyclic olefin monomer may be separated from the polymer and then recycled, e.g., to the polymerization reactor.
  • the Mw and other properties of the polymer may be regulated by incorporating one or more comonomers into the process.
  • a non-cyclic olefin e.g., 1 -hexene or other linear alpha olefins
  • a non-cyclic olefin may be included with the cyclic olefin, optionally to reduce the polymer molecular weight.
  • Increasing the ratio of non-cyclic olefin (such as linear olefin) to cyclic olefin may result in a lower molecular weight polymer.
  • the cyclic olefin may be a single cyclic olefin, or a combination of cyclic olefins, including a mixture of two or more different cyclic olefins.
  • the cyclic olefins may be strained or unstrained, monocyclic, or polycyclic; and may optionally include heteroatoms and/or one or more functional groups.
  • Suitable cyclic olefins may include, but are not limited to, norbomene, norbomadiene, dicyclopentadiene (DCPD), cyclobutene, cyclopentene, cyclopentadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbomadiene, and substituted derivatives thereof.
  • DCPD dicyclopentadiene
  • DCPD dicyclopentadiene
  • cyclobutene cyclopentene
  • cyclopentadiene cycloheptene
  • cyclooctene cyclooctadiene
  • cyclododecene 7-oxanorbomene
  • 7-oxanorbomadiene 7-oxanorbomadiene
  • Suitable substituents may include, but are not limited to, hydroxyl, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen.
  • Suitable substituted cyclic olefins include, but are not limited to, l-hydroxy-4-cyclooctene, 1 -acetoxy-4-cyclooctene, 5-methylcyclopentene, and their respective homologs and derivatives.
  • the cyclic olefin is a strained olefin, preferably containing a four-membered or five-membered ring.
  • the cyclic olefin may be multi cyclic.
  • DCPD, norbomene, norbomadiene, ethylidene norbomene, and vinyl norbomene are multicyclic.
  • the cyclic olefin may be a C 5 -based cyclic olefin.
  • a C 5 -based cyclic olefin is an olefin (such as a C 5 to C 20 olefin) derived from substituted or unsubstituted cyclopentadiene, such as dicyclopentadiene, norbomene, norbomadiene, ethylidene norbomene, vinyl norbomene, and the like.
  • the feed comprises at least one C 4 -C 20 cyclic olefin selected from the group consisting of cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbomene, norbomadiene, such that at least one of the C 4 -C 20 cyclic olefins is cyclopentene.
  • the feed may include cyclopentene and dicyclopentadiene.
  • copolymers derived from cyclopentene and dicyclopentadiene may be produced according to certain embodiments of the present disclosure. Additional copolymers may include those formed from a cyclic olefin and a linear alpha olefin, such as a C6-C30 linear alpha olefin.
  • Polymers produced according to the present disclosure may further comprise chain- end functionality.
  • the polymer chains with the functionalized termination groups may have functionality at the chain ends. Both the concentration of the functionalized termination groups, and the selection of the functional groups allow for control over the physical properties of the resulting polymers. Furthermore, the control of the physical properties may be achieved by selecting the relative bulkiness of the ligand used to form multiple ligand environments with the same metal centers or by employing ligands having the same relative size (bulkiness) with different metal centers, or a combination thereof.
  • Polymers of the present disclosure can be characterized by their cis:trans ratio.
  • the cis:trans ratio of the polymer results in different physical properties. This phenomenon is thought to be due to the faster crystallization of trans conformation relative to the amorphous cis conformation.
  • the cis:trans ratios of the polymers can be controlled by selecting the ligands used to form the catalysts, the metal used to form the catalysts, or a combination thereof.
  • the polymer trans'.cis ratio can be measured with a 13 C NMR technique as follows. Samples is prepared with 66.67 mg/ml of CDCh (deuterated chloroform) in a 10 mm NMR tube. The 13 C NMR spectra are measured on a Bruker 600 MHz cryoprobe with inverse gated decoupling, 20s delay, 90° pulse, and 512 transients. Assignments are based on assignments from O. Dereli et al. (2006) European Polymer Journal, v.42, pp. 368-374. Three different positions are used for calculation of the trans/cis composition:
  • the present disclosure may further include copolymerization systems, wherein one or more different cyclic olefins serve as the comonomer to form the product copolymers.
  • Examples include the establishment of routes to long chain branching by the incorporation of side chain unsaturation, e.g., through vinyl norbomene, ethylidene norbomene, and/or the like in the backbone of the polymer.
  • the comonomers may then act as initiation points for ROMP or cross-metathesis reactions.
  • DCPD may be used as a comonomer to form polymers in which both rings of the monomer undergo opening to produce a four-armed star polymer.
  • properties of the product polymers may be controlled by employing polymerization systems comprising two or more reactors connected in a sequence. Embodiments may further include producing heterophasic copolymers.
  • Suitable polymerization reaction conditions may also include, for example, any high-pressure, solution, slurry and/or gas phase polymerization process.
  • the catalyst system may be located in a fixed bed, fluidized bed, ebullated bed, slurry bed, trickle bed, or like reactor system when conducting a polymerization reaction.
  • Any suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization process can be used in accordance with the disclosure herein.
  • Polymerization processes can be carried out in a batch, semi-batch, or continuous mode.
  • 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.
  • Homogeneous polymerization processes and slurry processes are useful.
  • a homogeneous polymerization process is defined to be a process where at least 90 wt% of the product is soluble in the reaction media.
  • a bulk homogeneous process can be used.
  • a bulk process is defined to be a process where monomer concentration in all feeds to the reactor is 70 vol% or more. 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).
  • the process is a slurry process.
  • slurry polymerization process means a polymerization process where a supported catalyst is employed and monomers are polymerized on the supported catalyst particles. At least 95 wt% of polymer products derived from the supported catalyst are in granular form as solid particles (not dissolved in the diluent).
  • a heterogeneous process is defined to be a process where the catalyst system is not soluble in the reaction media.
  • additives may also be used in the polymerization, as desired, such as one or more scavengers, promoters, modifiers, chain transfer agents (such as diethylzinc), hydrogen, or silanes.
  • chain transfer agents such as diethylzinc
  • Useful chain transfer agents also include alkylalumoxanes, such as methylalumoxane.
  • Suitable diluents/solvents for polymerization include non-coordinating or weakly coordinating inert liquids.
  • Examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (ISOPARTM); perhalogenated hydrocarbons, such as perfluorinated C 4-10 alkanes, chlorobenzene, and aromatic and alkyl-substituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene.
  • straight and branched-chain hydrocarbons such as is
  • Suitable solvents also include liquid olefins which may act as monomers or co-monomers including ethylene, propylene, 1 -butene, 1 -hexene, 1-pentene, 3-methyl-l-pentene, 4-methyl- 1-pentene, 1-octene, 1-decene, and mixtures thereof.
  • Aliphatic hydrocarbon may be 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.
  • Polymers produced using the catalyst systems of the present disclosure may be homopolymers (e.g., polypentenamer) or a copolymer of a cyclic olefin and anon-cyclic olefin, such as a linear alpha olefin.
  • polymers produced using the catalyst systems of the present disclosure may have a cis/trans ratio of about 50%/50%, such as about 45%/55%, such as about 40%/60%, such as about 35%/65%, such as about 30%/70%, such as about 25%/75%, such as about 20%/80%, such as about 15%/85%, such as about 10%/90%, or such as about 5%/95%.
  • polymers produced using the catalyst systems of the present disclosure may have a ratio of weight average molecular weight to number average molecular weight (Mw/Mn) of about 1 to 10, alternately about 1 to about 5, alternately about 1.2 to about 2.5, alternately about 1.2 to about 2.0, alternately 1.4 to 1.8 as determined by the LT GPC 3D process discussed further below.
  • Mw/Mn weight average molecular weight to number average molecular weight
  • polymers produced using the catalyst systems of the present disclosure may have a weight average molecular weight (Mw) of 50,000 g/mol to 2,000,000 g/mol, such as 75,000 g/mol to 1,750,000 g/mol, such as 100,000 g/mol to 1,500,000 g/mol, such as 200,000 g/mol to 1,250,000 g/mol, such as 300,000 g/mol to 1,000,000 g/mol, such as 400,000 g/mol to 750,000 g/mol, as determined by the LT GPC 3D process described below.
  • Mw weight average molecular weight
  • polymers produced using the catalyst systems of the present disclosure may have a weight average molecular weight (Mw) of 8,000 g/mol to 30,000 g/mol, alternately 200,000 g/mol to 2,600,000 g/mol, as determined by the LT GPC 3D process described below.
  • Mw weight average molecular weight
  • polymers produced using the catalyst systems of the present disclosure may have a number average molecular weight (Mn) of 25,000 g/mol to 1,000,000 g/mol, such as 30,000 g/mol to 800,000 g/mol, such as 50,000 g/mol to 750,000 g/mol, such as 100,000 g/mol to 600,000 g/mol, such as 150,000 g/mol to 500,000 g/mol, such as 200,000 g/mol to 400,000 g/mol, as determined by the LT GPC 3D process described below.
  • Mn number average molecular weight
  • polymers produced using the catalyst systems of the present disclosure may have a number average molecular weight (Mn) of 4,000 g/mol to 15,000 g/mol, alternately 100,000 g/mol to 1,300,000 g/mol, as determined by the LT GPC 3D process described below.
  • Mn number average molecular weight
  • polymers produced using the catalyst systems of the present disclosure may have a z average molecular weight (Mz) of 75,000 g/mol to 3,000,000 g/mol, such as 90,000 g/mol to 1,600,000 g/mol, such as 100,000 g/mol to 1,500,000 g/mol, such as 300,000 g/mol to 1,800,000 g/mol, such as 450,000 g/mol to 1,500,000 g/mol, such as 600,000 g/mol to 1,200,000 g/mol, as determined by the LT GPC 3D described below.
  • Mz z average molecular weight
  • polymers produced using the catalyst systems of the present disclosure may have a z average molecular weight (Mz) of 12,000 g/mol to 45,000 g/mol, alternately 300,000 g/mol to 4,000,000 g/mol, as determined by the LT GPC 3D described below.
  • Mz z average molecular weight
  • polyolefins produced using the catalyst systems of the present disclosure may have an Mw/Mn of 1 to 5, such as 1.25 to 3.5, such as 1.5 to 2.
  • polyolefins produced using the catalyst systems of the present disclosure may have a melting point (Tm) of from -100°C to 20°C, alternately -50°C to 10°C, alternately -20°C tol0°C, and alternately 4°C to 8°C, as determined by DSC described below.
  • Tm melting point
  • M n is the number average molecular weight
  • M w is the weight average molecular weight
  • M z is the z average molecular weight.
  • the molecular weight distribution, molecular weight moments (M w , M n , M w /M n ) and long chain branching indices were determined by using a Polymer Char GPC-IR, equipped with three in-line detectors, an 18-angle light scattering (“LS”) detector, a viscometer and a differential refractive index detector (“DRI”). Three Agilent PLgel 10 ⁇ m Mixed-B LS columns were used for the GPC tests herein. The nominal flow rate was 0.5 mL/min, and the nominal injection volume was 200 ⁇ L. The columns, viscometer and DRI detector were contained in ovens maintained at 40°C.
  • the tetrahydrofuran (THF) solvent with 250 ppm antioxidant butylated hydroxytoluene (BHT) was used as the mobile phase.
  • THF tetrahydrofuran
  • BHT butylated hydroxytoluene
  • the concentration, C, at each point in the chromatogram was calculated from the baseline-subtracted DRI signal, / DRI , using the following equation: where ADRI is a constant determined by calibrating the DRI, and (d n /d c ) is the incremental refractive index of polymer in THF solvent.
  • the conventional molecular weight was determined by combining universal calibration relationship with the column calibration, which was performed with a series of monodispersed polystyrene (PS) standards ranging from 300 g/mol to 12,000,000 g/mol.
  • PS monodispersed polystyrene
  • M molecular weight
  • the LS molecular weight, M, at each point in the chromatogram was determined by analyzing the LS output using the Zimm model for static light scattering and determined using the following equation:
  • AR(0) is the measured excess Rayleigh scattering intensity at scattering angle Q
  • “c” is the polymer concentration determined from the DRI analysis
  • A2 is the second virial coefficient
  • R(q) is the form factor for a mono-disperse random coil
  • a four capillaries viscometer with a Wheatstone bridge configuration was used to determine the intrinsic viscosity [h ⁇ from the measured specific viscosity ( ⁇ s) and the concentration “C” [0133]
  • the average intrinsic viscosity, of the sample was calculated using the following equation: where the summations are over the chromatographic slices, i, between the integration limits.
  • the M v is the viscosity-average molecular weight based on molecular weights determined by LS analysis.
  • the Mark-Houwink parameters a and k used for the reference linear polymer are 0.725 and 0.000291, respectively.
  • DSC measurements were carried out using a DSC2500TM (TA InstrumentsTM) with a 10°C/min heating rate. 4 to 8 mg of sample was loaded in hermetic DSC pans. The heat flow data during temperature ramps from 150°C to -150°C and from -150°C to 150°C were collected to measure the thermal transitions, Tg, Tm and Tc. For purposes herein, the melting temperature and glass transition temperature are determined by DSC analysis from the second heating ramp by heating of the sample at 10°C/min from -150°C to 150°C.
  • This invention also relates to:
  • a composition comprising: at least 1 wt%, based upon the weight of composition, of a transition metal complex comprising a pentavalent transition metal represented by the Formula (1): wherein: each M is independently a group 6 metal; each L is independently a monodentate anionic organic ligand; and each X is independently a halide.
  • each L is independently selected from the group consisting of an alkoxide, an aryloxide, an alkyl thiolate, and an aryl thiolate.
  • each L is independently selected from the group consisting of an alkoxide, an aryloxide, an alkyl thiolate, or an aryl thiolate.
  • organoaluminum compound comprises an alkyl aluminum selected from the group consisting of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri -n-hexyl aluminum. tri-n- octylaluminum, diethyl aluminum chloride, and any combination thereof.
  • a polymerization method comprising: contacting the catalyst system of any of paragraphs 9 to 13 with an olefmic feed comprising at least one C 4 -C 20 cyclic olefin.
  • the olefmic feed comprises at least one C 4 -C 20 cyclic olefin selected from the group consisting of cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cycloheptene, cyclooctene, cyclooctadiene, norbomene, norbomadiene, dicyclopentadiene, and any combination thereof.
  • WC1 6 and MoC1 5 aluminum alkyls (e.g., triethylaluminum (AlEt 3 ), cyclopentene, and solvents (e.g., toluene), and antioxidant, such as butylated hydroxytoluene (BHT) were purchased from Sigma-Aldrich and used without further purification unless explicitly stated otherwise. All solvents were anhydrous grade and were further treated with activated 3 ⁇ molecular sieves by storing the solvent in a container with 5 wt% to 10 wt% molecular sieves for at least 24 hours prior to use.
  • AlEt 3 triethylaluminum
  • solvents e.g., toluene
  • antioxidant such as butylated hydroxytoluene (BHT)
  • Cyclopentene was sparged with nitrogen for at least 30 min (1L of nitrogen per one min over one L of cyclopentene) and treated with 3 ⁇ molecular sieves by storing the cyclopentene in a container with 5 wt% to 10 wt% molecular sieves for at least 24 hours prior to use, and was passed through an activated basic alumina column before use. All deuterated solvents (CDC 1 3, C 6 D 6 ,. THF-d 8 and the like) were obtained from Cambridge Isotopes (Cambridge, MA) and dried over 3 A molecular sieves before use. Other chemicals such as aluminum alkyls were used as received. All reactions were performed under an anhydrous inert nitrogen atmosphere using standard laboratory techniques unless otherwise stated. [0141] (4-MeC 6 H 4 O) 2 AlCl Preparation: Dimethylaluminum chloride (21.38 g,
  • the dimeric transition metal complexes C1 2 W(RO) 2 ( ⁇ -CL)W(RO) 2 CL were prepared as specified below in Examples 1A, IB and 1C.
  • FIG. 1A shows a representation of the molecular structure of the transition metal complex produced in Example 1A, as determined using single-crystal X-ray diffraction.
  • FIG. IB shows a representation of the molecular structure of the transition metal complex produced in Example IB, as determined using single-crystal X-ray diffraction.
  • FIG. 1C shows a representation of the molecular structure of the transition metal complex produced in Example 1C, as determined using single-crystal X-ray diffraction.
  • Example 2A Polymerization: A solution of C1 2 W(4-MeC 6 H 4 O) 2 ( ⁇ -C1 2 )W(4- MeC 6 H 4 O) 2 C1 2 (100 mg, 0.099 mmol, 1.0 equiv) in toluene (10 mL) was added to a solution of cyclopentene (27 g, 396 mmol, 4000 equiv) and triethylaluminum (29 mg, 0.254 mmol, 2.56 equiv) at 0°C.
  • Example 2B Polymerization: A solution of triethylaluminum (199 mg, 1.74 mmol, 4 equiv) in toluene (10 mL) was added to the mixture containing ChW(4- MeC 6 H 4 O) 2 ( ⁇ -C1 2 )W(4-MeC 6 H 4 O) 2 C1 2 (440 mg, 0.436 mmol, 1.0 equiv), cyclopentene (59.4 g, 872 mmol, 2000 equiv) and toluene (500 mL) at 0°C.
  • Example 2C Polymerization: A solution of Cl 2 W(2-ClC 6 H 4 O) 2 ( ⁇ -C1 1 )W(2- C1C 6 H 4 O) 2 C1 2 (800 mg, 0.734 mmol, 1.0 equiv) in toluene (10 mL) was added to a solution of cyclopentene (100 g, 1,467 mmol, 2000 equiv) and triethylaluminum (335 mg, 0.294 mmol, 4 equiv) at 0°C.
  • compositions and methods are described herein in terms of “comprising” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps.
  • compositions and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps. All numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed. In particular, every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values.

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Abstract

La présente invention concerne une composition comprenant au moins 1 % en poids, sur la base du poids de la composition, d'un complexe de métal de transition comprenant un métal de transition pentavalent et représenté par la formule (1) : dans laquelle chaque M est indépendamment un métal du groupe 6, tel que Mo ou W ; chaque L est indépendamment un ligand organique aionique monodenté ; et chaque X est indépendamment un halogénure.
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