The present disclosure relates to bridged metallocene catalyst compounds comprising at least two —Si—Si— bridges, catalyst systems comprising such compounds, and uses thereof.
Olefin polymerization catalysts are of great use in industry and polyolefins are widely used commercially because of their robust physical properties. Hence, there is interest in finding new catalyst systems that increase the marketing value of the catalyst and allow the production of polymers having improved properties.
Polyolefins, such as polyethylene, typically have a comonomer (e.g., hexene), incorporated into the polyethylene backbone. These copolymers provide varying physical properties compared to polyethylene alone and are typically produced in a low pressure reactor, utilizing, for example, solution, slurry, or gas phase polymerization processes. Polymerization may take place in the presence of catalyst systems such as those using a Ziegler-Natta catalyst, a chromium based catalyst, or a metallocene catalyst.
Zirconocene based catalysts are catalysts of interest for polyolefin production. However, their capability to form polymers having high molecular weights is typically lower than other group 4 based catalysts, such as hafnocene based catalyst.
There is a need for catalysts having high productivity and capable of forming polyolefins, for example, with high molecular weight, high comonomer content, and narrow polydispersity indices. In particular, there is a need to develop new and improved group 4 metal-containing metallocene catalysts with enhanced molecular weight capability.
References of interest include: Miyake, S. et al. “Synthesis, Molecular Structure, and Racemate-Meso Interconversion for rac-(Me2Si)2{η5-C5H-3(CHMe2)-5-Me}2MCI2(M=Ti and Zr),” Organometallics, 1998, v.17(25), pp. 5528-5533; US Patent Publication No. 2003/0139617; US Patent Publication No. 2005/0049373; US Patent Publication No. 2006/0014909; JP 2005002279; JP 4184765 B2; JP 2003096135; U.S. Pat. No. 7,968,665.
The present disclosure relates to catalyst compounds represented by Formula (I):
wherein:
M is a group 4 metal;
each of R1, R2, and R3 is independently hydrogen, alkoxide, C1 to C40 substituted or unsubstituted hydrocarbyl, or —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ is independently hydrogen or C1 to C20 substituted or unsubstituted hydrocarbyl;
each of R4, R5, and R6 is independently hydrogen, alkoxide, C1 to C40 substituted or unsubstituted hydrocarbyl, or —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ is independently hydrogen or C1 to C20 substituted or unsubstituted hydrocarbyl, or two or more of R4, R5, and R6 form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent ring;
each of X1 and X2 is independently a univalent anionic ligand, a diene ligand, an alkylidene ligand, or X1 and X2 are joined to form a metallocyclic ring;
each of T1, T2, T3, and T4 is independently Si or Ge;
T1 is bonded to Carbon 1, Carbon 4, or Carbon 5;
R1 is bonded to Carbon 1, Carbon 4, or Carbon 5;
R2 is bonded to Carbon 1, Carbon 4, or Carbon 5;
T2 is bonded to Carbon 1′, Carbon 4′, or Carbon 5′;
R5 is bonded to Carbon 1′, Carbon 4′, or Carbon 5′; and
R6 is bonded to Carbon 1′, Carbon 4′, or Carbon 5′.
In yet another embodiment, the present disclosure provides a catalyst system including an activator and a catalyst of the present disclosure.
In yet another embodiment, the present disclosure provides a catalyst system including an activator and a catalyst of the present disclosure.
In yet another embodiment, the present disclosure provides a catalyst system including an activator, a catalyst support, and a catalyst of the present disclosure.
In still another embodiment, the present disclosure provides a polymerization process including contacting one or more olefin monomers with a catalyst system including an activator and a catalyst of the present disclosure.
In still another embodiment, the present disclosure provides a polyolefin formed by a catalyst system and or method of the present disclosure.
The present disclosure provides catalyst compounds including at least two Si—Si-bridges, catalyst systems including such catalyst compounds, and uses thereof. In at least one embodiment, the present disclosure is directed to metallocene compounds, metallocene-based-catalyst systems, and their use in polymerization processes to produce polyolefin polymers, such as polyethylene polymers and polypropylene polymers. Catalyst compounds of the present disclosure can be zirconium-containing compounds having one or more cyclopentadiene ligand(s) substituted with one or more silyl neopentyl group and linked with at least two Si—Si-containing bridges. Catalyst compounds of the present disclosure can be hafnium-containing compounds having one or more cyclopentadiene ligand(s) substituted with one or more silyl neopentyl group and linked with at least two Si—Si-containing bridges.
In another class of embodiments, the present disclosure is directed to polymerization processes to produce polyolefin polymers from catalyst systems including one or more olefin polymerization catalysts, at least one activator, and an optional support.
For example, the present disclosure is directed to a polymerization process to produce a polyethylene polymer, the process including contacting a catalyst system including one or more metallocene catalysts, at least one activator, and at least one support, with ethylene and one or more C3-C10 alpha-olefin comonomers under polymerization conditions.
Catalysts, catalyst systems, and processes of the present disclosure can provide polyolefins at high Mw (e.g., 150,000 g/mol or greater), Mn values of 100,000 g/mol or greater, narrow M (e.g., about 1 to about 3), and/or high Mz values (e.g., 300,000 g/mol or greater). Catalysts, catalyst systems, and processes of the present disclosure can provide polymers having a comonomer content from about 0.05 wt % to about 12 wt %.
For the purposes of the present disclosure, the numbering scheme for the Periodic Table Groups is used as described in Chemical and Engineering News, v. 63(5), pg. 27 (1985). Therefore, a “group 4 metal” is an element from group 4 of the Periodic Table, e.g., Hf, Ti, or Zr.
The following abbreviations may be used herein: Me is methyl, Et is ethyl, Ph is phenyl, tBu is tertiary butyl, Cp is cyclopentadiene, PDI is polydispersity index, MAO is methylalumoxane, NMR is nuclear magnetic resonance, THF is tetrahydrofuran.
The specification describes group 4 metal complexes. The term complex is used to describe molecules in which an ancillary ligand is coordinated to a central transition metal atom. The ligand is bulky and stably bonded to the transition metal so as to maintain its influence during use of the catalyst, such as polymerization. The ligand may be coordinated to the transition metal by covalent bond and or electron donation coordination or intermediate bonds. The transition metal complexes are generally subjected to activation to perform their polymerization or oligomerization function using an activator which, without being bound by theory, is believed to create a cation as a result of the removal of an anionic group, often referred to as a leaving group, from the transition metal.
As used herein, “olefin polymerization catalyst(s)” refers to any catalyst, such as an organometallic complex or compound that is capable of coordination polymerization addition where successive monomers are added in a monomer chain at the organometallic active center.
The terms “substituent,” “radical,” “group,” and “moiety” may be used interchangeably.
“Conversion” is the amount of monomer that is converted to polymer product, and is reported as mol % and is calculated based on the polymer yield and the amount of monomer fed into the reactor.
An “olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as including an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an “ethylene” content of 35 wt % to 55 wt %, it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt % to 55 wt %, based upon the weight of the copolymer. A “polymer” has two or more of the same or different mer units. A “homopolymer” is a polymer having mer units that are the same. A “copolymer” is a polymer having two or more mer units that are different from each other. A “terpolymer” is a polymer having three mer units that are different from each other. “Different” is used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically. Accordingly, the definition of copolymer, as used herein, includes terpolymers. An “ethylene polymer” or “ethylene copolymer” is a polymer or copolymer including at least 50 mol % ethylene derived units, a “propylene polymer” or “propylene copolymer” is a polymer or copolymer including at least 50 mol % propylene derived units, and so on. An “ethylene polymer” or “ethylene copolymer” is a polymer or copolymer including at least 50 mol % ethylene derived units, a “propylene polymer” or “propylene copolymer” is a polymer or copolymer including at least 50 mol % propylene derived units, and so on.
The term “alpha-olefin” refers to an olefin having a terminal carbon-to-carbon double bond in the structure thereof ((R″R′″)—C═CH2, where R″ and R′″ can be independently hydrogen or any hydrocarbyl group; such as R″ is hydrogen and R′″ is an alkyl group). A “linear alpha-olefin” is an alpha-olefin defined in this paragraph wherein R″ is hydrogen, and R′″ is hydrogen or a linear alkyl group.
For the purposes of the present disclosure, ethylene shall be considered an alpha-olefin.
As used herein, and unless otherwise specified, the term “Cn” means hydrocarbon(s) having n carbon atom(s) per molecule, wherein n is a positive integer. The term “hydrocarbon” means a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and or unsaturated), including mixtures of hydrocarbon compounds having different values of n. Likewise, a “Cm-Cy” group or compound refers to a group or compound including carbon atoms at a total number thereof from m to y. Thus, a C1-C50 alkyl group refers to an alkyl group including carbon atoms at a total number thereof from about 1 to about 50.
Unless otherwise indicated, (e.g., the definition of “substituted hydrocarbyl”, “substituted aromatic”, etc.), the term “substituted” means that at least one hydrogen atom has been replaced with at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as —NR*2, —OR*, —SeR*, —TeR*, —PR*2, —AsR*2, —SbR*2, —SR*, —BR*2, —SiR*3, —GeR*3, —SnR*3, —PbR*3, —(CH2)q-SiR*3, where q is 1 to 10 and each R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted completely saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within a hydrocarbyl ring.
The term “substituted hydrocarbyl” means a hydrocarbyl radical in which at least one hydrogen atom of the hydrocarbyl radical has been substituted with at least one heteroatom (such as halogen, e.g., Br, Cl, F or I) or heteroatom-containing group (such as a functional group, e.g., —NR*2, —OR*, —SeR*, —TeR*, —PR*2, —AsR*2, —SbR*2, —SR*, —BR*2, —SiR*3, —GeR*3, —SnR*3, —PbR*3, —(CH2)q-SiR*3, where q is 1 to 10 and each R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted completely saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within a hydrocarbyl ring. The term “hydrocarbyl substituted phenyl” means a phenyl group having 1, 2, 3, 4 or 5 hydrogen groups replaced by a hydrocarbyl or substituted hydrocarbyl group. For example, the “hydrocarbyl substituted phenyl” group can be represented by the formula:
where each of Ra, Rb, Rc, Rd, and Re can be independently selected from hydrogen, C1-C40 hydrocarbyl or C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group (provided that at least one of Ra, Rb, Rc, Rd, and Re is not H), or two or more of Ra, Rb, Rc, Rd, and Re can be joined together to form a C4-C62 cyclic or polycyclic hydrocarbyl ring structure, or a combination thereof.
The term “substituted aromatic,” means an aromatic group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group.
The term “substituted phenyl,” mean a phenyl group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group.
The term “substituted naphthyl,” means a naphthyl group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group.
The term “substituted benzyl” means a benzyl group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group, such as a substituted benzyl group is represented by the formula:
where each of Ra′, Rb′, Rc′, Rd′, and Re′ and Z is independently selected from hydrogen, C1-C40 hydrocarbyl or C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group (provided that at least one of Ra′, Rb′, Rc′, Rd′, and Re′ and Z is not H), or two or more of Ra′, Rb′, Rc′, Rd′, and Re′ and Z are joined together to form a C4-C62 cyclic or polycyclic ring structure, or a combination thereof.
The terms “alkoxy” and “alkoxide” mean an alkyl or aryl group bound to an oxygen atom, such as an alkyl ether or aryl ether group/radical connected to an oxygen atom and can include those where the alkyl/aryl group is a C1 to C10 hydrocarbyl. The alkyl group may be straight chain, branched, or cyclic. The alkyl group may be saturated or unsaturated. Examples of suitable alkoxy radicals can include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, phenoxyl.
The term “alkenyl” means a straight-chain, branched-chain, or cyclic hydrocarbon radical having one or more double bonds. These alkenyl radicals may be optionally substituted. Examples of suitable alkenyl radicals can include ethenyl, propenyl, allyl, 1,4-butadienyl cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloctenyl, including their substituted analogues.
The terms “alkyl radical,” and “alkyl” are used interchangeably throughout this disclosure. For purposes of this disclosure, “alkyl radical” is defined to be C1-C100 alkyls, that may be linear, branched, or cyclic. Examples of such radicals can include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, including their substituted analogues. Substituted alkyl radicals are radicals in which at least one hydrogen atom of the alkyl radical has been substituted with at least a non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as —NR*2, —OR*, —SeR*, —TeR*, —PR*2, —AsR*2, —SbR*2, —SR*, —BR*2, —SiR*3, —GeR*3, —SnR*3, —PbR*3, or —(CH2)—SiR*3, and each R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted completely saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within a hydrocarbyl ring.
The term “aryl” or “aryl group” means an aromatic ring and the substituted variants thereof, such as phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, 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. As used herein, the term “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.
Where isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl) reference to one member of the group (e.g., n-butyl) shall expressly disclose the remaining isomers (e.g., iso-butyl, sec-butyl, and tert-butyl) in the family Likewise, reference to an alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer (e.g., butyl) expressly discloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl).
The term “ring atom” means an atom that is part of a cyclic ring structure. By this definition, 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. For example, tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. Other examples of heterocycles may include pyridine, imidazole, and thiazole.
The terms “hydrocarbyl radical,” “hydrocarbyl group,” or “hydrocarbyl” may be used interchangeably and are defined to mean a group including hydrogen and carbon atoms only. For example, a hydrocarbyl can be a C1-C100 radical that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic. Examples of such radicals may include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and aryl groups, such as phenyl, benzyl naphthyl.
Unless otherwise indicated, as used herein, “low comonomer content” is defined as a polyolefin having less than 8 wt % of comonomer based upon the total weight of the polyolefin. As used herein, “high comonomer content” is defined as a polyolefin having greater than or equal to 8 wt % of comonomer based upon the total weight of the polyolefin.
As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, and Mz is z average molecular weight, wt % is weight percent, and mol % is mole percent. Molecular weight distribution (MWD), also referred to as polydispersity (PDI), is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units (e.g., Mw, Mn, Mz) are g/mol.
Unless otherwise indicated, as used herein, “high molecular weight” is defined as a number average molecular weight (Mn) value of 100,000 g/mol or more. “Low molecular weight” is defined as an Mn value of less than 100,000 g/mol.
A “catalyst system” is a combination of at least one catalyst compound, at least one activator, an optional coactivator, and an optional support material. The terms “catalyst compound”, “catalyst complex”, “transition metal complex”, “transition metal compound”, “precatalyst compound”, and “precatalyst complex” are used interchangeably. When “catalyst system” is used to describe such a pair before activation, it means the unactivated catalyst complex (precatalyst) together with an activator and, optionally, a coactivator. When it is used to describe such a pair after activation, it means the activated complex and the activator or other charge-balancing moiety. The transition metal compound may be neutral as in a precatalyst, or a charged species with a counter ion as in an activated catalyst system. For the purposes of the present disclosure and the claims thereto, when catalyst systems are described as including neutral stable forms of the components, it is well understood by one of ordinary skill in the art, that the ionic form of the component is the form that reacts with the monomers to produce polymers. A polymerization catalyst system is a catalyst system that can polymerize monomers to polymer. Furthermore, catalyst compounds and activators represented by formulae herein are intended to embrace both neutral and ionic forms of the catalyst compounds and activators.
In the description herein, the catalyst may be described as a catalyst, a catalyst precursor, a pre-catalyst compound, catalyst compound or a transition metal compound, and these terms are used interchangeably.
An “anionic ligand” is a negatively charged ligand which donates one or more pairs of electrons to a metal ion. A “Lewis base” is a neutrally charged ligand which donates one or more pairs of electrons to a metal ion. Examples of Lewis bases include ethylether, trimethylamine, pyridine, tetrahydrofuran, dimethylsulfide, and triphenylphosphine. The term “heterocyclic Lewis base” refers to Lewis bases that are also heterocycles. Examples of heteroyclic Lewis bases include pyridine, imidazole, thiazole, and furan.
A scavenger is a compound that can be added to facilitate polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as coactivators. A coactivator, that is not a scavenger, may also be used in conjunction with an activator in order to form an active catalyst. In at least one embodiment, a coactivator can be pre-mixed with the transition metal compound to form an alkylated transition metal compound.
Noncoordinating anion (NCA) is defined to mean an anion either that does not coordinate to the catalyst metal cation or that does coordinate to the metal cation, but only weakly. The term NCA is also defined to include multicomponent NCA-containing activators, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, that contain an acidic cationic group and the non-coordinating anion. The term NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, that can react with a catalyst to form an activated species by abstraction of an anionic group. A Lewis acid is defined to be a compound or element that can react with an electron donor to form a bond. An NCA coordinates weakly enough that a Lewis base, such as an olefin monomer can displace it from the catalyst center. Any metal or metalloid that can form a compatible, weakly coordinating complex may be used or contained in the noncoordinating anion. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus, and silicon.
The term “continuous” means a system that operates without interruption or cessation. For example a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn.
A solution polymerization means a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert solvent or monomer(s) or their blends. A solution polymerization can be homogeneous. A homogeneous polymerization is one where the polymer product is dissolved in the polymerization medium. Suitable systems may be not turbid as described in Oliveira, J. V. et al. (2000) “High-Pressure Phase Equilibria for Polypropylene-Hydrocarbon Systems,” Ind. Eng. Chem. Res., v. 39(12), p. 4627.
A bulk polymerization means a polymerization process in which the monomers and or comonomers being polymerized are used as a solvent or diluent using little or no inert solvent as a solvent or diluent. A small fraction of inert solvent might be used as a carrier for catalyst and scavenger. A bulk polymerization system contains less than 25 wt % of inert solvent or diluent, such as less than 10 wt %, such as less than 1 wt %, such as 0 wt %.
Transition Metal Complexes
In at least one embodiment, the present disclosure relates to novel bridged metallocene transition metal complexes, where the complexes include at least one cyclopentadienyl ligand with suitable combinations of substituents and bridged with, for example, at least two —Si—Si— groups. In at least one embodiment, the bridge is characterized in that it has at least one functionality, either included in the bridge or bonded to it, this being a Si—Y or Ge—Y-type unity, such as Si—Y, Y being hydrocarbyl; such as Y is C1-C10 hydrocarbyl.
In at least one embodiment, a catalyst compound is represented by Formula (I):
wherein:
M is a group 4 metal;
each of R1, R2, and R3 is independently hydrogen, alkoxide, C1 to C40 substituted or unsubstituted hydrocarbyl, or —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ is independently hydrogen or C1 to C20 substituted or unsubstituted hydrocarbyl;
each of R4, R5, and R6 is independently hydrogen, alkoxide, C1 to C40 substituted or unsubstituted hydrocarbyl, or —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ is independently hydrogen or C1 to C20 substituted or unsubstituted hydrocarbyl, or two or more of R4, R5, and R6 form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent ring;
each of X1 and X2 is independently a univalent anionic ligand, a diene ligand, an alkylidene ligand, or X1 and X2 are joined to form a metallocyclic ring;
each of T1, T2, T3, and T4 is independently Si or Ge;
T1 is bonded to Carbon 1, Carbon 4, or Carbon 5;
R1 is bonded to Carbon 1, Carbon 4, or Carbon 5;
R2 is bonded to Carbon 1, Carbon 4, or Carbon 5;
T2 is bonded to Carbon 1′, Carbon 4′, or Carbon 5′;
R5 is bonded to Carbon 1′, Carbon 4′, or Carbon 5′; and
R6 is bonded to Carbon 1′, Carbon 4′, or Carbon 5′.
In at least one embodiment, M is Hf, Zr or Ti, such as Hf or Zr.
In at least one embodiment, each R7, R8, R9, R10, R11, R12, R13, and R14 is independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl group.
In at least one embodiment, one or more of T1 and T2 is Si, and each of R7, R8, R9, and R10 is independently C1 to C20 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a C1 to C20 substituted hydrocarbyl. For example, —((R7)(R8)T1-T2(R9)(R10))— is the bridging group —(Me2)Si—Si(Me2)—.
In at least one embodiment, one or more of T3 and T4 is Si, and each of R11, R12, R13, R14 is independently C1 to C20 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a C1 to C20 substituted hydrocarbyl. For example, —((R11)(R12)T3-T4(R13)(R14))— is the bridging group —(Me2)Si—Si(Me2)—.
In at least one embodiment, each of R1 and R2 together do not form a ring and or each of R2 and R3 together do not form a ring. In at least one embodiment, each of R4 and R5 together do not form a ring and or each of R5 and R6 together do not form a ring.
In at least one embodiment, each of X1 and X2 is independently selected from hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, or ethers. X1 and X2 may combine to form a part of a fused ring or a ring system. In at least one embodiment, each of X1 and X2 is independently selected from halide or C1 to C5 alkyl groups (such as methyl). In at least one embodiment, each X1 and X2 is selected from chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.
Alternatively, X1 and X2 may also be joined together to form an alkanediyl group or a conjugated C4-C40 diene ligand which is coordinated to M to form a metallocycle. X1 and X2 may also be identical or different conjugated dienes, optionally substituted with one or more hydrocarbyl, tri (hydrocarbyl) silyl groups or tri (hydrocarbyl) silylhydrocarbyl groups, said dienes having up to 30 atoms not counting hydrogen and forming a π-complex with M.
Exemplary groups suitable for X1 and or X2 include independently 1,4-diphenyl, 1,3-butadiene, 1,3-pentadiene, 2-methyl 1,3-pentadiene, 2,4-hexadiene, phenyl, 1,3-pentadiene, 1,4-dibenzyl, 1,3-butadiene, 1,4-ditolyl-1,3-butadiene, 1,4-bis (trimethylsilyl)-1,3-butadiene, and 1,4-dinaphthyl-1,3-butadiene; such as X1 and X2 are identical and are a C1-C3 alkyl or alkoxy group, a C6-C10 aryl or aryloxy group, a C2-C4 alkenyl group, a C7-C10 arylalkyl group, a C7-C12 alkylaryl group, or a halogen atom, such as chlorine.
In at least one embodiment, R1, R2, R3, R4, R5, or R6 of Formula (I) may be independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, or a substituted or unsubstituted phenyl, such as hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, such as hydrogen or methyl.
In at least one embodiment, R1, R2, R3, R4, R5, or R6 of Formula (I) are hydrogen.
In at least one embodiment, at least one of R1, R2, R3, R4, R5, and R6 is —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ is independently hydrogen or C1 to C20 substituted or unsubstituted hydrocarbyl.
Furthermore, R1, R2, R3, R4, R5, and R6 of Formula (I) may be identical or different and can be each independently a hydrogen atom, a halogen atom, a C1-C10 alkyl group (methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof) which may be halogenated, or a C6-C10 aryl group which may be halogenated, wherein at least one of R1, R2, and R3 is independently hydrogen, alkoxide, C1 to C40 substituted or unsubstituted hydrocarbyl, or —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ is independently H or C1 to C20 substituted or unsubstituted hydrocarbyl.
In at least one embodiment, R1, R2, R3, R4, R5, and R6 of Formula (I) are identical or different and are independently selected from a hydrogen atom, C2-C20 alkyl group (such as C3 to C16, such as C4 to C12, such as butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof) which may be halogenated, a C6-C10 aryl group which may be halogenated, wherein at least one of R1, R2, R3, R4, R5, and R6 is —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R is independently C1 to C20 substituted or unsubstituted hydrocarbyl. Furthermore, R1, R2, R3, R4, R5, and R6 may be the same or different and can be each independently a butyl group, an aryl group, an isopropyl group, or a fluoroalkyl group, such as wherein each of R1, R2, R3, R4, R5, and R6 can be selected from the group including methyl, ethyl, propyl, isopropyl, n-propyl, n-butyl-, iso-butyl-, and tert-butyl groups, wherein at least one of R1, R2, R3, R4, R5, and R6 can be —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ can be independently C1 to C20 substituted or unsubstituted hydrocarbyl.
In at least one embodiment, R1, R2, R3, R4, R5, and R6 are the same or different and are each independently a methyl group, ethyl group, propyl group, butyl group, an aryl group, an isopropyl group, or a fluoroalkyl group, such as wherein each of R1, R2, R3, R4, R5, and R6 is independently selected from the group including of methyl, ethyl, propyl, butyl, aryl, isopropyl, n-propyl, n-butyl-, iso-butyl-, and tert-butyl groups, and R1, R2, R3, R4, R5, and R6 may be independently substituted with —NR′2, —SR′, —OR′, —OSiR′3, —CH2SiR′3 or a —PR′2 radical, wherein R′ is one of a hydrogen atom, halogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group. One or more of R1, R2, R3, R4, R5, and R6 may be independently —CH2SiR′3 wherein R′ is a C1-C10 alkyl group, such as methyl group, ethyl group, propyl, butyl group, an aryl group, isopropyl, n-propyl, n-butyl-, iso-butyl-, and tert-butyl, such as methyl, wherein at least one of R1, R2, R3, R4, R5, and R6 is —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ is independently C1 to C20 substituted or unsubstituted hydrocarbyl.
In at least one embodiment, each of R1 and R4 is a —CH2SiR′3 group and each of R2, R3, R5, and R6 is hydrogen.
In another embodiment, each of R1 and R3 is independently substituted or unsubstituted, branched or unbranched C1-C20 alkyl, such as C1-C5 alkyl, R2 is —CH2SiR′3, and R4, R5, and R6 are hydrogen.
Each of R1, R2, and R3 can be independently substituted or unsubstituted, branched or unbranched C1-C20 alkyl, such as C1-C5 alkyl, R5 can be —CH2SiR′3, and R4 and R6 can be hydrogen.
In at least one embodiment, R2 and R5 are independently —CH2SiR′3 and R1, R3, R4, and R6 are independently hydrogen.
Transition metal complexes may include Zr-based or Hf-based complexes. Additionally, some such transition metal complexes can be bridged by a dialkyldisiladiyl group.
In at least one embodiment, transition metal complexes of the present disclosure are represented by Formula (I) above, wherein M can be selected from the group including titanium, zirconium, and hafnium, such as zirconium or hafnium.
For example, a transition metal complex represented by Formula (I) may include a bridge —((R7)(R8)T1-T2(R9)(R10))— where one or more of T1 and T2 is Si and R7, R8, R9, and R10 may be the same or different and are each independently selected from hydrogen or C1-C10 alkyl, such as C1-C2 alkyl (e.g., methyl or ethyl).
In another example, a transition metal complex represented by Formula (I) may include a bridge —((R11)(R12)T3-T4(R13)(R14))— wherein one or more of T3 and T4 is Si and R11, R12, R13, and R14 may be the same or different and are each independently selected from hydrogen or C1-C10 alkyl, such as C1-C2 alkyl (e.g., methyl or ethyl).
Furthermore, —((R7)(R8)T1-T2(R9)(R10))— can be the bridging group —(Me2)Si—Si(Me2)—. Also, —((R11)(R12)T3-T4(R13)(R14))— can be the bridging group —(Me2)Si—Si(Me2)—.
Each X1 and X2 may be the same or different and can be each independently a C1-C10 alkyl group, such as C1-C2 alkyl, such as methyl; each of R2 and R5 may be the same or different and can be independently hydrogen or —CH2SiR′3 wherein R′ may be the same or different and can be each independently C1-C10 alkyl, such as C1-C2 alkyl, such as methyl; each of R1, R3, R4, and R6 may be the same or different and can be each independently hydrogen or C1-C10 alkyl, such as each can be hydrogen; one or more of T1 and T2 is Si, and R7, R8, R9, and R10 may be the same or different and can be each independently hydrogen or C1-C10 alkyl, such as methyl; and one or more of T3 and T4 is Si, and R11, R12, R13, and R14 may be the same or different and can be each independently hydrogen or C1-C10 alkyl, such as methyl.
In at least one embodiment, transition metal complexes according to Formula (I) include those wherein X1 and X2 are methyl or chloro; each of R2 and R5 is —CH2SiR′3 wherein R′ is methyl; each of R1, R3, R4, and R6 is hydrogen; —((R7)(R8)T1-T2(R9)(R10))— is —(CH3)2Si—Si(CH3)2—; —((R11)(R12)T3-T4(R13)(R14))— is —(CH3)2Si—Si(CH3)2—; and M is hafnium.
In at least one embodiment, transition metal complexes according to Formula (I) include those wherein X1 and X2 are methyl or chloro; each of R2 and R5 is —CH2SiR′3 wherein R′ is methyl; each of R1, R3, R4, and R6 is hydrogen; —((R7)(R8)T1-T2(R9)(R10))— is —(CH3)2Si—Si(CH3)2—; —((R11)(R12)T3-T4(R13)(R14))— is —(CH3)2Si—Si(CH3)2—; and M is zirconium.
In at least one embodiment, transition metal complexes according to Formula (I) include those wherein X1 and X2 are methyl or chloro; each R1, R2, R3, R4, R5, and R6 are methyl, wherein at least one of R1, R2, R3, R4, R5, and R6 is —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ is independently C1 to C20 substituted or unsubstituted hydrocarbyl. —((R7)(R8)T1-T2(R9)(R10))— is —(CH3)2Si—Si(CH3)2; —((R11)(R12)T3-T4(R13)(R14))— is (CH3)2Si—Si(CH3)2—; and M is hafnium.
In at least one embodiment, transition metal complexes according to Formula (I) include those wherein X1 and X2 are methyl or chloro; each R1, R2, R3, R4, R5, and R6 are methyl groups, wherein at least one of R1, R2, R3, R4, R5, and R6 is —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ is independently C1 to C20 substituted or unsubstituted hydrocarbyl. —((R7)(R8)T1-T2(R9)(R10))— is —(CH3)2Si—Si(CH3)2—; —((R11)(R12)T3-T4(R13)(R14))— is —(CH3)2Si—Si(CH3)2—; M is zirconium.
In at least one embodiment, the catalyst compound represented by Formula (I) is represented by Formula (II):
wherein:
M is a group 4 metal;
each of R1, R2, and R3 is independently hydrogen, alkoxide, C1 to C40 substituted or unsubstituted hydrocarbyl, or —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ is independently hydrogen or C1 to C20 substituted or unsubstituted hydrocarbyl;
each of R4, R5, and R6 is independently hydrogen, alkoxide, C1 to C40 substituted or unsubstituted hydrocarbyl, or —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ is independently hydrogen or C1 to C20 substituted or unsubstituted hydrocarbyl, or two or more of R4, R5, and R6 form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent ring;
each of X1 and X2 is independently a univalent anionic ligand, a diene ligand, an alkylidene ligand, or X1 and X2 are joined to form a metallocyclic ring;
each of T1, T2, T3, and T4 is independently Si or Ge; and
In at least one embodiment, M is Hf, Zr or Ti, such as Hf or Zr.
In at least one embodiment, each R7, R8, R9, R10, R11, R12, R13, and R14 is independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl group.
In at least one embodiment, one or more of T1 and T2 is Si, and each of R7, R8, R9, and R10 is independently C1 to C20 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a C1 to C20 substituted hydrocarbyl. For example, —((R7)(R8)T1-T2(R9)(R10))— is the bridging group —(Me2)Si—Si(Me2)—.
In at least one embodiment, one or more of T3 and T4 is Si, and each of R11, R12, R13, R14 is independently C1 to C20 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a C1 to C20 substituted hydrocarbyl. For example, —((R11)(R12)T3-T4(R13)(R14))— is the bridging group —(Me2)Si—Si(Me2)—.
In at least one embodiment, each of R1 and R2 together do not form a ring and or each of R2 and R3 together do not form a ring. In at least one embodiment, each of R4 and R5 together do not form a ring and or each of R5 and R6 together do not form a ring.
In at least one embodiment, each of X1 and X2 is independently selected from hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, or ethers. X1 and X2 may combine to form a part of a fused ring or a ring system. In at least one embodiment, each of X1 and X2 is independently selected from halide or C1 to C5 alkyl groups (such as methyl). In at least one embodiment, each X1 and X2 is selected from chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.
Alternatively, X1 and X2 may also be joined together to form an alkanediyl group or a conjugated C4-C40 diene ligand which is coordinated to M to form a metallocycle. X1 and X2 may also be identical or different conjugated dienes, optionally substituted with one or more hydrocarbyl, tri (hydrocarbyl) silyl groups or tri (hydrocarbyl) silylhydrocarbyl groups, said dienes having up to 30 atoms not counting hydrogen and forming a π-complex with M.
Exemplary groups suitable for X1 and or X2 include independently 1,4-diphenyl, 1,3-butadiene, 1,3-pentadiene, 2-methyl 1,3-pentadiene, 2,4-hexadiene, phenyl, 1,3-pentadiene, 1,4-dibenzyl, 1,3-butadiene, 1,4-ditolyl-1,3-butadiene, 1,4-bis (trimethylsilyl)-1,3-butadiene, and 1,4-dinaphthyl-1,3-butadiene; such as X1 and X2 are identical and are a C1-C3 alkyl or alkoxy group, a C6-C10 aryl or aryloxy group, a C2-C4 alkenyl group, a C7-C10 arylalkyl group, a C7-C12 alkylaryl group, or a halogen atom, such as chlorine.
In at least one embodiment, R1, R2, R3, R4, R5, or R6 of Formula (II) may be independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, or a substituted or unsubstituted phenyl, such as hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, such as hydrogen or methyl.
In at least one embodiment, R1, R2, R3, R4, R5, or R6 of Formula (II) are hydrogen.
Furthermore, R1, R2, R3, R4, R5, and R6 of Formula (II) may be identical or different and can be each independently a hydrogen atom, a halogen atom, a C1-C10 alkyl group (methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof) which may be halogenated, or a C6-C10 aryl group which may be halogenated, wherein at least one of R1, R2, and R3 is independently hydrogen, alkoxide, C1 to C40 substituted or unsubstituted hydrocarbyl, or —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ is independently H or C1 to C20 substituted or unsubstituted hydrocarbyl.
In at least one embodiment, R1, R2, R3, R4, R5, and R6 of Formula (II) are identical or different and are independently selected from a hydrogen atom, C2-C20 alkyl group (such as C3 to C16, such as C4 to C12, such as butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof) which may be halogenated, a C6-C10 aryl group which may be halogenated, wherein at least one of R1, R2, R3, R4, R5, and R6 is —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R is independently C1 to C20 substituted or unsubstituted hydrocarbyl. Furthermore, R1, R2, R3, R4, R5, and R6 may be the same or different and can be each independently a butyl group, an aryl group, an isopropyl group, or a fluoroalkyl group, such as wherein each of R1, R2, R3, R4, R5, and R6 can be selected from the group including methyl, ethyl, propyl, isopropyl, n-propyl, n-butyl-, iso-butyl-, and tert-butyl groups, wherein at least one of R1, R2, R3, R4, R5, and R6 can be —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ can be independently C1 to C20 substituted or unsubstituted hydrocarbyl.
In at least one embodiment, R1, R2, R3, R4, R5, and R6 are the same or different and are each independently a methyl group, ethyl group, propyl group, butyl group, an aryl group, an isopropyl group, or a fluoroalkyl group, such as wherein each of R1, R2, R3, R4, R5, and R6 is independently selected from the group including of methyl, ethyl, propyl, butyl, aryl, isopropyl, n-propyl, n-butyl-, iso-butyl-, and tert-butyl groups, and R1, R2, R3, R4, R5, and R6 may be independently substituted with —NR′2, —SR′, —OR′, —OSiR′3, —CH2SiR′3 or a —PR′2 radical, wherein R′ is one of a hydrogen atom, halogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group. One or more of R1, R2, R3, R4, R5, and R6 may be independently —CH2SiR′3 wherein R′ is a C1-C10 alkyl group, such as methyl group, ethyl group, propyl, butyl group, an aryl group, isopropyl, n-propyl, n-butyl-, iso-butyl-, and tert-butyl, such as methyl, wherein at least one of R1, R2, R3, R4, R5, and R6 is —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ is independently C1 to C20 substituted or unsubstituted hydrocarbyl.
In at least one embodiment, each of R1 and R4 is a —CH2SiR′3 group and each of R2, R3, R5, and R6 is hydrogen.
In at least one embodiment, at least one of R1, R2, R3, R4, R5, and R6 is —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ is independently hydrogen or C1 to C20 substituted or unsubstituted hydrocarbyl.
In another embodiment, each of R1 and R3 is independently substituted or unsubstituted, branched or unbranched C1-C20 alkyl, such as C1-C5 alkyl, R2 is —CH2SiR′3, and R4, R5, and R6 are hydrogen.
Each of R1, R2, and R3 can be independently substituted or unsubstituted, branched or unbranched C1-C20 alkyl, such as C1-C5 alkyl, R5 can be —CH2SiR′3, and R4 and R6 can be hydrogen.
In at least one embodiment, R2 and R5 are independently —CH2SiR′3 and R1, R3, R4, and R6 are independently hydrogen.
Transition metal complexes may include Zr-based or Hf-based complexes. Additionally, some such transition metal complexes can be bridged by a dialkyldisiladiyl group.
In at least one embodiment, transition metal complexes of the present disclosure are represented by Formula (II) above, wherein M can be selected from the group including titanium, zirconium, and hafnium, such as zirconium or hafnium.
For example, a transition metal complex represented by Formula (II) may include a bridge —((R7)(R8)T1-T2(R9)(R10))— where one or more of T1 and T2 is Si and R7, R8, R9, and R10 may be the same or different and are each independently selected from hydrogen or C1-C10 alkyl, such as C1-C2 alkyl (e.g., methyl or ethyl).
In another example, a transition metal complex represented by Formula (II) may include a bridge —((R11)(R12)T3-T4(R13)(R14))— wherein one or more of T3 and T4 is Si and R11, R12, R13, and R14 may be the same or different and are each independently selected from hydrogen or C1-C10 alkyl, such as C1-C2 alkyl (e.g., methyl or ethyl).
Furthermore, —((R7)(R8)T1-T2(R9)(R10))— can be the bridging group —(Me2)Si—Si(Me2)—. Also, —((R11)(R12)T3-T4(R13)(R14)) can be the bridging group —(Me2)Si—Si(Me2)—.
Each X1 and X2 may be the same or different and can be each independently a C1-C10 alkyl group, such as C1-C2 alkyl, such as methyl; each of R2 and R5 may be the same or different and can be independently hydrogen or —CH2SiR′3 wherein R′ may be the same or different and can be each independently C1-C10 alkyl, such as C1-C2 alkyl, such as methyl; each of R1, R3, R4, and R6 may be the same or different and can be each independently hydrogen or C1-C10 alkyl, such as each can be hydrogen; one or more of T1 and T2 is Si, and R7, R8, R9, and R10 may be the same or different and can be each independently hydrogen or C1-C10 alkyl, such as methyl; and one or more of T3 and T4 is Si, and R11, R12, R13, and R14 may be the same or different and can be each independently hydrogen or C1-C10 alkyl, such as methyl.
In at least one embodiment, transition metal complexes according to Formula (II) include those wherein X1 and X2 are methyl or chloro; each of R2 and R5 is —CH2SiR′3 wherein R′ is methyl; each of R1, R3, R4, and R6 is hydrogen; —((R7)(R8)T1-T2(R9)(R10))— is —(CH3)2Si—Si(CH3)2—; —((R11)(R12)T3-T4(R13)(R14))— is —(CH3)2Si—Si(CH3)2—; and M is hafnium.
In at least one embodiment, transition metal complexes according to Formula (II) include those wherein X1 and X2 are methyl or chloro; each of R2 and R5 is —CH2SiR′3 wherein R′ is methyl; each of R1, R3, R4, and R6 is hydrogen; —((R7)(R8)T1-T2(R9)(R10))— is —(CH3)2Si—Si(CH3)2—; —((R11)(R12)T3-T4(R13)(R14))— is —(CH3)2Si—Si(CH3)2—; and M is zirconium.
In at least one embodiment, transition metal complexes according to Formula (II) include those wherein X1 and X2 are methyl or chloro; each R1, R2, R3, R4, R5, and R6 are methyl, wherein at least one of R1, R2, R3, R4, R5, and R6 is —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ is independently C1 to C20 substituted or unsubstituted hydrocarbyl. —((R7)(R8)T1-T2(R9)(R10))— is —(CH3)2Si—Si(CH3)2—; —((R11)(R12)T3-T4(R13)(R14))— is —(CH3)2Si—Si(CH3)2—; and M is hafnium.
In at least one embodiment, transition metal complexes according to Formula (II) include those wherein X1 and X2 are methyl or chloro; each R1, R2, R3, R4, R5, and R6 are methyl groups, wherein at least one of R1, R2, R3, R4, R5, and R6 is —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R is independently C1 to C20 substituted or unsubstituted hydrocarbyl. —((R7)(R8)T1-T2(R9)(R10))— is —(CH3)2Si—Si(CH3)2—; —((R11)(R12)T3-T4(R13)(R14))— is —(CH3)2Si—Si(CH3)2—; M is zirconium.
The following zirconium-containing metallocenes and their hafnium-containing analogs include: bis(tetramethyldisilyl)-bis(trimethylsilylmethylcyclopentadienyl) zirconium dimethyl, bis(tetramethyldisilyl)-bis(trimethylsilylmethylcyclopentadienyl) hafnium dimethyl.
Likewise, while the dimethyl-substituted compounds (—Hf(CH3)2 and —Zr(CH3)2) are enumerated above, the compounds can be where each of the methyl groups are replaced with ethyl groups (e.g., —HfEt2 and —ZrEt2), n-propyl groups (e.g., —HfPr2 and —ZrPr2), n-butyl groups (e.g., —HfBu2 and —ZrBu2), benzyl groups (e.g., —Hf(Bz)2 and —Zr(Bz)2), phenyl groups (e.g., —HfPh2 and —ZrPh2), trimethylsilylmethyl groups (e.g., —Hf(CH2SiMe3)2 and —Zr(CH2SiMe3)2), neopentyl groups (e.g., —Hf(CH2CMe3)2 and —Zr(CH2CMe3)2), chloride atoms (e.g., —HfCl2 and —ZrCl2).
In at least one embodiment, the catalyst compound represented by Formula (I) or Formula (II) is selected from the following GROUP A: (Me4Si2)2(4-Me3SiCH2Cp)2ZrCl2, (Et4Si2)2(4-Me3SiCH2Cp)2ZrCl2, (iPr4Si2)2(4-Me3SiCH2Cp)2ZrCl2, (Ph4Si2)2(4-Me3SiCH2Cp)2ZrCl2, ((MeMeSi)(PhPhSi))2(4-Me3SiCH2Cp)2ZrCl2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)2ZrCl2, (Me4Si2)2(4-Et3SiCH2Cp)2ZrCl2, (Et4Si2)2(4-Et3SiCH2Cp)2ZrCl2, (iPr4Si2)2(4-Et3SiCH2Cp)2ZrCl2, (Ph4Si2)2(4-Et3SiCH2Cp)2ZrCl2, ((MeMeSi)(PhPhSi))2(4-Et3SiCH2Cp)2ZrCl2, ((MePhSi)(MePhSi))2(4-Et3SiCH2Cp)2ZrCl2, (Me4Si2)2(4-Cy3SiCH2Cp)2ZrCl2, (Et4Si2)2(4-Cy3SiCH2Cp)2ZrCl2, (iPr4Si2)2(4-Cy3SiCH2Cp)2ZrCl2, (Ph4Si2)2(4-Cy3SiCH2Cp)2ZrCl2, ((MePhSi)(MePhSi))2(4-Cy3SiCH2Cp)2ZrCl2, ((MeMeSi)(PhPhSi))2(4-Cy3SiCH2Cp)2ZrCl2, (Me4Si2)2(4-Me2PhSiCH2Cp)2ZrCl2, (Et4Si2)2(4-Me2PhSiCH2Cp)2ZrCl2, (iPr4Si2)2(4-Me2PhSiCH2Cp)2ZrCl2, (Ph4Si2)2(4-Me2PhSiCH2Cp)2ZrCl2, ((MeMeSi)(PhPhSi))2(4-Me2PhSiCH2Cp)2ZrCl2, ((MePhSi)(MePhSi))2(4-Me2PhSiCH2Cp)2ZrCl2, (Me4Si2)2(4-MePh2SiCH2Cp)2ZrCl2, (Et4Si2)2(4-MePh2SiCH2Cp)\2ZrCl2, (iPr4Si2)2(4-MePh2SiCH2Cp)2ZrCl2, (Ph4Si2)2(4-MePh2SiCH2Cp)2ZrCl2, ((MeMeSi)(PhPhSi))2(4-MePh2SiCH2Cp)2ZrCl2, ((MePhSi)(MePhSi))2(4-MePh2SiCH2Cp)2ZrCl2, (Me4Si2)2(4-Ph3SiCH2Cp)2ZrCl2, (Et4Si2)2(4-Ph3SiCH2Cp)2ZrCl2, (iPr4Si2)2(4-Ph3SiCH2Cp)2ZrCl2, (Ph4Si2)2(4-Ph3SiCH2Cp)2ZrCl2, ((MeMeSi)(PhPhSi))2(4-Ph3SiCH2Cp)2ZrCl2, ((MePhSi)(MePhSi))2(4-Ph3SiCH2Cp)2ZrCl2, (Me4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrCl2, (Et4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrCl2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrCl2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrCl2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrCl2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrCl2, (Me4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrCl2, (Et4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrCl2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrCl2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrCl2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrCl2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrCl2, (Me4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrCl2, (Et4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrCl2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrCl2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrCl2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrCl2, (Me4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrCl2, (Et4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrCl2, (iPr4Si2)2(3,4,5- Me3Cp)(4-Me2PhSiCH2Cp)ZrCl2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrCl2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrCl2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrCl2, (Me4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrCl2, (Et4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrCl2, (iPr4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrCl2, (Ph4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrCl2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrCl2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrCl2, (Me4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrCl2, (Et4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrCl2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrCl2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrCl2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrCl2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrCl2, (Me4Si2)2(Cp)(4-Me3SiCH2Cp)ZrCl2, (Et4Si2)2(Cp)(4-Me3SiCH2Cp)ZrCl2, (iPr4Si2)2(Cp)(4-Me3SiCH2Cp)ZrCl2, (Ph4Si2)2(Cp)(4-Me3SiCH2Cp)ZrCl2, ((MeMeSi)(PhPhSi))2(Cp)(4-Me3SiCH2Cp)ZrCl2, ((MePhSi)(MePhSi))2(Cp)(4-Me3SiCH2Cp)ZrCl2, (Me4Si2)2(Cp)(4-Et3SiCH2Cp)ZrCl2, (Et4Si2)2(Cp)(4-Et3SiCH2Cp)ZrCl2, (iPr4Si2)2(Cp)(4-Et3SiCH2Cp)ZrCl2, (Ph4Si2)2(Cp)(4-Et3SiCH2Cp)ZrCl2, ((MeMeSi)(PhPhSi))2(Cp)(4-Et3SiCH2Cp)ZrCl2, ((MePhSi)(MePhSi))2(Cp)(4-Et3SiCH2Cp)ZrCl2, (Me4Si2)2(Cp)(4-Cy3SiCH2Cp)ZrCl2, (Et4Si2)2(Cp)(4-Cy3SiCH2Cp)ZrCl2, (iPr4Si2)2(Cp)(4-Cy3SiCH2Cp)ZrCl2, (Ph4Si2)2(Cp)(4-Cy3SiCH2Cp)ZrCl2, ((MeMeSi)(PhPhSi))2(Cp)(4-Cy3SiCH2Cp)ZrCl2, ((MePhSi)(MePhSi))2(Cp)(4-Cy3SiCH2Cp)ZrCl2, (Me4Si2)2(Cp)(4-Me2PhSiCH2Cp)ZrCl2, (Et4Si2)2(Cp)(4-Me2PhSiCH2Cp)ZrCl2, (iPr4Si2)2(Cp)(4-Me2PhSiCH2Cp)ZrCl2, (Ph4Si2)2(Cp)(4-Me2PhSiCH2Cp)ZrCl2, ((MeMeSi)(PhPhSi))2(Cp)(4-Me2PhSiCH2Cp)ZrCl2, ((MePhSi)(MePhSi))2(Cp)(4-Me2PhSiCH2Cp)ZrCl2, ((MeMeSi)(PhPhSi))2(Cp)(4-MePh2SiCH2Cp)ZrCl2, ((MePhSi)(MePhSi))2(Cp)(4-MePh2SiCH2Cp)ZrCl2, (Me4Si2)2(Cp)(4-Ph3SiCH2Cp)ZrCl2, (Et4Si2)2(Cp)(4-Ph3SiCH2Cp)ZrCl2, (iPr4Si2)2(Cp)(4-Ph3SiCH2Cp)ZrCl2, (Ph4Si2)2(Cp)(4-Ph3SiCH2Cp)ZrCl2, ((MeMeSi)(PhPhSi))2(Cp)(4-Ph3SiCH2Cp)ZrCl2, ((MePhSi)(MePhSi))2(Cp)(4-Ph3SiCH2Cp)ZrCl2, (Me4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrCl2, (Et4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrCl2, (iPr4Si2)2(4- Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrCl2, (Ph4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrCl2, ((MeMeSi)(PhPhSi))2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrCl2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrCl2, (Me4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrCl2, (Et4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrCl2, (iPr4Si2)2(4-Et3SiCH2Cp)(4- Cy3SiCH2Cp)ZrCl2, (Ph4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrCl2, ((MeMeSi)(PhPhSi))2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrCl2, ((MePhSi)(MePhSi))2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrCl2, (Me4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrCl2, (Et4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrCl2, (iPr4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrCl2, (Ph4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrCl2, ((MeMeSi)(PhPhSi))2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrCl2, ((MePhSi)(MePhSi))2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrCl2, (Me4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrCl2, (Et4Si2)2(4-Me2PhSiCH2Cp)(4- MePh2SiCH2Cp)ZrCl2, (iPr4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrCl2, (Ph4Si2)2(4- Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrCl2, ((MeMeSi)(PhPhSi))2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrCl2, ((MePhSi)(MePhSi))2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrCl2, (Me4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrCl2, (Et4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrCl2, (iPr4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrCl2, (Ph4Si2)2(4- MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrCl2, ((MeMeSi)(PhPhSi))2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrCl2, ((MePhSi)(MePhSi))2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrCl2, (Me4Si2)2(4-Ph3SiCH2Cp)2ZrCl2, (Et4Si2)2(4-Ph3SiCH2Cp)2ZrCl2, (iPr4Si2)2(4-Ph3SiCH2Cp)2ZrCl2, (Ph4Si2)2(4-Ph3SiCH2Cp)2ZrCl2, ((MeMeSi)(PhPhSi))2(1-Ph3SiCH2Cp)2ZrCl2, and ((MePhSi)(MePhSi))2(1-Ph3SiCH2Cp)2ZrCl2.
In at least one embodiment, the catalyst compound represented by Formula (I) or Formula (II) is selected from: (Me4Si2)2(4-Me3SiCH2Cp)2ZrMe2, (Et4Si2)2(4-Me3SiCH2Cp)2ZrMe2, (iPr4Si2)2(4-Me3SiCH2Cp)2ZrMe2, (Ph4Si2)2(4-Me3SiCH2Cp)2ZrMe2, ((MeMeSi)(PhPhSi))2(4-Me3SiCH2Cp)2ZrMe2, (Me4Si2)2(4-Et3SiCH2Cp)2ZrMe2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)2ZrMe2, (iPr4Si2)2(4-Et3SiCH2Cp)2ZrMe2, (Ph4Si2)2(4-Et3SiCH2Cp)2ZrMe2, ((MeMeSi)(PhPhSi))2(4-Et3SiCH2Cp)2ZrMe2, ((MePhSi)(MePhSi))2(4-Et3SiCH2Cp)2ZrMe2, (Me4Si2)2(4-Cy3SiCH2Cp)2ZrMe2, (Et4Si2)2(4-Cy3SiCH2Cp)2ZrMe2, (iPr4Si2)2(4-Cy3SiCH2Cp)2ZrMe2, (Ph4Si2)2(4-Cy3SiCH2Cp)2ZrMe2, ((MeMeSi)(PhPhSi))2(4-Cy3SiCH2Cp)2ZrMe2, ((MePhSi)(MePhSi))2(4-Cy3SiCH2Cp)2ZrMe2, (Me4Si2)2(4-Me2PhSiCH2Cp)2ZrMe2, (Et4Si2)2(4-Me2PhSiCH2Cp)2ZrMe2, (iPr4Si2)2(4-Me2PhSiCH2Cp)2ZrMe2, (Ph4Si2)2(4-Me2PhSiCH2Cp)2ZrMe2, ((MeMeSi)(PhPhSi))2(4-Me2PhSiCH2Cp)2ZrMe2, ((MePhSi)(MePhSi))2(4-Me2PhSiCH2Cp)2ZrMe2, (Me4Si2)2(4-MePh2SiCH2Cp)2ZrMe2, (Et4Si2)2(4-MePh2SiCH2Cp)\2ZrMe2, (iPr4Si2)2(4-MePh2SiCH2Cp)2ZrMe2, (Ph4Si2)2(4-MePh2SiCH2Cp)2ZrMe2, ((MeMeSi)(PhPhSi))2(4-MePh2SiCH2Cp)2ZrMe2, ((MePhSi)(MePhSi))2(4-MePh2SiCH2Cp)2ZrMe2, (Me4Si2)2(4-Ph3SiCH2Cp)2ZrMe2, (Et4Si2)2(4-Ph3SiCH2Cp)2ZrMe2, (iPr4Si2)2(4-Ph3SiCH2Cp)2ZrMe2, (Ph4Si2)2(4-Ph3SiCH2Cp)2ZrMe2, ((MeMeSi)(PhPhSi))2(4-Ph3SiCH2Cp)2ZrMe2, ((MePhSi)(MePhSi))2(4-Ph3SiCH2Cp)2ZrMe2, (Me4Si2)2(3,4,5-Me3 Cp) (4-Me3 SiCH2Cp)ZrMe2, (Et4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrMe2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrMe2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Me3 SiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrMe2, ((MePhSi)(MePhSi)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrMe2, (Me4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrMe2, (Et4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrMe2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrMe2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrMe2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrMe2, (Me4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrMe2, (Et4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrMe2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrMe2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Cy3 SiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrMe2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrMe2, (Me4Si2)2(3,4,5-Me3 Cp) (4-Me2PhSiCH2Cp)ZrMe2, (Et4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrMe2, (iPr4Si2)2(3,4,5- Me3Cp)(4-Me2PhSiCH2Cp)ZrMe2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrMe2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrMe2, (Me4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrMe2, (Et4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrMe2, (iPr4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrMe2, (Ph4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrMe2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrMe2, (Me4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrMe2, (Et4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrMe2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrMe2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrMe2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrMe2, (Me4Si2)2(Cp)(4-Me3SiCH2Cp)ZrMe2, (Et4Si2)2(Cp)(4-Me3SiCH2Cp)ZrMe2, (iPr4Si2)2(Cp)(4-Me3SiCH2Cp)ZrMe2, (Ph4Si2)2(Cp)(4-Me3SiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi))2(Cp)(4-Me3SiCH2Cp)ZrMe2, ((MePhSi)(MePhSi))2(Cp)(4-Me3SiCH2Cp)ZrMe2, (Me4Si2)2(Cp)(4-Et3SiCH2Cp)ZrMe2, (Et4Si2)2(Cp)(4-Et3SiCH2Cp)ZrMe2, (iPr4Si2)2(Cp)(4-Et3SiCH2Cp)ZrMe2, (Ph4Si2)2(Cp)(4-Et3SiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi))2(Cp)(4-Et3SiCH2Cp)ZrMe2, ((MePhSi)(MePhSi))2(Cp)(4-Et3SiCH2Cp)ZrMe2, (Me4Si2)2(Cp)(4-Cy3SiCH2Cp)ZrMe2, (Et4Si2)2(Cp)(4-Cy3SiCH2Cp)ZrMe2, (iPr4Si2)2(Cp)(4-Cy3SiCH2Cp)ZrMe2, (Ph4Si2)2(Cp)(4-Cy3SiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi))2(Cp)(4-Cy3SiCH2Cp)ZrMe2, ((MePhSi)(MePhSi))2(Cp)(4-Cy3SiCH2Cp)ZrMe2, (Me4Si2)2(Cp)(4-Me2PhSiCH2Cp)ZrMe2, (Et4Si2)2(Cp)(4-Me2PhSiCH2Cp)ZrMe2, (iPr4Si2)2(Cp)(4-Me2PhSiCH2Cp)ZrMe2, (Ph4Si2)2(Cp)(4-Me2PhSiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi))2(Cp)(4-Me2PhSiCH2Cp)ZrMe2, ((MePhSi)(MePhSi))2(Cp)(4-Me2PhSiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi))2(Cp)(4-MePh2SiCH2Cp)ZrMe2, ((MePhSi)(MePhSi))2(Cp)(4-MePh2SiCH2Cp)ZrMe2, (Me4Si2)2(Cp)(4-Ph3SiCH2Cp)ZrMe2, (Et4Si2)2(Cp)(4-Ph3SiCH2Cp)ZrMe2, (iPr4Si2)2(Cp)(4-Ph3SiCH2Cp)ZrMe2, (Ph4Si2)2(Cp)(4-Ph3SiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi))2(Cp)(4-Ph3SiCH2Cp)ZrMe2, ((MePhSi)(MePhSi))2(Cp)(4-Ph3SiCH2Cp)ZrMe2, (Me4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrMe2, (Et4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrMe2, (iPr4Si2)2(4- Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrMe2, (Ph4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi))2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrMe2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrMe2, (Me4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrMe2, (Et4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrMe2, (iPr4Si2)2(4-Et3SiCH2Cp)(4- Cy3SiCH2Cp)ZrMe2, (Ph4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi))2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrMe2, ((MePhSi)(MePhSi))2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrMe2, (Me4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrMe2, (Et4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrMe2, (iPr4Si2)2(4-Cy3SiCH2Cp)(4- Me2PhSiCH2Cp)ZrMe2, (Ph4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi))2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrMe2, ((MePhSi)(MePhSi))2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrMe2, (Me4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrMe2, (Et4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrMe2, (iPr4Si2)2(4- Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrMe2, (Ph4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi))2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrMe2, ((MePhSi)(MePhSi))2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrMe2, (Me4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrMe2, (Et4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrMe2, (iPr4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrMe2, (Ph4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi))2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrMe2, ((MePhSi)(MePhSi))2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrMe2, (Me4Si2)2(4-Ph3SiCH2Cp)2ZrMe2, (Et4Si2)2(4-Ph3SiCH2Cp)2ZrMe2, (iPr4Si2)2(4-Ph3SiCH2Cp)2ZrMe2, (Ph4Si2)2(4-Ph3SiCH2Cp)2ZrMe2, ((MeMeSi)(PhPhSi))2(1-Ph3SiCH2Cp)2ZrMe2, and ((MePhSi)(MePhSi))2(1-Ph3SiCH2Cp)2ZrMe2.
In at least one embodiment, the catalyst compound represented by Formula (I) or Formula (II) is selected from the following GROUP B: (Me4Si2)2(4-Me3SiCH2Cp)2ZrBu2, (Et4Si2)2(4-Me3SiCH2Cp)2ZrBu2, (iPr4Si2)2(4-Me3SiCH2Cp)2ZrBu2, (Ph4Si2)2(4-Me3SiCH2Cp)2ZrBu2, ((MeMeSi)(PhPhSi))2(4-Me3SiCH2Cp)2ZrBu2, (Me4Si2)2(4-Et3SiCH2Cp)2ZrBu2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)2ZrBu2, (Me4Si2)2(4-Et3SiCH2Cp)2ZrBu2, (Et4Si2)2(4-Et3SiCH2Cp)2ZrBu2, (iPr4Si2)2(4-Et3SiCH2Cp)2ZrBu2, (Ph4Si2)2(4-Et3SiCH2Cp)2ZrBu2, ((MeMeSi)(PhPhSi))2(4-Et3SiCH2Cp)2ZrBu2, ((MePhSi)(MePhSi))2(4-Et3SiCH2Cp)2ZrBu2, (Me4Si2)2(4-Cy3SiCH2Cp)2ZrBu2, (Et4Si2)2(4-Cy3SiCH2Cp)2ZrBu2, (iPr4Si2)2(4-Cy3SiCH2Cp)2ZrBu2, (Ph4Si2)2(4-Cy3SiCH2Cp)2ZrBu2, ((MeMeSi)(PhPhSi))2(4-Cy3SiCH2Cp)2ZrBu2, ((MePhSi)(MePhSi))2(4-Cy3SiCH2Cp)2ZrBu2, (Me4Si2)2(4-Me2PhSiCH2Cp)2ZrBu2, (Et4Si2)2(4-Me2PhSiCH2Cp)2ZrBu2, (iPr4Si2)2(4-Me2PhSiCH2Cp)2ZrBu2, (Ph4Si2)2(4-Me2PhSiCH2Cp)2ZrBu2, ((MeMeSi)(PhPhSi)2(4-Me2PhSiCH2Cp)2ZrBu2, ((MePhSi)(MePhSi))2(4-Me2PhSiCH2Cp)2ZrBu2, (Me4Si2)2(4-MePh2SiCH2Cp)2ZrBu2, (Et4Si2)2(4-MePh2SiCH2Cp)\2ZrBu2, (iPr4Si2)2(4-MePh2SiCH2Cp)2ZrBu2, (Ph4Si2)2(4-MePh2SiCH2Cp)2ZrBu2, ((MeMeSi)(PhPhSi)2(4-MePh2SiCH2Cp)2ZrBu2, ((MePhSi)(MePhSi))2(4-MePh2SiCH2Cp)2ZrBu2, (Me4Si2)2(4-Ph3SiCH2Cp)2ZrBu2, (Et4Si2)2(4-Ph3SiCH2Cp)2ZrBu2, (iPr4Si2)2(4-Ph3SiCH2Cp)2ZrBu2, (Ph4Si2)2(4-Ph3SiCH2Cp)2ZrBu2, ((MeMeSi)(PhPhSi))2(4-Ph3SiCH2Cp)2ZrBu2, ((MePhSi)(MePhSi))2(4-Ph3SiCH2Cp)2ZrBu2, (Me4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrBu2, (Et4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrBu2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrBu2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrBu2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrBu2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrBu2, (Me4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrBu2, (Et4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrBu2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrBu2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrBu2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrBu2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrBu2, (Me4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrBu2, (Et4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrBu2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrBu2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrBu2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrBu2, (Me4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrBu2, (Et4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrBu2, (iPr4Si2)2(3,4,5- Me3Cp)(4-Me2PhSiCH2Cp)ZrBu2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrBu2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrBu2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrBu2, (Me4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrBu2, (Et4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrBu2, (iPr4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrBu2, (Ph4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrBu2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrBu2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrBu2, (Me4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrBu2, (Et4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrBu2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrBu2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrBu2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrBu2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrBu2, (Me4Si2)2(Cp)(4-Me3SiCH2Cp)ZrBu2, (Et4Si2)2(Cp)(4-Me3SiCH2Cp)ZrBu2, (iPr4Si2)2(Cp)(4-Me3SiCH2Cp)ZrBu2, (Ph4Si2)2(Cp)(4-Me3SiCH2Cp)ZrBu2, ((MeMeSi)(PhPhSi))2(Cp)(4-Me3SiCH2Cp)ZrBu2, ((MePhSi)(MePhSi))2(Cp)(4-Me3SiCH2Cp)ZrBu2, (Me4Si2)2(Cp)(4-Et3SiCH2Cp)ZrBu2, (Et4Si2)2(Cp)(4-Et3SiCH2Cp)ZrBu2, (iPr4Si2)2(Cp)(4-Et3SiCH2Cp)ZrBu2, (Ph4Si2)2(Cp)(4-Et3SiCH2Cp)ZrBu2, ((MeMeSi)(PhPhSi))2(Cp)(4-Et3SiCH2Cp)ZrBu2, ((MePhSi)(MePhSi))2(Cp)(4-Et3SiCH2Cp)ZrBu2, (Me4Si2)2(Cp)(4-Cy3SiCH2Cp)ZrBu2, (Et4Si2)2(Cp)(4-Cy3SiCH2Cp)ZrBu2, (iPr4Si2)2(Cp)(4-Cy3SiCH2Cp)ZrBu2, (Ph4Si2)2(Cp)(4-Cy3SiCH2Cp)ZrBu2, ((MeMeSi)(PhPhSi))2(Cp)(4-Cy3SiCH2Cp)ZrBu2, ((MePhSi)(MePhSi))2(Cp)(4-Cy3SiCH2Cp)ZrBu2, (Me4Si2)2(Cp)(4-Me2PhSiCH2Cp)ZrBu2, (Et4Si2)2(Cp)(4-Me2PhSiCH2Cp)ZrBu2, (iPr4Si2)2(Cp)(4-Me2PhSiCH2Cp)ZrBu2, (Ph4Si2)2(Cp)(4-Me2PhSiCH2Cp)ZrBu2, ((MeMeSi)(PhPhSi))2(Cp)(4-Me2PhSiCH2Cp)ZrBu2, ((MePhSi)(MePhSi))2(Cp)(4-Me2PhSiCH2Cp)ZrBu2, ((MeMeSi)(PhPhSi))2(Cp)(4-MePh2SiCH2Cp)ZrBu2, ((MePhSi)(MePhSi))2(Cp)(4-MePh2SiCH2Cp)ZrBu2, (Me4Si2)2(Cp)(4-Ph3SiCH2Cp)ZrBu2, (Et4Si2)2(Cp)(4-Ph3SiCH2Cp)ZrBu2, (iPr4Si2)2(Cp)(4-Ph3SiCH2Cp)ZrBu2, (Ph4Si2)2(Cp)(4-Ph3SiCH2Cp)ZrBu2, ((MeMeSi)(PhPhSi))2(Cp) (4-Ph3SiCH2Cp)ZrBu2, ((MePhSi)(MePhSi))2(Cp)(4-Ph3SiCH2Cp)ZrBu2, (Me4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrBu2, (Et4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrBu2, (iPr4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrBu2, (Ph4Si2)2(4-Me3SiCH2Cp)(4- Et3SiCH2Cp)ZrBu2, ((MeMeSi)(PhPhSi))2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrBu2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrBu2, (Me4Si2)2(4-Et3SiCH2Cp) (4-Cy3SiCH2Cp)ZrBu2, (Et4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrBu2, (iPr4Si2)2(4- Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrBu2, (Ph4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrBu2, ((MeMeSi)(PhPhSi))2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrBu2, ((MePhSi)(MePhSi))2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrBu2, (Me4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrBu2, (Et4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrBu2, (iPr4Si2)2(4-Cy3SiCH2Cp)(4- Me2PhSiCH2Cp)ZrBu2, (Ph4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrBu2, ((MeMeSi)(PhPhSi))2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrBu2, ((MePhSi)(MePhSi))2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrBu2, (Me4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrBu2, (Et4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrBu2, (iPr4Si2)2(4- Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrBu2, (Ph4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrBu2, ((MeMeSi)(PhPhSi))2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrBu2, ((MePhSi)(MePhSi))2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrBu2, (Me4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrBu2, (Et4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrBu2, (iPr4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrBu2, (Ph4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrBu2, ((MeMeSi)(PhPhSi))2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrBu2, ((MePhSi)(MePhSi))2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrBu2, (Me4Si2)2(4-Ph3SiCH2Cp)2ZrBu2, (Et4Si2)2(4-Ph3SiCH2Cp)2ZrBu2, (iPr4Si2)2(4-Ph3SiCH2Cp)2ZrBu2, (Ph4Si2)2(4-Ph3SiCH2Cp)2ZrBu2, ((MeMeSi)(PhPhSi))2(1-Ph3SiCH2Cp)2ZrBu2, and ((MePhSi)(MePhSi))2(1-Ph3SiCH2Cp)2ZrBu2.
In at least one embodiment, the catalyst compound represented by Formula (I) or Formula (II) is selected from the Following GROUP C: (Me4Si2)2(4-Me3SiCH2Cp)2ZrPh2, (Et4Si2)2(4-Me3SiCH2Cp)2ZrPh2, (iPr4Si2)2(4-Me3SiCH2Cp)2ZrPh2, (Ph4Si2)2(4-Me3SiCH2Cp)2ZrPh2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)2ZrPh2, ((MeMeSi)(PhPhSi))2(4-Me3SiCH2Cp)2ZrPh2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)2ZrPh2, (Me4Si2)2(4-Et3SiCH2Cp)2ZrPh2, (Et4Si2)2(4-Et3SiCH2Cp)2ZrPh2, (iPr4Si2)2(4-Et3SiCH2Cp)2ZrPh2, (Ph4Si2)2(4-Et3SiCH2Cp)2ZrPh2, ((MeMeSi)(PhPhSi))2(4-Et3SiCH2Cp)2ZrPh2, ((MePhSi)(MePhSi))2(4-Et3SiCH2Cp)2ZrPh2, (Me4Si2)2(4-Cy3SiCH2Cp)2ZrPh2, (Et4Si2)2(4-Cy3SiCH2Cp)2ZrPh2, (iPr4Si2)2(4-Cy3SiCH2Cp)2ZrPh2, (Ph4Si2)2(4-Cy3SiCH2Cp)2ZrPh2, ((MeMeSi)(PhPhSi))2(4-Cy3SiCH2Cp)2ZrPh2, ((MePhSi)(MePhSi))2(4-Cy3SiCH2Cp)2ZrPh2, (Me4Si2)2(4-Me2PhSiCH2Cp)2ZrPh2, (Et4Si2)2(4-Me2PhSiCH2Cp)2ZrPh2, (iPr4Si2)2(4-Me2PhSiCH2Cp)2ZrPh2, (Ph4Si2)2(4-Me2PhSiCH2Cp)2ZrPh2, ((MeMeSi)(PhPhSi))2(4-Me2PhSiCH2Cp)2ZrPh2, ((MePhSi)(MePhSi))2(4-Me2PhSiCH2Cp)2ZrPh2, (Me4Si2)2(4-MePh2SiCH2Cp)2ZrPh2, (Et4Si2)2(4-MePh2SiCH2Cp)\2ZrPh2, (iPr4Si2)2(4-MePh2SiCH2Cp)2ZrPh2, (Ph4Si2)2(4-MePh2SiCH2Cp)2ZrPh2, ((MeMeSi)(PhPhSi))2(4-MePh2SiCH2Cp)2ZrPh2, ((MePhSi)(MePhSi))2(4-MePh2SiCH2Cp)2ZrPh2, (Me4Si2)2(4-Ph3SiCH2Cp)2ZrPh2, (Et4Si2)2(4-Ph3SiCH2Cp)2ZrPh2, (iPr4Si2)2(4-Ph3SiCH2Cp)2ZrPh2, (Ph4Si2)2(4-Ph3SiCH2Cp)2ZrPh2, ((MeMeSi)(PhPhSi))2(4-Ph3SiCH2Cp)2ZrPh2, ((MePhSi)(MePhSi))2(4-Ph3SiCH2Cp)2ZrPh2, (Me4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrPh2, (Et4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrPh2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrPh2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrPh2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrPh2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrPh2, (Me4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrPh2, (Et4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrPh2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrPh2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrPh2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrPh2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrPh2, (Me4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrPh2, (Et4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrPh2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrPh2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrPh2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrPh2, (Me4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrPh2, (Et4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrPh2, (iPr4Si2)2(3,4,5- Me3Cp)(4-Me2PhSiCH2Cp)ZrPh2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrPh2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrPh2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrPh2, (Me4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrPh2, (Et4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrPh2, (iPr4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrPh2, (Ph4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrPh2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrPh2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrPh2, (Me4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrPh2, (Et4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrPh2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrPh2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrPh2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrPh2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrPh2, (Me4Si2)2(Cp)(4-Me3SiCH2Cp)ZrPh2, (Et4Si2)2(Cp)(4-Me3SiCH2Cp)ZrPh2, (iPr4Si2)2(Cp)(4-Me3SiCH2Cp)ZrPh2, (Ph4Si2)2(Cp)(4-Me3SiCH2Cp)ZrPh2, ((MeMeSi)(PhPhSi))2(Cp)(4-Me3SiCH2Cp)ZrPh2, ((MePhSi)(MePhSi))2(Cp)(4-Me3SiCH2Cp)ZrPh2, (Me4Si2)2(Cp)(4-Et3SiCH2Cp)ZrPh2, (Et4Si2)2(Cp)(4-Et3SiCH2Cp)ZrPh2, (iPr4Si2)2(Cp)(4-Et3SiCH2Cp)ZrPh2, (Ph4Si2)2(Cp)(4-Et3SiCH2Cp)ZrPh2, ((MeMeSi)(PhPhSi))2(Cp)(4-Et3SiCH2Cp)ZrPh2, ((MePhSi)(MePhSi))2(Cp)(4-Et3SiCH2Cp)ZrPh2, (Me4Si2)2(Cp)(4-Cy3SiCH2Cp)ZrPh2, (Et4Si2)2(Cp)(4-Cy3SiCH2Cp)ZrPh2, (iPr4Si2)2(Cp)(4-Cy3SiCH2Cp)ZrPh2, (Ph4Si2)2(Cp)(4-Cy3SiCH2Cp)ZrPh2, ((MeMeSi)(PhPhSi))2(Cp)(4-Cy3SiCH2Cp)ZrPh2, ((MePhSi)(MePhSi))2(Cp)(4-Cy3SiCH2Cp)ZrPh2, (Me4Si2)2(Cp)(4-Me2PhSiCH2Cp)ZrPh2, (Et4Si2)2(Cp)(4-Me2PhSiCH2Cp)ZrPh2, (iPr4Si2)2(Cp)(4-Me2PhSiCH2Cp)ZrPh2, (Ph4Si2)2(Cp)(4-Me2PhSiCH2Cp)ZrPh2, ((MeMeSi)(PhPhSi))2(Cp)(4-Me2PhSiCH2Cp)ZrPh2, ((MePhSi)(MePhSi))2(Cp)(4-Me2PhSiCH2Cp)ZrPh2, ((MeMeSi)(PhPhSi))2(Cp)(4-MePh2SiCH2Cp)ZrPh2, ((MePhSi)(MePhSi))2(Cp)(4-MePh2SiCH2Cp)ZrPh2, (Me4Si2)2(Cp)(4-Ph3SiCH2Cp)ZrPh2, (Et4Si2)2(Cp)(4-Ph3SiCH2Cp)ZrPh2, (iPr4Si2)2(Cp)(4-Ph3SiCH2Cp)ZrPh2, (Ph4Si2)2(Cp)(4-Ph3SiCH2Cp)ZrPh2, ((MeMeSi)(PhPhSi))2(Cp)(4-Ph3SiCH2Cp)ZrPh2, ((MePhSi)(MePhSi))2(Cp)(4-Ph3SiCH2Cp)ZrPh2, (Me4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrPh2, (Et4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrPh2, (iPr4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrPh2, (Ph4Si2)2(4-Me3SiCH2Cp)(4- Et3SiCH2Cp)ZrPh2, ((MeMeSi)(PhPhSi))2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrPh2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrPh2, (Me4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrPh2, (Et4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrPh2, (iPr4Si2)2(4- Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrPh2, (Ph4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrPh2, ((MeMeSi)(PhPhSi))2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrPh2, ((MePhSi)(MePhSi))2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrPh2, (Me4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrPh2, (Et4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrPh2, (iPr4Si2)2(4-Cy3SiCH2Cp)(4- Me2PhSiCH2Cp)ZrPh2, (Ph4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrPh2, ((MeMeSi)(PhPhSi))2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrPh2, ((MePhSi)(MePhSi))2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrPh2, (Me4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrPh2, (Et4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrPh2, (iPr4Si2)2(4- Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrPh2, (Ph4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrPh2, ((MeMeSi)(PhPhSi))2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrPh2, ((MePhSi)(MePhSi))2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrPh2, (Me4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrPh2, (Et4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrPh2, (iPr4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrPh2, (Ph4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrPh2, ((MeMeSi)(PhPhSi))2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrPh2, ((MePhSi)(MePhSi))2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrPh2, (Me4Si2)2(4-Ph3SiCH2Cp)2ZrPh2, (Et4Si2)2(4-Ph3SiCH2Cp)2ZrPh2, (iPr4Si2)2(4-Ph3SiCH2Cp)2ZrPh2, (Ph4Si2)2(4-Ph3SiCH2Cp)2ZrPh2, ((MeMeSi)(PhPhSi))2(1-Ph3SiCH2Cp)2ZrPh2, ((MePhSi)(MePhSi))2(1-Ph3SiCH2Cp)2ZrPh2.
In at least one embodiment, the catalyst compound represented by Formula (I) or Formula (II) is selected from the following GROUP D: (Me4Si2)2(4-Me3SiCH2Cp)2ZrBn2, (Et4Si2)2(4-Me3 SiCH2Cp)2ZrBn2, (iPr4Si2)2(4-Me3 SiCH2Cp)2ZrBn2, (Ph4Si2)2(4-Me3SiCH2Cp)2ZrBn2, ((MeMeSi)(PhPhSi))2(4-Me3SiCH2Cp)2ZrBn2, (Me4Si2)2(4-Et3SiCH2Cp)2ZrBn2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)2ZrBn2, (Et4Si2)2(4-Et3 SiCH2Cp)2ZrBn2, (iPr4Si2)2(4-Et3SiCH2Cp)2ZrBn2, (Ph4Si2)2(4-Et3SiCH2Cp)2ZrBn2, ((MeMeSi)(PhPhSi))2(4-Et3SiCH2Cp)2ZrBn2, ((MePhSi)(MePhSi))2(4-Et3SiCH2Cp)2ZrBn2, (Me4Si2)2(4-Cy3SiCH2Cp)2ZrBn2, (Et4Si2)2(4-Cy3SiCH2Cp)2ZrBn2, (iPr4Si2)2(4-Cy3SiCH2Cp)2ZrBn2, (Ph4Si2)2(4-Cy3SiCH2Cp)2ZrBn2, ((MeMeSi)(PhPhSi))2(4-Cy3SiCH2Cp)2ZrBn2, ((MePhSi)(MePhSi))2(4-Cy3SiCH2Cp)2ZrBn2, (Me4Si2)2(4-Me2PhSiCH2Cp)2ZrBn2, (Et4Si2)2(4-Me2PhSiCH2Cp)2ZrBn2, (iPr4Si2)2(4-Me2PhSiCH2Cp)2ZrBn2, (Ph4Si2)2(4-Me2PhSiCH2Cp)2ZrBn2, ((MeMeSi)(PhPhSi)2(4-Me2PhSiCH2Cp)2ZrBn2, ((MePhSi) (MePhSi))2(4-Me2PhSiCH2Cp)2ZrBn2, (Me4Si2)2(4-MePh2SiCH2Cp)2ZrBn2, (Et4Si2)2(4-MePh2SiCH2Cp)2ZrBn2, (iPr4Si2)2(4-MePh2SiCH2Cp)2ZrBn2, (Ph4Si2)2(4-MePh2SiCH2Cp)2ZrBn2, ((MeMeSi)(PhPhSi)2(4-MePh2SiCH2Cp)2ZrBn2, ((MePhSi) (MePhSi))2(4-MePh2SiCH2Cp)2ZrBn2, (Me4Si2)2(4-Ph3SiCH2Cp)2ZrBn2, (Et4Si2)2(4-Ph3SiCH2Cp)2ZrBn2, (iPr4Si2)2(4-Ph3SiCH2Cp)2ZrBn2, (Ph4Si2)2(4-Ph3SiCH2Cp)2ZrBn2, ((MeMeSi)(PhPhSi))2(4-Ph3SiCH2Cp)2ZrBn2, ((MePhSi)(MePhSi))2(4-Ph3SiCH2Cp)2ZrBn2, (Me4Si2)2(3,4,5-Me3 Cp) (4-Me3SiCH2Cp)ZrBn2, (Et4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrBn2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrBn2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrBn2, ((MeMeSi)(PhPhSi)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrBn2, ((MePhSi)(MePhSi)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)ZrBn2, (Me4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrBn2, (Et4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrBn2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrBn2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrBn2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3 Cp) (4-Et3SiCH2Cp)ZrBn2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)ZrBn2, (Me4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrBn2, (Et4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrBn2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrBn2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrMe2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrBn2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)ZrBn2, (Me4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrBn2, (Et4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrBn2, (iPr4Si2)2(3,4,5- Me3Cp)(4-Me2PhSiCH2Cp)ZrBn2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrBn2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrBn2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)ZrBn2, (Me4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrBn2, (Et4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrBn2, (iPr4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrBn2, (Ph4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrBn2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrBn2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)ZrBn2, (Me4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrBn2, (Et4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrBn2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrBn2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrBn2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrBn2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)ZrBn2, (Me4Si2)2(Cp)(4-Me3SiCH2Cp)ZrBn2, (Et4Si2)2(Cp)(4-Me3SiCH2Cp)ZrBn2, (iPr4Si2)2(Cp)(4-Me3SiCH2Cp)ZrBn2, (Ph4Si2)2(Cp)(4-Me3SiCH2Cp)ZrBn2, ((MeMeSi)(PhPhSi))2(Cp)(4-Me3SiCH2Cp)ZrBn2, ((MePhSi)(MePhSi))2(Cp)(4-Me3SiCH2Cp)ZrBn2, (Me4Si2)2(Cp)(4-Et3SiCH2Cp)ZrBn2, (Et4Si2)2(Cp)(4-Et3SiCH2Cp)ZrBn2, (iPr4Si2)2(Cp)(4-Et3SiCH2Cp)ZrBn2, (Ph4Si2)2(Cp)(4-Et3SiCH2Cp)ZrBn2, ((MeMeSi)(PhPhSi))2(Cp)(4-Et3SiCH2Cp)ZrBn2, ((MePhSi)(MePhSi))2(Cp)(4-Et3SiCH2Cp)ZrBn2, (Me4Si2)2(Cp)(4-Cy3SiCH2Cp)ZrBn2, (Et4Si2)2(Cp)(4-Cy3SiCH2Cp)ZrBn2, (iPr4Si2)2(Cp)(4-Cy3SiCH2Cp)ZrBn2, (Ph4Si2)2(Cp)(4-Cy3SiCH2Cp)ZrBn2, ((MeMeSi)(PhPhSi))2(Cp)(4-Cy3SiCH2Cp)ZrBn2, ((MePhSi)(MePhSi))2(Cp)(4-Cy3SiCH2Cp)ZrBn2, (Me4Si2)2(Cp)(4-Me2PhSiCH2Cp)ZrBn2, (Et4Si2)2(Cp)(4-Me2PhSiCH2Cp)ZrBn2, (iPr4Si2)2(Cp)(4-Me2PhSiCH2Cp)ZrBn2, (Ph4Si2)2(Cp)(4-Me2PhSiCH2Cp)ZrBn2, ((MeMeSi)(PhPhSi))2(Cp)(4-Me2PhSiCH2Cp)ZrBn2, ((MePhSi)(MePhSi))2(Cp)(4-Me2PhSiCH2Cp)ZrBn2, ((MeMeSi)(PhPhSi))2(Cp)(4-MePh2SiCH2Cp)ZrBn2, ((MePhSi)(MePhSi))2(Cp)(4-MePh2SiCH2Cp)ZrBn2, (Me4Si2)2(Cp)(4-Ph3SiCH2Cp)ZrBn2, (Et4Si2)2(Cp)(4-Ph3SiCH2Cp)ZrBn2, (iPr4Si2)2(Cp)(4-Ph3SiCH2Cp)ZrBn2, (Ph4Si2)2(Cp)(4-Ph3SiCH2Cp)ZrBn2, ((MeMeSi)(PhPhSi))2(Cp)(4-Ph3SiCH2Cp)ZrBn2, ((MePhSi)(MePhSi))2(Cp)(4-Ph3SiCH2Cp)ZrBn2, (Me4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrBn2, (Et4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrBn2, (iPr4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrBn2, (Ph4Si2)2(4-Me3SiCH2Cp)(4- Et3SiCH2Cp)ZrBn2, ((MeMeSi)(PhPhSi))2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrBn2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)ZrBn2, (Me4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrBn2, (Et4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrBn2, (iPr4Si2)2(4- Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrBn2, (Ph4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrBn2, ((MeMeSi)(PhPhSi))2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrBn2, ((MePhSi)(MePhSi))2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)ZrBn2, (Me4Si2)2(4-Cy3SiCH2Cp) (4-Me2PhSiCH2Cp)ZrBn2, (Et4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrBn2, (iPr4Si2)2(4-Cy3SiCH2Cp)(4- Me2PhSiCH2Cp)ZrBn2, (Ph4Si2)2(4-Cy3SiCH2Cp) (4-Me2PhSiCH2Cp)ZrBn2, ((MeMeSi)(PhPhSi))2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrBn2, ((MePhSi) (MePhSi)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)ZrBn2, (Me4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrBn2, (Et4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrBn2, (iPr4Si2)2(4- Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrBn2, (Ph4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrBn2, ((MeMeSi)(PhPhSi))2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrBn2, ((MePhSi)(MePhSi))2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)ZrBn2, (Me4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrBn2, (Et4Si2)2(4-MePh2SiCH2Cp)(4-Ph3 SiCH2Cp)ZrBn2, (iPr4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrBn2, (Ph4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrBn2, ((MeMeSi)(PhPhSi))2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrBn2, ((MePhSi)(MePhSi))2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)ZrBn2, (Me4Si2)2(4-Ph3SiCH2Cp)2ZrBn2, (Et4Si2)2(4-Ph3SiCH2Cp)2ZrBn2, (iPr4Si2)2(4-Ph3SiCH2Cp)2ZrBn2, (Ph4Si2)2(4-Ph3 SiCH2Cp)2ZrBn2, ((MeMeSi)(PhPhSi))2(1-Ph3SiCH2Cp)2ZrBn2, ((MePhSi)(MePhSi))2(1-Ph3SiCH2Cp)2ZrBn2.
In at least one embodiment, the catalyst compound represented by Formula (I) or Formula (II) is selected from the following GROUP E: (Me4Si2)2(4-Me3SiCH2Cp)2HfCl2, (Et4Si2)2(4-Me3SiCH2Cp)2HfCl2, (iPr4Si2)2(4-Me3SiCH2Cp)2HfCl2, (Ph4Si2)2(4-Me3SiCH2Cp)2HfCl2, ((MeMeSi)(PhPhSi))2(4-Me3SiCH2Cp)2HfCl2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)2HfCl2, (Me4Si2)2(4-Et3SiCH2Cp)2HfCl2, (Et4Si2)2(4-Et3SiCH2Cp)2HfCl2, (iPr4Si2)2(4-Et3SiCH2Cp)2HfCl2, (Ph4Si2)2(4-Et3SiCH2Cp)2HfCl2, ((MeMeSi)(PhPhSi)2(4-Et3SiCH2Cp)2HfCl2, ((MePhSi)(MePhSi))2(4-Et3SiCH2Cp)2HfCl2, (Me4Si2)2(4-Cy3SiCH2Cp)2HfCl2, (Et4Si2)2(4-Cy3SiCH2Cp)2HfCl2, (iPr4Si2)2(4-Cy3SiCH2Cp)2HfCl2, (Ph4Si2)2(4-Cy3SiCH2Cp)2HfCl2, ((MeMeSi)(PhPhSi))2(4-Cy3SiCH2Cp)2HfCl2, ((MePhSi)(MePhSi))2(4-Cy3SiCH2Cp)2HfCl2, (Me4Si2)2(4-Me2PhSiCH2Cp)2HfCl2, (Et4Si2)2(4-Me2PhSiCH2Cp)2HfCl2, (iPr4Si2)2(4-Me2PhSiCH2Cp)2HfCl2, (Ph4Si2)2(4-Me2PhSiCH2Cp)2HfCl2, ((MeMeSi)(PhPhSi))2(4-Me2PhSiCH2Cp)2HfCl2, ((MePhSi)(MePhSi))2(4-Me2PhSiCH2Cp)2HfCl2,(Me4Si2)2(4-MePh2SiCH2Cp)2HfCl2, (Et4Si2)2(4-MePh2SiCH2Cp)\2HfCl2, (iPr4Si2)2(4-MePh2SiCH2Cp)2HfCl2, (Ph4Si2)2(4-MePh2SiCH2Cp)2HfCl2, ((MeMeSi)(PhPhSi))2(4-MePh2SiCH2Cp)2HfCl2, ((MePhSi)(MePhSi))2(4-MePh2SiCH2Cp)2HfCl2, (Me4Si2)2(4-Ph3SiCH2Cp)2HfCl2, (Et4Si2)2(4-Ph3SiCH2Cp)2HfCl2, (iPr4Si2)2(4-Ph3SiCH2Cp)2HfCl2, (Ph4Si2)2(4-Ph3SiCH2Cp)2HfCl2, ((MeMeSi)(PhPhSi))2(4-Ph3SiCH2Cp)2HfCl2, ((MePhSi)(MePhSi))2(4-Ph3SiCH2Cp)2HfCl2, (Me4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfCl2, (Et4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfCl2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfCl2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfCl2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfCl2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfCl2, (Me4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfCl2, (Et4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfCl2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfCl2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfCl2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfCl2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfCl2, (Me4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfCl2, (Et4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfCl2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfCl2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfCl2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfCl2, (Me4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfCl2, (Et4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfCl2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfCl2, (Ph4Si2)2(3,4,5- Me3Cp)(4-Me2PhSiCH2Cp)HfCl2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfCl2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfCl2, (Me4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfCl2, (Et4S12)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfCl2, (iPr4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfCl2, (Ph4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfCl2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfCl2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfCl2, (Me4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfCl2, (Et4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfCl2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfCl2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfCl2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfCl2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfCl2, (Me4Si2)2(Cp)(4-Me3SiCH2Cp)HfCl2, (Et4Si2)2(Cp)(4-Me3SiCH2Cp)HfCl2, (iPr4Si2)2(Cp)(4-Me3SiCH2Cp)HfCl2, (Ph4Si2)2(Cp)(4-Me3SiCH2Cp)HfCl2, ((MeMeSi)(PhPhSi))2(Cp)(4-Me3SiCH2Cp)HfCl2, ((MePhSi)(MePhSi))2(Cp)(4-Me3SiCH2Cp)HfCl2, (Me4Si2)2(Cp)(4-Et3SiCH2Cp)HfCl2, (Et4Si2)2(Cp)(4-Et3SiCH2Cp)HfCl2, (iPr4Si2)2(Cp)(4-Et3SiCH2Cp)HfCl2, (Ph4Si2)2(Cp)(4-Et3SiCH2Cp)HfCl2, ((MeMeSi)(PhPhSi))2(Cp)(4-Et3SiCH2Cp)HfCl2, ((MePhSi)(MePhSi))2(Cp)(4-Et3SiCH2Cp)HfCl2, (Me4Si2)2(Cp)(4-Cy3SiCH2Cp)HfCl2, (Et4Si2)2(Cp)(4-Cy3SiCH2Cp)HfCl2, (iPr4Si2)2(Cp)(4-Cy3SiCH2Cp)HfCl2, (Ph4Si2)2(Cp)(4-Cy3SiCH2Cp)HfCl2, ((MeMeSi)(PhPhSi))2(Cp)(4-Cy3SiCH2Cp)HfCl2, ((MePhSi)(MePhSi))2(Cp)(4-Cy3SiCH2Cp)HfCl2, (Me4Si2)2(Cp)(4-Me2PhSiCH2Cp)HfCl2, (Et4Si2)2(Cp)(4-Me2PhSiCH2Cp)HfCl2, (iPr4Si2)2(Cp)(4-Me2PhSiCH2Cp)HfCl2, (Ph4Si2)2(Cp)(4-Me2PhSiCH2Cp)HfCl2, ((MeMeSi)(PhPhSi))2(Cp)(4-Me2PhSiCH2Cp)HfCl2, ((MePhSi)(MePhSi))2(Cp)(4-Me2PhSiCH2Cp)HfCl2, ((MeMeSi)(PhPhSi))2(Cp)(4-MePh2SiCH2Cp)HfCl2, ((MePhSi)(MePhSi))2(Cp)(4-MePh2SiCH2Cp)HfCl2, (Me4Si2)2(Cp)(4-Ph3SiCH2Cp)HfCl2, (Et4Si2)2(Cp)(4-Ph3SiCH2Cp)HfCl2, (iPr4Si2)2(Cp)(4-Ph3SiCH2Cp)HfCl2, (Ph4Si2)2(Cp)(4-Ph3SiCH2Cp)HfCl2, ((MeMeSi)(PhPhSi))2(Cp)(4-Ph3SiCH2Cp)HfCl2, ((MePhSi)(MePhSi))2(Cp)(4-Ph3SiCH2Cp)HfCl2, (Me4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfCl2, (Et4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfCl2, (iPr4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfCl2, (Ph4Si2)2(4-Me3SiCH2Cp)(4- Et3SiCH2Cp)HfCl2, ((MeMeSi)(PhPhSi))2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfCl2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfCl2, (Me4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfCl2, (Et4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfCl2, (iPr4Si2)2(4- Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfCl2, (Ph4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfCl2, ((MeMeSi)(PhPhSi))2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfCl2, ((MePhSi)(MePhSi))2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfCl2, (Me4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfCl2, (Et4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfCl2, (iPr4Si2)2(4-Cy3SiCH2Cp)(4- Me2PhSiCH2Cp)HfCl2, (Ph4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfCl2, ((MeMeSi)(PhPhSi))2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfCl2, ((MePhSi)(MePhSi))2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfCl2, (Me4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfCl2, (Et4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfCl2, (iPr4Si2)2(4- Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfCl2, (Ph4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfCl2, ((MeMeSi)(PhPhSi))2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfCl2, ((MePhSi)(MePhSi))2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfCl2, (Me4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfCl2, (Et4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfCl2, (iPr4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfCl2, (Ph4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfCl2, ((MeMeSi)(PhPhSi))2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfCl2, ((MePhSi)(MePhSi))2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfCl2, (Me4Si2)2(4-Ph3SiCH2Cp)2HfCl2, (Et4Si2)2(4-Ph3SiCH2Cp)2HfCl2, (iPr4Si2)2(4-Ph3SiCH2Cp)2HfCl2, (Ph4Si2)2(4-Ph3SiCH2Cp)2HfCl2, ((MeMeSi)(PhPhSi))2(1-Ph3SiCH2Cp)2HfCl2, and ((MePhSi)(MePhSi))2(1-Ph3SiCH2Cp)2HfCl2.
In at least one embodiment, the catalyst compound represented by Formula (I) or Formula (II) is selected from the following GROUP F: (Me4Si2)2(4-Me3SiCH2Cp)2Cp)2HfMe2, (Et4Si2)2(4-Me3SiCH2Cp)2HfMe2, (iPr4Si2)2(4-Me3SiCH2Cp)2HfMe2, (Ph4Si2)2(4-Me3SiCH2Cp)2HfMe2, ((MeMeSi)(PhPhSi))2(4-Me3SiCH2Cp)2HfMe2, (Me4Si2)2(4-Et3SiCH2Cp)2HfMe2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)2HfMe2, (Et4Si2)2(4-Et3SiCH2Cp)2HfMe2, (iPr4Si2)2(4-Et3SiCH2Cp)2HfMe2, (Ph4Si2)2(4-Et3SiCH2Cp)2HfMe2, ((MeMeSi)(PhPhSi))2(4-Et3SiCH2Cp)2HfMe2, ((MePhSi)(MePhSi))2(4-Et3SiCH2Cp)2HfMe2, (Me4Si2)2(4-Cy3SiCH2Cp)2HfMe2, (Et4Si2)2(4-Cy3SiCH2Cp)2HfMe2, (iPr4Si2)2(4-Cy3SiCH2Cp)2HfMe2, (Ph4Si2)2(4-Cy3SiCH2Cp)2HfMe2, ((MeMeSi)(PhPhSi))2(4-Cy3SiCH2Cp)2HfMe2, ((MePhSi)(MePhSi))2(4-Cy3SiCH2Cp)2HfMe2, (Me4Si2)2(4-Me2PhSiCH2Cp)2HfMe2, (Et4Si2)2(4-Me2PhSiCH2Cp)2HfMe2, (iPr4Si2)2(4-Me2PhSiCH2Cp)2HfMe2, (Ph4Si2)2(4-Me2PhSiCH2Cp)2HfMe2, ((MeMeSi)(PhPhSi))2(4-Me2PhSiCH2Cp)2HfMe2, ((MePhSi)(MePhSi))2(4-Me2PhSiCH2Cp)2HfMe2, (Me4Si2)2(4-MePh2SiCH2Cp)2HfMe2, (Et4Si2)2(4-MePh2SiCH2Cp)\2HfMe2, (iPr4Si2)2(4-MePh2SiCH2Cp)2HfMe2, (Ph4Si2)2(4-MePh2SiCH2Cp)2HfMe2, ((MeMeSi)(PhPhSi))2(4-MePh2SiCH2Cp)2HfMe2, ((MePhSi)(MePhSi))2(4-MePh2SiCH2Cp)2HfMe2, (Me4Si2)2(4-Ph3SiCH2Cp)2HfMe2, (Et4Si2)2(4-Ph3SiCH2Cp)2HfMe2, (iPr4Si2)2(4-Ph3SiCH2Cp)2HfMe2, (Ph4Si2)2(4-Ph3SiCH2Cp)2HfMe2, ((MeMeSi)(PhPhSi))2(4-Ph3SiCH2Cp)2HfMe2, ((MePhSi)(MePhSi))2(4-Ph3SiCH2Cp)2HfMe2, (Me4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfMe2, (Et4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfMe2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfMe2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfMe2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfMe2, (Me4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfMe2, (Et4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfMe2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfMe2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfMe2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfMe2, (Me4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfMe2, (Et4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfMe2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfMe2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfMe2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfMe2, (Me4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfMe2, (Et4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfMe2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfMe2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfMe2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfMe2, (Me4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfMe2, (Et4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfMe2, (iPr4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfMe2, (Ph4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfMe2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfMe2, (Me4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfMe2, (Et4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfMe2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfMe2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfMe2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfMe2, (Me4Si2)2(Cp)(4-Me3SiCH2Cp)HfMe2, (Et4Si2)2(Cp)(4-Me3SiCH2Cp)HfMe2, (iPr4Si2)2(Cp)(4-Me3SiCH2Cp)HfMe2, (Ph4Si2)2(Cp)(4-Me3SiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi))2(Cp)(4-Me3SiCH2Cp)HfMe2, ((MePhSi)(MePhSi))2(Cp)(4-Me3SiCH2Cp)HfMe2, (Me4Si2)2(Cp)(4-Et3SiCH2Cp)HfMe2, (Et4Si2)2(Cp)(4-Et3SiCH2Cp)HfMe2, (iPr4Si2)2(Cp)(4-Et3SiCH2Cp)HfMe2, (Ph4Si2)2(Cp)(4-Et3SiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi))2(Cp)(4-Et3SiCH2Cp)HfMe2, ((MePhSi)(MePhSi))2(Cp)(4-Et3SiCH2Cp)HfMe2, (Me4Si2)2(Cp)(4-Cy3SiCH2Cp)HfMe2, (Et4Si2)2(Cp)(4-Cy3SiCH2Cp)HfMe2, (iPr4Si2)2(Cp)(4-Cy3SiCH2Cp)HfMe2, (Ph4Si2)2(Cp)(4-Cy3SiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi))2(Cp)(4-Cy3SiCH2Cp)HfMe2, ((MePhSi)(MePhSi))2(Cp)(4-Cy3SiCH2Cp)HfMe2, (Me4Si2)2(Cp)(4-Me2PhSiCH2Cp)HfMe2, (Et4Si2)2(Cp)(4-Me2PhSiCH2Cp)HfMe2, (iPr4Si2)2(Cp)(4-Me2PhSiCH2Cp)HfMe2, (Ph4Si2)2(Cp)(4-Me2PhSiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi))2(Cp)(4-Me2PhSiCH2Cp)HfMe2, ((MePhSi)(MePhSi))2(Cp)(4-Me2PhSiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi))2(Cp)(4-MePh2SiCH2Cp)HfMe2, ((MePhSi)(MePhSi))2(Cp)(4-MePh2SiCH2Cp)HfMe2, (Me4Si2)2(Cp)(4-Ph3SiCH2Cp)HfMe2, (Et4Si2)2(Cp)(4-Ph3SiCH2Cp)HfMe2, (iPr4Si2)2(Cp)(4-Ph3SiCH2Cp)HfMe2, (Ph4Si2)2(Cp)(4-Ph3SiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi))2(Cp)(4-Ph3SiCH2Cp)HfMe2, ((MePhSi)(MePhSi))2(Cp)(4-Ph3SiCH2Cp)HfMe2, (Me4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfMe2, (Et4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfMe2, (iPr4Si2)2(4- Me3SiCH2Cp)(4-Et3SiCH2Cp)HfMe2, (Ph4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi))2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfMe2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfMe2, (Me4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfMe2, (Et4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfMe2, (iPr4Si2)2(4-Et3SiCH2Cp)(4- Cy3SiCH2Cp)HfMe2, (Ph4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi))2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfMe2, ((MePhSi)(MePhSi))2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfMe2, (Me4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfMe2, (Et4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfMe2, (iPr4Si2)2(4-Cy3SiCH2Cp)(4- Me2PhSiCH2Cp)HfMe2, (Ph4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi))2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfMe2, ((MePhSi)(MePhSi))2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfMe2, (Me4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfMe2, (Et4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfMe2, (iPr4Si2)2(4- Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfMe2, (Ph4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi))2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfMe2, ((MePhSi)(MePhSi))2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfMe2, (Me4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfMe2, (Et4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfMe2, (iPr4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfMe2, (Ph4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi))2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfMe2, ((MePhSi)(MePhSi))2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfMe2, (Me4Si2)2(4-Ph3SiCH2Cp)2HfMe2, (Et4Si2)2(4-Ph3SiCH2Cp)2HfMe2, (iPr4Si2)2(4-Ph3SiCH2Cp)2HfMe2, (Ph4Si2)2(4-Ph3SiCH2Cp)2HfMe2, ((MeMeSi)(PhPhSi))2(1-Ph3SiCH2Cp)2HfMe2, and ((MePhSi)(MePhSi))2(1-Ph3SiCH2Cp)2HfMe2.
In at least one embodiment, the catalyst compound represented by Formula (I) or Formula (II) is selected from the following GROUP G: (Me4Si2)2(4-Me3SiCH2Cp)2HfBu2, (Et4Si2)2(4-Me3SiCH2Cp)2HfBu2, (iPr4Si2)2(4-Me3SiCH2Cp)2HfBu2, (Ph4Si2)2(4-Me3SiCH2Cp)2HfBu2, ((MeMeSi)(PhPhSi))2(4-Me3SiCH2Cp)2HfBu2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)2HfBu2, (Me4Si2)2(4-Et3SiCH2Cp)2HfBu2, (Et4Si2)2(4-Et3SiCH2Cp)2HfBu2, (iPr4Si2)2(4-Et3SiCH2Cp)2HfBu2, (Ph4Si2)2(4-Et3SiCH2Cp)2HfBu2, ((MeMeSi)(PhPhSi))2(4-Et3SiCH2Cp)2HfBu2, ((MePhSi)(MePhSi))2(4-Et3SiCH2Cp)2HfBu2, (Me4Si2)2(4-Cy3SiCH2Cp)2HfBu2, (Et4Si2)2(4-Cy3SiCH2Cp)2HfBu2, (iPr4Si2)2(4-Cy3SiCH2Cp)2HfBu2, (Ph4Si2)2(4-Cy3SiCH2Cp)2HfBu2, ((MeMeSi)(PhPhSi))2(4-Cy3SiCH2Cp)2HfBu2, ((MePhSi)(MePhSi))2(4-Cy3SiCH2Cp)2HfBu2, (Me4Si2)2(4-Me2PhSiCH2Cp)2HfBu2, (Et4Si2)2(4-Me2PhSiCH2Cp)2HfBu2, (iPr4Si2)2(4-Me2PhSiCH2Cp)2HfBu2, (Ph4Si2)2(4-Me2PhSiCH2Cp)2HfBu2, ((MeMeSi)(PhPhSi))2(4-Me2PhSiCH2Cp)2HfBu2, ((MePhSi)(MePhSi))2(4-Me2PhSiCH2Cp)2HfBu2, (Me4Si2)2(4-MePh2SiCH2Cp)2HfBu2, (Et4Si2)2(4-MePh2SiCH2Cp)\2HfBu2, (iPr4Si2)2(4-MePh2SiCH2Cp)2HfBu2, (Ph4Si2)2(4-MePh2SiCH2Cp)2HfBu2, ((MeMeSi)(PhPhSi))2(4-MePh2SiCH2Cp)2HfBu2, ((MePhSi)(MePhSi))2(4-MePh2SiCH2Cp)2HfBu2, (Me4Si2)2(4-Ph3SiCH2Cp)2HfBu2, (Et4Si2)2(4-Ph3SiCH2Cp)2HfBu2, (iPr4Si2)2(4-Ph3SiCH2Cp)2HfBu2, (Ph4Si2)2(4-Ph3SiCH2Cp)2HfBu2, ((MeMeSi)(PhPhSi))2(4-Ph3SiCH2Cp)2HfBu2, ((MePhSi)(MePhSi))2(4-Ph3SiCH2Cp)2HfBu2, (Me4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfBu2, (Et4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfBu2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfBu2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfBu2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfBu2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfBu2, (Me4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfBu2, (Et4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfBu2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfBu2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfBu2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfBu2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfBu2, (Me4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfBu2, (Et4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfBu2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfBu2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfBu2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfBu2, (Me4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfBu2, (Et4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfBu2, (iPr4Si2)2(3,4,5- Me3Cp)(4-Me2PhSiCH2Cp)HfBu2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfBu2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfBu2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfBu2, (Me4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfBu2, (Et4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfBu2, (iPr4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfBu2, (Ph4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfBu2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfBu2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfBu2, (Me4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfBu2, (Et4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfBu2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfBu2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfBu2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfBu2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfBu2, (Me4Si2)2(Cp)(4-Me3SiCH2Cp)HfBu2, (Et4Si2)2(Cp)(4-Me3SiCH2Cp)HfBu2, (iPr4Si2)2(Cp)(4-Me3SiCH2Cp)HfBu2, (Ph4Si2)2(Cp)(4-Me3SiCH2Cp)HfBu2, ((MeMeSi)(PhPhSi))2(Cp)(4-Me3SiCH2Cp)HfBu2, ((MePhSi)(MePhSi))2(Cp)(4-Me3SiCH2Cp)HfBu2, (Me4Si2)2(Cp)(4-Et3SiCH2Cp)HfBu2, (Et4Si2)2(Cp)(4-Et3SiCH2Cp)HfBu2, (iPr4Si2)2(Cp)(4-Et3SiCH2Cp)HfBu2, (Ph4Si2)2(Cp)(4-Et3SiCH2Cp)HfBu2, ((MeMeSi)(PhPhSi))2(Cp)(4-Et3SiCH2Cp)HfBu2, ((MePhSi)(MePhSi))2(Cp)(4-Et3SiCH2Cp)HfBu2, (Me4Si2)2(Cp)(4-Cy3SiCH2Cp)HfBu2, (Et4Si2)2(Cp)(4-Cy3SiCH2Cp)HfBu2, (iPr4Si2)2(Cp)(4-Cy3SiCH2Cp)HfBu2, (Ph4Si2)2(Cp)(4-Cy3SiCH2Cp)HfBu2, ((MeMeSi)(PhPhSi))2(Cp)(4-Cy3SiCH2Cp)HfBu2, ((MePhSi)(MePhSi))2(Cp)(4-Cy3SiCH2Cp)HfBu2, (Me4Si2)2(Cp)(4-Me2PhSiCH2Cp)HfBu2, (Et4Si2)2(CP)(4-Me2PhSiCH2Cp)HfBu2, (iPr4Si2)2(Cp)(4-Me2PhSiCH2Cp)HfBu2, (Ph4Si2)2(Cp)(4-Me2PhSiCH2Cp)HfBu2, ((MeMeSi)(PhPhSi))2(Cp)(4-Me2PhSiCH2Cp)HfBu2, ((MePhSi)(MePhSi))2(Cp)(4-Me2PhSiCH2Cp)HfBu2, ((MeMeSi)(PhPhSi))2(Cp)(4-MePh2SiCH2Cp)HfBu2, ((MePhSi)(MePhSi))2(Cp)(4-MePh2SiCH2Cp)HfBu2, (Me4Si2)2(Cp)(4-Ph3SiCH2Cp)HfBu2, (Et4Si2)2(Cp)(4-Ph3SiCH2Cp)HfBu2, (iPr4Si2)2(Cp)(4-Ph3SiCH2Cp)HfBu2, (Ph4Si2)2(Cp)(4-Ph3SiCH2Cp)HfBu2, ((MeMeSi)(PhPhSi))2(Cp)(4-Ph3SiCH2Cp)HfBu2, ((MePhSi)(MePhSi))2(Cp)(4-Ph3SiCH2Cp)HfBu2, (Me4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfBu2, (Et4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfBu2, (iPr4Si2)2(4- Me3SiCH2Cp)(4-Et3SiCH2Cp)HfBu2, (Ph4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfBu2, ((MeMeSi)(PhPhSi))2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfBu2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfBu2, (Me4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfBu2, (Et4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfBu2, (iPr4Si2)2(4-Et3SiCH2Cp)(4- Cy3SiCH2Cp)HfBu2, (Ph4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfBu2, ((MeMeSi)(PhPhSi))2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfBu2, ((MePhSi)(MePhSi))2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfBu2, (Me4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfBu2, (Et4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfBu2, (iPr4Si2)2(4-Cy3SiCH2Cp)(4- Me2PhSiCH2Cp)HfBu2, (Ph4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfBu2, ((MeMeSi)(PhPhSi))2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfBu2, ((MePhSi)(MePhSi))2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfBu2, (Me4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfBu2, (Et4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfBu2, (iPr4Si2)2(4- Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfBu2, (Ph4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfBu2, ((MeMeSi)(PhPhSi))2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfBu2, ((MePhSi)(MePhSi))2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfBu2, (Me4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfBu2, (Et4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfBu2, (iPr4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfBu2, (Ph4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfBu2, ((MeMeSi)(PhPhSi))2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfBu2, ((MePhSi)(MePhSi))2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfBu2, (Me4Si2)2(4-Ph3SiCH2Cp)2HfBu2, (Et4Si2)2(4-Ph3SiCH2Cp)2HfBu2, (iPr4Si2)2(4-Ph3SiCH2Cp)2HfBu2, (Ph4Si2)2(4-Ph3SiCH2Cp)2HfBu2, ((MeMeSi)(PhPhSi))2(1-Ph3SiCH2Cp)2HfBu2, ((MePhSi)(MePhSi))2(1-Ph3SiCH2Cp)2HfBu2.
In at least one embodiment, the catalyst compound represented by Formula (I) or Formula (II) is selected from the following GROUP H: (Me4Si2)2(4-Me3SiCH2Cp)2HfPh2, (Et4Si2)2(4-Me3SiCH2Cp)2HfPh2, (iPr4Si2)2(4-Me3SiCH2Cp)2HfPh2, (Ph4Si2)2(4-Me3SiCH2Cp)2HfPh2, ((MeMeSi)(PhPhSi))2(4-Me3SiCH2Cp)2HfPh2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)2HfPh2, (Me4Si2)2(4-Et3SiCH2Cp)2HfPh2, (Et4Si2)2(4-Et3SiCH2Cp)2HfPh2, (iPr4Si2)2(4-Et3SiCH2Cp)2HfPh2, (Ph4Si2)2(4-Et3SiCH2Cp)2HfPh2, ((MeMeSi)(PhPhSi))2(4-Et3SiCH2Cp)2HfPh2, ((MePhSi)(MePhSi))2(4-Et3SiCH2Cp)2HfPh2, (Me4Si2)2(4-Cy3SiCH2Cp)2HfPh2, (Et4Si2)2(4-Cy3SiCH2Cp)2HfPh2, (iPr4Si2)2(4-Cy3SiCH2Cp)2HfPh2, (Ph4Si2)2(4-Cy3SiCH2Cp)2HfPh2, ((MeMeSi)(PhPhSi))2(4-Cy3SiCH2Cp)2HfPh2, ((MePhSi)(MePhSi))2(4-Cy3SiCH2Cp)2HfPh2, (Me4Si2)2(4-Me2PhSiCH2Cp)2HfPh2, (Et4Si2)2(4-Me2PhSiCH2Cp)2HfPh2, (iPr4Si2)2(4-Me2PhSiCH2Cp)2HfPh2, (Ph4Si2)2(4-Me2PhSiCH2Cp)2HfPh2, ((MeMeSi)(PhPhSi))2(4-Me2PhSiCH2Cp)2HfPh2, ((MePhSi)(MePhSi))2(4-Me2PhSiCH2Cp)2HfPh2, (Me4Si2)2(4-MePh2SiCH2Cp)2HfPh2, (Et4Si2)2(4-MePh2SiCH2Cp)\2HfPh2, (iPr4Si2)2(4-MePh2SiCH2Cp)2HfPh2, (Ph4Si2)2(4-MePh2SiCH2Cp)2HfPh2, ((MeMeSi)(PhPhSi))2(4-MePh2SiCH2Cp)2HfPh2, ((MePhSi)(MePhSi))2(4-MePh2SiCH2Cp)2HfPh2, (Me4Si2)2(4-Ph3SiCH2Cp)2HfPh2, (Et4Si2)2(4-Ph3SiCH2Cp)2HfPh2, (iPr4Si2)2(4-Ph3SiCH2Cp)2HfPh2, (Ph4Si2)2(4-Ph3SiCH2Cp)2HfPh2, ((MeMeSi)(PhPhSi))2(4-Ph3SiCH2Cp)2HfPh2, ((MePhSi)(MePhSi))2(4-Ph3SiCH2Cp)2HfPh2, (Me4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfPh2, (Et4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfPh2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfPh2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfPh2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfPh2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfPh2, (Me4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfPh2, (Et4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfPh2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfPh2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfPh2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfPh2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfPh2, (Me4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfPh2, (Et4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfPh2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfPh2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfPh2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfPh2, (Me4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfPh2, (Et4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfPh2, (iPr4Si2)2(3,4,5- Me3Cp)(4-Me2PhSiCH2Cp)HfPh2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfPh2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfPh2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfPh2, (Me4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfPh2, (Et4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfPh2, (iPr4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfPh2, (Ph4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfPh2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfPh2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfPh2, (Me4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfPh2, (Et4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfPh2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfPh2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfPh2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfPh2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfPh2, (Me4Si2)2(Cp)(4-Me3SiCH2Cp)HfPh2, (Et4Si2)2(Cp)(4-Me3SiCH2Cp)HfPh2, (iPr4Si2)2(Cp)(4-Me3SiCH2Cp)HfPh2, (Ph4Si2)2(Cp)(4-Me3SiCH2Cp)HfPh2, ((MeMeSi)(PhPhSi))2(Cp)(4-Me3SiCH2Cp)HfPh2, ((MePhSi)(MePhSi))2(Cp)(4-Me3SiCH2Cp)HfPh2, (Me4Si2)2(Cp)(4-Et3SiCH2Cp)HfPh2, (Et4Si2)2(Cp)(4-Et3SiCH2Cp)HfPh2, (iPr4Si2)2(Cp)(4-Et3SiCH2Cp)HfPh2, (Ph4Si2)2(Cp)(4-Et3SiCH2Cp)HfPh2, ((MeMeSi)(PhPhSi))2(Cp)(4-Et3SiCH2Cp)HfPh2, ((MePhSi)(MePhSi))2(Cp)(4-Et3SiCH2Cp)HfPh2, (Me4Si2)2(Cp)(4-Cy3SiCH2Cp)HfPh2, (Et4Si2)2(Cp)(4-Cy3SiCH2Cp)HfPh2, (iPr4Si2)2(Cp)(4-Cy3SiCH2Cp)HfPh2, (Ph4Si2)2(Cp)(4-Cy3SiCH2Cp)HfPh2, ((MeMeSi)(PhPhSi))2(Cp)(4-Cy3SiCH2Cp)HfPh2, ((MePhSi)(MePhSi))2(Cp)(4-Cy3SiCH2Cp)HfPh2, (Me4Si2)2(Cp)(4-Me2PhSiCH2Cp)HfPh2, (Et4Si2)2(Cp)(4-Me2PhSiCH2Cp)HfPh2, (iPr4Si2)2(Cp)(4-Me2PhSiCH2Cp)HfPh2, (Ph4Si2)2(Cp)(4-Me2PhSiCH2Cp)HfPh2, ((MeMeSi)(PhPhSi))2(Cp)(4-Me2PhSiCH2Cp)HfPh2, ((MePhSi)(MePhSi))2(Cp)(4-Me2PhSiCH2Cp)HfPh2, ((MeMeSi)(PhPhSi))2(Cp)(4-MePh2SiCH2Cp)HfPh2, ((MePhSi)(MePhSi))2(Cp)(4-MePh2SiCH2Cp)HfPh2, (Me4Si2)2(Cp)(4-Ph3SiCH2Cp)HfPh2, (Et4Si2)2(Cp)(4-Ph3SiCH2Cp)HfPh2, (iPr4Si2)2(Cp)(4-Ph3SiCH2Cp)HfPh2, (Ph4Si2)2(Cp)(4-Ph3SiCH2Cp)HfPh2, ((MeMeSi)(PhPhSi))2(Cp)(4-Ph3SiCH2Cp)HfPh2, ((MePhSi)(MePhSi))2(Cp)(4-Ph3SiCH2Cp)HfPh2, (Me4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfPh2, (Et4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfPh2, (iPr4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfPh2, (Ph4Si2)2(4-Me3SiCH2Cp)(4- Et3SiCH2Cp)HfPh2, ((MeMeSi)(PhPhSi))2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfPh2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfPh2, (Me4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfPh2, (Et4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfPh2, (iPr4Si2)2(4- Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfPh2, (Ph4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfPh2, ((MeMeSi)(PhPhSi))2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfPh2, ((MePhSi)(MePhSi))2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfPh2, (Me4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfPh2, (Et4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfPh2, (iPr4Si2)2(4-Cy3SiCH2Cp)(4- Me2PhSiCH2Cp)HfPh2, (Ph4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfPh2, ((MeMeSi)(PhPhSi))2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfPh2, ((MePhSi)(MePhSi))2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfPh2, (Me4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfPh2, (Et4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfPh2, (iPr4Si2)2(4- Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfPh2, (Ph4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfPh2, ((MeMeSi)(PhPhSi))2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfPh2, ((MePhSi)(MePhSi))2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfPh2, (Me4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfPh2, (Et4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfPh2, (iPr4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfPh2, (Ph4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfPh2, ((MeMeSi)(PhPhSi))2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfPh2, ((MePhSi)(MePhSi))2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfPh2, (Me4Si2)2(4-Ph3SiCH2Cp)2HfPh2, (Et4Si2)2(4-Ph3SiCH2Cp)2HfPh2, (iPr4Si2)2(4-Ph3SiCH2Cp)2HfPh2, (Ph4Si2)2(4-Ph3SiCH2Cp)2HfPh2, ((MeMeSi)(PhPhSi))2(1-Ph3 SiCH2Cp)2HfPh2, ((MePhSi)(MePhSi))2(1-Ph3SiCH2Cp)2HfPh2.
In at least one embodiment, the catalyst compound represented by Formula (I) or Formula (II) is selected from the following GROUP I: (Me4Si2)2(4-Me3SiCH2Cp)2HfBn2, (Et4Si2)2(4-Me3SiCH2Cp)2HfBn2, (iPr4Si2)2(4-Me3SiCH2Cp)2HfBn2, (Ph4Si2)2(4-Me3SiCH2Cp)2HfBn2, ((MeMeSi)(PhPhSi))2(4-Me3SiCH2Cp)2HfBn2, (Me4Si2)2(4-Et3SiCH2Cp)2HfBn2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)2HfBn2, (Et4Si2)2(4-Et3SiCH2Cp)2HfBn2, (iPr4Si2)2(4-Et3SiCH2Cp)2HfBn2, (Ph4Si2)2(4-Et3SiCH2Cp)2HfBn2, ((MeMeSi)(PhPhSi))2(4-Et3SiCH2Cp)2HfBn2, ((MePhSi)(MePhSi))2(4-Et3SiCH2Cp)2HfBn2, (Me4Si2)2(4-Cy3SiCH2Cp)2HfBn2, (Et4Si2)2(4-Cy3SiCH2Cp)2HfBn2, (iPr4Si2)2(4-Cy3SiCH2Cp)2HfBn2, (Ph4Si2)2(4-Cy3SiCH2Cp)2HfBn2, ((MeMeSi)(PhPhSi))2(4-Cy3SiCH2Cp)2HfBn2, ((MePhSi)(MePhSi))2(4-Cy3SiCH2Cp)2HfBn2, (Me4Si2)2(4-Me2PhSiCH2Cp)2HfBn2, (Et4Si2)2(4-Me2PhSiCH2Cp)2HfBn2, (iPr4Si2)2(4-Me2PhSiCH2Cp)2HfBn2, (Ph4Si2)2(4-Me2PhSiCH2Cp)2HfBn2, ((MeMeSi)(PhPhSi))2(4-Me2PhSiCH2Cp)2HfBn2, ((MePhSi)(MePhSi))2(4-Me2PhSiCH2Cp)2HfBn2, (Me4Si2)2(4-MePh2SiCH2Cp)2HfBn2, (Et4Si2)2(4-MePh2SiCH2Cp)\2HfBn2, (iPr4Si2)2(4-MePh2SiCH2Cp)2HfBn2, (Ph4Si2)2(4-MePh2SiCH2Cp)2HfBn2, ((MeMeSi)(PhPhSi))2(4-MePh2SiCH2Cp)2HfBn2, ((MePhSi)(MePhSi))2(4-MePh2SiCH2Cp)2HfBn2, (Me4Si2)2(4-Ph3SiCH2Cp)2HfBn2, (Et4Si2)2(4-Ph3SiCH2Cp)2HfBn2, (iPr4Si2)2(4-Ph3SiCH2Cp)2HfBn2, (Ph4Si2)2(4-Ph3SiCH2Cp)2HfBn2, ((MeMeSi)(PhPhSi))2(4-Ph3SiCH2Cp)2HfBn2, ((MePhSi)(MePhSi))2(4-Ph3SiCH2Cp)2HfBn2, (Me4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfBn2, (Et4Si2)2(3,4,5-Me3Cp) (4-Me3SiCH2Cp)HfBn2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfBn2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfBn2, ((MeMeSi)(PhPhSi)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfBn2, ((MePhSi)(MePhSi)2(3,4,5-Me3Cp)(4-Me3SiCH2Cp)HfBn2, (Me4Si2)2(3,4,5-Me3 Cp)(4-Et3SiCH2Cp)HfBn2, (Et4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfBn2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfBn2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfBn2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3 Cp) (4-Et3SiCH2Cp)HfBn2, ((MePhSi)(MePhSi)2(3,4,5-Me3Cp)(4-Et3SiCH2Cp)HfBn2, (Me4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfBn2, (Et4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfBn2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfBn2, (Ph4Si2)2(3,4,5-Me3Cp) (4-Cy3SiCH2Cp)HfMe2, ((MeMeSi)(PhPhSi)2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfBn2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Cy3SiCH2Cp)HfBn2, (Me4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfBn2, (Et4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfBn2, (iPr4Si2)2(3,4,5- Me3Cp)(4-Me2PhSiCH2Cp)HfBn2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfBn2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfBn2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Me2PhSiCH2Cp)HfBn2, (Me4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfBn2, (Et4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfBn2, (iPr4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfBn2, (Ph4Si2)2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfBn2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfBn2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-MePh2SiCH2Cp)HfBn2, (Me4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfBn2, (Et4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfBn2, (iPr4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfBn2, (Ph4Si2)2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfBn2, ((MeMeSi)(PhPhSi))2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfBn2, ((MePhSi)(MePhSi))2(3,4,5-Me3Cp)(4-Ph3SiCH2Cp)HfBn2, (Me4Si2)2(Cp)(4-Me3SiCH2Cp)HfBn2, (Et4Si2)2(Cp)(4-Me3SiCH2Cp)HfBn2, (iPr4Si2)2(Cp)(4-Me3SiCH2Cp)HfBn2, (Ph4Si2)2(Cp)(4-Me3SiCH2Cp)HfBn2, ((MeMeSi)(PhPhSi))2(Cp)(4-Me3SiCH2Cp)HfBn2, ((MePhSi)(MePhSi))2(Cp)(4-Me3SiCH2Cp)HfBn2, (Me4Si2)2(Cp)(4-Et3SiCH2Cp)HfBn2, (Et4Si2)2(Cp)(4-Et3SiCH2Cp)HfBn2, (iPr4Si2)2(Cp)(4-Et3SiCH2Cp)HfBn2, (Ph4Si2)2(Cp)(4-Et3SiCH2Cp)HfBn2, ((MeMeSi)(PhPhSi))2(Cp)(4-Et3SiCH2Cp)HfBn2, ((MePhSi)(MePhSi))2(Cp)(4-Et3SiCH2Cp)HfBn2, (Me4Si2)2(Cp)(4-Cy3SiCH2Cp)HfBn2, (Et4Si2)2(Cp)(4-Cy3SiCH2Cp)HfBn2, (iPr4Si2)2(Cp)(4-Cy3SiCH2Cp)HfBn2, (Ph4Si2)2(Cp)(4-Cy3SiCH2Cp)HfBn2, ((MeMeSi)(PhPhSi))2(Cp)(4-Cy3SiCH2Cp)HfBn2, ((MePhSi)(MePhSi))2(Cp)(4-Cy3SiCH2Cp)HfBn2, (Me4Si2)2(Cp)(4-Me2PhSiCH2Cp)HfBn2, (Et4Si2)2(Cp) (4-Me2PhSiCH2Cp)HfBn2, (iPr4Si2)2(Cp)(4-Me2PhSiCH2Cp)HfBn2, (Ph4Si2)2(Cp)(4-Me2PhSiCH2Cp)HfBn2, ((MeMeSi)(PhPhSi))2(Cp)(4-Me2PhSiCH2Cp)HfBn2, ((MePhSi)(MePhSi))2(Cp)(4-Me2PhSiCH2Cp)HfBn2, ((MeMeSi)(PhPhSi))2(Cp)(4-MePh2SiCH2Cp)HfBn2, ((MePhSi)(MePhSi))2(Cp)(4-MePh2SiCH2Cp)HfBn2, (Me4Si2)2(Cp)(4-Ph3SiCH2Cp)HfBn2, (Et4Si2)2(Cp)(4-Ph3SiCH2Cp)HfBn2, (iPr4Si2)2(Cp)(4-Ph3SiCH2Cp)HfBn2, (Ph4Si2)2(Cp)(4-Ph3SiCH2Cp)HfBn2, ((MeMeSi)(PhPhSi))2(Cp)(4-Ph3SiCH2Cp)HfBn2, ((MePhSi)(MePhSi))2(Cp)(4-Ph3SiCH2Cp)HfBn2, (Me4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfBn2, (Et4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfBn2, (iPr4Si2)2(4- Me3SiCH2Cp)(4-Et3SiCH2Cp)HfBn2, (Ph4Si2)2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfBn2, ((MeMeSi)(PhPhSi))2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfBn2, ((MePhSi)(MePhSi))2(4-Me3SiCH2Cp)(4-Et3SiCH2Cp)HfBn2, (Me4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfBn2, (Et4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfBn2, (iPr4Si2)2(4-Et3SiCH2Cp)(4- Cy3SiCH2Cp)HfBn2, (Ph4Si2)2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfBn2, ((MeMeSi)(PhPhSi))2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfBn2, ((MePhSi)(MePhSi))2(4-Et3SiCH2Cp)(4-Cy3SiCH2Cp)HfBn2, (Me4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfBn2, (Et4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfBn2, (iPr4Si2)2(4-Cy3SiCH2Cp)(4- Me2PhSiCH2Cp)HfBn2, (Ph4Si2)2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfBn2, ((MeMeSi)(PhPhSi))2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfBn2, ((MePhSi)(MePhSi))2(4-Cy3SiCH2Cp)(4-Me2PhSiCH2Cp)HfBn2, (Me4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfBn2, (Et4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfBn2, (iPr4Si2)2(4- Me2PhSiCH2Cp)(4MePh2SiCH2Cp)HfBn2, (Ph4Si2)2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfBn2, ((MeMeSi)(PhPhSi))2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfBn2, ((MePhSi)(MePhSi))2(4-Me2PhSiCH2Cp)(4-MePh2SiCH2Cp)HfBn2, (Me4Si2)2(4-MePh2SiCH2Cp) (4-Ph3SiCH2Cp)HfBn2, (Et4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfBn2, (iPr4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfBn2, (Ph4Si2)2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfBn2, ((MeMeSi)(PhPhSi))2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfBn2, ((MePhSi)(MePhSi))2(4-MePh2SiCH2Cp)(4-Ph3SiCH2Cp)HfBn2, (Me4Si2)2(4-Ph3SiCH2Cp)2HfBn2, (Et4Si2)2(4-Ph3SiCH2Cp)2HfBn2, (iPr4Si2)2(4-Ph3SiCH2Cp)2HfBn2, (Ph4Si2)2(4-Ph3SiCH2Cp)2HfBn2, ((MeMeSi)(PhPhSi))2(1-Ph3SiCH2Cp)2HfBn2, ((MePhSi) (MePhSi))2(1-Ph3SiCH2Cp)2HfBn2.
In at least one embodiment, the rac/meso ratio of the metallocene catalyst is from 99.9:0.1 to 0.11:99.9 such as 80:1 or greater, such as 70:1 or greater, such as 60:1 or greater, such as 50:1 or greater, such as 40:1 or greater, such as 30:1 or greater, such as 20:1 or greater, such as 15:1 or greater, such as 10:1 or greater, such as 7:1 or greater, such as 5:1 or greater.
In one aspect, an advantage is provided in that the separation of meso from rac isomers is not performed after synthesis of the catalysts of the present disclosure. In certain aspects, the meso isomer is formed in a ratio of 99.9:0.1 or greater than the rac isomer. Amounts of rac and meso isomers are determined by 1H NMR spectroscopy, and further atom connectivity can be established by single crystal X-ray crystallography.
In at least one embodiment, one catalyst compound is used, e.g., the catalyst compounds are not different. For purposes of the present disclosure, one metallocene catalyst compound is considered different from another if they differ by at least one atom. For example, “biscyclopentadienyl hafnium dichloride” is different from “(cyclopentadienyl)(2-methylcyclopentadienyl) hafnium dichloride” which is different from “(cyclopentadienyl)(2-methylcyclopentadienyl) zirconium dichloride.”
In at least one embodiment, two or more different catalyst compounds are present in a catalyst system. In at least one embodiment, two or more different catalyst compounds are present in the reaction zone where the process(es) described herein occur. When two transition metal compound based catalysts are used in one reactor as a mixed catalyst system, the two transition metal compounds can be chosen such that the two are compatible. A simple screening method, such as by 1H or 13C NMR, can be used to determine which transition metal compounds are compatible. The same activator can be used for the transition metal compounds, however, two different activators, such as a non-coordinating anion activator and an alumoxane, can be used in combination. If one or more transition metal compounds contain an X1 or X2 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.
In at least one embodiment, one or more different catalyst compounds are present in a catalyst system. One or more different catalyst compounds can be present in the reaction zone where the process(es) described herein occur. The same activator can be used for the transition metal compounds, however, two different activators, such as a non-coordinating anion activator and an alumoxane, can be used in combination.
The two transition metal compounds (pre-catalysts) may be used in any ratio. Molar ratios of (A) transition metal compound to (B) transition metal compound can be (A:B) of from 1:1000 to 1000:1, alternatively 1:100 to 500:1, alternatively 1:10 to 200:1, alternatively 1:1 to 100:1, alternatively 1:1 to 75:1, and alternatively 5:1 to 50:1. The suitable ratio chosen will depend on the exact pre-catalysts chosen, the method of activation, and the end product desired. In at least one embodiment, when using the two pre-catalysts, where both are activated with the same activator, mole percentages, based upon the molecular weight of the pre-catalysts, can be from 10% to 99.9% A to 0.1% to 90% B, alternatively 25% to 99% A to 0.5% to 75% B, alternatively 50% to 99% A to 1% to 50% B, and alternatively 75% to 99% A to 1% to 10% B.
Methods to Prepare the Catalyst Compounds.
The following is a description illustrating one way to prepare the catalysts described herein and further exemplified in the examples. Metallocenes of the present disclosure can be synthesized as shown below where a deprotonation via a metal salt of alkyl anion (e.g., nBuLi) can be performed to form a cyclopentadienide. The preparation of the catalyst of the present disclosure can include a reaction of the cyclopentadienide with an appropriate bridging precursor (e.g., ClMe2SiSiMe2Cl). A double deprotonation via an alkyl anion (e.g., nBuLi) can be performed to form a dianion. The lithiation may be regioselective. The preparation of the catalyst of the present disclosure can include a reaction of the dianion with a metal halide (e.g., ZrCl4, or HfCl4). An alkylation reaction of the group 4 metal (e.g., Zr, or Hf) can be performed with an organolithium reagent (e.g., MeLi) or a Grignard reagent (e.g., MeMgBr).
Activators
The terms “cocatalyst” and “activator” are used herein interchangeably.
The catalyst systems described herein may comprise a catalyst complex as described above and an activator such as alumoxane or a non-coordinating anion and may be formed by combining the catalyst components described herein with activators in any suitable manner, including combining them with supports, such as silica. The catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in the monomer). Catalyst systems of the present disclosure may have one or more activators and one, two or more catalyst components. Activators are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral metal compound to a catalytically active metal compound cation. Non-limiting activators, for example, may include alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and conventional-type cocatalysts. Suitable activators may include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract a reactive, σ-bound, metal ligand making the metal compound cationic and providing a charge-balancing non-coordinating or weakly coordinating anion, e.g., a non-coordinating anion.
In at least one embodiment, the catalyst system includes an activator and the catalyst compound of Formula (I) or Formula (II).
Alumoxane Activators
Alumoxane activators are utilized as activators in the catalyst systems described herein. Alumoxanes are generally oligomeric compounds containing —Al(Ra′″)—O— sub-units, where Ra″′ is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, such as when the abstractable ligand is an alkyl, halide, alkoxide or amide. Mixtures of different alumoxanes and modified alumoxanes may also be used. It may be suitable to use a visually clear methylalumoxane. A cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution. A useful alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, covered under patent number U.S. Pat. No. 5,041,584, which is incorporated by reference herein). Another useful alumoxane is solid polymethylaluminoxane as described in U.S. Pat. Nos. 9,340,630, 8,404,880, and 8,975,209, which are incorporated by reference herein.
When the activator is an alumoxane (modified or unmodified), at least one embodiment select the maximum amount of activator at up to a 5,000-fold molar excess Al/M over the catalyst compound (per metal catalytic site). The minimum activator-to-catalyst-compound can be a 1:1 molar ratio. Alternate ranges may include from 1:1 to 500:1, alternately from 1:1 to 200:1, alternately from 1:1 to 100:1, or alternately from 1:1 to 50:1.
In an alternate embodiment, little or no alumoxane is used in the polymerization processes described herein. For example, alumoxane can be present at zero mol %, alternately the alumoxane can be present at a molar ratio of aluminum to catalyst compound transition metal less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.
Ionizing/Non-Coordinating Anion Activators
The term “non-coordinating anion” (NCA) means an anion which either does not coordinate to a cation or which is only weakly coordinated to a cation thereby remaining sufficiently labile to be displaced by a Lewis base. “Compatible” non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral transition metal compound and a neutral by-product from the anion. Non-coordinating anions useful in accordance with the present disclosure are those that are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge at +1, and yet retain sufficient lability to permit displacement during polymerization. Suitable ionizing activators may include an NCA, such as a compatible NCA.
It is within the scope of the present disclosure to use an ionizing activator, neutral or ionic. It is also within the scope of the present disclosure to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators. For descriptions of suitable activators please see U.S. Pat. Nos. 8,658,556 and 6,211,105.
The catalyst systems of the present disclosure can include at least one non-coordinating anion (NCA) activator. In at least one embodiment, boron containing NCA activators represented by the formula below can be used:
Zd+ (Ad−)
where: Z is (L-H) or a reducible Lewis acid; L is a Lewis base; H is hydrogen; (L-H) is a Bronsted acid; Ad− is a boron containing non-coordinating anion having the charge d−; d is 1, 2, or 3.
The cation component, Zd+ may include Bronsted acids such as protons or protonated Lewis bases or reducible Lewis acids capable of protonating or abstracting a moiety, such as an alkyl or aryl, from the bulky ligand transition metal catalyst precursor, resulting in a cationic transition metal species.
The activating cation Zd+ may also be a moiety such as silver, tropylium, carbeniums, ferroceniums and mixtures, such as carbeniums and ferroceniums. Zd+ can be triphenyl carbenium. Reducible Lewis acids can be a triaryl carbenium (where the aryl can be substituted or unsubstituted, such as those represented by the formula: (Ar3C+), where Ar is aryl or aryl substituted with a heteroatom, a C1 to C40 hydrocarbyl, or a substituted C1 to C40 hydrocarbyl), such as the reducible Lewis acids “Z” may include those represented by the formula: (Ph3C), where Ph is a substituted or unsubstituted phenyl, such as substituted with C1 to C40 hydrocarbyls or substituted a C1 to C40 hydrocarbyls, such as C1 to C20 alkyls or aromatics or substituted C1 to C20 alkyls or aromatics, such as Z is a triphenylcarbenium.
When Zd+ is the activating cation (L-H)d+, it can be a Bronsted acid, capable of donating a proton to the transition metal catalytic precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof, such as ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, dioctadecylmethylamine, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such as dimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniums from thioethers, such as diethyl thioethers, tetrahydrothiophene, and mixtures thereof.
The anion component Ad− includes those having the formula [Mk+Qn]d− where k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (such as 1, 2, 3, or 4); n−k=d; M is an element selected from Group 13 of the Periodic Table of the Elements, such as boron or aluminum, and Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Q having up to 20 carbon atoms with the proviso that in not more than 1 occurrence is Q a halide. Each Q can be a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, such as each Q is a fluorinated aryl group, and such as each Q is a pentafluoryl aryl group. Examples of suitable Ad− also include diboron compounds as disclosed in U.S. Pat. No. 5,447,895, which is fully incorporated herein by reference.
Illustrative, but not limiting, examples of boron compounds which may be used as an activating cocatalyst are the compounds described as activators in U.S. Pat. No. 8,658,556, which is incorporated by reference herein.
The ionic stoichiometric activator Zd+ (Ad−) can be one or more of N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, dioctadecylmethylammonium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbenium tetra(perfluorophenyl)borate.
Bulky activators are also useful herein as NCAs. “Bulky activator” as used herein refers to anionic activators represented by the formula:
where:
each RA is independently a halide, such as a fluoride;
Ar is substituted or unsubstituted aryl group (such as a substituted or unsubstituted phenyl), such as substituted with C1 to C40 hydrocarbyls, such as C1 to C20 alkyls or aromatics;
each RB is independently a halide, a C6 to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula —O—Si—RD, where RD is a C1 to C20 hydrocarbyl or hydrocarbylsilyl group (such as RB is a fluoride or a perfluorinated phenyl group);
each RC is a halide, C6 to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula —O—Si—RD, where RD is a C1 to C20 hydrocarbyl or hydrocarbylsilyl group (such as RD is a fluoride or a C6 perfluorinated aromatic hydrocarbyl group); where RB and RC can form one or more saturated or unsaturated, substituted or unsubstituted rings (such as RB and RC form a perfluorinated phenyl ring);
L is a Lewis base; (L-H)+ is a Bronsted acid; d is 1, 2, or 3;
where the anion has a molecular weight of greater than 1,020 g/mol; and
where at least three of the substituents on the B atom each have a molecular volume of greater than 250 cubic Å, alternately greater than 300 cubic Å, or alternately greater than 500 cubic Å.
For example, (Ar3C)d+ can be (Ph3C)d+, where Ph is a substituted or unsubstituted phenyl, such as substituted with C1 to C40 hydrocarbyls or substituted C1 to C40 hydrocarbyls, such as C1 to C20 alkyls or aromatics or substituted C1 to C20 alkyls or aromatics.
“Molecular volume” is used herein as an approximation of spatial steric bulk of an activator molecule in solution. Comparison of substituents with differing molecular volumes allows the substituent with the smaller molecular volume to be considered “less bulky” in comparison to the substituent with the larger molecular volume. Conversely, a substituent with a larger molecular volume may be considered “more bulky” than a substituent with a smaller molecular volume.
Molecular volume may be calculated as reported in Girolami, Gregory S. (1994) “A Simple “Back of the Envelope” Method for Estimating the Densities and Molecular Volumes of Liquids and Solids,” Journal of Chemical Education, v. 71(11), November 1994, pp. 962-964, which is incorporated by reference herein. Molecular volume (MV), in units of cubic Å, is calculated using the formula: MV=8.3VS, where VS is the scaled volume. VS is the sum of the relative volumes of the constituent atoms, and is calculated from the molecular formula of the substituent using the following table of relative volumes. For fused rings, the VS is decreased by 7.5% per fused ring.
For a list of suitable bulky activators please see U.S. Pat. No. 8,658,556, which is incorporated by reference herein.
In another embodiment, one or more of the NCA activators is chosen from the activators described in U.S. Pat. No. 6,211,105.
In a at least one embodiment, the activator is selected from one or more of a triaryl carbenium (such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis (3,5-bis(trifluoromethyl)phenyl)borate).
In another embodiment, the activator is selected from one or more of trialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(perfluoronaphthyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-dialkylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate, N,N-dialkylanilinium tetrakis(perfluoronaphthyl)borate, trialkylammonium tetrakis(perfluorobiphenyl)borate, N,N-dialkylanilinium tetrakis(perfluorobiphenyl)borate, trialkylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkyl-(2,4,6-trimethylanilinium) tetrakis (3,5-bis(trifluoromethyl)phenyl)borate, di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, (where alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl, or t-butyl).
Suitable activator-to-catalyst ratio, e.g., all NCA activators-to-catalyst ratio may be about a 1:1 molar ratio. Alternate ranges include from 0.1:1 to 100:1, alternately from 0.5:1 to 200:1, alternately from 1:1 to 500:1, alternately from 1:1 to 1000:1. Suitable ranges can be from 0.5:1 to 10:1, such as 1:1 to 5:1.
It is also within the scope of the present disclosure that the catalyst compounds can be combined with combinations of alumoxanes and NCA's (see for example, U.S. Pat. Nos. 5,153,157; 5,453,410; EP 0 573 120 B1; WO 1994/007928; and WO 1995/014044 which discuss the use of an alumoxane in combination with an ionizing activator).
Useful chain transfer agents can be hydrogen, alkylalumoxanes, a compound represented by the formula AlR3, ZnR2 (where each R is, independently, a C1-C8 aliphatic radical, such as methyl, ethyl, propyl, butyl, pentyl, hexyl octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof.
Furthermore, a catalyst system of the present disclosure may include a metal hydrocarbenyl chain transfer agent represented by the formula:
Al(R′)3-v(R″)v
where each R′ can be independently a C1-C30 hydrocarbyl group, and or each R″, can be independently a C4-C20 hydrocarbenyl group having an end-vinyl group; and v can be from 0.1 to 3.
Optional Scavengers or Coactivators
In addition to these activator compounds, scavengers or coactivators may be used. Aluminum alkyl or alumoxane compounds which may be utilized as scavengers or coactivators may include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, methylalumoxane (MAO), modified methylalumoxane (MMAO), MMAO-3A, and diethyl zinc.
Optional Support Materials
In embodiments herein, the catalyst system may include an inert support material. The supported material can be a porous support material, for example, talc, and inorganic oxides. Other support materials include zeolites, clays, organoclays, or another organic or inorganic support material, or mixtures thereof.
The support material can be an inorganic oxide in a finely divided form. Suitable inorganic oxide materials for use in catalyst systems herein may include groups 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides that may be employed either alone or in combination with the silica, or alumina can be magnesia, titania, zirconia. Other suitable support materials, however, can be employed, for example, finely divided functionalized polyolefins, such as finely divided polyethylene. Examples of suitable supports may include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays. Also, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica-titania. In at least one embodiment, the support material is selected from Al2O3, ZrO2, SiO2, SiO2/Al2O3, SiO2/TiO2, silica clay, silicon oxide/clay, or mixtures thereof.
The support material, such as an inorganic oxide, can have a surface area of from about 10 m2/g to about 700 m2/g, pore volume of from about 0.1 cm3/g to about 4.0 cm3/g and average particle size of from about 5 μm to about 500 μm. The surface area of the support material can be of from about 50 m2/g to about 500 m2/g, pore volume of from about 0.5 cm3/g to about 3.5 cm3/g and average particle size of from about 10 μm to about 200 μm. For example, the surface area of the support material can be from about 100 m2/g to about 400 m2/g, pore volume from about 0.8 cm3/g to about 3.0 cm3/g and average particle size can be from about 5μm to about 100 μm. The average pore size of the support material useful in the present disclosure can be of from 10 Å to 1000 Å, such as 50 Å to about 500 Å, and such as 75 Å to about 350 Å. In at least one embodiment, the support material is a high surface area, amorphous silica (surface area=300 m2/gm; pore volume of 1.65 cm3/gm). For example, suitable silicas can be the silicas 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. Alternatively, a silica can be ES-70™ silica (PQ Corporation, Malvern, Pa.) that has been calcined, for example (such as at 875° C.).
The support material should be dry, that is, free of absorbed water. Drying of the support material can be effected by heating or calcining at about 100° C. to about 1,000° C., such as at least about 600° C. When the support material is silica, it is heated to at least 200° C., such as about 200° C. to about 850° C., and such as at about 600° C.; and for a time of about 1 minute to about 100 hours, from about 12 hours to about 72 hours, or from about 24 hours to about 60 hours. The calcined support material must have at least some reactive hydroxyl (OH) groups to produce supported catalyst systems of the present disclosure. The calcined support material is then contacted with at least one polymerization catalyst including at least one catalyst compound and an activator.
The support material, having reactive surface groups, such as hydroxyl groups, is slurried in a non-polar solvent and the resulting slurry is contacted with a solution of a catalyst compound and an activator. In at least one embodiment, the slurry of the support material is first contacted with the activator for a period of time 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 catalyst compound is then contacted with the isolated support/activator. In at least one embodiment, the supported catalyst system is generated in situ. In alternate embodiment, the slurry of the support material is first contacted with the catalyst compound for a period of time 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 catalyst compound is then contacted with the activator solution.
The mixture of the catalyst, activator and support is heated from about 0° C. to about 70° C., such as from about 23° C. to about 60° C., such as at room temperature. Contact times can be from about 0.5 hours to about 24 hours, such as from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.
Suitable non-polar solvents are materials in which all of the reactants used herein, e.g., the activator and the catalyst compound, are at least partially soluble and which are liquid at reaction temperatures. Non-polar solvents can be alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, although a variety of other materials including cycloalkanes, such as cyclohexane, aromatics, such as benzene, toluene, and ethylbenzene, may also be employed.
Polymerization Processes
The present disclosure relates to polymerization processes where monomer (e.g., ethylene; propylene), and optionally comonomer, are contacted with a catalyst system including an activator and at least one catalyst compound, as described above. The catalyst compound and activator may be combined in any order. The catalyst compound and activator may be combined prior to contacting with the monomer. Alternatively the catalyst compound and activator may be introduced into the polymerization reactor separately, wherein they subsequently react to form the active catalyst.
Monomers may 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. In at least one embodiment, the monomer includes ethylene and an optional comonomer including one or more C3 to C40 olefins, such as C4 to C20 olefins, such as C6 to C12 olefins. The C3 to C40 olefin monomers may be linear, branched, or cyclic. The C3 to C40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and or one or more functional groups. In another embodiment, the monomer includes propylene and an optional comonomer including one or more ethylene or C4 to C40 olefins, such as C4 to C20 olefins, such as C6 to C12 olefins. The C4 to C40 olefin monomers may be linear, branched, or cyclic. The C4 to C40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and or one or more functional groups.
Exemplary C2 to C40 olefin monomers and optional comonomers may include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, ethylidenenorbornene, vinylnorbornene, 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, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and their respective homologs and derivatives, such as norbornene, norbornadiene, and dicyclopentadiene.
Polymerization processes of the present disclosure can be carried out in any suitable manner Any suitable suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization process can be used. Such processes can be run in a batch, semi-batch, or continuous mode. Homogeneous polymerization processes and slurry processes can be used. A bulk homogeneous process can be used. Alternately, no solvent or diluent is present or added in the reaction medium, (except for the small amounts used as the carrier for the catalyst system or other additives, or amounts found with the monomer; e.g., propane in propylene). In another embodiment, the process is a slurry process. As used herein, the term “slurry polymerization process” means a polymerization process where a supported catalyst is employed and monomers are polymerized on the supported catalyst particles. At least 95 wt % of polymer products derived from the supported catalyst are in granular form as solid particles (not dissolved in the diluent).
Suitable diluents/solvents for polymerization may include non-coordinating, inert liquids. Examples of diluents/solvents for polymerization may include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (Isopar™); perhalogenated hydrocarbons, such as perfluorinated C4 to C10 alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene. Suitable solvents may also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In at least one embodiment, 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. In another embodiment, the solvent is not aromatic, such as aromatics are present in the solvent at less than 1 wt %, such as less than 0.5 wt %, such as less than 0 wt % based upon the weight of the solvents.
In at least one embodiment, 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. In at least one embodiment, the polymerization is run in a bulk process.
Polymerizations can be run at any temperature and or pressure suitable to obtain the desired polymers. Suitable temperatures and or pressures include a temperature of from about 0° C. to about 300° C., such as about 20° C. to about 200° C., such as about 35° C. to about 160° C., such as from about 80° C. to about 160° C., such as from about 90° C. to about 140° C. Polymerizations can be run at a pressure of from about 0.1 MPa to about 25 MPa, such as from about 0.45 MPa to about 6 MPa, or from about 0.5 MPa to about 4 MPa.
In a suitable polymerization, the run time of the reaction can be up to 300 minutes, such as from about 5 minutes to 250 minutes, such as from about 10 minutes to 120 minutes, such as from about 20 minutes to 90 minutes, such as from about 30 minutes to 60 minutes. In a continuous process the run time may be the average residence time of the reactor. In at least one embodiment, the run time of the reaction is from about 5 minutes to about 25 minutes. In a continuous process, the run time may be the average residence time of the reactor.
In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of 0.001 psig to 50 psig (0.007 kPa to 345 kPa), such as from 0.01 psig to 25 psig (0.07 kPa to 172 kPa), such as from 0.1 psig to 10 psig (0.7 kPa to 70 kPa).
In at least one embodiment, little or no alumoxane is used in the process to produce the polymers. For example, alumoxane can be present at zero mol %, alternately the alumoxane can be present at a molar ratio of aluminum to transition metal less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.
In at least one embodiment, the polymerization: 1) is conducted at temperatures of 0° C. to 300° C. (such as 25° C. to 250° C., such as 80° C. to 160° C., such as 100° C. to 140° C.); 2) is conducted at a pressure of atmospheric pressure to 10 MPa (such as 0.35 MPa to 10 MPa, such as from 0.45 MPa to 6 MPa, such as from 0.5 MPa to 4 MPa); 3) is conducted in an aliphatic hydrocarbon solvent (such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; such as where aromatics are present in the solvent at less than 1 wt %, such as less than 0.5 wt %, such as at 0 wt % based upon the weight of the solvents); 4) wherein the catalyst system used in the polymerization comprises less than 0.5 mol %, such as 0 mol % alumoxane, alternately the alumoxane is present at a molar ratio of aluminum to transition metal less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1; 5) the polymerization occurs in one reaction zone; 6) optionally scavengers (such as trialkyl aluminum compounds) are absent (e.g., present at zero mol %, alternately the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, such as less than 50:1, such as less than 15:1, such as less than 10:1); and 7) optionally hydrogen is present in the polymerization reactor at a partial pressure of 0.001 psig to 50 psig (0.007 kPa to 345 kPa) (such as from 0.01 psig to 25 psig (0.07 kPa to 172 kPa), such as 0.1 psig to 10 psig (0.7 kPa to 70 kPa)). In at least one embodiment, the catalyst system used in the polymerization includes no more than one catalyst compound. A “reaction zone” also referred to as a “polymerization zone” is a vessel where polymerization takes place, for example a stirred-tank reactor or a loop reactor. When multiple reactors are used in a continuous polymerization process, each reactor is considered as a separate polymerization zone. For a multi-stage polymerization in a batch polymerization process, each polymerization stage is considered as a separate polymerization zone. In at least one embodiment, the polymerization occurs in one reaction zone. Room temperature is 23° C. unless otherwise noted.
In at least one embodiment, the present disclosure provides a process for the production of an ethylene based polymer including: polymerizing ethylene by contacting the ethylene with the catalyst system of the present disclosure described above in one or more continuous stirred tank reactors or loop reactors, in series or in parallel, at a reactor pressure of from 0.05 MPa to 1,500 MPa and a reactor temperature of from 30° C. to 230° C. to form an ethylene based polymer. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of from about 5 psig to about 300 psig, such as from about 10 psig to about 250 psig, such as from about 30 psig to about 200 psig, such as from about 20 psig to about 150 psig, such as from about 50 psig to about 100 psig (e.g., 75 psig).
In another embodiment, the present disclosure provides a process for the production of propylene based polymer including: polymerizing propylene by contacting the propylene with the catalyst system of the present disclosure described above in one or more continuous stirred tank reactors or loop reactors, in series or in parallel, at a reactor pressure of from 0.5 MPa to 1,500 MPa and a reactor temperature of from 30° C. to 230° C. to form a propylene based polymer. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure from about 10 psig to about 300 psig, such as from about 20 psig to about 250 psig, such as from about 30 psig to about 200 psig, such as from about 40 psig to about 150 psig, such as from about 50 psig to about 100 psig (e.g., 75 psig).
In another embodiment, the present disclosure provides a process for the production of an ethylene alpha-olefin copolymer including: polymerizing ethylene and at least one C3-C20 alpha-olefin (e.g., hexene) by contacting the ethylene and the at least one C3-C20 alpha-olefin (e.g., hexene) with a catalyst system described above in one or more continuous stirred tank reactors or loop reactors, in series or in parallel, at a reactor pressure of from 0.05 MPa to 1,500 MPa and a reactor temperature of from 30° C. to 230° C. to form an ethylene alpha-olefin copolymer. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of from about 10 psig to about 300 psig, such as from about 20 psig to about 250 psig, such as from about 30 psig to about 200 psig, such as from about 40 psig to about 150 psig, such as from about 50 psig to about 100 psig (e.g., 75 psig), alternatively from about 150 psig to about 300 psig (e.g., 200 psig).
In another embodiment, the present disclosure provides a process for the production of a propylene alpha-olefin copolymer including: polymerizing propylene and at least one ethylene and or at least one C4-C20 alpha-olefin by contacting the propylene and the at least one ethylene and or at least one C3-C20 alpha-olefin with a catalyst system described above in one or more continuous stirred tank reactors or loop reactors, in series or in parallel, at a reactor pressure of from 0.05 MPa to 1,500 MPa and a reactor temperature of from 30° C. to 230° C. to form an ethylene alpha-olefin copolymer. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of from about 10 psig to about 300 psig, such as from about 20 psig to about 250 psig, such as from about 30 psig to about 200 psig, such as from about 40 psig to about 150 psig, such as from about 50 psig to about 100 psig (e.g., 75 psig), alternatively from about 150 psig to about 300 psig (e.g., 200 psig).
In at least one embodiment, 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.
In at least one embodiment, little or no alumoxane is used in the process to produce the polymers. For example, alumoxane is present at zero mol %, alternately the alumoxane is present at a molar ratio of aluminum to transition metal less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.
In at least one embodiment, little or no scavenger is used in the process to produce the ethylene polymer. For example, scavenger (such as tri alkyl aluminum) is present at zero mol %, alternately the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, such as less than 50:1, such as less than 15:1, such as less than 10:1.
Other additives may also be used in the polymerization, as desired, such as one or more scavengers, hydrogen, aluminum alkyls, or chain transfer agents (such as alkylalumoxanes, a compound represented by the formula AlR3 or ZnR2 (where each R is, independently, a C1-C8 aliphatic radical, such as methyl, ethyl, propyl, butyl, pentyl, hexyl octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof).
Solution polymerization
A solution polymerization is a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert solvent or monomer(s) or their blends. A solution polymerization is typically homogeneous. A homogeneous polymerization is one where the polymer product is dissolved in the polymerization medium. Such systems are not turbid as described in Oliveira, J. V. et al. (2000) “High-Pressure Phase Equilibria for Polypropylene-Hydrocarbon Systems,” Ind. Eng. Chem. Res., v. 39(12), p. 4627. Solution polymerization may involve polymerization in a continuous reactor in which the polymer formed, the starting monomer and catalyst materials supplied are agitated to reduce or avoid concentration gradients and in which the monomer acts as a diluent or solvent or in which a hydrocarbon is used as a diluent or solvent. Suitable processes can operate at temperatures from about 0° C. to about 250° C., such as from about 50° C. to about 170° C., such as from about 80° C. to about 150° C., such as from about 100° C. to about 140° C., and or at pressures of about 0.1 MPa or more, such as 2 MPa or more. The upper pressure limit is not critically constrained but can be about 200 MPa or less, such as 120 MPa or less, such as 30 MPa or less. Temperature control in the reactor can generally be obtained by balancing the heat of polymerization and with reactor cooling by reactor jackets or cooling coils to cool the contents of the reactor, auto refrigeration, pre-chilled feeds, vaporization of liquid medium (diluent, monomers or solvent) or combinations of all three. Adiabatic reactors with pre-chilled feeds can also be used. The purity, type, and amount of solvent can be optimized for the maximum catalyst productivity for a particular type of polymerization. The solvent can be also introduced as a catalyst carrier. The solvent can be introduced as a gas phase or as a liquid phase depending on the pressure and temperature. Advantageously, the solvent can be kept in the liquid phase and introduced as a liquid. Solvent can be introduced in the feed to the polymerization reactors.
A process described herein can be a solution polymerization process that may be performed in a batchwise fashion (e.g., batch; semi-batch) or in a continuous process. Suitable reactors may include tank, loop, and tube designs. In at least one embodiment, the process is performed in a continuous fashion and dual loop reactors in a series configuration are used. In at least one embodiment, the process is performed in a continuous fashion and dual continuous stirred-tank reactors (CSTRs) in a series configuration are used. Furthermore, the process can be performed in a continuous fashion and a tube reactor can be used. In another embodiment, the process is performed in a continuous fashion and one loop reactor and one CSTR are used in a series configuration. The process can also be performed in a batchwise fashion and a single stirred tank reactor can be used.
Polyolefin Products
The present disclosure relates to compositions of matter produced by the methods described herein.
In at least one embodiment, a process described herein produces C2 to C20 olefin homopolymers (e.g., polyethylene; polypropylene), or C2 to C20 olefin copolymers (e.g., ethylene-octene, ethylene-propylene) and or propylene-alpha-olefin copolymers, such as C3 to C20 copolymers (such as propylene-hexene copolymers or propylene-octene copolymers) having low comonomer incorporation (such as C6 wt %) and or broad molecular weight distribution (MWD).
In at least one embodiment, a polymer of the present disclosure has an Mw from about 150,000 g/mol to about 1,000,000 g/mol, such as from about 175,000 g/mol to about 750,000 g/mol, such as from about 250,000 g/mol to about 500,000 g/mol.
In at least one embodiment, a polymer of the present disclosure has an Mz from about 300,000 g/mol to about 2,000,000 g/mol, such as from about 400,000 g/mol to about 1,500,000 g/mol, such as from about 600,000 g/mol to about 1,250,000 g/mol.
In at least one embodiment, a polymer of the present disclosure has an Mn from about 100,000 g/mol to about 600,000 g/mol, such as from about 120,000 g/mol to about 500,000 g/mol, such as from about 140,000 g/mol to about 300,000 g/mol.
In at least one embodiment, a polymer of the present disclosure has an Mw/Mn (PDI) value from about 1 to about 5, such as from about 2 to about 4, such as from about 2.5 to about 3.5, such as from about 3 to about 3.5, alternatively from about 1.5 to about 2.5.
Likewise, the process of the present disclosure produces olefin polymers, such as polyethylene and polypropylene homopolymers and copolymers. In at least one embodiment, the polymers produced herein are homopolymers of ethylene or copolymers of ethylene having, for example, from about 0.05 wt % to about 25 wt % (alternately from about 0.5 wt % to about 20 wt %, alternately from about 1 wt % to about 15 wt %, such as from about 1 wt % to about 10 wt %, alternatively from about 0.5 wt % to about 6 wt %) 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). In at least one embodiment, the monomer is ethylene and the comonomer is hexene, such as from about 0.0.5 wt % to about 15 wt % hexene, such as from about 0.1 wt % to about 14 wt % hexene, such as from about 2 wt % to about 12 wt % hexene, alternately about 0.5 wt % to about 7 wt % based on the weight of the polymer.
In at least one embodiment, the polymers produced herein are homopolymers of propylene or are copolymers of propylene having, for example, from about 0.05 wt % to about 25 wt % (alternately from about 0.5 wt % to about 20 wt %, alternately from about 1 wt % to about 15 wt %, such as from about 3 wt % to about 10 wt %) of one or more of C2 or C4 to C20 olefin comonomer (such as ethylene or C4 to C12 alpha-olefin, such as ethylene, butene, hexene, octene, decene, dodecene, such as ethylene, butene, hexene, octene). In at least one embodiment, the monomer is propylene and the comonomer is hexene, such as from about 0.1 wt % to about 15 wt % hexene, such as from about 2 wt % to about 14 wt % hexene, such as from about 3 wt % to about 12 wt % hexene, alternately about 0.5 wt % to about 7 wt %, based on the weight of the polymer.
In at least one embodiment, the polymers produced herein have an Mw of about 150,000 g/mol to about 1,000,000 g/mol, an Mn from about 100,000 g/mol to about 600,000 g/mol, an Mz from about 300,000 g/mol to about 2,000,000 g/mol, and or an Mw/Mn (PDI) of about 1 to 5.
In at least one embodiment, a polymer produced herein has a unimodal or multimodal molecular weight distribution as determined by Gel Permeation Chromatography (GPC). By “unimodal” is meant that the GPC trace has one peak or inflection point. By “multimodal” is meant that the GPC trace has at least two peaks or inflection points. An inflection point is that point where the second derivative of the curve changes in sign (e.g., from negative to positive or vice versus).
GPC 4-D
For purposes of the claims, and unless otherwise indicated, the distribution and the moments of molecular weight (Mw, Mn, Mz, Mw/Mn, etc.), the comonomer content and the branching index (g′) are determined by using a high temperature Gel Permeation Chromatography (Polymer Char GPC-IR) equipped with a multiple-channel band-filter based Infrared detector IR5 with a multiple-channel band filter based infrared detector ensemble IR5 with band region covering from about 2,700 cm−1 to about 3,000 cm−1 (representing saturated C—H stretching vibration) , an 18-angle light scattering detector and a viscometer. Three Agilent PLgel 10-μm Mixed-B LS columns are used to provide polymer separation. Reagent grade 1,2,4-trichlorobenzene (TCB) (from Sigma-Aldrich) including ˜300 ppm antioxidant BHT can be used as the mobile phase at a nominal flow rate of ˜1 mL/min and a nominal injection volume of ˜200 μL. The whole system including transfer lines, columns, and detectors can be contained in an oven maintained at ˜145° C. A given amount of sample can be weighed and sealed in a standard vial with ˜10 μL flow marker (heptane) added thereto. After loading the vial in the auto-sampler, the oligomer or polymer may automatically be dissolved in the instrument with ˜8 mL added TCB solvent at ˜160° C. with continuous shaking. The sample solution concentration can be from ˜0.2 to ˜2 mg/ml, with lower concentrations used for higher molecular weight samples.
The concentration, c, at each point in the chromatogram can be calculated from the baseline-subtracted IR5 broadband signal, I, using the equation: c=αI, where α is the mass constant determined with polyethylene or polypropylene standards. The mass recovery can be calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume. The conventional molecular weight (IR MW) is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to 10M gm/mole. The MW at each elution volume is calculated with following equation:
where the variables with subscript “PS” stand for polystyrene while those without a subscript are for the test samples. In this method, αPS=0.67 and KPS=0.000175, α and K for other materials are as calculated as published in literature (see for example, Sun, T. et al. (2001) “Effect of Short Chain Branching on the Coil Dimensions of Polyolefins in Dilute Solution,” Macromolecules, v. 34(19), pp. 6812-6820), except that for purposes of this present disclosure and claims thereto, α=0.695+(0.01*(wt. fraction propylene)) and K=0.000579−(0.0003502*(wt. fraction propylene)) for ethylene-propylene copolymers and ethylene-propylene-diene terpolymers, α=0.695 and K=0.000579 for linear ethylene polymers, α=0.705 and K=0.0002288 for linear propylene polymers, α=0.695 and K=0.000181 for linear butene polymers, α is 0.695 and K is 0.000579*(1−0.0087*w2b+0.000018*(w2b){circumflex over ( )}2) for ethylene-butene copolymer where w2b is a bulk weight percent of butene comonomer, α is 0.695 and K is 0.000579*(1−0.0075 *w2b) for ethylenehexene copolymer where w2b is a bulk weight percent of hexene comonomer, and α is 0.695 and K is 0.000579*(1−0.0077*w2b) for ethyleneoctene copolymer where w2b is a bulk weight percent of octene comonomer. Concentrations are expressed in g/cm3, molecular weight is expressed in g/mol, and intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL/g unless otherwise noted.
The comonomer composition is determined by the ratio of the IR5 detector intensity corresponding to CH2 and CH3 channel calibrated with a series of PE and PP homo/copolymer standards whose nominal value are predetermined by NMR or FTIR. In particular, this provides the methyls per 1,000 total carbons (CH3/1000TC) as a function of molecular weight. The short-chain branch (SCB) content per 1,000TC (SCB/1000TC) is then computed as a function of molecular weight by applying a chain-end correction to the CH3/1000TC function, assuming each chain to be linear and terminated by a methyl group at each end. The weight % comonomer is then obtained from the following expression in which f is 0.3, 0.4, 0.6, 0.8, and so on for C3, C4, C6, C8, and so on co-monomers, respectively:
w2=f*SCB/1000TC
The bulk composition of the polymer from the GPC-IR and GPC-4D analyses is obtained by considering the entire signals of the CH3 and CH2 channels between the integration limits of the concentration chromatogram. First, the following ratio is obtained
Then the same calibration of the CH3 and CH2 signal ratio, as mentioned previously in obtaining the CH3/1000TC as a function of molecular weight, is applied to obtain the bulk CH3/1000TC. A bulk methyl chain ends per 1,000TC (bulk CH3end/1000TC) is obtained by weight-averaging the chain-end correction over the molecular-weight range according to the following equations:
w2b=f*bulk CH3/1000TC
bulk SCB/1000TC=bulk CH3/1000TC−bulk CH3end/1000TC
where bulk SCB/1000TC is converted to bulk w2 in the same manner as described above.
The LS detector is the 18-angle Wyatt Technology High Temperature DAWN HELEOSII. The LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (Light Scattering from Polymer Solutions; Huglin, M. B., Ed.; Academic Press, 1972.):
Here, ΔR(θ) is the measured excess Rayleigh scattering intensity at scattering angle θ, c is the polymer concentration determined from the IR5 analysis, A2 is the second virial coefficient, P(θ) is the form factor for a monodisperse random coil, and KO is the optical constant for the system:
where NA is Avogadro's number, and (dn/dc) is the refractive index increment for the system. The refractive index, n=1.500 for TCB at 145° C. and λ=665 nm. For analyzing polyethylene homopolymers, ethylene-hexene copolymers, and ethylene-octene copolymers, dn/dc=0.1048 ml/mg and A2=0.0015; for analyzing ethylene-butene copolymers, dn/dc=0.1048*(1−0.00126*w2) ml/mg and A2=0.0015 where w2 is weight percent butene comonomer.
A high temperature Agilent (or Viscotek Corporation) viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity, ηS, for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [η], at each point in the chromatogram is calculated from the equation [η]=ηS/c, where c is concentration and is determined from the IR5 broadband channel output. The viscosity MW at each point is calculated as M=KPSMα
The branching index (g′vis) is calculated using the output of the GPC-IR5-LS-VIS method as follows. The average intrinsic viscosity, [η]avg, of the sample is calculated by:
where the summations are over the chromatographic slices, i, between the integration limits. The branching index g′vis defined as
where Mv is the viscosity-average molecular weight based on molecular weights determined by LS analysis and the K and α are for the reference linear polymer are as described above. Concentrations are expressed in g/cm3, molecular weight is expressed in g/mole, and intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL/g unless otherwise noted. Calculation of the w2b values is as discussed above.
In at least one embodiment the polymer produced 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 1993/003093, published Feb. 18, 1993, specifically columns 7 and 8 as well as in Wild, L. et al. (1982) “Determination of Branching Distributions in Polyethylene and Ethylene Copolymers,” Journal Polymer Science, Poly. Phys., v. 20(3), pp. 441-455 and U.S. Pat. No. 5,008,204, including that fractions having a weight average molecular weight (Mw) below 15,000 g/mol are ignored when determining CDBI.
Blends
In another embodiment, the polymer (such as the polyethylene or polypropylene) produced herein is combined with one or more additional polymers prior to being formed into a film, molded part or other article. Other useful 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 copolymers, polyamides, polycarbonates, PET resins, cross linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidine fluoride, polyethylene glycols, and or polyisobutylene.
In at least one embodiment, the polymer (such as the polyethylene or polypropylene) is present in the above blends, at from 10 wt % to 99 wt %, based upon the weight of the polymers in the blend, such as 20 wt % to 95 wt %, such as at least 30 wt % to 90 wt %, such as at least 40 wt % to 90 wt %, such as at least 50 wt % to 90 wt %, such as at least 60 wt % to 90 wt %, such as at least 70 to 90 wt %.
The blends described above may be produced by mixing the polymers of the present disclosure with one or more polymers (as described above), by connecting reactors together in series to make reactor blends or by using more than one catalyst in the same reactor to produce multiple species of polymer. The polymers can be mixed together prior to being put into the extruder or may be mixed in an extruder.
The blends may be formed using conventional equipment and methods, such as by dry blending the individual components and subsequently melt mixing in a mixer, or by mixing the components together directly in a mixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin-screw extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization process, which may include blending powders or pellets of the resins at the hopper of the film extruder. Additionally, additives may be included in the blend, in one or more components of the blend, and or in a product formed from the blend, such as a film, as desired. Suitable additives can include, for example: fillers; antioxidants (e.g., hindered phenolics such as IRGANOX™ 1010 or IRGANOX™ 1076 available from Ciba-Geigy); phosphites (e.g., IRGAFOS™ 168 available from Ciba-Geigy); anti-cling additives; tackifiers, such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosins; UV stabilizers; heat stabilizers; anti-blocking agents; release agents; anti-static agents; pigments; colorants; dyes; waxes; silica; fillers; talc.
Films
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 suitable 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 suitable 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. For example, 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. Likewise, 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. For example, the films can be oriented in the Machine Direction (MD) at a ratio of up to 15, such as from about 5 to about 7, and in the Transverse Direction (TD) at a ratio of up to 15, such as from about 7 to about 9. However, in another embodiment 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 μm to 50 μm can be suitable. Films intended for packaging can be from 10 μm to 50 μm thick. The thickness of the sealing layer can be from 0.2 μm to 50 μm. There may be a sealing layer on both the inner and outer surfaces of the film or the sealing layer may be present on only the inner or the outer surface.
In another embodiment, one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwave. In at least one embodiment, one or both of the surface layers is modified by corona treatment.
The present disclosure provides, among others, the following embodiments, each of which may be considered as optionally including any alternate embodiments.
wherein:
M is a group 4 metal;
each of R1, R2, and R3 is independently hydrogen, alkoxide, C1 to C40 substituted or unsubstituted hydrocarbyl, or —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ is independently hydrogen or C1 to C20 substituted or unsubstituted hydrocarbyl;
each of R4, R5, and R6 is independently hydrogen, alkoxide, C1 to C40 substituted or unsubstituted hydrocarbyl, or —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ is independently hydrogen or C1 to C20 substituted or unsubstituted hydrocarbyl, or two or more of R4, R5, and R6 form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent ring;
each of X1 and X2 is independently a univalent anionic ligand, a diene ligand, an alkylidene ligand, or X1 and X2 are joined to form a metallocyclic ring;
each of T1, T2, T3, and T4 is independently Si or Ge;
each of R7, R8, R9, R10, R11, R12, R13, and R14 is independently hydrogen or a C1-C20 containing hydrocarbyl, substituted hydrocarbyl, or one or more of R7 and R8, R9 and R10, R11 and R12, and R13 and R14 join to form a substituted or unsubstituted, saturated, partially unsaturated, cyclic or polycyclic substituent;
T1 is bonded to Carbon 1, Carbon 4, or Carbon 5;
R1 is bonded to Carbon 1, Carbon 4, or Carbon 5;
R2 is bonded to Carbon 1, Carbon 4, or Carbon 5;
T2 is bonded to Carbon 1′, Carbon 4′, or Carbon 5′;
R5 is bonded to Carbon 1′, Carbon 4′, or Carbon 5′; and
R6 is bonded to Carbon 1′, Carbon 4′, or Carbon 5′.
wherein:
M is a group 4 metal;
each of R1, R2, and R3 is independently hydrogen, alkoxide, C1 to C40 substituted or unsubstituted hydrocarbyl, or —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ is independently hydrogen or C1 to C20 substituted or unsubstituted hydrocarbyl;
each of R4, R5, and R6 is independently hydrogen, alkoxide, C1 to C40 substituted or unsubstituted hydrocarbyl, or —R15—SiR′3 where R15 is C1 to C4 hydrocarbyl, and each R′ is independently hydrogen or C1 to C20 substituted or unsubstituted hydrocarbyl, or two or more of R4, R5, and R6 form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent ring;
each of X1 and X2 is independently a univalent anionic ligand, a diene ligand, an alkylidene ligand, or X1 and X2 are joined to form a metallocyclic ring;
each of T1, T2, T3, and T4 is independently Si or Ge; and
each of R7, R8, R9, R10, R11, R12, R13, and R14 is independently hydrogen or a C1-C20 containing hydrocarbyl, substituted hydrocarbyl, or one or more of R7 and R8, R9 and R10, R11 and R12, and R13 and R14 join to form a substituted or unsubstituted, saturated, partially unsaturated, cyclic or polycyclic substituent.
General Considerations for Synthesis
All reagents were purchased from commercial vendors (Sigma Aldrich) and used as received unless otherwise noted. Solvents were sparged with N2 and dried over 3 Å molecular sieves. All chemical manipulations were performed in a nitrogen environment unless otherwise stated. Flash column chromatography was carried out with Sigma Aldrich silica gel 60 Å (70 Mesh-230 Mesh) using solvent systems specified. All anhydrous solvents were purchased from Fisher Chemical and were degassed and dried over molecular sieves prior to use. Deuterated solvents were purchased from Cambridge Isotope Laboratories and were degassed and dried over molecular sieves prior to use. 1H NMR spectroscopic data were acquired at 250 MHz, 400 MHz, or 500 MHz using solutions prepared by dissolving approximately 10 mg of a sample in either C6D6, CD2Cl2, CDCl3, D8-toluene, THF-d8, or other deuterated solvent. The chemical shifts (δ) presented are relative to the residual protium in the deuterated solvent at 7.15 ppm, 5.32 ppm, 7.24 ppm, 2.09 ppm, and (1.73 ppm, 3.58 ppm) for C6D6, CD2Cl2, CDCl3, D8-toluene, THF-d8, respectively.
Experimental
All manipulations were performed in an inert N2 purged glove box unless otherwise stated. All anhydrous solvents were purchased from Fisher Chemical and were degassed and dried over molecular sieves prior to use. Deuterated solvents were purchased from Cambridge Isotope Laboratories and dried over molecular sieves prior to use. n-Butyl lithium (2.5 M solution in hexane), tetramethyldichlorodisilane (Me4Si2Cl2) and methylmagnesium bromide (3.0 M solution in diethyl ether) were purchased from Sigma-Aldrich. Hafnium tetrachloride (HfCl4) 99+%, trimethylsilylmethyl trifluoromethanesulfonate was procured from TCI America and used as received. Potassium cyclopentadienide (KCp) was prepared according to the literature procedure (Panda, T. K. et al. (2003) “An Improved Synthesis of Sodium and Potassium Cyclopentadienide,” Organometallics, v. 22(4), pp. 877-878). The 1H NMR measurements were recorded on a 400 MHz Bruker spectrometer.
Synthesis of Trimethylsilylmethylcyclopentadiene, Me3SiCH2CpH A neat trimethylsilylmethyl trifluoromethanesulfonate (25.0 g, 105.8 mmol) was dissolved in 300 mL of diethyl ether and cooled to −25° C., and a solid potassium cyclopentadienide (11.14 g, 106.9 mmol) was slowly added to the mixture over a period of 10 minutes to 15 minutes. The resulting mixture was stirred overnight at room temperature. Insoluble materials were filtered out. Volatiles from the reaction mixture were carefully removed under dynamic vacuum to avoid evaporating the volatile trimethylsilylmethylcyclopentadiene, (Me3Si)CH2CpH. The reaction flask (250 mL round bottom flask) and frit with celite were weighted to calculate yield of the product after extraction. The crude materials were then extracted into pentane (3×50 mL) and used without any further purification. Yield: 15.47 g (95.2%). The 1H NMR spectrum was recorded for the crude material to ensure the product formation. 1H NMR (400 MHz, C6D6): δ −0.05 (9H, s, Si—CH3), 1.77 (2H, d, JHH=1.2 Hz, Me3Si—CH2), 2.83 (1H, sex, JHH=1.5 Hz, Cp-CH), 5.80-6.49 (4H, m, Cp-CH) ppm.
Synthesis of Lithium trimethylsilylmethylcyclopentadienide, Me3SiCH2CpLi An hexane solution of n-butyl lithium (41.5 mL, 103.8 mmol, 2.5 M solution) was added dropwise to a precooled solution (1:1 mixture of pentane and diethyl ether, 200 mL) of Me3SiCH2CpH (15.47 g, 101.7 mmol) over a period of 40 minutes to 50 minutes at −25° C. The resulting mixture was gradually brought to room temperature and then continuously stirred overnight. Volatiles were removed in vacuo and remaining crude materials were thoroughly washed with pentane. The final materials were dried under vacuum to obtain a colorless crystalline solid of Me3SiCH2CpLi in 13.6 g (84.6%) yield. 1H NMR (400 MHz, THF-d8): δ −0.09 (9H, s, Si—CH3), 1.84 (2H, s, Me3Si—CH2), 5.36 (2H, t, JHH=2.6 Hz, Cp-CH), 5.47 (2H, t, JHH=2.6 Hz, Cp-CH) ppm.
Synthesis of Tetramethyldisilyl-bis(trimethylsilylmethylcyclopentadiene), Me4Si2(Me3SiCH2CpH)2 A neat Me4Si2Cl2 (2.0 g, 10.8 mmol) was dissolved in 100 mL of THF and cooled to −25° C. A solid Me3SiCH2CpLi (3.44 g, 21.7) was added to the above mixture and the resulting mixture was stirred overnight at room temperature to ensure completion of the reaction. Volatiles from the reaction mixture were removed in vacuo and subsequently triturated with hexane to remove trace of THF. The crude materials were extracted into hexane and followed by solvent removal under vacuum afforded a thick yellow viscous oil of Me4Si2(Me3SiCH2CpH)2 in 4.3 g (96.1%) yield.
Synthesis of Lithium tetramethyldisilyl-bis(trimethylsilylmethylcyclopentadienide), Me4Si2(Me3SiCH2Cp)2Li2 An hexane solution of n-butyllithium (9.4 mL, 23.4 mmol, 2.5 M solution) was added dropwise to a precooled solution of Me4Si2(Me3SiCH2CpH)2 (4.85 g, 11.6 mmol) in 100 mL of THF over a period of 25 minutes to 30 minutes. The resulting mixture was gradually warmed to room temperature and then continuously stirred for 2 hours at room temperature. Volatiles from the reaction mixture were removed in vacuo, and triturated with hexane. The crude materials were thoroughly washed with hexane to remove any soluble impurities, and dried under vacuum to obtain the colorless crystalline solid of Me4Si2(Me3SiCH2Cp)2Li2 in 4.4 g (99.5%) yield. 1H NMR (400 MHz, THF-d8): δ −0.07(18H, s, SiMe3—CH3), 0.18 (12H, s, SiMe2—CH3), 1.72 (4H, s, Me3Si—CH2), 5.25 (2H, s, Cp-CH), 5.32 (2H, s, Cp-CH), 5.35 (2H, s, Cp-CH) ppm.
Synthesis of Octamethyltetrasilyl-bis(trimethylsilylmethylcyclopentadiene), Me8Si4(Me3SiCH2CpH)2 A solid Me4Si2(Me3SiCH2Cp)2Li2 (2.0 g, 4.6 mmol) was dissolved in 50 mL of THF and cooled to −25° C. To this mixture, a neat Me4Si2Cl2 (0.7 g, 4.6 mmol) was added. The resulting mixture was stirred overnight at room temperature. Volatiles from the reaction mixture were removed in vacuo and subsequently triturated with hexane to remove trace of THF. The crude materials were extracted into hexane and followed by solvent removal under vacuum afforded a thick yellow viscous oil of Me8Si4(Me3SiCH2CpH)2 in 2.46 g (99.8%) yield.
Synthesis of Lithium octamethyltetrasilyl-bis(trimethylsilylmethylcyclopentadienide), Me8Si4(Me3SiCH2Cp)2Li2 An hexane solution of n-butyllithium (4.4 mL, 11.1 mmol, 2.5 M solution) was added dropwise to a precooled solution of Me8Si4(Me3SiCH2CpH)2 (2.46 g, 5.5 mmol) in 50 mL of Et2O over a period of time of approximately 30 minutes. The resulting mixture was gradually warmed to room temperature and then continuously stirred overnight at room temperature. Volatiles from the reaction mixture were removed in vacuo, and triturated with hexane to obtain the colorless semi-crystalline solid of Me8Si4(Me3SiCH2Cp)2Li2 in 1.75 g (69.3%) yield. The product was soluble in hexane and pentane, thus unable to clean-up further, therefore used without any further purification.
Synthesis of Octamethyltetrasilyl-bis(trimethylsilylmethylcyclopentadienyl)zirconium dichloride, Me8Si4(Me3SiCH2Cp)2ZrCl2. Lithium salt of Me8Si4(Me3SiCH2Cp)2 (0.81 g, 1.5 mmol) was dissolved in 50 mL of Et2O and chilled at −25° C., and a solid ZrCl4 (0.35 g, 1.5 mmol) was added. The resulting mixture was stirred overnight at room temperature and insoluble were filtered out. All volatiles were removed and crude materials were triturated with hexane to obtain a pale yellow waxy material of Me8Si4(Me3SiCH2Cp)2ZrCl2 in 0.95 g (92.2%) yield.
Synthesis of Octamethyltetrasilyl-bis(trimethylsilylmethylcyclopentadienyl)hafnium dichloride, Me8Si4(Me3SiCH2Cp)2HfCl2 Lithium salt of Me8Si4(Me3SiCH2Cp)2 (0.9 g, 1.65 mmol) was dissolved in 100 mL of Et2O and chilled at −25° C., and a solid HfCl4 (0.53 g, 1.65 mmol) was added. The resulting mixture was stirred overnight at room temperature and insoluble were filtered out. All volatiles were removed and crude materials were triturated with hexane to obtain a pale yellow waxy material of Me8Si4(Me3SiCH2Cp)2HfCl2 in 1.2 g (93.1%) yield.
Synthesis of Octamethyltetrasilyl-bis(trimethylsilylmethylcyclopentadienyl)zirconium dimethyl, Me8Si4(Me3SiCH2Cp)2ZrMe2. Catalyst Compound 3 A pale yellow waxy material of Me8Si4(Me3SiCH2Cp)2ZrCl2 (0.94 g, 1.4 mmol) was dissolved in 50 mL of Et2O and chilled at −25° C. To this mixture, a solution of MeLi (1.72 mL, 2.75 mmol) was added. The resulting mixture was stirred overnight at room temperature. All volatiles were removed in vacuo and triturated with hexane. The crude materials were then extracted into hexane to obtain a thick pale yellow oil of Me8Si4(Me3SiCH2Cp)2ZrMe2 in 0.5 g (56.6%) yield.
Synthesis of Octamethyltetrasilyl-bis(trimethylsilylmethylcyclopentadienyl)hafnium dimethyl, Me8Si4(Me3SiCH2Cp)2HfMe2 Catalyst Compound 4. A pale yellow waxy material of Me8Si4(Me3SiCH2Cp)2HfCl2 (1.2 g, 1.5 mmol) was dissolved in 50 mL of Et2O and chilled at −25° C. To this mixture, a solution of MeLi (2.0 mL, 3.2 mmol) was added. The resulting mixture was stirred overnight at room temperature. All volatiles were removed in vacuo and triturated with hexane. The crude materials were then extracted into hexane to obtain a thick pale yellow oil of Me8Si4(Me3SiCH2Cp)2HfMe2 in 0.9 g (75.0%) yield.
Supported Catalysts:
Catalyst 1: Added 1.0 g of ES70 875C SMAO to a Celestir vessel with 20 mL of toluene. Next, 0.028 grams catalyst was added to the slurry which was then stirred for 3 hours. The slurry was then filtered, washed with toluene (1×10 mL) and then hexane (2×10 mL). The supported catalyst was then dried under vacuum overnight. Yield 0.93g light yellow silica.
Catalyst 2: Added 1.0 g of ES70 875C SMAO to a Celestir vessel with 20 mL of toluene. Next, 0.30 grams catalyst was added to the slurry which was then stirred for 3 hours. The slurry was then filtered, washed with toluene (1×10 mL) and then hexane (2×10 mL). The supported catalyst was then dried under vacuum overnight. Yield 0.93 g light yellow silica.
General Procedure for High Throughput Ethylene/1-hexene Polymerization and Polymer Characterization (Table 1)
Preparation of catalyst slurry for high throughput run: In a dry box, 45 mg of supported catalyst was weighed into a 20 mL glass vial. 15 mL of toluene was added to the vial to make a slurry that contained 3 mg supported catalyst/mL slurry. The resulting mixture was vortexed prior to injection.
High Throughput—Polymerizations
Transition metal compounds were supported as detailed in the examples above. Solvents, polymerization grade toluene and isohexane were supplied by ExxonMobil Chemical Company and thoroughly dried and degassed prior to use. Polymerization grade ethylene was used and further purified by passing it through a series of columns: 500 cm3 Oxyclear™ cylinder from Labclear (Oakland, Calif.) followed by a 500 cm3 column packed with dried 3 Å molecular sieves purchased from Aldrich Chemical Company, and a 500 cm3 column packed with dried 5 Å molecular sieves purchased from Aldrich Chemical Company. TnOAl was used as a 2 mmol/L solution in toluene.
Reactor Description and Preparation
Polymerizations were conducted in an inert atmosphere (N2) dry box using autoclaves equipped with an external heater for temperature control, glass inserts (internal volume of reactor=22.5 mL), septum inlets, regulated supply of nitrogen, ethylene and hexene, and equipped with disposable PEEK mechanical stirrers (800 RPM). The autoclaves were prepared by purging with dry nitrogen prior to use.
Ethylene/1-hexene Copolymerization
The reactor was prepared as described above, and then purged with ethylene. Isohexane, 1-hexene and TnOAl were added via syringe at room temperature and atmospheric pressure. The reactor was then brought at a process temperature (85° C.) and charged with ethylene at a process pressure (130 psig=896 kPa).
Table 1 illustrates the results of polymers having different properties that were obtained by the polymerization of ethylene in the presence of 300 ppm H2, while stirring at 800 RPM. The transition metal compound (100 μL of a 3 mg/mL toluene slurry, unless indicated otherwise) was added via syringe to the reactor at process conditions. TnOAl was used as 200 μL of a 20 mmol/L in isohexane solution. Ethylene was allowed to enter (through the use of computer controlled solenoid valves) the autoclaves during polymerization to maintain reactor gauge pressure (+/−2 psig). Reactor temperature was monitored and typically maintained within +/−1° C. Polymerizations were halted by addition of approximately 50 psi O2/Ar (5 mole % O2) gas mixture to the autoclaves for approximately 30 seconds. The polymerizations were quenched after a predetermined cumulative amount of ethylene had been added or for a maximum of 45 minutes polymerization time. The final conversion (in psi) of ethylene added/consumed was reported in Table 1, in addition to the quench time for each run. The reactors were cooled and vented. The polymer was isolated after the solvent was removed in vacuo.
Products were characterized as follows:
1H NMR: 1H NMR data was collected at room temperature in a 5 mm probe using a Varian spectrometer with a 1H frequency of at least 400 MHz. Data was recorded using a maximum pulse width of 45° C., 8 seconds between pulses and signal averaging 120 transients.
High temperature size exclusion chromatography was performed using an automated “Rapid GPC” system as described in U.S. Pat. Nos. 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388; each of which is incorporated by reference. Molecular weights (weight average molecular weight (Mw) and number average molecular weight (Mn)) and molecular weight distribution (MWD=Mw/Mn), which is also sometimes referred to as the polydispersity (PDI) of the polymer, were measured by Gel Permeation Chromatography using a Symyx Technology GPC equipped with evaporative light scattering detector and calibrated using polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit S-M-10: Mp (peak Mw) between 5,000 and 3,390,000 g/mol). Samples (250 μL of a polymer solution in TCB were injected into the system) were run at an eluent flow rate of 2.0 mL/minute (135° C. sample temperatures, 165° C. oven/columns) using three Polymer Laboratories: PLgel 10 μm Mixed-B 300×7.5mm columns in series. No column spreading corrections were employed. Numerical analyses were performed using Epoch® software available from Symyx Technologies or Automation Studio software available from Freeslate. The molecular weights obtained are relative to linear polystyrene standards.
All molecular weights are reported in g/mol unless otherwise noted.
C6 wt % is determined by 1H NMR.
As shown in Table 1, Catalyst Compound 3 and Catalyst Compound 4 were both found to be active catalyst compounds for olefin polymerization. Higher molecular weight capability of Catalyst Compound 3 was observed, as compared to Catalyst Compound 4. Hence, zirconocene-containing metallocene catalysts, such as Catalyst Compound 3, with enhanced molecular weight capability has been developed.
Overall, catalysts, catalyst systems, and processes of the present disclosure can provide polyolefins at high Mw (e.g., 150,000 g/mol or greater), Mn values of 100,000 g/mol or greater, narrow PDI (e.g., about 1 to about 3), high Mz values (e.g., 300,000 g/mol or greater). Catalysts, catalyst systems, and processes of the present disclosure can provide polymers having a comonomer content from about 0.05 wt % to about 12 wt %. In particular, the present disclosure can provide new and improved group 4 metal-containing metallocene catalysts such as zirconocenes and hafnocenes with enhanced molecular weight capability.
The phrases, unless otherwise specified, “consists essentially of” and “consisting essentially of” do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of the present disclosure, additionally, they do not exclude impurities and variances normally associated with the elements and materials used.
For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.
All documents described herein are incorporated by reference herein, including any priority documents and or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended that the present disclosure be limited thereby. Likewise, the term “comprising” is considered synonymous with the term “including.” Likewise whenever a composition, an element or a group of elements is 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.
While the present disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the present disclosure.
This application claims the priority benefit of Provisional Application No. 62/835,191, filed Apr. 17, 2019, the disclosure of which is incorporated herein by reference.
Number | Name | Date | Kind |
---|---|---|---|
5017714 | Welborn | May 1991 | A |
6414090 | Minami | Jul 2002 | B2 |
7968665 | Minami et al. | Jun 2011 | B2 |
8729284 | Yabukami et al. | May 2014 | B2 |
20030069320 | Minami | Apr 2003 | A1 |
20030139617 | Nakamura et al. | Jul 2003 | A1 |
20050049373 | Minami et al. | Mar 2005 | A1 |
20060014909 | Kanamaru et al. | Jan 2006 | A1 |
20170015686 | Yang | Jan 2017 | A1 |
20180237559 | Kuppuswamy | Aug 2018 | A1 |
20180244817 | Hagadorn et al. | Aug 2018 | A1 |
20190144571 | Yang | May 2019 | A1 |
Number | Date | Country |
---|---|---|
1561762 | Aug 2005 | EP |
2003096135 | Apr 2003 | JP |
2005002279 | Jan 2005 | JP |
4184765 | Nov 2008 | JP |
2010-037417 | Feb 2010 | JP |
WO2013-151863 | Oct 2013 | WO |
Entry |
---|
Bochmann, M. et al. (1999) “Cationic Zirconocene Complexes with Benzyl and Si(SiMe3)3 Substituted Cyclopentadienyl Ligands,” Jrnl. Chem. Soc. Dalton Trans.,, v.1, pp. 43-50. |
Hengge, E. et al. (1996) “Si-H-Containing Cyclosilanes and their Behaviour in the Dehydrogenative Polymerization Reaction,” Jrnl. Organo. Chem., v.521(1), pp. 145-155. |
Miyake, S. et al. “Synthesis, Molecular Structure, and Racemate-Meso Interconversion for rac-(Me2Si)2{η5—C5H—3(CHMe2)—5—Me}2MCI2(M=Ti and Zr),” Organometallics, 1998, v. 17(25), pp. 5528-5533. |
Pinkas, J. et al. (2011) “Dehydrocoupling of SiMe2H Substituents In Permethylated Zirconocene Complexes,” Chem. Commun., v.76(3), pp. 177-191, XP055755157. |
Schafer, A. et al. (2017) “Synthesis and Structure of [2]Tetrelocenophanes,” EurJIC, v.2017(1), pp. 35-38. |
Number | Date | Country | |
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20200332031 A1 | Oct 2020 | US |
Number | Date | Country | |
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62835191 | Apr 2019 | US |