EP3568418A2 - Complexes de métal de transition bis(indényle) pontés, production et utilisation de ceux-ci - Google Patents

Complexes de métal de transition bis(indényle) pontés, production et utilisation de ceux-ci

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Publication number
EP3568418A2
EP3568418A2 EP17891908.0A EP17891908A EP3568418A2 EP 3568418 A2 EP3568418 A2 EP 3568418A2 EP 17891908 A EP17891908 A EP 17891908A EP 3568418 A2 EP3568418 A2 EP 3568418A2
Authority
EP
European Patent Office
Prior art keywords
indenyl
isopropyl
biphenyl
methoxyphenyl
indacenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17891908.0A
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German (de)
English (en)
Other versions
EP3568418A4 (fr
Inventor
Jian Yang
Xiongdong Lian
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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Priority claimed from PCT/US2017/068158 external-priority patent/WO2018132247A2/fr
Publication of EP3568418A2 publication Critical patent/EP3568418A2/fr
Publication of EP3568418A4 publication Critical patent/EP3568418A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer

Definitions

  • the present disclosure relates to catalyst compounds comprising bridged bis(indenyl) transition metal complexes and uses thereof.
  • Polyolefins are widely used commercially because of their robust physical properties. For example, various types of poly ethylenes, including high density, low density, and linear low density polyethylenes, are some of the most commercially useful. Polyolefins are typically prepared with a catalyst that polymerizes olefin monomers. Therefore, there is interest in finding new catalysts and catalyst systems that provide polymers having improved properties.
  • Catalysts for olefin polymerization typically have transition metals, e.g., the catalysts are metallocenes and can be activated by alumoxane or an activator containing a non-coordinating anion.
  • polymerization conditions can be adjusted to provide polyolefins having desired properties. For example, increasing polymerization reactor temperature from 70°C to 110°C typically decreases the molecular weight of polyolefin products, which may be desirable for certain polyolefins.
  • Tm melting temperature
  • the melting temperature of a polyolefin formed at 110°C is typically 10°C (or more) less than the melting temperature of a polyolefin formed at 70°C, all other polymerization conditions being equal.
  • Such a large decrease in melting temperature may negate any advantage brought by the lower molecular weights of the polymers formed at higher temperatures.
  • multifunctional catalysts are catalysts capable of forming a variety of polyolefins having different structures and properties.
  • isotactic polypropylene (iPP) having a Tm above about 145°C and average molecular weight (Mw) above about 50,000 g/mol is valuable in the polyolefin industry.
  • ethylene -propylene (EP) copolymers having Mw values above about 250,000 g/mol are also valuable in the polyolefin industry.
  • a catalyst capable of forming both of these types of polymers would be valuable because the polymer formed in a reactor could be adjusted by, for example, adjusting ethylene/propylene flow parameters into the reactor.
  • metallocenes for example, C2 symmetrical 2-methyl-4-aryl ansa- metallocenes
  • C2 symmetrical 2-methyl-4-aryl ansa- metallocenes have been shown to be active for producing iPP having a Tm value above about 145 °C and average molecular weight (Mw) above about 50,000 g/mol.
  • Mw average molecular weight
  • these metallocenes often produce EP copolymers having Mw values below 250,000 g/mol.
  • Certain assymetric (CI symmetry) metallocenes produce EP copolymers having higher Mw values than the symmetrical metallocenes, but the iPP Mw values remain low, and these metallocenes appear to have significantly reduced iPP Tm values at higher polymerization temperatures, for example, at temperatures above 70°C.
  • references of interest include: US 2015/0025208; WO 2016/196331 ; PCT/US2016/033583; PCT/US2016/034784; US 2015-0025208; US 2015-0025206; US 2015-0183893; US 2015-0141590; US 2016-0355653; US 2016-0355656; WO 2016/196331; WO 2016/196334; and WO 2016/196339.
  • M 1 is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;
  • R 1 and R 2 are independently hydrogen, halogen, hydroxyl, hydrocarbyl, or substituted hydrocarbyl (such as Ci-Cio alkyl, Ci-Cio alkoxy, C6-C20 aryl, C6-C10 aryloxy, C2-C10 alkenyl, C2-C40 alkenyl, C7-C40 arylalkyl, C7-C40 alkylaryl, C8-C40 arylalkenyl, or conjugated diene which is optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl) silyl or tri(hydrocarbyl) silylhydrocarbyl, said diene having up to 30 atoms other than hydrogen);
  • R 3 is linear alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl);
  • R 9 is C3-C10 branched alkyl
  • each of R 4 , R 6 , R 7 , R 8 , R 10 , R 11 , R 12 , and R 13 is independently hydrogen, halogen, C1-C40 hydrocarbyl or C1-C40 substituted hydrocarbyl (such as C1-C10 alkyl which may be substituted, C6-C40 aryl which may be substituted, C2-C10 alkenyl, C7-C40 arylalkyl, C7-C40 alkylaryl, C 8 - C 4 o arylalkenyl), -NR' 2 , -SR', -OR, -OSiR'3, -PR'2, where each R is hydrogen, halogen, Ci- C10 alkyl, or C6-C10 aryl;
  • R 5 is hydrogen, halogen, C1-C40 hydrocarbyl or C1-C40 substituted hydrocarbyl (such as C1-C10 alkyl which may be substituted, C6-C40 aryl which may be substituted, C2-C10 alkenyl, C7-C40 arylalkyl, C7-C40 alkylaryl, C 8 -C 40 arylalkenyl), -NR'2, -SR, -OR, -OS1R3, -PR'2, where each R' is hydrogen, halogen, C1-C10 alkyl, or C 6 -Cio aryl, or two or more adjacent radicals R 5 to R 8 together form one or more saturated or unsaturated rings;
  • R 19 is -B(R 20 )-, -A1(R 20 )-, -Ge-, -Sn-, -0-, -S-, -SO-, -SO2-, -N(R 20 )-,
  • each of R 20 , R 21 , R 22 is independently hydrogen, halogen, C1-C20 alkyl, C1-C20 fluoroalkyl or silaalkyl, C6-C30 aryl, C6-C30 fluoroaryl, C1-C20 alkoxy, C2-C20 alkenyl, C7-C40 arylalkyl, C8-C40 arylalkenyl, C7-C40 alkylaryl, or one R 20 and one R 21 , together with the atoms in R 19 connecting them, form one or more rings;
  • M 2 is one or more carbon, silicon, germanium or tin;
  • R 14 is substituted or unsubstituted C 6 -Cio aryl (such as phenyl or substituted phenyl);
  • R 18 is hydrogen, halogen, substituted or unsubstituted C3-C20 alkyl, substituted or unsubstituted C6-C40 aryl (such as C7-C40 arylalkyl, C7-C40 alkylaryl, C8-C40 arylalkenyl, biphenyl), C2-C10 alkenyl, , -NR' 2 , -SR', -OR, -OS1R3 or -PR' 2 , wherein each R is hydrogen, halogen, C1-C10 alkyl, or C 6 -Cio aryl;
  • R 15 and R 17 are independently hydrogen, C2-C20 alkyl which may be substituted (such as halogenated), C6-C40 aryl which may be substituted (such as halogenated aryl, C7-C20 arylalkyl, C7-C20 alkylaryl, C8-C20 arylalkenyl), or C2-C10 alkenyl; and
  • R 16 is selected from hydrogen, halogen, C1-C10 alkyl which may be substituted (such as halogenated), C6-C20 aryl which may be substituted (such as halogenated aryl, C7-C40 arylalkyl, C7-C40 alkylaryl, C8-C40 arylalkenyl), C2-C10 alkenyl which may be substituted, or two or more adjacent radicals R 15 to R 18 together form one or more rings, and -XR'n, wherein X is a Group 14-17 heteroatom having an atomic weight of 13 to 79 and R' is one of hydrogen, halogen, C1-C10 alkyl, or C 6 -Cio aryl and n is 0, 1, 2, or 3.
  • the present disclosure further relates to bridged transition metal complexes represented by the formula (II):
  • each of R 18 , R 23 , and R 27 is independently hydrogen, halogen, substituted or unsubstituted C3-C20 alkyl, substituted or unsubstituted C6-C40 aryl (such as C7-C40 arylalkyl, C7-C40 alkylaryl, C 8 -C 40 arylalkenyl, biphenyl), C2-C10 alkenyl, -NR' 2 , -SR', -OR, -OSiR'3 or -PR'2, wherein each R' is hydrogen, halogen, C1-C10 alkyl, or C 6 -Cio aryl;
  • R 24 and R 26 are independently substituted or unsubstituted C2-C20 alkyl, substituted or unsubstituted C6-C40 aryl (such as C7-C20 arylalkyl, C7-C20 alkylaryl, or C8-C20 arylalkenyl), C2-C10 alkenyl; and
  • R 16 and R 25 are independently -(XR'n), wherein X is a Group 14-17 heteroatom having an atomic weight of 13 to 79 and R' is one of hydrogen, halogen, C1-C10 alkyl, or Ce- C10 aryl and n is 0, 1 2, or 3,
  • R 19 are as defined above for formula (I).
  • embodiments of the present disclosure provide a catalyst system comprising an activator and a catalyst of the present disclosure.
  • embodiments of the present disclosure provide 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.
  • FIG. 1 is a scheme illustrating a general reaction pathway suitable for preparing catalysts of the present disclosure.
  • FIG. 2 is a graph illustrating molecular weight values of isotactic polypropylene and ethylene-propylene copolymers formed by catalysts of the present disclosure.
  • FIG. 3 is a graph illustrating melting temperature values of isotactic polypropylene formed by catalysts of the present disclosure.
  • FIG. 4 is a graph illustrating the change in melting temperature (as a function of polymerization temperature) of isotactic polypropylene formed by catalysts of the present disclosure.
  • FIG. 5 is a graph illustrating molecular weight values of ethylene-propylene copolymers formed by catalysts of the present disclosure.
  • Catalysts of the present disclosure have a branched alkyl moiety located at a certain position on the catalysts which helps to provide ethylene-propylene copolymers having Mw values above 250,000 g/mol, isotactic polypropylene having Mw values above 40,000 g/mol, Tm values greater than 145°C, and ATm values less than 10°C.
  • catalysts of the present disclosure are represented by Formula (I) or (II) and have an isopropyl moiety at the R 9 position, as described in more detail below.
  • the specification describes catalysts that can be 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 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.
  • a "Group 4 metal” is an element from Group 4 of the Periodic Table, e.g., Hf, Ti, or Zr.
  • o-biphenyl is an element from Group 4 of the Periodic Table, e.g., Hf, Ti, or Zr.
  • dme is 1 ,2- dimethoxyethane
  • Me is methyl
  • Ph is phenyl
  • Et is ethyl
  • Pr is propyl
  • iPr is isopropyl
  • n-Pr is normal propyl
  • cPr is cyclopropyl
  • Bu is butyl
  • iBu is isobutyl
  • tBu is tertiary butyl
  • p-tBu is para-tertiary butyl
  • nBu is normal butyl
  • sBu is sec-butyl
  • TMS is trimethylsilyl
  • TIBAL is triisobutylaluminum
  • TNOAL is tri(n-octyl)aluminum
  • MAO is methylalumoxane
  • p-Me is para-methyl
  • Ph is phenyl
  • Bn is benzyl (i.e., CH2PI1)
  • THF also
  • substituted means that at least one hydrogen atom has been replaced 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, CI, F or I) or at least one functional group such as -NR* 2 , -OR*, -SeR*, -TeR*, -PR* 2 , -AsR* 2 , -SbR* 2 , -SR*, -BR* 2 , -SiR* 3 , -GeR* 3 , -SnR* 3 , -PbR* 3 , and the like, where each 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, or where at least one heterogen (such as Br, CI, F
  • hydrocarbyl radical is defined to be Ci-Cioo radicals, that may be linear, branched, or cyclic, and when cyclic, aromatic or non- aromatic.
  • radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like including their substituted analogues.
  • Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom of the hydrocarbyl 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, CI, F or I) or at least one functional group such as -NR* 2 , -OR*, -SeR*, -TeR*, -PR* 2 , -AsR* 2 , -SbR* 2 , -SR*, -BR* 2 , -SiR* 3 , -GeR* 3 , -SnR* 3 , -PbR* 3 , and the like, or where at least one heteroatom has been inserted within a hydrocarbyl ring.
  • a non-hydrogen group such as a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as hal
  • alkenyl means a straight-chain, branched-chain, or cyclic hydrocarbon radical having one or more carbon-carbon double bonds. These alkenyl radicals may be substituted. Examples of suitable alkenyl radicals include, but are not limited to, ethenyl, propenyl, allyl, 1 ,4-butadienyl cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloctenyl and the like including their substituted analogues.
  • arylalkenyl means an aryl group where a hydrogen has been replaced with an alkenyl or substituted alkenyl group.
  • styryl indenyl is an indene substituted with an arylalkenyl group (a styrene group).
  • alkoxy or "alkoxide” means an alkyl ether or aryl ether radical wherein the term alkyl is as defined above.
  • suitable alkyl ether radicals include, but are not limited to, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, phenoxy, and the like.
  • aryl or "aryl group” means a carbon-containing aromatic ring and the substituted variants thereof, including but not limited to, phenyl, 2-methyl-phenyl, xylyl, 4- bromo-xylyl.
  • heteroaryl means an aryl group where a ring carbon atom (or two or 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.
  • alkylaryl means an alkyl group where a hydrogen has been replaced with an aryl or substituted arylgroup.
  • ethylbenzyl indenyl is an indene substituted with an ethyl group bound to a benzyl group.
  • 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.
  • 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.
  • catalyst system is defined to mean a complex/activator pair.
  • Catalyst system means the unactivated catalyst complex (precatalyst) together with an activator and, optionally, a co-activator.
  • it means the activated complex and the activator or other charge-balancing moiety.
  • the transition metal compound may be neutral as in a precatalyst, or a charged species with a counter ion as in an activated catalyst system.
  • Complex as used herein, is also often referred to as catalyst precursor, precatalyst, catalyst, catalyst compound, transition metal compound, or transition metal complex. These words are used interchangeably. Activator and cocatalyst are also used interchangeably.
  • a scavenger is a compound that is typically added to facilitate polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co- activators. A co-activator, that is not a scavenger, may also be used in conjunction with an activator in order to form an active catalyst. In some embodiments a co-activator can be pre- mixed with the transition metal compound to form an alkylated transition metal compound.
  • Non-coordinating anion means an anion either that does not coordinate to the catalyst metal cation or that does coordinate to the metal cation, but only weakly.
  • NCA is also defined to include multicomponent NCA-containing activators, such as ⁇ , ⁇ -dimethylanilinium tetrakis(pentafluorophenyl)borate, that contain an acidic cationic group and the non-coordinating anion.
  • NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, that can react with a catalyst to form an activated species by abstraction of an anionic group.
  • NCA coordinates weakly enough that a neutral Lewis base, such as an olefinically or acetylenically unsaturated monomer can displace it from the catalyst center.
  • a neutral Lewis base such as an olefinically or acetylenically unsaturated monomer can displace it from the catalyst center.
  • Any metal or metalloid that can form a compatible, weakly coordinating complex may be used or contained in the 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.
  • the term non-coordinating anion activator includes neutral activators, ionic activators, and Lewis acid activators.
  • a metallocene catalyst may be described as a catalyst precursor, a pre-catalyst compound, metallocene catalyst compound or a transition metal compound, and these terms are used interchangeably.
  • a polymerization catalyst system is a catalyst system that can polymerize monomers into polymer.
  • An "anionic ligand” is a negatively charged ligand which donates one or more pairs of electrons to a metal ion.
  • a "neutral donor ligand” is a neutrally charged ligand which donates one or more pairs of electrons to a metal ion.
  • a metallocene catalyst is defined as an organometallic compound with at least one ⁇ -bound cyclopentadienyl moiety (or substituted cyclopentadienyl moiety) and more frequently two ⁇ -bound cyclopentadienyl moieties or substituted cyclopentadienyl moieties.
  • substituted means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom, or a heteroatom containing group.
  • methyl cyclopentadiene (Cp) is a Cp group substituted with a methyl group.
  • Catalyst productivity is a measure of how many grams of polymer (P) are produced using a polymerization catalyst comprising W g of catalyst (cat), over a period of time of T hours; and may be expressed by the following formula: P/(T x W) and expressed in units of gPgcat ⁇ hr 1 .
  • Conversion is the amount of monomer that is converted to polymer product, and is reported as mol% and is calculated based on the polymer yield and the amount of monomer fed into the reactor.
  • Catalyst activity is a measure of the level of activity of the catalyst and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kgP/molcat).
  • an "olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound comprising carbon and hydrogen having at least one double bond.
  • alkene is a linear, branched, or cyclic compound comprising 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 a "propylene" content of 35 wt% to 55 wt%, it is understood that the mer unit in the copolymer is derived from propylene in the polymerization reaction and the 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 monomer (“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. "Different” in reference 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 and the like.
  • An oligomer is typically a polymer having a low molecular weight, such an Mn of less than 25,000 g/mol, or less than 2,500 g/mol, or a low number of mer units, such as 75 mer units or less or 50 mer units or less.
  • An "ethylene polymer” or “ethylene copolymer” is a polymer or copolymer comprising at least 50 mole% ethylene derived units
  • a "propylene polymer” or “propylene copolymer” is a polymer or copolymer comprising at least 50 mole% propylene derived units, and so on.
  • 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
  • continuous means a system that operates without interruption or cessation for a period of time, preferably where reactants are continually fed into a reaction zone and products are continually or regularly withdrawn without stopping the reaction in the reaction zone.
  • 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 polymerization is conducted in a liquid polymerization medium, such as an inert solvent or monomer(s) or their blends.
  • a solution polymerization is typically homogeneous.
  • a homogeneous polymerization is one where the polymer product is dissolved in the polymerization medium.
  • Such systems are preferably not turbid as described in J. Vladimir Oliveira, C. Dariva and J. C. Pinto, Ind. Eng. Chem. Res. (2000), 29, 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 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 about 25 wt% of inert solvent or diluent, such as less than about 10 wt%, such as less than about 1 wt%, such as 0 wt%.
  • the present disclosure relates to bridged metallocene catalysts, where the catalysts have at least one indenyl ligand substituted at the 2-position with an alkyl group, particularly a bulky alkyl group such as isopropyl, and at the 4-position with a phenyl group, the phenyl group being substituted at the 3' , 4' , and 5 ' positions with particular combinations of substituents.
  • the catalysts have at least one indenyl ligand substituted at the 2-position with an alkyl group, particularly a bulky alkyl group such as isopropyl, and at the 4-position with a phenyl group, the phenyl group being substituted at the 3' , 4' , and 5 ' positions with particular combinations of substituents.
  • the 3 ' and 5' positions of the phenyl ring are selected to be sterically hindering (e.g., branched hydrocarbyl groups) and the 4' -substituent is selected from (XR' n ) ⁇ , wherein X is a Group 14, 15, 16 or 17 heteroatom having an atomic weight of 13 to 79 (such as N, O, S, P, or Si) and R' is one of a hydrogen atom, halogen atom, a Ci-Cio alkyl group (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl or an isomer thereof), or a C6-C10 aryl group and n is 0, 1, 2, or 3; such as (XR'n) " is -NR' 2 , -SR' , -OR' , -OSiR' 3, -Si
  • the present disclosure relates to a catalyst compound, and catalyst systems comprisi by the formula (I):
  • M 1 is selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;
  • R 1 and R 2 are independently hydrogen, halogen, hydroxyl, hydrocarbyl, or substituted hydrocarbyl (such as C1-C10 alkyl, C1-C10 alkoxy, C 6 -C 2 o aryl, C 6 -Cio aryloxy, C 2 -Cio alkenyl, C 2 -C 4 o alkenyl, C 7 -C 4 o arylalkyl, C 7 -C 4 o alkylaryl, Cs-C 4 o arylalkenyl, or conjugated diene which is optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl) silyl or tri(hydrocarbyl) silylhydrocarbyl, said diene having up to 30 atoms other than hydrogen);
  • hydrocarbyl such as C1-C10 alkyl, C1-C10 alkoxy, C 6 -C 2 o aryl, C 6 -Cio ary
  • R 3 is linear alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl);
  • R 9 is C3-C10 branched alkyl; each of R 4 , R 6 , R 7 , R 8 , R 10 , R 11 , R 12 , and R 13 is independently hydrogen, halogen, C1-C40 hydrocarbyl or C1-C40 substituted hydrocarbyl (such as C1-C10 alkyl which may be substituted, C6-C40 aryl which may be substituted, C2-C10 alkenyl, C7-C40 arylalkyl, C7-C40 alkylaryl, C 8 - C 4 o arylalkenyl), -NR' 2 , -SR', -OR, -OSiR'3, -PR'2, where each R' is hydrogen, halogen, Ci- Cio alkyl, or C 6 -Cio aryl;
  • R 5 is hydrogen, halogen, C1-C40 hydrocarbyl or C1-C40 substituted hydrocarbyl (such as C1-C10 alkyl which may be substituted, C6-C40 aryl which may be substituted, C2-C10 alkenyl, C7-C40 arylalkyl, C7-C40 alkylaryl, C 8 -C 4 o arylalkenyl), -NR' 2 , -SR, -OR, -OSiR'3, -PR'2, where each R' is hydrogen, halogen, C1-C10 alkyl, or C 6 -Cio aryl, or two or more adjacent radicals R 5 to R 8 together form one or more saturated or unsaturated rings;
  • R 19 is -B(R 20 )-, -A1(R 20 )-, -Ge-, -Sn-, -0-, -S-, -SO-, -SO2-, -N(R 20 )-, -CO-, -P(R 20 )-, or -P(0)(R 20 )-, an amidoborane radical or one of the following:
  • each of R 20 , R 21 , R 22 is independently hydrogen, halogen, C1-C20 alkyl, C1-C20 fluoroalkyl or silaalkyl, C6-C30 aryl, C6-C30 fluoroaryl, C1-C20 alkoxy, C2-C20 alkenyl, C7-C40 arylalkyl, C8-C40 arylalkenyl, C7-C40 alkylaryl, or one R 20 and one R 21 , together with the atoms in R 19 connecting them, form one or more rings;
  • M 2 is one or more carbon, silicon, germanium or tin;
  • R 14 is substituted or unsubstituted C 6 -Cio aryl (such as phenyl or substituted phenyl).
  • R 14 is substituted with one or more of C1-C10 alkyl which may be substituted (such as halogenated), C6-C20 aryl which may be substituted (such as halogenated aryl, C7-C40 arylalkyl, C7-C40 alkylaryl, C8-C40 arylalkenyl), C2-C10 alkenyl which may be substituted, a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as halogen (such as Br, CI, F or I) or at least one functional group such as -NR* 2 , -OR*, -SeR*, -TeR*, -PR* 2 , -AsR* 2 , -SbR* 2 , -SR*, -BR* 2
  • R 18 is hydrogen, halogen, substituted or unsubstituted C3-C20 alkyl, substituted or unsubstituted C6-C40 aryl (such as C7-C40 arylalkyl, C7-C40 alkylaryl, C8-C40 arylalkenyl, biphenyl), C2-C10 alkenyl, -NR 2 , -SR, -OR, -OSiR'3 or -PR 2 , wherein each R' is hydrogen, halogen, C1-C10 alkyl, or C 6 -Cio aryl;
  • R 15 and R 17 are independently hydrogen, C2-C20 alkyl which may be substituted (such as halogenated), C6-C40 aryl which may be substituted (such as halogenated aryl, C7-C20 arylalkyl, C7-C20 alkylaryl, C8-C20 arylalkenyl), or C2-C10 alkenyl; and
  • R 16 is selected from hydrogen, halogen, C1-C10 alkyl which may be substituted (such as halogenated), C6-C20 aryl which may be substituted (such as halogenated aryl, C7-C40 arylalkyl, C7-C40 alkylaryl, C8-C40 arylalkenyl), C2-C10 alkenyl which may be substituted, or two or more adjacent radicals R 15 to R 18 together form one or more rings, and -XR'n, wherein X is a Group 14-17 heteroatom having an atomic weight of 13 to 79 and R' is one of hydrogen, halogen, C1-C10 alkyl, or C 6 -Cio aryl and n is 0, 1, 2, or 3.
  • C3-C10 branched alkyl includes an alkyl group branched at the cc-position.
  • the carbon atom bonded to the indene (of the catalyst compound of formula (I)) is substituted with two alkyl moieties (such as a group represented by the formula:
  • C3-C10 branched alkyl includes isopropyl, isobutyl, isopentyl, isohexyl, isoheptyl, isooctyl, isononyl, and isodecyl. Branched alkyl does not include cyclopropyl.
  • the present disclosure further relates to a catalyst compound, and catalyst systems comprising such compounds, represented by the formula (II):
  • M 1 , R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 17 , and R 19 are as defined for formula (I);
  • each of R 18 , R 23 , and R 27 is independently hydrogen, halogen, substituted or unsubstituted C3- C20 alkyl, substituted or unsubstituted C6-C40 aryl (such as C7-C40 arylalkyl, C7-C40 alkylaryl, C 8 -C 4 o arylalkenyl, biphenyl), C2-C10 alkenyl, -NR' 2 , -SR', -OR, -OSiR'3 or -PR 2 , wherein each R' is hydrogen, halogen, C1-C10 alkyl, or C 6 -Cio aryl;
  • R 24 and R 26 are independently substituted or unsubstituted C2-C20 alkyl, substituted or unsubstituted C6-C40 aryl (such as C7-C20 arylalkyl, C7-C20 alkylaryl, or C8-C20 arylalkenyl), C2-C10 alkenyl; and
  • R 16 and R 25 are independently -(XR'n), wherein X is a Group 14-17 heteroatom having an atomic weight of 13 to 79 and R' is one of hydrogen, halogen, C1-C10 alkyl, or C 6 - C10 aryl and n is 0, 1 2, or 3.
  • the present disclosure further relates to a catalyst compound, and catalyst systems comprising such compounds, represented by the formula (III):
  • R 26 , and R 27 are as defined for formulas (I) and (II), and each R 30 , R 31 , and R 32 is independently selected from hydrogen, halogen, Ci-Cio alkyl which may be halogenated, C 6 - Cio aryl which may be halogenated, C2-C10 alkenyl, C7-C40 arylalkyl, C7-C40 alkylaryl, C8-C40 arylalkenyl, -NR'2, -SR, -OR, -OSiR'3, -PR'2, wherein R' is one of hydrogen, halogen, C1-C10 alkyl, or C 6 -Cio aryl or two or more adjacent radicals R 30 to R 32 together form one or more saturated or unsaturated rings.
  • R 5 is
  • R 6 and R 7 or R 7 and R 8 can combine to form a cyclobutyl ring, a cyclopentyl ring or cyclohexyl ring. It has been discovered that a cyclic ring fused to the indenyl ring (that does not contain the branched alkyl moiety at the 2-position (R 9 )) provides an electron-rich indenyl ring that stabilizes the catalyst and can be used to yield high molecular weight EP copolymers. R 6 and R 7 can combine to form a cyclopentyl ring.
  • R 3 is linear alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In at least one embodiment, R 3 is methyl.
  • M 1 is Hf, Zr, or Ti, such as Hf or Zr, such as Zr.
  • M 2 is Si, C, or Ge, such as C or Si, such as Si.
  • R 15 , R 16 , and R 17 can be hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl.
  • R 19 is represented by the formula R3 ⁇ 4J, where J is C, Si, or Ge, and each R a is, independently, hydrogen, halogen, C 1 to C 2 o hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a C 1 to C 20 substituted hydrocarbyl, and two R a can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system.
  • C 1 to C 2 o hydrocarbyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl
  • two R a can form a cyclic structure including aromatic, partially
  • R 19 can be a bridging group comprising carbon or silica, such as dialkylsilyl, such as R 19 is selected from CH 2 , CH 2 CH 2 , C(CH 3 ) 2 , SiMe 2 , SiPh 2 , SiMePh, silylcyclobutyl (Si(CH 2 ) 3 ), (Ph) 2 C, (p- (Et) 3 SiPh) 2 C, and cyclopentasilylene (Si(CH 2 ) 4 ).
  • dialkylsilyl such as R 19 is selected from CH 2 , CH 2 CH 2 , C(CH 3 ) 2 , SiMe 2 , SiPh 2 , SiMePh, silylcyclobutyl (Si(CH 2 ) 3 ), (Ph) 2 C, (p- (Et) 3 SiPh) 2 C, and cyclopentasilylene (Si(CH 2 ) 4 ).
  • each R 1 and R 2 is independently hydrocarbyl having from 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide, dienyl, amine, phosphine, ether, or a combination thereof.
  • R 1 and R 2 may form a part of a fused ring or a ring system.
  • each R 1 and R 2 is independently halide or C l to
  • R 1 and R 2 can be independently chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.
  • R 1 and R 2 may also be joined together to form an alkanediyl group or a conjugated C4-C40 diene ligand which is coordinated to M 1 in a metallocyclopentene fashion.
  • R 1 and R 2 may also be identical or different conjugated dienes, optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl) silyl or tri(hydrocarbyl) silylhydrocarbyl, said dienes having up to 30 atoms not counting hydrogen and/or forming a ⁇ -complex with M 1 .
  • Exemplary groups suitable for R 1 and or R 2 include 1 ,4-diphenyl, 1,3-butadiene, 1,3-pentadiene, 2-methyl 1,3-pentadiene, 2,4-hexadiene, 1-phenyl, 1,3-pentadiene, 1,4- dibenzyl, 1,3-butadiene, 1,4-ditolyl- 1,3-butadiene, 1,4-bis (trimethylsilyl)- 1,3-butadiene, and l,4-dinaphthyl-l,3-butadiene.
  • R 1 and R 2 can be identical and are C1-C3 alkyl or alkoxy, C 6 - C10 aryl or aryloxy, C2-C4 alkenyl, C7-C10 arylalkyl, C7-C12 alkylaryl, or halogen, such as chlorine.
  • R 3 may be selected from substituted or unsubstituted methyl, ethyl, n-propyl, n-butyl, pentyl, hexyl, heptyl, or octyl.
  • R 3 in formula I or II is a hydrocarbyl radical having from 1 to 20 carbon atoms that is not substituted with a heteroatom.
  • each of R 4 , R 6 , R 7 , R 8 , R 10 , R 11 , R 12 , R 13 is independently hydrogen, halogen, Ci-Cio alkyl which may be halogenated (such as C2 to C10, such as C3 to Cio, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof), C 6 -Cio aryl which may be halogenated, C2-C10 alkenyl, C7-C40 arylalkyl, C7-C40 alkylaryl, C 8 -C 40 arylalkenyl, -NR' 2 , -SR, -OR, -OSiR'3, -PR'2, wherein R' is one of hydrogen, halogen, C
  • each of R 4 , R 6 , R 7 , R 8 , R 10 , R 11 , R 12 , R 13 is independently hydrogen, halogen, C1-C40 hydrocarbyl or C1-C40 substituted hydrocarbyl (such as C1-C10 alkyl which may be substituted, C6-C40 aryl which may be substituted, C2-C10 alkenyl, C7-C40 arylalkyl, C7-C40 alkylaryl, Cs-Gw arylalkenyl).
  • R 5 is hydrogen, halogen, C1-C40 hydrocarbyl or C1-C40 substituted hydrocarbyl (such as C1-C10 alkyl which may be substituted, C6-C40 aryl which may be substituted, C2-C10 alkenyl, C7-C40 arylalkyl, C7-C40 alkylaryl, C8-C40 arylalkenyl), -NR' 2 , -SR', -OR, -OSiR'3, -PR2, where each R is hydrogen, halogen, C1-C10 alkyl, or C 6 -Cio aryl, or two or more adjacent radicals R 5 to R 8 together form one or more saturated or unsaturated rings.
  • C1-C40 hydrocarbyl or C1-C40 substituted hydrocarbyl such as C1-C10 alkyl which may be substituted, C6-C40 aryl which may be substituted, C2-C10 alkenyl, C7-C40
  • R 18 is hydrogen, halogen, C1-C10 alkyl (such as C2 to Cio, such as C3 to Cio, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof) which may be halogenated, C 6 -Cio aryl (such as phenyl), which may be halogenated, preferably R 18 is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, octyl, nonyl, decyl, undecyl, dodecyl, preferably methyl, ethyl, or phenyl.
  • C1-C10 alkyl such as C2 to Cio, such as C3 to Cio, such as methyl, e
  • R 15 and R 17 are independently hydrogen, C2-C20 alkyl (such as C3 to Ci6, such as C4 to C12, such as butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof) which may be halogenated, C6-C10 aryl which may be halogenated.
  • R 15 and R 17 may be independently hydrogen, butyl, aryl, isopropyl, fluoroalkyl, n-propyl, n-butyl, iso-butyl, or tert-butyl.
  • R 15 and R 17 are independently hydrogen, C4 to C20, such as C4 to C12 alkyl, and R 3 is a hydrocarbyl radical having from 1 to 20 carbon atoms that is not substituted with a heteroatom.
  • R 16 is selected from -NR' 2 , -SR', -OR', -OSiR' 3 and PR'2 radical, wherein R' is one of a hydrogen atom, halogen atom, a C1-C10 alkyl group, or a C 6 -Cio aryl group, such as wherein R 16 is -OR' wherein R' is a C1-C10 alkyl group, such as a methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, iso-butoxy, sec-butoxy, or t-butoxy group, such as methoxy.
  • R 5 is a substituted or unsubstituted C 6 -Cio aryl group (such as phenyl, naphthyl, indenyl, such as phenyl) which may be substituted (such as halogenated), e.g., a substituted or unsubstituted phenyl, napthyl, or indenyl.
  • C 6 -Cio aryl group such as phenyl, naphthyl, indenyl, such as phenyl
  • R 5 is a substituted or unsubstituted C 6 -Cio aryl group (such as phenyl, naphthyl, indenyl, such as phenyl) which may be substituted (such as halogenated), e.g., a substituted or unsubstituted phenyl, napthyl, or indenyl.
  • R 5 can be phenyl, such as 3'- and/or 5 '-substituted phenyl, such as wherein the 3' and/or 5' substituents are selected from C2-C20 alkyl group which may be halogenated, a C 6 -Cio aryl group which may be halogenated, a C2-C10 alkenyl group, a C7-C20 arylalkyl group, a C7-C20 alkylaryl group, a C8-C20 arylalkenyl group.
  • R 5 is phenyl
  • the 3' and 5' (i.e., R 24 and R 26 ) positions are indpendently butyl, aryl, isopropyl, or fluoroalkyl, such as wherein each is independently n-butyl, iso-butyl, or tert-butyl, such as wherein each is tert- butyl.
  • R 5 is phenyl
  • the 3' and 5' positions are independently butyl, aryl, isopropyl, or fluoroalkyl (such as wherein each is selected from n- butyl-, iso-butyl-, and tert-butyl, such as wherein each is tert-butyl)
  • the phenyl is also substituted at the 4' position (i.e., R 25 ) with a -NR'2, -SR', -OR', -OSiR' 3 or -PR' 2 radical, wherein R' is one of hydrogen, halogen, C1-C10 alkyl, or C 6 -Cio aryl, such as alkyloxy, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, iso-butoxy, sec-butoxy, or t-butoxy.
  • R 3 is methyl
  • each of R 15 and R 17 is independently hydrogen, n-butyl, iso-butyl, or tert-butyl groups
  • R 16 is hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, iso-butoxy, sec-butoxy, or t-butoxy group, such as a methoxy group.
  • R 3 is methyl
  • each of R 15 , R 17 , R 24 and R 26 is independently hydrogen, n-butyl-, iso-butyl-, or tert-butyl.
  • R 16 and R 25 may be independently methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, iso-butoxy, sec-butoxy, or t-butoxy group, such as a methoxy group.
  • R 6 and R 7 form a saturated or unsaturated, single or multi-ring structure, preferably R 6 and R 7 form a saturated ring having 5 or 6 ring atoms, preferably R 6 and R 7 form a saturated ring having 5 ring atoms, such that the indenyl fragment is a substituted indacenyl group.
  • Some catalysts useful herein may be described as bridged bis(4-phenyl-indenyl) transition metal complexes wherein: at least one of the phenyl rings is substituted at the 3' and 5' positions (i.e., R 15 , R 17 , R 24 and R 26 ) by radicals which may be independently C2-C20 alkyl which may be halogenated, C 6 -Cio aryl which may be halogenated, C2-C10 alkenyl, C7-C20 arylalkyl, C7-C20 alkylaryl, C8-C20 arylalkenyl, wherein at least one of the phenyl rings substituted at the 3' and 5' positions is also substituted at the 4' position with -NR'2, -SR', -OR', -OSiR'3 or -PR'2, wherein R' is one of hydrogen, halogen, C1-C10 alkyl, or C 6 -Cio ary
  • each of the phenyl rings is substituted at the 3 ' and 5' positions by C2-C20 alkyl which may be halogenated, C 6 - C10 aryl which may be halogenated, C2-C10 alkenyl, C7-C20 arylalkyl, C7-C20 alkylaryl, C8-C20 arylalkenyl.
  • R 3 may be linear C1-C10 alkyl which may be halogenated.
  • R 3 when either R 3 is methyl or ethyl, then one or both phenyl rings are substituted at the 3' and 5' positions by n-butyl, sec-butyl, or t-butyl.
  • At least one 4- phenyl group is substituted at the 3' and 5 ' position with a tert-butyl group and at the 4' position with -OR', wherein R' is hydrogen, halogen, C1-C10 alkyl, such as methyl, or a C 6 -Cio aryl group.
  • catalysts of the present disclosure are Zr- or Hf-based complexes. Additionally, some such catalysts are bridged by a dialkylsiladiyl group or a diisopropylamidoborane group.
  • catalysts of the present disclosure are represented by formula (II) above where: M 1 is selected from titanium, zirconium, and hafnium, such as zirconium or hafnium, such as zirconium; R 1 and R 2 are independently hydrogen, C1-C10 alkyl (such as methyl, ethyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof), or halogen (such as CI, Br, F or I).
  • M 1 is selected from titanium, zirconium, and hafnium, such as zirconium or hafnium, such as zirconium
  • R 1 and R 2 are independently hydrogen, C1-C10 alkyl (such as methyl, ethyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, de
  • R 3 is linear C1-C10 alkyl (such as C2 to C10, such as C3 to C 8 , such as methyl, ethyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) which may be halogenated.
  • R 4 , R 6 , R 7 , R 8 , R 10 , R 11 , R 12 and R 13 are independently hydrogen, halogen, C1-C10 alkyl (such as methyl, ethyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof) which may be halogenated, or C6-C10 aryl which may be halogenated.
  • C1-C10 alkyl such as methyl, ethyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof
  • C6-C10 aryl which may be halogenated.
  • R 4 , R 6 , R 7 , R 8 , R 10 , R 11 , R 12 and R 13 adjacent to each other together form one or more rings, such as 4- 8 membered ring, such as a five membered ring, preferably R 6 and R 7 form a saturated ring having 5 ring carbon atoms.
  • R 19 is -SiR" 2 - wherein each R" is independently hydrogen or C1-C10 alkyl, such as C1-C2 alkyl (e.g., methyl or ethyl) or R 19 is a C1-C10 dialkylamidoborane.
  • R 18 is independently hydrogen, halogen, C3-C10 alkyl which may be halogenated, C 6 -Cio aryl which may be halogenated.
  • each R 15 and R 17 is independently hydrogen, C1-C20 alkyl which may be halogenated, C 6 -Cio aryl group which may be halogenated, C2-C10 alkenyl, C7-C20 arylalkyl, C7-C20 alkylaryl, or C8-C20 arylalkenyl.
  • R 15 and R 17 are independently hydrogen, n-butyl, sec-butyl, or tertiary butyl, aryl, isopropyl, fluoroalkyl, trialkyl silyl, or other groups of similar size, such as butyl, such as n-butyl-, iso-butyl-, and tert-butyl.
  • R 16 and/or R 25 is selected from (XR' n ) ⁇ , wherein X is a Group 14-17 heteroatom having an atomic weight of 13 to 79 and R' is one of a hydrogen atom, halogen atom, a C1-C10 alkyl group, or a Ce-Cio aryl group and n is 0, 1, 2, or 3.
  • R 16 and/or R 25 may be -NR' 2 , -SR', -OR', -OSiR' 3, -SiR' 3, or-PR'2, such as R 16 and/or R 25 is -NR' 2 , -SR', -OR', -OSiR' 3, or -PR' 2, wherein R is one of hydrogen, halogen, C1-C10 alkyl or C6-C10 aryl.
  • R 16 and/or R 25 can be -NR' 2 or -PR' 2, or R 16 and/or R 25 is -OR'.
  • R 16 and/or R 25 is -NH2, -NH(methyl), -NH(ethyl), -NH(n-propyl), -NH(iso-propyl), -NH(phenyl), -N(methyl) 2 , -N(methyl) (ethyl), -N(n-propyl) (phenyl), ⁇ (isopropyl) (phenyl), -N(methyl)(phenyl), N(e thy 1) (ethyl), -N(ethyl)(n-propyl), -N(ethyl)(iso- propyl), -N(n-propyl) (phenyl), -N(phenyl) (phenyl), -SH, -S(methyl), -S(ethyl), -S(n- propyl), -S(iso-propyl), -S(n-butyl), -S(iso-but
  • R 15 , R 17 , R 24 , and R 26 are independently hydrogen, n-butyl, sec-butyl, tertiary butyl, aryl, isopropyl, such as tert-butyl; and at least one of R 16 and R 25 is -OH, -O(methyl), -O(ethyl), -O(n-propyl), -O(iso-propyl), -O(n-butyl), -O(iso-butyl), -O(sec-butyl), -O(tert-butyl), -O(phenyl), such as -O(methyl).
  • R 16 and R 25 may be hydrogen, -OH, -O(methyl), -O(ethyl), -O(n-propyl), -O(iso-propyl), -O(n-butyl), -O(iso-butyl), -O(sec-butyl), -O(tert-butyl), -O(phenyl), such as R 25 is -O(methyl).
  • each R 1 and R 2 is independently halogen, such as G;
  • R 3 is a Ci-Cio alkyl group, such as methyl;
  • each of R 4 , R 6 , R 7 , R 8 , R 10 , R 11 , R 12 , and R 13 is independently hydrogen or Ci-Cio alkyl, such as each is hydrogen;
  • each R 24 and R 26 is a Ci- Cio alkyl group, such as n-butyl, iso-butyl, and tert-butyl, such as tert-butyl; and wherein each R 25 is -OH, -O(methyl), -O(ethyl), -O(n-propyl), -O(iso-propyl), -O(n-butyl), -O(iso-butyl), -O(sec-butyl), -O(tert-butyl), -O(phenyl), such as -O(methyl), -
  • catalysts represented by formula (II) include those wherein each R 1 and R 2 are chlorine; R 3 is methyl; each R 4 , R 6 , R 7 , R 8 , R 10 , R 11 and R 12 are hydrogen; R 19 is -Si(CH 3 )2-; R 9 is isopropyl; R 15 , R 16 , R 17 are hydrogen, and R 24 and R 26 are both a tert-butyl group.
  • catalysts represented by formula (II) include those wherein each R 1 and R 2 are chlorine or methyl; R 3 is methyl; each R 4 , R 8 , R 10 , R 11 and R 12 are hydrogen; R 19 is -Si(CH 3 )2-; R 9 is isopropyl; R 15 , R 16 , R 17 are hydrogen, and R 24 and R 26 are both a tert-butyl group; R 25 is methoxy and R 6 and R 7 form a saturated ring having 5 carbon ring atoms.
  • catalysts represented by formula (I), formula (II), or formula (III) include: dimethylsiladiyl (2-methyl, 4-[3',5'-di-tert-butyl-4'-methoxyphenyl] indenyl)(2-isopropyl, 4-[o-biphenyl] indenyfjZrCk; dimethylsiladiyl (2-methyl, 4-[3',5'-di- tert-butyl-4' -methoxyphenyl] , 1 ,5 ,6,7-tetrahydro-s-indacenyl)(2-isopropyl, 4- [o-biphenyl] indenyl)ZrCl2; dimethylsiladiyl (2-ethyl, 4-[3',5'-di-tert-butyl-4'-methoxyphenyl] indenyl)(2- isopropyl
  • catalysts represented by formula (I), formula (II), or formula (III) include: dimethylsiladiyl (2-methyl, 4-[3',5'-di-tert-butyl-4'-methoxyphenyl] indenyl)(2-isopropyl, 4-[o-biphenyl] indenyl)Zr(CH3)2; dimethylsiladiyl (2-methyl, 4-[3',5'-di- tert-butyl-4' -methoxyphenyl] , 1 ,5 ,6,7-tetrahydro-s-indacenyl)(2-isopropyl, 4- [o-biphenyl] indenyl)Zr(CH 3 )2; dimethylsiladiyl (2-ethyl, 4-[3',5'-di-tert-butyl-4'-methoxyphenyl] indenyl)(2-
  • catalysts represented by formula (I), formula (II), or formula (III) include: dimethylsiladiyl (2-methyl, 4-[3',5'-di-tert-butyl-4'-methoxyphenyl], l,5,6,7-tetrahydro-s-indacenyl)(2-isopropyl, 4-[o-biphenyl] indenyl)Zr(CH3)2; dimethylsiladiyl (2-ethyl, 4-[3',5'-di-tert-butyl-4'-methoxyphenyl], l,5,6,7-tetrahydro-5- indacenyl)(2-isopropyl, 4-[o-biphenyl] indenyl)Zr(CH3)2; dimethylsiladiyl (2-propyl, 4-[3',5'- di-tert-butyl-4' -methoxyphenyl], l,5,6,7
  • catalysts represented by formula (I), formula (II), or formula (III) include: dimethylsiladiyl (2-methyl, 4-[3',5'-di-tert-butyl-4'-methoxyphenyl], l,5,6,7-tetrahydro-s-indacenyl)(2-isopropyl, 4-[o-biphenyl] indenyfjZrCk; dimethylsiladiyl (2-ethyl, 4-[3',5'-di-tert-butyl-4' -methoxyphenyl], l,5,6,7-tetrahydro-s-indacenyl)(2-isopropyl, 4-[o-biphenyl] indenyl)ZrCl 2 ; dimethylsiladiyl (2-propyl, 4-[3',5'-di-tert-butyl-4'- methoxyphen
  • one catalyst compound is used, e.g., the catalyst compounds are not different.
  • one metallocene catalyst compound is considered different from another if they differ by at least one atom.
  • bisindenyl ZrCb is different from “(indenyl)(2- methylindenyl) ZrCk” which is different from “(indenyl)(2-methylindenyl) HfCh.”
  • Catalyst compounds that differ only by isomer are considered the same for purposes if the present disclosure, e.g., rac-dimethylsilylbis(2-methyl 4-phenyl)Hf(Me)2 is considered to be the same as meso-dimethylsilylbis(2-methyl 4-phenyl)Hf(Me)2.
  • two or more different catalysts are present in a catalyst system used herein.
  • two or more different catalyst compounds are present in the reaction zone where the process(es) of the present disclosure are performed.
  • Two or more different catalyst compounds include a first catalyst represented by formula (I), (II) or (III) and a second catalyst represented by formula (I), (II) or (III).
  • Two or more different catalyst compounds also includes a first catalyst represented by formula (I), (II), or (III) and a second catalyst that is a bridged or unbridged metallocene compound having one or more Cp, iPrCp, Cp(Me)5 rings, or mixtures thereof.
  • the two transition metal catalysts are preferably chosen such that the two are compatible.
  • a simple screening method such as by 3 ⁇ 4 or 13 C NMR, known to those of ordinary skill in the art, can be used to determine which catalysts are compatible. It is preferable to use the same activator for each of the catalysts, however, two different activators, such as a non-coordinating anion activator and an alumoxane, can be used in combination.
  • one or more catalysts contain an R 1 or R 2 ligand which is not a hydride, hydrocarbyl, or substituted hydrocarbyl, then the alumoxane should be contacted with the transition metal compounds prior to addition of the non-coordinating anion activator.
  • the catalyst compound represented by formula (I), (II) or (III) and the second catalyst compound may be used in any ratio (A:B).
  • the catalyst compound represented by formula (I) or (II) may be (A) if the second catalyst compound is (B).
  • the catalyst compound represented by formula (I) or (II) may be (B) if the second catalyst compound is (A).
  • Molar ratios of (A) to (B) can fall within the range of (A:B) about 1 : 1000 to about 1000: 1 , such as between about 1 : 100 and about 500: 1, such as between about 1 : 10 and about 200: 1, such as between about 1 : 1 and about 100: 1 , such as about 1 : 1 to about 75 : 1, such as about 5: 1 to about 50: 1.
  • the ratio chosen will depend on the exact catalysts chosen, the method of activation, and the end product desired.
  • useful mole percents when using the two catalyst compounds, where both are activated with the same activator, are between about 10 to about 99.9% of (A) to about 0.1 and about 90% of (B), such as between about 25 and about 99% (A) to about 0.5 and about 50% (B), such as between about 50 and about 99% (A) to about 1 and about 25% (B), such as between about 75 and about 99% (A) to about 1 to about 10% (B).
  • metallocenes of this type may be synthesized according to the schematic reaction procedure described in Figure 1 where (i) is a deprotonation via a metal salt of alkyl anion (e.g., n-BuLi) to form an indenide; (ii) is reaction of indenide with an appropriate bridging precursor (e.g., Me2SiCl2); (iii) is reaction of the above product with AgOTf; (iv) is reaction of the above triflate compound with another equivalent of indenide; (v) is deprotonation via an alkyl anion (e.g., n-BuLi) to form a dianion; (vi) is reaction of the dianion with a metal halide (e.g., ZrCU). The final products are obtained by recrystallization of the crude solids.
  • a metal salt of alkyl anion e.g., n-BuLi
  • an appropriate bridging precursor e.g.,
  • catalyst systems may be formed by combining them with activators in any suitable manner, including by supporting them for use in slurry or gas phase polymerization.
  • the catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in the monomer, i.e., no solvent).
  • the catalyst system typically comprises a transition metal complex as described above and an activator such as alumoxane or a non-coordinating anion activator.
  • Activation may be performed using alumoxane solution including methyl alumoxane, referred to as MAO, as well as modified MAO, referred to herein as MMAO, which contains some higher alkyl groups to improve the solubility.
  • MAO can be purchased from Albemarle Corporation, Baton Rouge, Louisiana, typically in a 10 wt% solution in toluene.
  • the catalyst system employed in the present disclosure can use an activator selected from alumoxanes, such as methyl alumoxane, modified methyl alumoxane, ethyl alumoxane, iso-butyl alumoxane, and the like.
  • the catalyst-to-activator molar ratio is from about 1 :3000 to about 10: 1; such as about 1 :2000 to about 10: 1 ; such as about 1: 1000 to about 10: 1; such as about 1:500 to about 1 :1 ; such as about 1 :300 to about 1: 1; such as about 1:200 to about 1: 1; such as about 1: 100 to about 1: 1; such as about 1:50 to about 1 : 1; such as about 1: 10 to about 1: 1.
  • some embodiments select the maximum amount of activator at a 5000-fold molar excess over the catalyst (per metal catalytic site).
  • the minimum activator-to-catalyst ratio can be 1: 1 molar ratio.
  • Activation may also be performed using non-coordinating anions, referred to as NCA's, of the type, for example, described in EP 277 003 Al and EP 277 004 Al.
  • NCA may be added in the form of an ion pair using, for example, [DMAHJ+ [NCA]- in which the N,N- dimethylanilinium (DMAH) cation reacts with a basic leaving group on the transition metal complex to form a transition metal complex cation and [NCA]-.
  • the cation in the precursor may, alternatively, be trityl.
  • the transition metal complex may be reacted with a neutral NCA precursor, such as B(C 6 F5)3, which abstracts an anionic group from the complex to form an activated species.
  • a neutral NCA precursor such as B(C 6 F5)3 abstracts an anionic group from the complex to form an activated species.
  • Useful activators include ⁇ , ⁇ -dimethylanilinium tetrakis (pentafluorophenyl)borate (i.e., [PhNMe2H]B(C6F5)4) and ⁇ , ⁇ -dimethylanilinium tetrakis (heptafluoronaphthyl)borate, where Ph is phenyl, and Me is methyl.
  • activators useful herein include those described in US 7,247,687 at column 169, line 50 to column 174, line 43, particularly column 172, line 24 to column 173, line 53.
  • non-coordinating anion activator is represented by the following formula (1):
  • Z is (L-H) or a reducible Lewis acid
  • L is a neutral Lewis base
  • H is hydrogen and (L- H) + is a Bronsted acid
  • a d ⁇ is a non-coordinating anion having the charge d-
  • d is an integer from 1 to 3.
  • the cation component may include Bronsted acids such as protonated Lewis bases capable of protonating a moiety, such as an alkyl or aryl, from the catalyst precursor, resulting in a cationic transition metal species, or the activating cation (L-H) d+ is a Bronsted acid, capable of donating a proton to the catalyst precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof, or ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, Methylamine, ⁇ , ⁇ -dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N- dimethylaniline, p-nitro-N,N-d
  • Z is a reducible Lewis acid
  • Ar is aryl or aryl substituted with a heteroatom, or a Ci to C 4 o hydrocarbyl
  • the reducible Lewis acid may be represented by the formula: (Ph3C+), where Ph is phenyl or phenyl substituted with a heteroatom, and/or a Ci to C 4 o hydrocarbyl.
  • the reducible Lewis acid is triphenyl carbenium.
  • Each Q may be a fluorinated hydrocarbyl radical having 1 to 20 carbon atoms, or each Q is a fluorinated aryl radical, or each Q is a pentafluoryl aryl radical.
  • suitable Ad- components also include diboron compounds as disclosed in US 5,447,895, which is fully incorporated herein by reference.
  • the present disclosure also relates to a method to polymerize olefins comprising contacting olefins (such as propylene) with a catalyst complex as described above and an NCA activator represented by the Formula (2):
  • R is a monoanionic ligand
  • M** is a Group 13 metal or metalloid
  • ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclic aromatic ring, or aromatic ring assembly in which two or more rings (or fused ring systems) are joined directly to one another or together
  • n is 0, 1, 2, or 3.
  • the NCA comprising an anion of Formula 2 also comprises a suitable cation that is essentially non-interfering with the ionic catalyst complexes formed with the transition metal compounds, or the cation is Zd+ as described above.
  • R is selected from the group consisting of Ci to C30 hydrocarbyl radicals.
  • Ci to C30 hydrocarbyl radicals may be substituted with one or more Ci to C20 hydrocarbyl radicals, halide, hydrocarbyl substituted organometalloid, dialkylamido, alkoxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido, arylphosphide, or other anionic substituent; fluoride; bulky alkoxides, where bulky means C 4 to C20 hydrocarbyl radicals;— SRa, -NRa2, and -PRa2, where each Ra is independently a monovalent C 4 to C20 hydrocarbyl radical comprising a molecular volume greater than or equal to the molecular volume of an isopropyl substitution or a C 4 to C20 hydrocarbyl substitute
  • the NCA also comprises cation comprising a reducible Lewis acid represented by the formula: (Ar3C+), where Ar is aryl or aryl substituted with a heteroatom, and/or a Ci to C40 hydrocarbyl, or the reducible Lewis acid represented by the formula: (PI13C+), where Ph is phenyl or phenyl substituted with one or more heteroatoms, and/or Ci to C40 hydrocarbyls.
  • a reducible Lewis acid represented by the formula: (Ar3C+) where Ar is aryl or aryl substituted with a heteroatom, and/or a Ci to C40 hydrocarbyl
  • PI13C+ the reducible Lewis acid represented by the formula:
  • the NCA may also comprise a cation represented by the formula, (L-H) d+ , wherein L is an neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or 3, or (L-H) d+ is a Bronsted acid selected from ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof.
  • an activator useful herein comprises a salt of a cationic oxidizing agent and a non-coordinating, compatible anion represented by the Formula (3):
  • OX e+ is a cationic oxidizing agent having a charge of e+; e is 1, 2 or 3; d is 1, 2 or 3; and A d_ is a non-coordinating anion having the charge of d- (as further described above).
  • cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag + , or Pb +2 .
  • Suitable embodiments of Ad- include tetrakis(pentafluorophenyl)borate.
  • Activators useful in catalyst systems herein include: trimethylammonium tetrakis(perfluoronaphthyl)borate, ⁇ , ⁇ -dimethylanilinium tetrakis(perfluoronaphthyl)borate, ⁇ , ⁇ -diethylanilinium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, trimethylammonium tetrakis(perfluorobiphenyl)borate, ⁇ , ⁇ -dimethylanilinium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, and the types disclosed in US 7,297,653, which is fully incorporated by reference herein.
  • Suitable activators also include: N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, ⁇ , ⁇ -dimethylanilinium tetrakis(perfluorobiphenyl)borate, ⁇ , ⁇ -dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Ph 3 C + ][B(C 6 F 5 )4 ], [Me 3 NH + ][ B(C 6 F 5 )
  • the activator comprises a triaryl carbonium (such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).
  • a triaryl carbonium such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetra
  • two NCA activators may be used in the polymerization and the molar ratio of the first NCA activator to the second NCA activator can be any ratio. In at least one embodiment, the molar ratio of the first NCA activator to the second NCA activator is 0.01:1 to 10,000:1, or 0.1:1 to 1000:1, or 1:1 to 100:1.
  • the NCA activator-to-catalyst ratio is a 1: 1 molar ratio, or 0.1:1 to 100:1, or 0.5:1 to 200:1, or 1:1 to 500:1 or 1:1 to 1000:1. In at least one embodiment, the NCA activator-to-catalyst ratio is 0.5:1 to 10:1, or 1:1 to 5:1.
  • the catalyst compounds can be combined with combinations of alumoxanes and NCA's (see for example, US 5,153,157, US 5,453,410, EP 0 573 120 Bl, WO 94/07928, and WO 95/14044 which discuss the use of an alumoxane in combination with an ionizing activator, all of which are incorporated by reference herein).
  • the catalyst-to-activator molar ratio is typically from 1:10 to 1:1; 1:10 to 10:1; 1:10 to 2:1; 1:10 to 3:1; 1:10 to 5:1; 1:2 to 1.2:1; 1:2 to 10:1; 1:2 to 2:1; 1:2 to 3:1; 1:2 to 5:1; 1:3 to 1:2; 1:3 to 10:1; 1:3 to 2:1; 1:3 to 3:1; 1:3 to 5:1; 1:5 to 1:1; 1:5 to 10:1; 1:5 to 2:1; 1:5 to 3:1; 1:5 to 5:1; 1:1 to 1:1.2.
  • an NCA such as an ionic or neutral stoichiometric activator
  • a co-activator such as a group 1, 2, or 13 organometallic species (e.g., an alkyl aluminum compound such as tri-n-octyl aluminum), may be used in the catalyst system herein.
  • the catalyst-to-co-activator molar ratio is from 1:100 to 100:1; 1:75 to 75:1; 1:50 to 50:1; 1:25 to 25:1; 1:15 to 15:1; 1:10 to 10:1; 1:5 to 5:1; 1:2 to 2:1; 1:100 to 1:1; 1:75 to 1:1; 1:50 to 1:1; 1:25 to 1:1; 1:15 to 1:1; 1:10 to 1:1; 1:5 to 1:1; 1:2 to 1:1; 1:10 to 2:1.
  • the catalyst system may comprise an inert support material.
  • the supported material is a porous support material, for example, talc, or inorganic oxides.
  • Other support materials include zeolites, clays, organoclays, or any other suitable organic or inorganic support material and the like, or mixtures thereof.
  • the support material is an inorganic oxide. Suitable inorganic oxide materials for use in metallocene catalyst systems herein include Groups 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof.
  • inorganic oxides that may be employed either alone or in combination with the silica, or alumina are magnesia, titania, zirconia, and the like.
  • suitable support materials can be employed, for example, functionalized polyolefins, such as polyethylene.
  • Supports include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, and the like.
  • combinations of these support materials may be used, for example, silica-chromium, silica- alumina, silica- titania, and the like.
  • Support materials include S1O2, AI2O3, Zr02, S1O2, and combinations thereof.
  • the support material such as an inorganic oxide, can have a surface area in the range of from about 10 to about 700 m 2 /g, pore volume in the range of from about 0.1 to about 4.0 cc/g and average particle size in the range of from about 5 to about 500 ⁇ .
  • the surface area of the support material is in the range of from about 50 to about 500 m 2 /g, pore volume of from about 0.5 to about 3.5 cc/g and average particle size of from about 10 to about 200 ⁇ .
  • the surface area of the support material is in the range is from about 100 to about 400 m 2 /g, pore volume from about 0.8 to about 3.0 cc/g and average particle size is from about 5 to about 100 ⁇ .
  • the average pore size of the support material useful in the present disclosure is in the range of from 10 to 1000 A, such as 50 to about 500 A, such as 75 to about 350 A.
  • Silicas are marketed under the tradenames of Davison 952 or Davison 955 by the Davison Chemical Division of W.R. Grace and Company. In other embodiments DAVISON 948 is used.
  • the support material should be dry, that is, substantially free of absorbed water. Drying of the support material can be effected by heating or calcining at about 100°C to about 1000°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, 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 should 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 metallocene compound and an activator.
  • the support material having reactive surface groups, typically hydroxyl groups, is slurried in a non-polar solvent and the resulting slurry is contacted with a solution of a metallocene 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 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.
  • the solution of the metallocene 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 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.
  • the slurry of the supported metallocene compound is then contacted with the activator solution.
  • the mixture of the catalyst, activator and support is heated to about 0°C to about 70°C, such as to about 23 °C to about 60°C, such as at room temperature.
  • Contact times typically range from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.
  • Suitable non-polar solvents are materials in which all of the reactants used herein, e.g., the activator, and the catalyst compound, are at least partially soluble and which are liquid at room temperature.
  • Non- limiting example non-polar solvents are alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, cycloalkanes, such as cyclohexane, aromatics, such as benzene, toluene, and ethylbenzene.
  • the present disclosure relates to polymerization processes where monomer (such as propylene or ethylene), and optionally comonomer, are contacted with a catalyst system comprising an activator and at least one metallocene compound, as described above.
  • the catalyst compound and activator may be combined in any order, and are combined typically prior to contacting with the monomer.
  • a polymerization process includes a) contacting one or more olefin monomers with a catalyst system comprising: i) an activator and ii) a catalyst compound of the present disclosure.
  • the activator may be an alumoxane or a non- coordinating anion activator.
  • the one or more olefin monomers may be propylene and or ethylene and the polymerization process further comprises heating the one or more olefin monomers and the catalyst system to 90°C or more to form isotactic polypropylene.
  • the isotactic polypropylene has a melting point (Tm) of about 149°C to about 162°C.
  • This range of Tm values of the polypropylene may be achieved when polymerization is performed from about 70°C to about 110°C.
  • the difference in Tm values of polypropylene formed at about 70°C and at about 110°C is less than 10°C, such as from about 0°C to about 8°C, such as from about 1°C to about 7°C, such as from about 2°C to about 5°C.
  • the isotactic polypropylenes of the present disclosure may have an M w value of about 60,000 to about 1,400,000 g/mol and an Mw/Mn value from about 1.5 to about 4.5, such as from about 1.5 to about 3.5.
  • the one or more alkene monomers comprises ethylene and propylene and the polymerization process further comprises heating the one or more alkene monomers and the catalyst system to 70°C or less to form an ethylene-propylene copolymer.
  • the copolymer may have an M w value of 300,000 to 1,400,000 g/mol and an Mw/Mn value from about 1.5 to about 4.5, such as from about 1.5 to about 3.5.
  • Monomers useful herein 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.
  • 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 comprises propylene and an optional comonomer(s) comprising one or more ethylene or C 4 to C 4 o olefins, such as C 4 to C20 olefins, such as C 6 to C12 olefins.
  • the C 4 to C 4 o olefin monomers may be linear, branched, or cyclic.
  • the C 4 to C 4 o cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.
  • the monomer comprises ethylene and an optional comonomers comprising one or more C3 to C 4 o olefins, such as C 4 to C20 olefins, such as C 6 to C12 olefins.
  • the C3 to C 4 o olefin monomers may be linear, branched, or cyclic.
  • the C3 to C 4 o 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 C 4 o olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, such as hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, l-hydroxy-4-cyclooctene, l-acetoxy-4-cycloocten
  • one or more dienes are present in the polymer produced herein at up to 10 wt %, such as at 0.00001 to 1.0 wt %, such as 0.002 to 0.5 wt %, such as 0.003 to 0.2 wt %, based upon the total weight of the composition.
  • 500 ppm or less of diene is added to the polymerization, such as 400 ppm or less, such as 300 ppm or less.
  • at least 50 ppm of diene is added to the polymerization, or 100 ppm or more, or 150 ppm or more.
  • Diolefin monomers include any hydrocarbon structure, such as C 4 to C30, having at least two unsaturated bonds, wherein at least two of the unsaturated bonds are readily incorporated into a polymer by either a stereospecific or a non-stereospecific catalyst(s).
  • the diolefin monomers can be selected from alpha, omega-diene monomers (i.e., di-vinyl monomers).
  • the diolefin monomers are linear di-vinyl monomers, such as those containing from 4 to 30 carbon atoms.
  • dienes examples include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1 ,9-decadiene, 1,10- unde
  • Cyclic dienes include cyclopentadiene, vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene or higher ring containing diolefins with or without substituents at various ring positions.
  • 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 performed. (A useful homogeneous polymerization process is one where at least 90 wt% of the product is soluble in the reaction media.) A bulk homogeneous process can be used.
  • the process is a slurry polymerization 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).
  • Suitable diluents/solvents for polymerization include non-coordinating, inert liquids.
  • examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (IsoparTM); perhalogenated hydrocarbons, such as perfluorinated C4-C10 alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene.
  • straight and branched-chain hydrocarbons such as isobut
  • Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1-butene, 1-hexene, 1- pentene, 3-methyl-l-pentene, 4-methyl-l-pentene, 1-octene, 1-decene, and mixtures thereof.
  • aliphatic hydrocarbon solvents are used as the solvent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof.
  • the solvent is not aromatic, such that 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 can be performed in a bulk process.
  • Polymerizations can be performed at any temperature and/or pressure suitable to obtain the desired polymers, such as ethylene and or propylene 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 150°C, such as about 40°C to about 120°C, such as about 45°C to about 80°C; and at a pressure in the range of from about 0.35 MPa to about 10 MPa, such as about 0.45 MPa to about 6 MPa, such as about 0.5 MPa to about 4 MPa.
  • the run time of the reaction is up to 300 minutes, such as in the range of from about 5 to 250 minutes, such as about 10 to 120 minutes.
  • hydrogen is present in the polymerization reactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa), such as from 0.01 to 25 psig (0.07 to 172 kPa), such as 0.1 to 10 psig (0.7 to 70 kPa).
  • the activity of the catalyst is at least 50 g/mmol/hour, such as 500 or more g/mmol/hour, such as 5000 or more g/mmol/hr, such as 40,000 or more g/mmol/hr.
  • the conversion of olefin monomer is at least 10%, based upon polymer yield and the weight of the monomer entering the reaction zone, such as 20% or more, such as 30% or more, such as 50% or more, such as 80% or more.
  • a catalyst of the present disclosure has an activity of 150,000 to about 320,000 g/mmol/hour.
  • a catalyst of the present disclosure is capable of producing an isotactic polypropylene having a Tm of from about 149°C to about 170°C, such as from about 155°C to about 165°C, such as from about 158°C to about 162°C, such as about 158.5°C, about 159.0°C, about 159.5°C, about 160.0°C, about 160.5°C, about 161.0°C, about 161.5°C, or about 162.0°C.
  • isotactic polypropylene is defined as a polypropylene where substantially all of the chiral carbon atoms of the polypropylene backbone have the same stereochemical configuration, i.e., substantially all of the methyl substituents of the polypropylene are located on the same side of the polypropylene backbone.
  • a catalyst of the present disclosure is capable of producing an isotactic polypropylene having an Mw from about 40,000 to about 1,000,000, such as from about 60,000 to about 500,000, such as from about 70,000 to about 300,000, such as from about 80,000 to about 150,000.
  • a catalyst of the present disclosure is capable of producing an ethylene-propylene copolymer having an Mw from about 300,000 to about 2,000,000, such as from about 350,000 to about 1,500,000, such as from about 400,000 to about 1,000,000, such as from about 400,000 to about 600,000.
  • alumoxane is used in the process to produce the polymers.
  • Alumoxane can be 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.
  • scavenger such as tri alkyl aluminum
  • Scavenger can be 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.
  • the polymerization 1) is conducted at temperatures of 0 to 300°C (such as 25 to 150°C, such as 40 to 120°C, such as 70 to 110°C); 2) is conducted at a pressure of atmospheric pressure to 10 MPa (such as 0.35 to 10 MPa, such as from 0.45 to 6 MPa, such as from 0.5 to 4 MPa); 3) is conducted in an aliphatic hydrocarbon solvent (such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, where aromatics are present in the solvent at less than 1 wt%, such as less than 0.5 wt%, such as at 0
  • the catalyst system used in the polymerization comprises no more than one catalyst compound.
  • a "reaction zone” also referred to as a “polymerization zone” is a vessel where polymerization takes place, for example a batch reactor. When multiple reactors are used in either series or parallel configuration, each reactor is considered as a separate polymerization zone. For a multi-stage polymerization in both a batch reactor and a continuous reactor, each polymerization stage is considered as a separate polymerization zone. In at least one embodiment, the polymerization occurs in one reaction zone.
  • additives may also be used in the polymerization, as desired, such as one or more scavengers, promoters, modifiers, chain transfer agents (such as diethyl zinc), reducing agents, oxidizing agents, hydrogen, aluminum alkyls, or silanes.
  • Useful chain transfer agents are typically alkylalumoxanes, a compound represented by the formula AIR3, ZnR2 (where each R is, independently, a Ci-C 8 aliphatic radical, such as methyl, ethyl, propyl, butyl, phenyl, hexyl octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof.
  • the present disclosure also relates to compositions of matter produced by the methods described herein.
  • the process described herein produces propylene homopolymers or propylene copolymers, such as propylene-ethylene and/or propylene- alphaolefin (such as C3 to C20) copolymers (such as propylene-hexene copolymers or propylene-octene copolymers) having an Mw/Mn of greater than 1 to 4 (such as greater than 1 to 3).
  • propylene homopolymers or propylene copolymers such as propylene-ethylene and/or propylene- alphaolefin (such as C3 to C20) copolymers (such as propylene-hexene copolymers or propylene-octene copolymers) having an Mw/Mn of greater than 1 to 4 (such as greater than 1 to 3).
  • the process of the present disclosure produces olefin polymers, such as polyethylene and polypropylene homopolymers and copolymers.
  • the polymers produced herein are homopolymers of ethylene or propylene, are copolymers of ethylene such as copolymer of ethylene having from 0 to 25 mol% (such as from 0.5 to 20 mol%, such as from 1 to 15 mol%, such as from 3 to 10 mol%) of one or more C3 to C20 olefin comonomer (such as C3 to C12 alpha-olefin, such as propylene, butene, hexene, octene, decene, dodecene, such as propylene, butene, hexene, octene), or are copolymers of propylene such as copolymers of propylene having from 0 to 25 mol% (such as from 0.5 to 20 mol%, such
  • the monomer is propylene and the comonomer is hexene, such as from 1 to 15 mol% hexene, such as 1 to 10 mol%.
  • the polymers produced herein have an Mw of 5,000 to 1 ,000,000 g/mol (such as 25,000 to 750,000 g/mol, such as 40,000 to 500,000 g/mol), and/or an Mw/Mn of greater than 1 to 40 (such as 1.2 to 20, such as 1.3 to 10, such as 1.4 to 5, such as 1.5 to 4, such as 1.5 to 3).
  • the polymer produced herein has a unimodal or multimodal molecular weight distribution as determined by Gel Permeation Chromotography (GPC).
  • GPC Gel Permeation Chromotography
  • unimodal is meant that the GPC trace has one peak or inflection point.
  • multimodal is meant that the GPC trace has at least two peaks or inflection points.
  • An inflection point is that point where the second derivative of the curve changes in sign (e.g., from negative to positive or vice versus).
  • the polymer produced herein has a composition distribution breadth index (CDBI) of 50% or more, such as 60% or more, such as 70% or more.
  • CDBI is a measure of the composition distribution of monomer within the polymer chains and is measured by the procedure described in PCT publication WO 93/03093, published February 18, 1993, specifically columns 7 and 8 as well as in Wild et al, J. Poly. Sci., Poly. Phys. Ed., Vol. 20, p. 441 (1982) and US 5,008,204, including that fractions having a weight average molecular weight (Mw) below 15,000 are ignored when determining CDBI.
  • Mw weight average molecular weight
  • the polymer (such as 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, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene- 1, isotactic polybutene, ABS resins, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic block
  • the polymer (such as polyethylene or polypropylene) is present in the above blends, at from 10 to 99 wt%, based upon the weight of the polymers in the blend, such as 20 to 95 wt%, such as at least 30 to 90 wt%, such as at least 40 to 90 wt%, such as at least 50 to 90 wt%, such as at least 60 to 90 wt%, such as at least 70 to 90 wt%.
  • the blends described above may be produced by mixing the polymers of the present disclosure with one or more polymers (as described above), by connecting reactors together in series to make reactor blends or by using more than one catalyst in the same reactor to produce multiple species of polymer.
  • the polymers can be mixed together prior to being put into the extruder or may be mixed in an extruder.
  • the blends may be formed using conventional equipment and methods, such as by dry blending the individual components and subsequently melt mixing in a mixer, or by mixing the components together directly in a mixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin-screw extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization process, which may include blending powders or pellets of the resins at the hopper of the film extruder. Additionally, additives may be included in the blend, in one or more components of the blend, and/or in a product formed from the blend, such as a film, as desired.
  • a mixer such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin-screw extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization
  • additives are well known in the art, and can include, for example: fillers; antioxidants (e.g., hindered phenolics such as IRGANOXTM 1010 or IRGANOXTM 1076 available from Ciba-Geigy); phosphites (e.g.
  • IRGAFOSTM 168 available from Ciba-Geigy
  • anti-cling additives such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosins
  • UV stabilizers heat stabilizers
  • anti-blocking agents release agents; anti-static agents; pigments; colorants; dyes; waxes; silica; fillers; talc; and the like.
  • 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.
  • Films may be subsequently unoriented, uniaxially oriented, or biaxially oriented to the same or different extents.
  • One or more of the layers of the film may be oriented in the transverse and/or longitudinal directions to the same or different extents.
  • the uniaxially orientation can be accomplished using typical cold drawing or hot drawing methods.
  • Biaxial orientation can be accomplished using tenter frame equipment or a double bubble processes and may occur before or after the individual layers are brought together.
  • a polyethylene layer can be extrusion coated or laminated onto an oriented polypropylene layer or the polyethylene and polypropylene can be coextruded together into a film then oriented.
  • oriented polypropylene could be laminated to oriented polyethylene or oriented polyethylene could be coated onto polypropylene then optionally the combination could be oriented even further.
  • the films are oriented in the Machine Direction (MD) at a ratio of up to 15, such as between 5 and 7, and in the Transverse Direction (TD) at a ratio of up to 15, such as 7 to 9.
  • MD Machine Direction
  • TD Transverse Direction
  • the film is oriented to the same extent in both the MD and TD directions.
  • the films may vary in thickness depending on the intended application; however, films of a thickness from 1 to 50 ⁇ are usually suitable. Films intended for packaging are usually from 10 to 50 ⁇ thick.
  • the thickness of the sealing layer is typically 0.2 to 50 ⁇ .
  • 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.
  • ⁇ NMR for Metallocene Characterization Chemical structures and rac/meso- isomers of catalysts of the present disclosure are determined by 1H NMR. 1H NMR data are collected at 23 °C in a 5 mm probe using a 400 MHz Bruker spectrometer with deuterated methylene chloride or deuterated benzene. Data is recorded using a maximum pulse width of 45°, 8 seconds between pulses and signal averaging 16 transients. The spectrum is normalized to protonated benzene in the deuterated benzene, which is expected to show a peak at 7.16 ppm. Examples
  • Experimental Catalyst A is dimethylsilyl (4-phenyl-2- methyl-l,5,6,7-tetrahydro-s-indacenyl) (2-isopropyl-4-(4'-tert-butyl-phenyl)-indenyl) zirconium dimethyl.
  • Catalyst B (Comparative Example) is dimethylsilyl (4-o-biphenyl indenyl) (2-isopropyl-4-(3',5'-di onium dichloride.
  • Catalyst C is dimethylsilyl (4-o-biphenyl-2-isopropyl indenyl) (4-(3',5'-di-i ⁇ ?ri- butyl-4'-methoxyphenyl)-2-methyl indenyl) zirconium dimethyl.
  • Catalyst D is dimethylsilyl (4-o-biphenyl-2-isopropyl indenyl) (4-(3,5-di-i ⁇ ?ri- butyl-4-methoxyphenyl)-2-methy - 1 ,5 ,6,7-tetrahydro-s-indacenyl) zirconium dimethyl.
  • Catalyst D-Ch (zirconium dichloride derivatives of Catalyst D) is dimethylsilyl (4- o-biphenyl-2-isopropyl indenyl) (4-(3,5-di-1 ⁇ 2ri-butyl-4-methoxyphenyl)-2-methyl-l, 5,6,7- tetrahydro-s-indacenyl) zirconium dichloride.
  • Catalyst E is dimethylsilyl (4-o-biphenyl-2-cyclopropyl indenyl) (4-(3',5'-di-i ⁇ ?ri- butyl-4'-methoxyphenyl)-2-methyl indenyl) zirconium dichloride.
  • MAO is methyl alumoxane (30 wt% in toluene) obtained from Albemarle Corporation, Baton Rouge, Louisiana.
  • Dimethylsilyl (4-o-biphenyl-2-hexyl-inden-l-yl) trifluoromethanesulfonate A solution of chlorodimethyl (4-o-biphenyl-2-isopropyl-inden-l-yl) silane (10.30 g, 25.6 mmol) in toluene (50 mL) was treated with silver trifluoromethanesulfonate (7.22 g, 28.2 mmol) while stirring. The white slurry was stirred at room temperature for 3 h. Toluene was evaporated under vacuum and the residue was extracted with hexane (50 mL x 2). The filtrate was concentrated in vacuo to give colorless oil as the product (12.84 g).
  • Lithium ⁇ 4-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-l,5,6,7-tetrahydro-s- indacenide ⁇ A precooled solution of 8-(3,5-di-1 ⁇ 2ri-butyl-4-methoxyphenyl)-6-methyl- 1,2,3, 5-tetrahydro-s-indacene (3.80 g, 9.8 mmol) in diethyl ether (30 mL) was treated with n BuLi (2.5 M in hexane, 4.1 mL, 10.3 mmol). The reaction was stirred for 3 hours at room temperature. Then all volatiles were evaporated. The residue was washed with hexane (10 mL) and dried under vacuum to yield an off-white solid as the product (3.60 g).
  • the solid was further recrystallized (3 mL of toluene and 20 mL of hexane, refluxed to room temperature) to get the raoisomer metallocene (1.11 g, ratio of raclmeso
  • a pre-weighed glass vial insert and disposable stirring paddle were fitted to each reaction vessel of the reactor, which contains 48 individual reaction vessels.
  • the reactor was then closed and propylene gas was introduced to each vessel to purge the nitrogen out of the system. If any modules receive hydrogen, it was added in during the purge process.
  • the solvent typically isohexane
  • scavenger and/or co-catalyst and/or a chain transfer agent such as tri-n-octylaluminum in toluene (100-1000 nmol) was added.
  • the contents of the vessels were stirred at 800 rpm.
  • the propylene was added as gas to a set pressure.
  • the reactor vessels were heated to their set run temperature (usually between 50°C and 110°C). If any modules receive ethylene, it was added as a gas to a predetermined pressure (typically 40-220 psi) above the pressure of the propylene while the reactor vessels were heated to a set run temperature.
  • a predetermined pressure typically 40-220 psi
  • a toluene solution of catalyst (typically at a concentration of 0.2 mmol/L in toluene which usually provides about 15 nmol of catalyst) was injected into the reactors. The reaction was then allowed to proceed until a pre-determined amount of pressure had been taken up by the reaction. Alternatively, the reaction may be allowed to proceed for a set amount of time. The reaction was quenched by pressurizing the vessel with compressed air. After the polymerization reaction, the glass vial insert containing the polymer product and solvent was removed from the pressure cell and the inert atmosphere glove box, and the volatile components were removed using a Genevac HT-12 centrifuge and Genevac VC3000D vacuum evaporator operating at elevated temperature and reduced pressure. The vial was then weighed to determine the yield of the polymer product. The resultant polymer was analyzed by Rapid GPC (see below) to determine the molecular weight and by DSC (see below) to determine melting point.
  • Rapid GPC see below
  • DSC see below
  • scavenger and/or co-catalyst and/or a chain transfer agent such as tri-n-octylaluminum in toluene (100- 1000 nmol) was added.
  • the contents of the vessels were stirred at 800 rpm.
  • the propylene was added as gas to a set pressure.
  • the reactor vessels were heated to their set run temperature (usually between 50°C and 110°C).
  • the ethylene was added as a gas to a predetermined pressure (typically 40-220 psi) above the pressure of the propylene while the reactor vessels were heated to a set run temperature.
  • the catalyst slurry was vortexed to suspend the catalyst particles into a solution.
  • the buffer toluene typically 100 microliters
  • the toluene solution of catalyst typically 3 mg/ml concentration
  • another aliquot of toluene 500 microliters
  • the reaction was then allowed to proceed until a pre-determined amount of pressure had been taken up by the reaction. Alternatively, the reaction may be allowed to proceed for a set amount of time. At this point, the reaction was quenched by pressurizing the vessel with compressed air.
  • the glass vial insert containing the polymer product and solvent was removed from the pressure cell and the inert atmosphere glove box, and the volatile components were removed using a Genevac HT-12 centrifuge and Genevac VC3000D vacuum evaporator operating at elevated temperature and reduced pressure.
  • the vial was then weighed to determine the yield of the polymer product.
  • the resultant polymer was analyzed by Rapid GPC (see below) to determine the molecular weight and by DSC (see below) to determine melting point. Data are reported in Tables 1 to 4.
  • the system was operated at an eluent flow rate of 2.0 mL/minutes and an oven temperature of 165°C. 1,2,4-trichlorobenzene was used as the eluent.
  • the polymer samples were dissolved in 1,2,4-trichlorobenzene at a concentration of 0.1 - 0.9 mg/mL. 250 uL of a polymer solution was injected into the system. The concentration of the polymer in the eluent was monitored using a Polymer Char IR4 detector. The molecular weights presented are relative to linear polystyrene standards and are uncorrected.
  • the Rapid- GPC Mw (weight average molecular weight) data can be divided by 1.9 to approximate GPC- 3D Mw results for ethylene -propylene copolymers.
  • the Rapid-GPC Mw data for propylene homopolymers can be divided by 1.5 to approximate GPC-3D Mw results.
  • DSC Procedure-1 Differential Scanning Calorimetry (DSC Procedure-1) measurements were performed on a TA-Q200 instrument to determine the melting point of the polymers. Samples were pre- annealed at 220 °C for 15 minutes and then allowed to cool to room temperature overnight. The samples were then heated to 220°C at a rate of 100°C/minutes and then cooled at a rate of 50°C/min. Melting points were collected during the heating period. [00188] The amount of ethylene incorporated in the polymers (weight %) was determined by rapid FT-IR spectroscopy on a Bruker Vertex 70 IR in reflection mode. Samples were prepared in a thin film format by evaporative deposition techniques. Weight percent ethylene was obtained from the ratio of peak heights at 729.8 and 1157.9 cm 1 . This method was calibrated using a set of ethylene/propylene copolymers with a range of known wt% ethylene content.
  • Prepolymerization 1.0 g of slurry catalyst was charged to a catalyst tube in the dry box, followed by 1 ml hexane (N 2 sparged and sieves purified). Then, 1.75 ml TIBAL was charged to a 3 mL syringe (7.6 mL neat tri-isobutylaluminum + hexane to 100 mL, 7.6 vol%). The catalyst tube and the 3 ml syringe containing TIBAL were removed from the dry box and attached to the reactor while the reactor was being purged with nitrogen. The TIBAL solution in the syringe was injected into the reactor via a scavenger port capped with a rubber septum. The scavenger port valve was then switched off.
  • MFR Melt Flow Rate
  • Mw, Mn and Mw/Mn are determined by using a High Temperature Gel Permeation Chromatography (Polymer Laboratories), equipped with a differential refractive index detector (DRI). Three Polymer Laboratories PLgel ⁇ Mixed-B columns are used. The nominal flow rate is 1.0 niL/min, and the nominal injection volume is 300 ⁇ . The various transfer lines, columns, and differential refractometer (the DRI detector) are contained in an oven maintained at 160°C. Solvent for the experiment is prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1, 2, 4 trichlorobenzene (TCB).
  • TCB Aldrich reagent grade 1, 2, 4 trichlorobenzene
  • the TCB mixture is then filtered through a 0.1 ⁇ Teflon filter.
  • the TCB is then degassed with an online degasser before entering the GPC instrument.
  • Polymer solutions are prepared by placing dry polymer in glass vials, adding the desired amount of TCB, then heating the mixture at 160°C with continuous shaking for about 2 hours. All quantities are measured gravimetrically.
  • the injection concentration is from 0.5 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
  • the DRI detector Prior to running each sample, the DRI detector is purged. Flow rate in the apparatus is then increased to 1.0 ml/minute, and the DRI is allowed to stabilize for 8 hours before injecting the first sample.
  • the molecular weight is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards.
  • PS monodispersed polystyrene
  • K DRI is a constant determined by calibrating the DRI
  • the mass recovery is 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.
  • DSC-Procedure-2 Melting Temperature, Tm, is measured by differential scanning calorimetry ("DSC") using a DSCQ200 unit.
  • the sample is first equilibrated at 25 °C and subsequently heated to 220°C using a heating rate of 10°C/min (first heat).
  • the sample is held at 220°C for 3 min.
  • the sample is subsequently cooled down to -100°C with a constant cooling rate of 10°C/min (first cool).
  • the sample is equilibrated at -100°C before being heated to 220 °C at a constant heating rate of 10°C/min (second heat).
  • the exothermic peak of crystallization (first cool) is analyzed using the TA Universal Analysis software and the corresponding to 10°C/min cooling rate is determined.
  • the endothermic peak of melting (second heat) is also analyzed using the TA Universal Analysis software and the peak melting temperature (Tm) corresponding to 10°C/min heating rate is determined.
  • DSC procedure-2 is used.
  • FIG. 2 is a graph illustrating molecular weight values of isotactic polypropylene and ethylethe-propylene copolymers formed by catalysts of the present disclosure. As shown in Table 1 and Figure 2, under similar polymerization conditions, catalysts D and C yield higher Mw polymers for both isotactic polypropylene and ethylene-propylene copolymers as compared to catalysts A and B.
  • FIG. 3 is a graph illustrating melting temperature values of isotactic polypropylene formed by catalysts of the present disclosure. As shown in Figure 3, while Tm values are about the same for polypropylene formed by all four catalysts at 70°C polymerization, at higher temperatures (100°C and 110°C), catalysts D and C provide polypropylene having higher Tm values than polypropylene formed by catalysts A and B under similar conditions.
  • FIG. 4 is a graph illustrating the change in melting temperature (as a function of polymerization temperature) of isotactic polypropylene formed by catalysts of the present disclosure.
  • the decrease in iPP Tm values from comparative catalysts A and B is about 10°C while the decrease from catalysts D and C is about 1.9°C and 3.6°C, respectively.
  • catalyst B has reduced iPP T m capabilities, e.g., T m of 147.6°C from 100°C polymerization and T m of 142.5°C from 110°C polymerization versus T m of 157.3 °C from 70°C polymerization.
  • catalyst A provides high Mw polypropylene (low MFR) and has low activity (Run 2).
  • Catalyst B has high activity but provides low Mw polypropylene (Run 3).
  • catalyst D- Ch has high activity and provides high Mw polypropylene (i.e., low melt flow rate).
  • FIG. 5 is a graph illustrating molecular weight values of ethylene- propylene copolymers formed by catalysts of the present disclosure. As shown in Figure 5, if the isopropyl moiety of catalyst C, is replaced by a cyclopropyl moiety, the catalyst does not produce high molecular weight ethylene-propylene copolymers.
  • catalysts of the present disclosure are multifunctional, providing ethylene- propylene copolymers having Mw values above 250,000 g/mol, isotactic polypropylene having Mw values above 40,000 g/mol, Tm values greater than 145 °C, and ATm values less than 10°C.
  • compositions, an element or a group of elements are preceded with the transitional phrase "comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.

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Abstract

La présente invention concerne des catalyseurs métallocènes pontés qui comprennent au moins un ligand indényle substitué en position 2 par un alkyle ramifié C3-C10, tel que l'isopropyle. L'invention concerne également des systèmes de catalyseur comprenant les catalyseurs, des procédés de polymérisation utilisant les catalyseurs, et des polymères fabriqués à l'aide des catalyseurs.
EP17891908.0A 2017-01-13 2017-12-22 Complexes de métal de transition bis(indényle) pontés, production et utilisation de ceux-ci Withdrawn EP3568418A4 (fr)

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US8299287B2 (en) * 2007-10-25 2012-10-30 Lammus Novolen Technology GmbH Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo- and copolymers
WO2015009470A1 (fr) * 2013-07-17 2015-01-22 Exxonmobil Chemical Patents Inc. Métallocènes et compositions de catalyseurs dérivées de ceux-ci

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