Methods for producing impact copolymers using c1 symmetric metallocene catalysts

Abstract

Impact copolymers may be prepared using a C1 symmetric metallocene. Methods for forming impact copolymers comprise: exposing a) propylene and optionally b) a C2 or C4-C20 alpha-olefin to first polymerization reaction conditions in the presence of a first polymerization catalyst and optionally hydrogen to form a matrix polypropylene; and exposing the matrix polypropylene and a) ethylene and a C3-C20 alpha olefin and optionally a diene monomer, or b) propylene and a C2 or C4-C20 alpha olefin and optionally a diene monomer to second polymerization reaction conditions in the presence of a second polymerization catalyst and optionally hydrogen to form an impact copolymer comprising a copolymer phase dispersed within the matrix polypropylene. The second polymerization reaction conditions comprise gas-phase polymerization reaction conditions, and the second polymerization catalyst comprises a C1 symmetric metallocene comprising a Group 4-6 metal.

Description

METHODS FOR PRODUCING IMPACT COPOLYMERS USING Cl SYMMETRIC METALLOCENE CATALYSTSFIELD

[0001] The present disclosure relates to impact copolymers and, more particularly, production of impact copolymers using metallocene catalysts.BACKGROUND

[0002] Impact copolymers (ICPs) are specialty polymers containing a crystalline phase, typically an isotactic polypropylene or a propylene-ethylene random copolymer containing predominantly propylene-derived monomer units, and a copolymer phase, which may be a rubber or elastomeric phase, having a relatively low glass transition temperature (Tg) intermixed as discrete, non- continuous domains within the crystalline phase, typically an ethylene-propylene rubber (EPR) or an ethylene-propylene-diene monomer (EPDM) rubber. Other types of rubber compounds may be used as well. The crystalline phase may convey stiffness and rigidity to the copolymer, while the copolymer phase acts as an impact modifier and conveys toughness. Because of their impact resistance, ICPs find considerable use in the automotive industry and other applications where such properties are desired.

[0003] ICPs having a crystalline phase with a broad molecular weight distribution and a copolymer phase having both a high molecular weight and narrow molecular weight distribution (poly dispersity index), as well as a narrow composition distribution, can be desirable for enhancing performance of ICPs. Unfortunately, the foregoing balance of properties between the crystalline phase and the copolymer phase of ICPs is not easily realized using current polymerization processes and polymerization catalysts.

[0004] ICPs may be prepared by compounding a copolymer phase within a crystalline phase, or by growing the copolymer phase within the crystalline phase during a staged polymerization process. Compounding processes are often difficult to perform, and staged polymerization processes are instead typically used to form ICPs through in-reactor blending via sequential formation of the crystalline phase and the copolymer phase. Production of ICPs through staged polymerization and in-reactor blending is often conducted using Ziegler-Natta and similar multisite catalysts in a staged slurry / gas-phase polymerization processes, wherein the crystalline phase is first produced using slurry polymerization, and the copolymer phase is then grown within the crystalline phase in one or more downstream reactors in a second polymerization stage by gas-phase polymerization. The same polymerization catalyst may promote polymerization in each polymerization stage, with the crystalline-phase polymer being grown around supported polymer particles in the first polymerization stage and the supported catalyst continuing to promote polymer growth and formation of the copolymer phase during the second polymerization stage. The properties of the ICPs can be tailored at least partly by the catalyst structure and through variance of the polymerization reaction conditions. While Ziegler-Natta catalysts may produce suitable ICPs, the ICPs may exhibit high oligomer contents and poor-quality copolymer phases in some cases, which may be detrimental to overall performance of the ICPs. For example, Ziegler-Natta catalysts may afford copolymer phases having an undesirably broad molecular weight distribution and relatively low molecular weights. Conventional metallocene catalysts, in contrast, may afford crystalline phases having a molecular weight distribution that is too narrow. Moreover, many conventional metallocene catalysts exhibit an undesirably low catalyst productivity when forming ICPs, and their high cost may be further problematic.SUMMARY

[0005] In various aspects, the present disclosure provides methods for forming impact copolymers, comprising: exposing a) propylene and optionally b) a C2or C4-C20alpha-olefin to first polymerization reaction conditions in the presence of a first polymerization catalyst and optionally hydrogen to form a matrix polypropylene; and exposing the matrix polypropylene and a) ethylene and a C3-C20alpha olefin and optionally a diene monomer, or b) propylene and a C2or C4-C20alpha olefin and optionally a diene monomer to second polymerization reaction conditions in the presence of a second polymerization catalyst and optionally hydrogen to form an impact copolymer comprising a copolymer phase dispersed within the matrix polypropylene; wherein the second polymerization reaction conditions comprise gas-phase polymerization reaction conditions, and the second polymerization catalyst comprises a Cl symmetric metallocene comprising a Group 4-6 metal.

[0006] These and other features and attributes of the disclosed systems and methods of the present disclosure and their advantageous applications and / or uses will be apparent from the detailed description which follows.BRIEF DESCRIPTION OF THE DRAWINGS

[0007] Not applicable.DETAILED DESCRIPTION

[0008] The present disclosure relates to impact copolymers and, more particularly, production of impact copolymers using metallocene catalysts.

[0009] The present disclosure provides polymerization methods for producing impact copolymers having desirable properties, in which a Cl symmetric metallocene catalyst may be utilized to promote polymerization in at least a second polymerization stage, and preferably in both first and second polymerization stages, to form a crystalline phase (matrix polypropylene) and a copolymer phase, which may be an elastomeric or rubber phase, sequentially to define an impact copolymer. By utilizing such metallocene catalysts during both the first and second polymerization stages when producing an impact copolymer, a number of advantages and operational efficiencies may be realized, as discussed hereinafter. At the very least, by using the same polymerization catalyst in both the first and second polymerization stages, the risk of incompatibilities between the first and second polymerization catalysts and their associated polymerization reaction conditions may be substantially averted.

[0010] Metallocenes having Cl symmetry (z.c., belonging to a Cl space group) may afford a number of advantages in regard to the foregoing. Such metallocenes are asymmetric, meaning the metallocenes have no planes of symmetry about any axis. The asymmetry is advantageous as no isomers (rac / meso) are formed during synthesis of the metallocenes, thereby providing a much higher yield of usable catalyst relative to other metallocenes that are symmetric but are capable of forming optical isomers. That is, metallocenes having Cl symmetry may be advantageous in terms of subverting the need to separate optical isomers of the metallocene prior to polymerization.

[0011] In addition to the foregoing benefits, Cl symmetric metallocenes are surprisingly effective at forming both isotactic polypropylene homopolymers as a matrix polypropylene and elastomeric polymers as a copolymer phase under appropriate polymerization reaction conditions. Advantageously, the Cl symmetric metallocenes may provide a balance between a sufficiently broad molecular weight distribution of the isotactic polypropylene homopolymer or similar matrix polypropylene and a sufficiently narrow molecular weight distribution and high molecular weight of the copolymer phase therein to afford a good impact copolymer performance, such as a balance between toughness and impact resistance. Furthermore, the ethyl ene-propylene copolymer composition for Cl symmetric catalysts is narrow across the molecular weight distribution, which may further contribute to improved performance of impact copolymers. The ability to target different molecular weight distributions is not believed to be common for other metallocenes.Moreover and further advantageously, the Cl symmetric metallocenes offer surprisingly high catalyst activities relative to other types of metallocene catalysts in accomplishing the foregoing.

[0012] As a final advantage, Cl symmetric metallocenes may be readily incorporated upon a support material for facilitating both slurry polymerization and gas-phase polymerization reaction processes. While located upon the support material, activation of the Cl symmetric metallocenes may be realized using various types of activators.Definitions

[0013] For the purposes of the present disclosure, the new numbering scheme for groups of the Periodic Table is used. In said numbering scheme, the groups (columns) are numbered sequentially from left to right from 1 through 18, excluding the f-block elements (lanthanides and actinides). Under this scheme, the term “transition metal” refers to any atom from Groups 3-12 of the Periodic Table, inclusive of the lanthanide and actinide elements. Ti, Zr, and Hf are Group 4 transition metals, for example.

[0014] 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 poly dispersity index (PDI), is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units (e.g., Mw, Mn, and Mz) are in units of g / mol (g●mol-1).

[0015] For purposes of this disclosure, when a polymer, copolymer, or oligomer, particularly a polyolefin, is referred to as comprising an olefin, the olefin present in such polymer, copolymer, or oligomer is the polymerized form of the olefin. For example, when a copolymer is said to have an "ethylene" content of 0 wt% to 5 wt%, it is to be understood that the mer unit in the copolymer is derived from the monomer ethylene in the polymerization reaction and said derived units are present at 0 wt% (i.e., absent) to 5 wt%, based upon the weight of the copolymer. As used herein, the terms “polymer” and oligomer” (and grammatical variations thereof) are used interchangeably to refer to a molecule having two or more of the same or different mer units. As used herein, the term “polymerize” (and grammatical variations thereof, e.g., polymerization) is used to refer to a process of generating a molecule having two or more of the same or different mer units from two or more of the same or different monomers. A “homopolymer” is a polymer (or oligomer) having mer units that are the same. A “copolymer” is a polymer (or oligomer) having two or more mer units that are different from each other. A “terpolymer” is a polymer (or oligomer) having threemer units that are different from each other. “Different,” as used to refer to mer units, indicates that the mer units differ from each other by at least one atom or are different isomerically. Accordingly, the definition of copolymer, as used herein, includes terpolymers and like higher polymers (or oligomers). A "decene polymer" or "decene copolymer," for example, is a polymer or copolymer comprising at least 50 mol% decene-derived units.

[0016] The term “independently,” when referenced to selection of multiple items from within a given group, means that the selected choice for a first item does not necessarily influence the choice of any second or subsequent item. That is, independent selection of multiple items within a given group means that the individual items may be the same as or different from one another.

[0017] The terms “group,” “radical,” and “substituent” may be used interchangeably herein.

[0018] The term “hydrocarbon” refers to a class of compounds having hydrogen bound to carbon, and encompasses saturated hydrocarbon compounds, unsaturated hydrocarbon compounds, and mixtures of hydrocarbon compounds (saturated and / or unsaturated), including mixtures of hydrocarbon compounds having different numbers of carbon atoms. The term “xn” refers to hydrocarbon(s) or a hydrocarbyl group having n carbon atom(s) per molecule or group, wherein n is a positive integer. Such hydrocarbon compounds may be one or more of linear, branched, cyclic, acyclic, saturated, unsaturated, aliphatic, and / or aromatic. As used herein, a cyclic hydrocarbon may be referred to as “carbocyclic,” which includes saturated, unsaturated, and partially unsaturated carbocyclic compounds, as well as aromatic compounds. The term “heterocyclic” refers to a carbocyclic ring containing at least one ring heteroatom as a replacement for a ring carbon atom.

[0019] The terms “hydrocarbyl radical,” “hydrocarbyl,” and “hydrocarbyl group” may be used interchangeably throughout this disclosure and refer to a group containing hydrogen atoms and carbon atoms and bearing at least one unfilled valence position when removed from a parent compound. Hydrocarbyl radicals may be optionally substituted in some cases. Suitable “hydrocarbyl radicals” may refer to Ci-Cioo radicals that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic in nature. Examples of saturated hydrocarbyl radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- xutyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, including their substituted analogues.

[0020] Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom of the hydrocarbyl radical has been substituted with at least a non-hydrogen group, such as a hydrocarbyl group, a halogen (e.g., Br, Cl, F or I), or at least one functional group such as NR*2, OR*, SeR*, TeR*, PR*2, ASR*2, SbR*2, SR*, BR*2, SiR*3, GeR*3, SnR*3, PbR*3, and the like, or where at least one heteroatom has been inserted within a hydrocarbyl ring or chain, wherein each R* is independently hydrogen, a hydrocarbyl or halocarbyl radical, or two or more R* may j oin together to form a substituted or unsubstituted, saturated, unsaturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure.

[0021] The term “optionally substituted” means that a hydrocarbon or hydrocarbyl group can be unsubstituted or substituted. For example, the term “optionally substituted hydrocarbyl” refers to replacement of at least one hydrogen atom or carbon atom in a hydrocarbyl group with a heteroatom or heteroatom functional group. Unless otherwise specified as being expressly unsubstituted, any of the hydrocarbyl groups herein may be optionally substituted.

[0022] The term “substituted” refers to replacement of at least one hydrogen atom or carbon atom of a hydrocarbon or hydrocarbyl group with a heteroatom or heteroatom functional group. Heteroatoms may include, but are not limited to, B, O, N, S, P, F, Cl, Br, I, Si, Pb, Ge, Sn, As, Sb, Se, and Te. Heteroatom functional groups that may be present in substituted hydrocarbons or hydrocarbyl groups include, but are not limited to, functional groups such as O, S, S=O, S(=O)2, NO2, F, Cl, Br, I, NR2, OR, SeR, TeR, PR2, AsR2, SbR2, SR, BR2, SiR3, GeR3, SnR3, PbR3, where R is a hydrocarbyl group or H. Suitable hydrocarbyl R groups may include alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, and the like, any of which may be optionally substituted.

[0023] The term “saturated hydrocarbon” means a hydrocarbon that contains zero carbon-carbon double bonds or carbon-carbon triple bonds. The saturated hydrocarbon can be a linear or cyclic hydrocarbon, either of which may be optionally branched. The saturated hydrocarbon can be a C2- C40hydrocarbon, such as a C4-C7hydrocarbon. In at least one embodiment, a C4-C7hydrocarbon may be isobutane, pentane, cyclopentane, cyclohexane, isopentane, isohexane, hexane, heptane, or mixtures thereof.

[0024] The term “alkyl” means a straight-chain, branched-chain, or cyclic hydrocarbon radical having only carbon-carbon single bonds. Such alkyl radicals may be substituted. Examples of alkyl radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, including their substituted analogues.

[0025] The term “alkylene” means a divalent alkyl radical. For example, a methylene group is a divalent alkylene radical.

[0026] The term “olefin” (alternately referred to as “alkene”) means a linear, branched, or cyclic compound of carbon and hydrogen having at least one double carbon-carbon bond.

[0027] The term “alkenyl” means a straight-chain, branched-chain, or cyclic hydrocarbon radical having one or more carbon-carbon double bonds. The alkenyl radicals may be optionally substituted. Examples of suitable alkenyl radicals include, but are not limited to, ethenyl, propenyl, allyl, 1,4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloctenyl, and the like, including their substituted analogues.

[0028] The term “aromatic” means a hydrocarbyl compound or group containing a planar unsaturated ring of atoms that is stabilized by interaction of the bonds forming the ring. Such compounds are often six-membered rings such as benzene and its derivatives. As used herein, the term “aromatic” also refers to pseudoaromatics which are compounds that have similar properties and structures (nearly planar) to aromatics, but are not by definition aromatic; likewise, the term aromatic also refers to substituted aromatic compounds and radicals. Aromatic (but not pseudoaromatic) hydrocarbons obey the Hiickel Rule and contain a cyclic cloud of 4n+2 n- electrons, where n is a positive integer.

[0029] The term “aryl” or “aryl group” means a carbon-containing aromatic ring or substituted variants thereof, including but not limited to, phenyl, 2-methylphenyl, xylyl, 4-bromoxylyl, and the like. Likewise, the term “heteroaryl” or “heteroaryl group” means an aryl group where a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, preferably 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 groups, but are not by definition aromatic.

[0030] A substituted aryl is an aryl group where at least one hydrogen atom of the aryl 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 (e.g., 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*, -SiR*3, -GeR*,and the like, where each R* is independently hydrogen, ahydrocarbyl or halocarbyl radical, or two or more R* may join together to form a substituted or unsubstituted, saturated, unsaturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure, or where at least one heteroatom has been inserted within a hydrocarbyl ring. For example, 3, 5 -dimethylphenyl and 2-methylphenyl are substituted aryl groups. The term “arylalkyl” may also refer to an aryl group where a hydrogen has been replaced with an alkyl or substituted alkyl group. The term “alkylaryl” means an alkyl group where a hydrogen has been replaced with an aryl or substituted aryl group. Thus, for example, 2-methylphenyl is an arylalkyl or substituted aryl group, and benzyl and phenethyl are alkylaryl groups.

[0031] Any aryl group herein may be an optionally substituted phenyl group. The term “substituted phenyl,” or “substituted phenyl group” means a phenyl group having one or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatomcontaining group, such as halogen (e.g., F, Cl, Br, I) or at least one functional group such as,and the like, where each R* is independently hydrogen, a hydrocarbyl, halogen, orhalocarbyl radical, or two or more R* may join together to form a substituted or unsubstituted, saturated, unsaturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure, or where at least one heteroatom has been inserted within a hydrocarbyl ring.

[0032] The term “heterocyclic” means a cyclic 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. 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-dimethylaminophenyl is a heteroatom-substituted ring.

[0033] The term “substituted heterocyclic” means a heterocyclic group where at least one hydrogen atom of the heterocyclic 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 (e.g., F, Cl, Br, I) or at least one functional group such asand thelike, where each R* is independently hydrogen, a hydrocarbyl or halocarbyl radical.

[0034] The term “ring atom” means an atom that is part of a cyclic ring structure. By this definition, a benzyl group has 6 ring atoms and tetrahydrofuran has five ring atoms.

[0035] 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).

[0036] The terms “catalyst productivity” and “catalyst activity” interchangeably refer to ameasure of how many grams of polymer (P) are produced using a polymerization catalyst comprising W g of catalyst (cat), over a period of time of T hours; and may be expressed by the following formula: P / (T*W) and expressed in units of gPgcat’1hr’1. Conversion is the amount of monomer that is converted to polymer product, and is reported as mol % and is calculated based on the polymer yield (weight) and the amount of monomer fed into the reactor. Catalyst activity is a measure of the level of activity of the catalyst and is reported as the mass of product polymer (P) produced per mass of catalyst (gP / g catalyst).

[0037] The term “catalyst system” refers to a combination of at least one catalyst compound (e.g., at least one C 1 symmetric metallocene) and an optional support material. The catalyst system may further include at least one activator and / or at least one co-activator. Accordingly, preferable catalyst systems may include at least one catalyst compound disposed upon a support material in combination with at least one activator. When catalyst systems are described as comprising neutral stable forms of the foregoing components, it is to be understood that the ionic form of the component is the form that reacts with monomers to produce polymers. For purposes of the present disclosure, a “catalyst system” may include both neutral and ionic forms of the components of the catalyst system.

[0038] In the present disclosure, a “catalyst” may be described as any of a catalyst precursor, a pre-catalyst compound, catalyst compound, a catalyst, or a transition metal compound, and these terms are used interchangeably herein. An “anionic ligand” is a negatively charged ligand which donates one or more pairs of electrons to a metal ion. A “neutral donor ligand” is a neutrally charged ligand which donates one or more pairs of electrons to a metal ion.

[0039] The term “alkoxide” means entities containing a C1to C40hydrocarbyl group bound to oxygen. The hydrocarbyl group may be straight-chain, branched, or cyclic, and be saturated or unsaturated, including aromatic. The terms “alkoxy” and “alkoxide” therefore refer to an alkyl ether or aryl ether radical. Examples of hydrocarbyl ether radicals include, but are not limited to, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, phenoxy, and the like.

[0040] The term “complex” means molecules in which an ancillary ligand is coordinated to a central metal atom. The ligand is stably bonded to the metal atom so as to maintain its influence during use of the complex during a catalytic process, such as polymerization. The ligand may be coordinated to the metal atom by a covalent bond and / or electron donation coordination or intermediate bonds. Metal complexes may be subjected to activation to perform their catalytic function, such as polymerization, using an activator which is believed to create a cation as a result of the removal of an anionic group, often referred to as a leaving group, from the metal atom.

[0041] The term “metallocene” means an organometallic compound with at least one %-bound cyclopentadienyl moiety or substituted cyclopentadienyl moiety (such as substituted or unsubstituted cyclopentadienyl (Cp) and / or indenyl (Ind)) and more frequently two (or three) π - bound cyclopentadienyl moieties or substituted cyclopentadienyl moieties. The terms “metallocene” and “metallocene catalyst” may be used interchangeably herein.

[0042] The term “scavenger” refers to a compound that may be added to a catalyst system to facilitate polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. A co-activator that is not a scavenger may also be used in conjunction with an activator in order to form an active catalyst system. In at least one embodiment, a co-activator can be pre-mixed with a complex to form an alkylated metal complex.

[0043] The term “continuous” means a system that operates without interruption or cessation for a period of time. For example, a continuous process to produce a polymer may continually introduce monomer into one or more reactors, and polymer product is continually withdrawn therefrom.

[0044] The term “bulk polymerization” or “slurry-phase polymerization” means a polymerization process in which the monomers and / or co-monomers being polymerized are used as a solvent or diluent using little or no inert solvent or diluent, wherein supported catalyst particles are dispersed in the solvent or diluent. A small fraction of inert solvent might be used as a carrierfor catalyst and scavenger. A slurry-phase polymerization contains less than about 25 wt% of inert solvent or diluent, such as less than about 10 wt%, such as less than about 1 wt%, such as 0 wt%. The polymerization reaction conditions associated with a slurry polymerization may include operation at a sufficient pressure to maintain the monomers and / or co-monomers in a liquid state.

[0045] The term “gas-phase polymerization” refers to a polymerization process in which monomers and / or co-monomers are present in a gaseous state and supported catalyst particles are fluidized within a reactor.

[0046] When used in the present disclosure, the following abbreviations may be used: dme is 1,2-dimethoxy ethane, Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is normal propyl, cPr is cyclopropyl, Bu is butyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu is para- tertiary butyl, nBu is normal butyl, sBu is sec-butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOAL is tri(n-octyl)aluminum, MAO is methyl alum oxane, sMAO is supported methylalumoxane, Bn is benzyl (z.e., CH2Ph), THF (also referred to as tetrahydrofuran, RT is room temperature (and is 23°C. unless otherwise indicated), tol is toluene, EtOAc is ethyl acetate, and Cy is cyclohexyl.Ligands and Metallocene Complexes

[0047] Suitable metallocenes having Cl symmetry and effective for promoting formation of impact copolymers according to the disclosure herein may comprise a Group 3-6 metal, preferably a Group 4 metal (e.g., Ti, Zr, or Hf). More generally, when suitably activated, the metallocenes may be effective for promoting polymerization of ethylenically unsaturated compounds, such as one or more alpha olefins or similar hydrocarbons comprising at least one alkene group, under a range of polymerization reaction conditions, preferably wherein the metallocenes are disposed upon a support material in combination with at least one activator, such as at least one alumoxane (aluminoxane). Further details regarding activation of the metallocenes and polymerization therewith is provided hereinbelow.

[0048] Metallocenes suitable for use in the present disclosure may have a structure represented by Formula 1Formula 1 wherein:

[0049] M is a transition metal of Group 3, 4, or 5 of the Periodic Table of Elements, such as a Group 4 metal, for example, Zr, Hf, or Ti;

[0050] T is a bridging group;

[0051] X1and X2are each a univalent anionic ligand, or X1and X2are joined to form a metallocycle ring, a chelating ligand, a diene ligand, or an alkylidene;

[0052] R1is hydrogen, halogen, optionally substituted C1-C40alkyl, optionally substituted C6- C14aryl, optionally substituted C3-C13heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, where R" is C1-C10alkylene and each R' is hydrogen, C1-C10alkyl, or C6-C10aryl; preferably, R1is C1-C10alkyl, and more preferably, R1is methyl;

[0053] R2and R6are independently hydrogen, halogen, optionally substituted C1-C40alkyl, optionally substituted C6-C14aryl, an optionally substituted C3-C13heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR’3, wherein R" is C1-C10alkylene and each R' is hydrogen, C1-C10alkyl, or C6-C10aryl; preferably, at least one of R2and R6are hydrogen, and more preferably, R2and R6are both hydrogen;

[0054] R3is an optionally substituted C1-C40alkyl, an optionally substituted C6-C18aryl, or an optionally substituted C3-C13heteroaryl; more preferably R3is a bulky alkyl group, such as optionally substituted cyclohexyl, optionally substituted norbomanyl, optionally substituted adamantanyl, or optionally substituted tert-butyl, such as cyclohexyl, 1-adamantyl, 2-adamantyl, (ls,4s)-bicyclo[2.2.1]heptan-7-ide, (lR,4S)-bicyclo[2.2.1]heptan-2-ide, or (Is, 4s)- bicyclo[2.2.1]heptan-l-ide; or R3is an optionally substituted aryl group, more preferably an optionally substituted phenyl group; even more preferably, R3is an optionally substituted phenyl group, an optionally substituted naphthyl group, or an optionally substituted anthracenyl group;

[0055] R4and R5are independently H, R1", or OR'", wherein R1" is an optionally substituted C1- C40alkyl, or R4and R5are joined to form a C3-C62 substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof; and

[0056] R7, R8, R9, and R10are independently hydrogen, halogen, optionally substituted C1-C40alkyl, optionally substituted C6-C14aryl, optionally substituted C3-C13heteroaryl, -NR'2, -SR', - OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10alkylene and R' is hydrogen, C1-C10alkyl, or C6-C10aryl, or one or more of R5and R6, R6and R7, or R7and R8are joined to form a C3- C62substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof; preferably R7, R8, R9, and R10are methyl.

[0057] As a non-limiting illustration, in Formula 1 when R4and R5are joined to form a polycyclic ring structure, the polycyclic ring structure may comprise a 5- or 6-membered ring, preferably a 5- or 6-membered carbocyclic ring lacking heteroatoms as ring atoms. For example, an indacenyl ligand contains such a 5-membered carbocyclic ring and a hexahydrobenz[ / ]indenyl ligand contains such a 6-membered carbocyclic ring.hexahydrobenz[ / ]indenyl ligandThe carbocyclic ring in the indacenyl ligand or the hexahydrobenz[f]indenyl ligand can be substituted or unsubstituted and can be part of multi-cyclic groups where the additional cyclic groups may be saturated or unsaturated, and substituted or unsubstituted. Typical substituents on the carbocyclic ring may include optionally substituted C1to C40hydrocarbyls, heteroatoms (such as halogens, including Br, F, Cl, or I), heteroatom-containing groups (such as a halocarbyl), or two or more substituents are joined together to form a cyclic or polycyclic ring structure (which may contain saturated and / or unsaturated rings), or a combination thereof. One or more of such substituents may be present. Example ligands in which R4and R5are fused to form a carbocyclic ring include those having structures represented by Formulas 2-4:Formula 2 Formula 3 Formula 4 where the wavy lines indicate a connection to M in Formula 1 (such as to Zr or Hf) and T (such as Me2Si or Ph2Si). The corresponding ligands lacking methyl group substitution on the unsaturated carbocyclic ring are also suitable for use herein. In any of the foregoing, R3may be a bulky alkyl group, preferably an optionally substituted cyclohexyl, optionally substituted norbornanyl, optionally substituted adamantyl, or optionally substituted tert-butyl, or an optionally substituted aryl group, such as an optionally substituted phenyl group. In any of the foregoing, R3may preferably be an optionally substituted phenyl group, optionally substituted naphthyl group, or optionally substituted anthracenyl group.

[0058] When R4and R5are not joined to form a polycyclic ring structure, preferably both R4and R5may be hydrogen, or R4may be OR'" and R5may be R1", wherein each R1" is independently selected. In specific examples, R4may be OR1", preferably OCH3and R5may be hydrogen.

[0059] In some embodiments of the present disclosure, X1and X2are each independently an optionally substituted C1-C40hydrocarbyl (such as an optionally substituted C2-C20hydrocarbyl), an optionally substituted C4-C62aryl, an optionally substituted C4-C62heteroaryl, hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine, phosphine, ether, or a combination thereof. For example, each of X1and X2may be independently a halide or a C1-C6hydrocarbyl or a C1-C10hydrocarbyl, such as methyl. In some embodiments, each of X1and X2is independently chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl. In some embodiments of the present disclosure, X1and X2may form a part of a fused ring or a ring system, which may define a metallocycle, a chelating ligand, or a diene ligand bound to M.

[0060] In some embodiments, T is represented by the formula, (R*2G)g, wherein each G is C, Si, or Ge, g is 1 or 2, and each R* is, independently, hydrogen, an optionally substituted C1-C20hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or phenyl), or the two or more R* are joined to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic ring structure. Insome embodiments, the bridging group may be represented by R'2C, R'2Si, R'2Ge, R'2CCR'2, R'2CCR'2CR'2, R'2CCR'2CR'2CR'2, R’C=CR', R'C=CR'CR’2, R'2CCR'=CR'CR'2, R'C=CR'CR'=CR', R'C=CR'CR'2CR'2, R'2CSiR'2, R'2SiSiR'2, R2CSiR'2CR'2, R'2SiCR'2SiR'2, R'C=CR'SiR'2, RbCGeRb, R'2GeGeR'2, R'2CGeR'2CR'2, R'2GeCR'2GeR'2, RbSiGeRb, R'C=CR'GeR'2, R'B, R’2C- BR', R'2C-BR'-CR'2, R'2C-O-CR'2, R'2CR'2C-O-CR'2CR'2, R'2C-O-CR'2CR'2, R'2C-O-CR'=CR', R'2C-S-CR'2, R'2CR'2C-S-CR'2CR'2, R'2C-S-CR'2CR'2, R'2C-S-CR'=CR', R'2C-Se-CR'2, R'2CR'2C-Se-CR'2CR'2, R'2C-Se-CR2CR'2, R'2C-Se-CR'=CR', R'2C-N=CR', R'2C-NR'-CR'2, RbC-NR-CRbCRb, R'2C-NR'-CR'=CR', RbCRbC-NR'-CRbCRb, R'2C-P=CR', or RbC-PR'- CR'2where each R' is independently hydrogen or an optionally substituted Ci-C2o hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or phenyl), a C1-C20halocarbyl, a C1-C20 silylcarbyl, or a C1-C20 germylcarbyl substituent, or two or more adjacent R' are joined to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic ring structure. In some embodiments of the present disclosure, T may be CH2, CH2CH2, C(CH3)2, (Ph)2C, (p-(Et)3SiPh)2C, SiMe2, SiPh2, SiMePh, Si(CH2)3, or Si(CH2)4. Preferably, T is CH2or SiMe2, and more preferably SiMe2or SiPh2.

[0061] Suitable alkyl groups in any selection herein may be optionally substituted and independently chosen from, but not limited to, methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl, docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl, nonacosynyl, triacontynyl, butadienyl, pentadienyl, hexadienyl, heptadienyl, octadienyl, nonadienyl, and decadienyl.

[0062] Suitable aryl groups in any selection herein may be optionally substituted and independently chosen from, but not limited to, phenyl, 1 -naphthyl, 2-naphthyl, 9-anthracenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3- dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4- dimethylphenyl, 3,5-dimethylphenyl, 2,4,5-trimethylphenyl, 3,4,5-trimethylphenyl, 2, 3, 4,5,6- pentamethylphenyl, 2-ethylphenyl, 3 -ethylphenyl, 4-ethylphenyl, 2,3-diethylphenyl, 2,4- diethylphenyl, 2,5-diethylphenyl, 2,6-diethylphenyl, 3,4-diethylphenyl, 3,5-diethylphenyl, 2- isopropyl phenyl, 3 -isopropyl phenyl, 4-isopropylphenyl, 3,5-di-isopropylphenyl, 2,5-di- isopropyl phenyl, 2-tert-butylphenyl, 3-tert-butylphenyl, 4-tert-butylphenyl, 3,5-di-tert- butylphenyl, 3,5-di-tert-butyl-4-methoxyphenyl, 3,5-di-tert-butyl-4-dimethylaminophenyl, 2,5-di- tert-butylphenyl, 2-trimethylsilylphenyl, 3-trimethylsilylphenyl, 4-trimethylsilylphenyl, 3,5- bis(trimethylsilyl)phenyl, 2-trifluoromethylphenyl, 3 -trifluoromethylphenyl, 4- trifluoromethylphenyl, and 3,5-bis(trifluoromethyl)phenyl.

[0063] Suitable cycloalkyl groups in any selection herein may be optionally substituted and independently chosen from, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, norbomanyl, adamantyl and the like.

[0064] In more specific examples, metallocenes suitable for forming an impact copolymer according to the disclosure herein may have a structure represented by Formula 1 and having bulky alkyl substitution at R3may include variables defined in accordance with the following:

[0065] M is a Group 4 metal; preferably, zirconium or hafnium, and more preferably hafnium;

[0066] T is a bridging group; preferably, CR11R12or SiR11R12, wherein R11and R12are independently hydrogen, an optionally substituted C1-C40hydrocarbyl, or an optionally substituted C6-C62aryl, or R11and R12are joined to form a substituted or unsubstituted C4-C62saturated or unsaturated cyclic or polycyclic ring structure; more preferably T is CH2, CH2CH2, C(CH3)2, (Ph)2C, (p-(Et)3SiPh)2C, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4, or Si(CH2)4; still more preferably T is CH2or SiMe2or more preferably, T is SiMe2or SiPh2;

[0067] X1and X2are each a univalent anionic ligand, or X1and X2are joined to form a metallocycle ring, a chelating ligand, a diene ligand, or an alkylidene, preferably X1and X2are independently a halide (F, Cl, Br, I) or a C1-C6hydrocarbyl, such as a C1-C6alkyl or phenyl, more preferably methyl;

[0068] R1is hydrogen, a halogen, an optionally substituted C1-C40hydrocarbyl, an optionally substituted C4-C62 aryl, an optionally substituted C4-C62heteroaryl, -NR'2, -SR', -OR’, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10alkylene and R' is hydrogen, C1-C10alkyl, or C6-C10aryl; preferably, R1is C1-C10alkyl; more preferably, R1is methyl;

[0069] R2and R6are independently hydrogen, a halogen, an optionally substituted C1-C40hydrocarbyl, an optionally substituted C4-C62aryl, an optionally substituted C4-C62 heteroaryl, - NR'2, -SR', -OR’, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10alkylene and R' is hydrogen, C1-C10alkyl, or C6-C10aryl; preferably R2is hydrogen; preferably R2and R6are each hydrogen, or R2is hydrogen and R6is hydrogen or optionally substituted phenyl;

[0070] R3is a bulky alkyl group; preferably R3is an optionally substituted cyclohexyl, optionally substituted norbornanyl, optionally substituted adamantyl (e.g., 1-adamantyl, 2-adamantyl, (ls,4s)-bicyclo[2.2.1]heptan-7-yl, (lR,4S)-bicyclo[2.2.1]heptan-2-yl, (Is, 4s)- bicyclo[2.2.1]heptan-l-yl) , or optionally substituted t-butyl;

[0071] R4and R5are independently H, R'", or OR'", wherein R'" is an optionally substituted Ci- C40 alkyl, or R4and R5are joined to form a C3-C62substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof; and

[0072] R7, R8, R9, and R10are independently hydrogen, a halogen, an optionally substituted C1- C40hydrocarbyl, an optionally substituted C4-C62 aryl, an optionally substituted C4-C62heteroaryl, -NR'2, -SR', -OR’, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10alkylene and R' is hydrogen, C1-C10alkyl, or C6-C10aryl, or one or more of R5and R6, R6and R7, or R7and R8are joined to form a substituted or unsubstituted C4-C62 saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof; preferably R5, R6, R7, and R8are each C1-C10alkyl; more preferably R5, R6, R7, and R8are each methyl.

[0073] If R4and R5are not joined to form a cyclic or polycyclic ring structure, preferably both R4and R5may be hydrogen, or R4may be OR"1and R may be R1", wherein each R'" is independently selected. In specific examples, R4may be OR"1, preferably OCH3, and R5may be hydrogen, or R4may be OR'", preferably OCH3, and R3may be an alkyl group, preferably t-butyl.

[0074] Accordingly, in some embodiments, suitable metallocenes having Cl symmetry and a bulky alkyl group at R3may have a structure represented by Formula 5Formula 5 wherein:

[0075] M is a Group 4 metal, preferably Zr or Hf, more preferably Hf;

[0076] X1and X2are independently a halide (F, Cl, Br, I) or a Ci-Ce alkyl; preferably X1and X2are each chloride or methyl;

[0077] R1is Ci-Cio alkyl group, preferably methyl;

[0078] R3is a bulky alkyl group, preferably optionally substituted cyclohexyl, optionally substituted norbomanyl, optionally substituted adamantyl, or optionally substituted t-butyl; preferable groups include 1-adamantyl, 2-adamantyl, (ls,4s)-bicyclo[2.2.1]heptan-7-ide, (1R,4S)- bicyclo[2.2.1]heptan-2-ide, or (ls,4s)-bicyclo[2.2.1]heptan-l-ide;

[0079] R4and R3are independently H, R'", or OR'", wherein R'" is an optionally substituted C1-C40alkyl, or R4and R5are joined to form a C3-C62substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof;

[0080] R6is hydrogen, halogen, optionally substituted C1-C40alkyl, optionally substituted C6- C14aryl, an optionally substituted C3-C13heteroaryl, -NR'2, -SR', -OR',-SiR'3, -OSiR'3, -PR'2, or -R"-SiR’3, wherein R" is C1-C10alkylene and each R' is hydrogen, C1-C10alkyl, or C6-C10aryl; preferably R6is hydrogen or optionally substituted phenyl;

[0081] R7, R8, R9, and R10are independently hydrogen, a halogen, an optionally substituted C1- C40hydrocarbyl, an optionally substituted C4-C62 aryl, an optionally substituted C4-C62heteroaryl, -NR'2, -SR', -OR’, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10alkylene and R' is hydrogen, C1-C10alkyl, or C6-C10aryl, or one or more of R5and R6, R6and R7, or R7and R8are joined to form a substituted or unsubstituted C4-C62saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof; preferably R3, R6, R7, and R8are each C1-C10alkyl; more preferably R5, R6, R7, and R8are each methyl; and

[0082] R11and R12are independently optionally substituted C1-C10alkyl, or optionally substituted C6-C10aryl, or R11and R12are joined to form a substituted or unsubstituted C2-C22saturated or unsaturated cyclic or polycyclic ring structure; preferably, R11and R12are each methyl or phenyl, and more preferably, R11and R12are each methyl.

[0083] In some examples, R4and R’ may form a 5-membered carbocyclic ring. Specific examples of such metallocenes having a bulky alkyl group at R3and having R4and R5fused as a 5-membered carbocyclic ring may have a structure represented by Formula 6A, preferably whereinR6is hydrogen or optionally substituted phenyl, and more preferably wherein R6is hydrogen. The metallocene represented by Formula 6B lacks the 5-membered carbocyclic ring fused to the indenyl group.Formula 6A Formula 6B wherein in Formula 6 A:

[0084] Q is an optional C1-C6alkyl group, and q is 0, 1, 2, 3, 4, 5, or 6. When presentoptional substitution Q may be present at any non-aromatic carbon atom of the 5-membered ring defined by R4and R5. Preferably, each occurrence of Q is a methyl group.

[0085] Illustrative examples of metallocenes having a structure represented by Formulas 5, 6A, and 6B may include, but are not limited to:

[0086] In other specific examples, metallocenes suitable for forming an impact copolymer according to the disclosure herein may have a structure represented by Formula 1 and having an optionally substituted aryl group at R3, preferably an optionally substituted phenyl group, an optionally substituted naphthyl group, or an optionally substituted anthracenyl group, which may include variables defined in accordance with the following.

[0087] M is a Group 4 metal; preferably, zirconium or hafnium;

[0088] T is a bridging group; preferably, CR11R12or SiR11R12, wherein R11and R12are independently hydrogen, an optionally substituted C1-C40hydrocarbyl, or optionally substituted C6-C62aryl, or R11and R12are joined to form a substituted or unsubstituted C4-C62saturated orunsaturated cyclic or polycyclic ring structure; more preferably T is CH2, CH2CH2, C(CH3)2, (Ph)2C, (p-(Et)3SiPh)2C, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4, or Si(CH2)4; still more preferably T is CH2or SiMe2and more preferably, T is SiMe2 or SiPh2;

[0089] X1and X2are each a univalent anionic ligand, or X1and X2are joined to form a metallocycle ring, a chelating ligand, a diene ligand, or an alkylidene, preferably X1and X2are independently a halide (F, Cl, Br, I) or a C1-C6hydrocarbyl, such as a C1-C6alkyl or phenyl, more preferably methyl;

[0090] R1is hydrogen, a halogen, an optionally substituted C1-C40hydrocarbyl, an optionally substituted C4-C62aryl, an optionally substituted C4-C62heteroaryl, -NR'2, -SR', -OR’, -SiR'3, - OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10alkylene and R' is hydrogen, C1-C10alkyl, or C6- C10aryl; preferably, R1is C1-C10alkyl; more preferably, R1is methyl;

[0091] R2and R6are independently hydrogen, a halogen, an optionally substituted C1-C40hydrocarbyl, an optionally substituted C4-C62aryl, an optionally substituted C4-C62heteroaryl, - NR'2, -SR', -OR’, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10alkylene and R' is hydrogen, C1-C10alkyl, or C6-C10aryl; preferably R2is hydrogen; preferably R2and R6are each hydrogen, or R2is hydrogen and R6is hydrogen or optionally substituted phenyl;

[0092] R3is optionally substituted phenyl, optionally substituted naphthyl, or optionally substituted anthracenyl;

[0093] R4and R5are independently H, R'", or OR'", wherein R'" is an optionally substituted Ci- C40alkyl, or R4and R3are joined to form a C3-C62substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof; and

[0094] R7, R8, R9, and R10are independently hydrogen, a halogen, an optionally substituted C1- C40hydrocarbyl, an optionally substituted C4-C62aryl, an optionally substituted C4-C62heteroaryl, -NR'2, -SR', -OR’, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10alkylene and R' is hydrogen, C1-C10alkyl, or C6-C10aryl, or one or more of R3and R6, R6and R7, or R7and R8are joined to form a substituted or unsubstituted C4-Ce2 saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof; preferably R5, R6, R7, and R8are each C1-C10alkyl; more preferably R3, R6, R7, and R8are each methyl.

[0095] Accordingly, in some embodiments, suitable metallocenes having Cl symmetry and an optionally substituted phenyl group at R3may have a structure represented by Formula 7Formula 7 wherein:

[0096] R13-R17are independently hydrogen, an optionally substituted C1-C40hydrocarbyl, an optionally substituted C4-C62 aryl, an optionally substituted C4-C62 heteroaryl, -NR'2, -SR', -OR’, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10alkyl and each R' is hydrogen, halogen, C1-C10alkyl, or C6-C10aryl, or R13and R14, R14and R15, R13and R16, or R16and R17, or any combination thereof are joined to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic ring structure;

[0097] M is a Group 4 metal, preferably Zr or Hf;

[0098] X1and X2are independently a halide (F, Cl, Br, I) or a C1-C6alkyl; preferably X1and X2are each chloride or methyl;

[0099] R1is C1-C10alkyl group, preferably methyl;

[0100] R4and R5are independently H, R'", or OR'", wherein R'" is an optionally substituted C1- C40alkyl, or R4and R3are joined to form a C3-C62substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof;

[0101] R6is hydrogen, halogen, optionally substituted C1-C40alkyl, optionally substituted C6- C14aryl, optionally substituted C3-C13heteroaryl, -NR'2, -SR', -OR',-SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10alkylene and each R' is hydrogen, C1-C10alkyl, or C6-C10aryl; preferably R6is hydrogen or optionally substituted phenyl;

[0102] R7, R8, R9, and R10are independently hydrogen, a halogen, an optionally substituted C1- C40hydrocarbyl, an optionally substituted C4-C62 aryl, an optionally substituted C4-C62heteroaryl, -NR'2, -SR', -OR’, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10alkylene and R' is hydrogen, C1-C10alkyl, or C6-C10aryl, or one or more of R3and R6, R6and R7, or R7and R8are joined to form a substituted or unsubstituted C4-C62 saturated or unsaturated cyclic or polycyclicring structure, or a combination thereof; preferably R3, R6, R7, and R8are each C1-C10alkyl; more preferably R5, R6, R7, and R8are each methyl; and

[0103] R11and R12are independently optionally substituted C1-C10alkyl, or optionally substituted C6-C10aryl, or R11and R12are joined to form a substituted or unsubstituted C2-C22saturated or unsaturated cyclic or polycyclic ring structure; more preferably R11and R12are each methyl or phenyl, and more preferably, R11and R12are each methyl.

[0104] In some examples, R4and R5may form a 5-membered carbocyclic ring. Specific examples of such metallocenes having an optionally substituted phenyl group at R3and having R4and R5fused as a 5-membered carbocyclic ring may have a structure represented by Formula 8A, preferably wherein R6is hydrogen or optionally substituted phenyl, and more preferably whereinR6is hydrogen. The metallocene represented by Formula 8B lacks the 5-membered carbocyclic ring fused to the indenyl group.wherein in Formula 8A:

[0105] Q is an optional C1-C6alkyl group, and q is 0, 1, 2, 3, 4, 5, or 6. When present (q 0), optional substitution Q may be present at any non-aromatic carbon atom of the 5-membered ring defined by R4and R5. Preferably, each occurrence of Q is a methyl group.

[0106] Illustrative examples of metallocenes having a structure represented by Formulas 7, 8A, or 8B may include, but are not limited to:Hf may replace Zr in any of the foregoing metallocenes.

[0107] For nomenclature purposes, the following numbering scheme is used for an indenyl ring.It should be noted that an indenyl ring can be considered a cyclopentadienyl group fused with a benzene ring. The structure below is drawn and named as an anion.

[0108] Also for clarity, the following ring structures are substituted indenyl groups, where substitutions at the 5- and 6- positions collectively define a ring structure. For specific compound nomenclature purposes, these ligands are described below. A similar numbering and nomenclature scheme is used for these types of substituted indenyls that include indacenyls, cyclopenta[b]naphthalenyls, heterocyclopentanaphthyls, heterocyclopentaindenyls, and the like, as illustrated below. Each structure is drawn and named as an anion.

[0109] Any of the foregoing metallocenes may be incorporated in catalyst systems comprising a support material, optionally an activator, optionally a co-activator, and optionally a scavenger. Preferably, the activator is present and disposed upon the support material in combination with the metallocene. The activator and optional co-activator may convert the metallocene into a formeffective for promoting olefin polymerization under suitable polymerization reaction conditions to form an impact copolymer, as described in further detail hereinbelow.Support Materials

[0110] In conducting polymerization reactions to form an impact copolymer according to the present disclosure, the Cl symmetric metallocene may be disposed upon a support material. When used, at least one activator may also be disposed upon the support material in combination with the Cl symmetric metallocene, optionally in further combination with a co-activator and / or a scavenger. Suitable activators may be disposed upon the support material by contacting the support material with a solution containing the activator or the activator may be formed in situ upon the support material. Additional activator details are provided below.[0U1] The support material may be an inorganic oxide in a finely divided form, such as silica, alumina, talc, zeolites, clays, organoclays, and the like, each having a highly porous structure. Suitable inorganic oxides upon which metallocenes may be disposed in accordance with the present disclosure include Groups 2, 4, 13, or 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides may be employed, either alone or in combination with the silica or alumina, such as magnesia, titania, zirconia, or the like. Particularly useful support materials may include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, silica, clays, silica clay, silicon oxide clay, and the like. Combinations of these support materials may be used such as, for example, silica-chromium, silica-alumina, silica-titania, and the like. In at least one embodiment, the support material may be selected from AI2O3, ZrO2, SiO2, SiO2 / Al2O3, silica clay, silicon oxide / clay, or mixtures thereof. Other suitable support materials may be employed as well such as, for example, finely divided functionalized polyolefins, such as finely divided polyethylene, polypropylene, and polystyrene with functional groups that are able to absorb water, (e.g., oxygen- or nitrogen-containing groups such as -OH, -RC=O, -OR, and -NR2). Still other organic or inorganic support materials may also be suitably used.

[0112] The support material may be optionally treated with an electron-withdrawing anion. The electron-withdrawing anion may increase the Lewis or Bronsted acidity of the support material, as compared to the support material that is not treated. The electron-withdrawing anion may be derived from a salt, an acid, or other compounds, such as a volatile organic compound, that serve as a source or precursor for the electron-withdrawing anion. Electron-withdrawing anions may include sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate,phosphate, fluorophosphate, trifluoroacetate, triflate (trifluoromethanesulfonate), fluorozirconate, fluorotitanate, phosphotungstate, or any combination thereof. Combinations of one or more different electron-withdrawing anions, in varying proportions, may be used to tailor the specific acidity of the support material to a desired level. Such combinations of electron-withdrawing anions may be contacted with the support material simultaneously or individually and in any order that provides a desired specific acidity.

[0113] The support material may be optionally fluorided by introducing a fluoride-containing anion. For example, a fluorided support may be a silicon dioxide support wherein a portion of the silica hydroxyl groups have been replaced with fluorine or a fluorine-containing compound. Suitable fluorine-containing compounds include, but are not limited to, inorganic fluorine- containing compounds and / or organic fluorine-containing compounds, either of which may be utilized for providing fluorine to the support material. Illustrative inorganic fluorine-containing compounds that may be used for fluoriding a support material include, for example, NH4BF4, (NH4)2SiF6, NH4PF6, NH4F, (NH4)2TaF7, NH4NbF4, (NH4)2GeF6, (NH4)2SmF6, (NH4)2TiF6, (NH4)2ZrF6, MOF6, ReF6, GaF3, SO2C1F, F2, SiF4, SF6, CIF3, C1F5, BrF5, IF7, NF3, HF, BF3, NHF2, NH4HF2, and combinations thereof.

[0114] Non-limiting examples of cations suitable for use in the present disclosure in combination with the electron-withdrawing anion include ammonium, trialkylammonium, tetraalkylammonium, tetraalkylphosphonium, H+, [H(OEt2)2]+, [HNR3]+(Ris a Ci-C2o hydrocarbyl group, which may be the same or different and optionally substituted), or combinations thereof.

[0115] The method by which the support material is contacted with the electron-withdrawing anion, may include, but is not limited to, gelling, co-gelling, impregnation of one compound onto another, the like, or combinations thereof. Following a particular contacting method, the treated support material may then be calcined.

[0116] The support material, such as an inorganic oxide and more preferably silica, may have a surface area about 10 m2 / g to about 800 m2 / g, or about 10 m2 / g to about 500 m2 / g, or about 10 m2 / g to about 100 m2 / g, or about 10 m2 / g to about 50 m2 / g, or about 50 m2 / g to about 800 m2 / g, or about 50 m2 / g to about 500 m2 / g, or about 50 m2 / g to about 100 m2 / g, or about 100 m2 / g to about 800 m2 / g, or about 100 m2 / g to about 500 m2 / g, or about 500 m2 / g to about 800 m2 / g.

[0117] The support material, such as an inorganic oxide and more preferably silica, may have a pore volume of about 0.1 cc / g to about 4.0 cc / g, or about 0.1 cc / g to about 1 cc / g, or about 1 cc / gto about 4 cc / g. The average pore size of the support material may be about 10 A to about 1000 A, or about 10 A to about 500 A, or about 10 A to about 100 A, or about 100 A to about 1000 A, or about 100 A to about 500 A, or about 500 A to about 1000 A.

[0118] The support material, such as an inorganic oxide and more preferably silica, may have an average particle size of about 5 pm to about 500 pm, or about 5 pm to about 100 pm, or about 5 pm to about 50 pm, or about 50 pm to about 500 pm, or about 50 pm to about 100 pm, or about 100 pm to about 500 pm.

[0119] Before employing the support material in a polymerization reaction or before disposing a metallocene thereon, the support material may be free or substantially free of absorbed water. Drying of the support material can be realized by heating or calcining at about 100°C to about 1000°C, preferably at least about 200°C. When the support material is silica, the silica may be heated to at least about 200°C, preferably about 200°C to about 850°C, and more preferably at about 400°C; and for a time of about 1 minute to about 100 hours, or from about 12 hours to about 72 hours, or from about 24 hours to about 60 hours. After calcination, the support material may be contacted with a metallocene and optionally an activator to produce a catalyst system.

[0120] To accomplish the foregoing, the support material may be slurried in a non-polar solvent and contacted with a solution of the metallocene and an activator. In some embodiments, the slurry of the support material may first be contacted with the activator for about 0.5 hours to about 24 hours, or from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours before disposing the metallocene thereon. Alternately, the slurry of the support material may first be contacted with the metallocene for about 0.5 hours to about 24 hours, or from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours before being contacted with an activator. Once the metallocene and the activator have been contacted with each other, the catalyst system may be aged, optionally with heating up to about 70°C, for about 0.5 hours to about 24 hours, or about 2 hours to about 16 hours, or about 4 hours to about 8 hours before being used to conduct a polymerization reaction.

[0121] Suitable non-polar solvents for loading the metallocene and the activator upon the support material may include those in which the metallocene and the activator are at least partially soluble and which are liquid at reaction temperatures. Preferred non-polar solvents are alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, although a variety of other materialsincluding cycloalkanes, such as cyclohexane. Aromatic hydrocarbons, such as benzene, toluene, and ethylbenzene, may also be employed.Activators

[0122] In most cases, at least one activator is present upon the support material in combination with the metallocene. Suitable activators may include, for example, alumoxanes (e.g., methylalumoxane-MAO), non-coordinating anions, or any combination thereof.

[0123] Alumoxanes are generally oligomeric compounds containing -A1(R)-O- sub-units, where R is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is an alkyl, halide, alkoxide or amide. Mixtures of different alumoxanes and modified alumoxanes can also be used. It may be preferable 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 3 A and described in U.S. Patent No. 5,041,584). Another useful alumoxane is solid polymethylaluminoxane as described in US Patents 9,340,630; 8,404,880; and 8,975,209.

[0124] When the activator is an alumoxane (modified or unmodified), some embodiments may select the maximum amount of activator at up to a 5000-fold molar excess Al / M over the catalyst compound (per metal catalytic site). The minimum activator-to-metal ratio is a 1 : 1 molar ratio. Suitable ranges may include from 1 : 1 to 500: 1, or from 1 : 1 to 200: 1, or from 1 : 1 to 100: 1, or from 1 : 1 to 50: 1.

[0125] Other suitable activators include compounds containing a non-coordinating anion, especially borane and borate compounds. Particularly useful borane and borate compounds containing a non-coordinating anion or similar entity include, for example, B(C6F5)3, [PhNMe2H]+[B(C6F5)4]-, [Ph3C]+[B(C6F5)4]-, and [PhNMe2H]+[B(CioF7)4]-.

[0126] 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 remainingsufficiently labile to be displaced by a neutral Lewis base. The term NCA is defined to include multicomponent NCA-containing activators, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis(heptafluoronaphthyl)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. Typically, NCAs coordinate weakly enough that a neutral Lewis base, such as an olefinically or acetylenically unsaturated monomer can displace it from the catalyst center. Any metal or metalloid that can form a compatible, weakly coordinating complex may be used or contained in the non-coordinating anion. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus, and silicon. The term non-coordinating anion includes neutral activators, ionic activators, and Lewis acid activators.

[0127] “Compatible” non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral transition metal compound and a neutral by-product from the anion. Non-coordinating anions useful in accordance with the present disclosure are those that are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge at +1, and yet retain sufficient lability to permit displacement during polymerization. Ionizing activators useful herein typically comprise an NCA, particularly a compatible NCA.

[0128] It is within the scope of the present disclosure to use an ionizing, neutral, or ionic activator, such as tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, a tris perfluorophenylboron metalloid precursor or a trisperfluoronaphthylboron metalloid precursor, poly halogenated heteroborane anions (WO 98 / 43983), boric acid (U.S. Patent No. 5,942,459), or any combination thereof. 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. Other useful activators may include those described in US Patents 8,658,556 and 6,211,105.

[0129] In preferred embodiments, boron-containing NCA activators represented by Formula 9 below may be used,Formula 9 where Z is (L-H) or a reducible Lewis acid; L is a neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; Ad-is a boron-containing non-coordinating anion having the charge d"; and d is 1, 2, or 3

[0130] 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 from the metal-ligand complexes to afford a cationic metal-ligand complex.

[0131] The cation component Zd+may also be a moiety such as silver, tropylium, carboniums, ferroceniums and mixtures thereof, preferably carboniums and ferroceniums. Suitable reducible Lewis acids include any triaryl carbonium (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 C1to C40hydrocarbyl, or a substituted C1to C40hydrocarbyl). Preferably, the reducible Lewis acids in Formula 9 above defined as "Z" include those represented by the formula: (PhaC), where Ph is a substituted or unsubstituted phenyl, preferably substituted with C1to C40hydrocarbyls or substituted a C1to C40hydrocarbyls, preferably C1to C20alkyls or aromatics or substituted C1to C20alkyls or aromatics, and preferably Zd+is triphenylcarbonium.

[0132] When Zd+is the activating cation (L-H)d+, it is preferably 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, preferably 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, phosphoniums from tri ethylphosphine, triphenylphosphine, and diphenylphosphine, oxoniums from ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane, sulfoniums from thioethers, such as diethyl thioethers, tetrahydrothiophene, and mixtures thereof.

[0133] The anion component Ad-includes those having the formula [Mk+G]d‘ wherein k is 1, 2, or 3; g is 1, 2, 3, 4, 5, or 6 (preferably 1, 2, 3, or 4); g - k = d; M is an element selected from Group 13 of the Periodic Table of the Elements, preferably boron or aluminum, and G is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halo-substituted hydrocarbyl radicals, said G having up to 20 carbon atoms with the proviso that in not more than 1 occurrence is G a halide.Preferably, each G is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably, each G is a fluorinated aryl group, and most preferably, each G is a pentafluoroaryl group. Examples of suitable Ad-also include diboron compounds as disclosed in U.S. Patent No. 5,447,895, which is fully incorporated herein by reference with respect to the diboron compounds disclosed therein.

[0134] Illustrative but not limiting examples of boron compounds which may be used as an activator are the compounds described as (and particularly those specifically listed as) activators in U.S. Patent 8,658,556, which is incorporated by reference herein with respect to the boron compounds disclosed therein.

[0135] Most preferably, the activator Zd+(Ad‘) is one or more of N,N-dimethylanilinium tetra(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)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. In any embodiment, the non-coordinating anion may be selected from N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Me3NH+][B(C6F5)4-], l-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl) pyrrolidinium; [Me3NH+][B(C6F5)4-], l-(4-(tris(pentafluorophenyl)borate)-2, 3,5,6- tetrafluorophenyl) pyrrolidinium, sodium tetrakis(pentafluorophenyl)borate, potassium tetrakis(pentafluorophenyl)borate, and 4-(tris(pentafluorophenyl)borate)-2, 3,5,6- tetrafluoropyridinium. Preferably, the non-coordinating anion may be N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate.

[0136] Bulky activators are also useful herein as NCAs. "Bulky activator" as used herein refers to anionic activators represented by Formulas 10 or 11 below.Formula 10 Formula 11In Formulas 10 and 11, each Rlais, independently, a halide, preferably a fluoride; Ar is substituted or unsubstituted aryl group (preferably a substituted or unsubstituted phenyl), preferably substituted withto C40hydrocarbyls, preferablyto C20alkyls or aromatics; each R2ais, independently, a halide, a C6to C20substituted aromatic hydrocarbyl group or a siloxy group of the formula -O-Si-Ra, where Rais a C, to C20hydrocarbyl or hydrocarbyl silyl group (preferably R2ais a fluoride or a perfluorinated phenyl group); each R3ais a halide, C6to C20substituted aromatic hydrocarbyl group or a siloxy group of the formula -O-Si-Ra, where Rais a C, to C20hydrocarbyl or hydrocarbylsilyl group (preferably R3ais a fluoride or a C6perfluorinated aromatic hydrocarbyl group); wherein R2aand R3acan form one or more saturated or unsaturated, substituted or unsubstituted rings (preferably R2aand R3aform a perfluorinated phenyl ring); and L is a neutral Lewis base; (L-H) is a Bronsted acid; d is 1, 2, or 3; wherein the anion has a molecular weight of greater than 1020 g / mol; wherein at least three of the substituents on the B atom each have a molecular volume of greater than 250 cubic A, greater than 300 cubic A, or greater than 500 cubic A, as specified below.

[0137] Preferably, (Ar3C)d+is (Ph3C)d+, where Ph is a substituted or unsubstituted phenyl, preferably substituted with C1to C40hydrocarbyls or substituted C1to C40hydrocarbyls, preferably C1to C20alkyls or aromatics or substituted C1to C20alkyls or aromatics.

[0138] "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 "A Simple "Back of the Envelope" Method for Estimating the Densities and Molecular Volumes of Liquids and Solids,"Journal of Chemical Education, Vol. 71, No. 11, November 1994, pp. 962-964. Molecular volume (MV), in units of cubic A, is calculated using the formula: MV = 8.3VS, where Vsis the scaled volume. Vsis the sum of the relative volumes of the constituent atoms, and is calculated from the molecular formula of the substituent as specified below. For fused rings, the Vsis decreased by 7.5% per fused ring. The Calculated Total MV of the anion is the sum of the MV per substituent, for example, the MV of perfluorophenyl is 183 A3, and the Calculated Total MV for tetrakis(perfluorophenyl)borate is four times 183 A3, or 732 A3.For a list of particularly useful bulky activators, U.S. Patent 8,658,556, which is incorporated by reference herein with respect to its disclosure of bulk activators, may be consulted.

[0139] In any embodiment, a NCA activator may be an activator as described in U.S. Patent No. 6,211,105. The NCA activator-to-catalyst ratio may be from about a 1 : 1 molar ratio to about a 1000: 1 molar ratio, which includes, from about 0.1 : 1 to about 100: 1, from about 0.5: 1 to about 200: 1, from about 1: 1 to about 500: 1, or from about 1 : 1 to about 1000: 1. A particularly useful range is from about 0.5: 1 to about 10: 1, preferably about 1: 1 to about 5: 1.

[0140] It is also within the scope of this disclosure that the metallocenes may be activated with combinations of alumoxanes and NCAs (see for example, U.S. Patents 5,153,157 and 5,453,410; EP 0 573 120 Bl, and International Patent Application Publications WO 94 / 07928 and WO 95 / 14044, which discuss the use of an alumoxane in combination with an ionizing activator). Thus, in some embodiments, a NCA may be a co-activator to an alumoxane, or vice versa.

[0141] In addition to activators, scavengers or co-activators can be used. Aluminum alkyl or organoaluminum compounds which may be utilized as scavengers or co-activators include, forexample, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n- octylaluminum, ethylaluminum dichloride, diethylaluminum chloride, and diethyl zinc.

[0142] Chain transfer agents can also be used in the compositions and / or processes described herein. Useful chain transfer agents are typically alkylalumoxanes, a compound represented by the formula AIR3, ZnR.2(where each R is, independently, a C1-C8aliphatic radical, preferably 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.

[0143] In any embodiment, an alumoxane, such as MAO, may be mixed in an inert solvent, such as toluene, and then be slurried with a support material, such as silica. Alumoxane deposition upon the support material may occur at a temperature from about 60°C to 120°C, or about 80°C to 120°C, or about 100°C to 120°C. Deposition occurring below 60°C, including room temperature deposition, may also be effective.Catalyst Systems

[0144] The present disclosure further provides catalyst systems comprising a support material; a metallocene having Cl symmetric disposed upon the support material; and an activator selected from an alumoxane or NCA also disposed upon the support material. The metallocene and the activator may be disposed upon the support material in any order, including concurrently. Suitable ratios of the activator to metal of the metallocene include the A1:M ratios specified above.Polymerization Methods

[0145] Polymerization methods for producing impact copolymers according to the present disclosure may comprise: exposing propylene and optionally a C2or C4-C20alpha olefin to first polymerization reaction conditions in the presence of a first polymerization catalyst and optionally hydrogen to form a matrix polypropylene; and exposing the matrix polypropylene and a) ethylene and a C3-C20alpha-olefin, or b) propylene and a C2or C4-C20alpha olefin and optionally a diene monomer to second polymerization reaction conditions in the presence of a second polymerization catalyst and optionally hydrogen to form an impact copolymer comprising a copolymer phase dispersed within the matrix polypropylene. The second polymerization reaction conditions comprise gas-phase polymerization reaction conditions, and the second polymerization catalyst comprises a Cl symmetric metallocene comprising a Group 4-6 metal, preferably a Group 4 metal, as described in more detail above.

[0146] The first polymerization reaction conditions may comprise slurry-phase polymerization reaction conditions or gas-phase polymerization reaction conditions. When the first polymerization reaction conditions comprise gas-phase polymerization reaction conditions, the first polymerization reaction conditions may be the same as or different than the second polymerization reaction conditions. Preferably, the first polymerization reaction conditions are slurry-phase polymerization reaction conditions. Suitable slurry-phase polymerization reaction conditions and gas-phase polymerization reaction conditions are discussed subsequently.

[0147] As indicated above, when producing impact copolymers according to the present disclosure, the matrix polypropylene may be formed under first polymerization reaction conditions involving slurry-phase polymerization, and the copolymer phase may be grown in the matrix polypropylene under second polymerization reaction conditions involving gas-phase polymerization. A slurry-phase polymerization process refers to a polymerization process in which a supported catalyst is employed (optionally also containing an activator), and monomers are polymerized on the supported catalyst particles such that the supported catalyst particles are retained in the polymer following polymerization, wherein at least one of the monomers undergoing polymerization is in liquid form and constitutes at least a portion of a fluid medium for the slurry. A gas-phase polymerization process refers to a polymerization process in which the monomers undergoing polymerization are in a gaseous state, and in which supported catalyst particles (optionally also containing an activator) are fluidized in a reactor producing the polymer. Either of such polymerization processes may be run in batch, semi-batch, or continuous mode. The term "continuous" means a system that operates without interruption or cessation, such that a polymer product may be withdrawn as one or more monomers or other reactants are being introduced to the reactor producing the polymer. In the case of a continuous process producing an impact copolymer containing a matrix polypropylene and an copolymer phase grown within the matrix polypropylene, the matrix polypropylene may be produced in a first reactor under the slurry-phase polymerization reaction conditions and the copolymer phase may be produced in a second reactor downstream from the first reactor under gas-phase polymerization reaction conditions. Batch and semi-batch processes, in contrast, may take place in the same reactor or in different reactors. Additional details regarding slurry-phase polymerization and gas-phase polymerization reaction conditions are discussed further below.

[0148] Accordingly, in various examples, the first polymerization reaction conditions and the second polymerization reaction conditions may be provided in a staged manner in a single reactor, or in a staged manner in separate reactors. When conducted in a staged manner in separate reactors, a first reactor may conduct a first polymerization stage under the first polymerization reaction conditions to produce the matrix polypropylene and a second reactor may conduct a second polymerization stage under the second polymerization reaction condition to produce the copolymer phase within the matrix polypropylene.

[0149] Both slurry-phase polymerizations and gas-phase polymerizations may be conducted in the presence of an aliphatic hydrocarbon solvent / diluent / condensing agent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; or cyclic aliphatic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. Preferably, aromatics are present in the solvent / diluent / condensing agent at less than 1 wt%, more preferably less than 0.5 wt%, and still more preferably at 0 wt% based upon the weight of the solvents / diluent / condensing agent.

[0150] Slurry-phase polymerization processes may operate at atmospheric pressure or above, preferably in a pressure range of about 140 psi (965 kPa) to about 750 psi (5171 kPa) or even greater and a ranging temperature from about 0°C to about 120°C or about 20°C to about 110°C. Optionally, hydrogen gas may be present to alter the molecular weight of the polymer being produced. In slurry- phase polymerization processes, a suspension of polymer particles (matrix polypropylene) is formed in a fluid medium comprising at least one of the monomers undergoing polymerization and optionally a hydrocarbon diluent. The suspension, including diluent, is intermittently or continuously removed from the reactor where the volatile components may separated from the polymer and recycled, optionally after a distillation, to the reactor, or these components may be conveyed directly to a reactor forming an copolymer phase by gas-phase polymerization. Non-limiting examples of slurry-phase polymerization processes include continuous loop or stirred tank processes. Other examples of slurry- phase polymerization processes are described in U.S. Pat. No. 4,613,484, which is incorporated herein by reference.

[0151] Gas-phase polymerization processes may operate by circulating one or more gaseous monomers through a reactor under gas-phase reaction conditions in the presence of a suitable catalyst. The gaseous monomers need not necessarily be introduced to the reactor as a gas i.e., they may be introduced as a condensed liquid), but they are in a gas state at least while contactingthe catalyst system. Typically, the one or more gaseous monomers are withdrawn from the reactor as an effluent stream, which is recycled back to the reactor to increase conversion, and the polymer is collected from the reactor separate from the effluent stream. Illustrative gas-phase polymerization reaction conditions may include a temperature ranging from about 25°C to about 150°C, or about 50°C to about 140°C, or about 60°C to about 110°C, and a pressure of about 10 psi (69 kPa) to about 450 psi (3103 kPa), or about 150 psi (1034 kPa) to about 400 psi (2758 kPa), or about 200 psi (1379 kPa) to about 300 psi (2068 kPa) or about 330 psi (2275 kPa). Optionally, hydrogen gas may be present to alter the molecular weight of the polymer being produced. Illustrative gas-phase polymerization processes are described in U.S. Pat. Nos. 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,453,471; 5,462,999; 5,616,661; and 5,668,228, each of which is incorporated herein by reference.

[0152] The first polymerization reaction conditions may include a pressure that is higher than that of the second polymerization reaction conditions. In non-limiting examples, the pressure under the second polymerization reaction conditions (z.e., under the gas-phase polymerization reaction conditions) may be about 330 psi (2275 kPa) or below, or about 300 psi (2068 kPa) or below, or about 200 psi (1379 kPa) or below, or about 100 psi (690 kPa) or below.

[0153] Slurry-phase polymerization reactions and gas-phase polymerization reactions may be conducted in the presence or absence of one or more scavengers. Typical scavengers include trimethyl aluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, diethyl zinc, or excess alumoxane activator.

[0154] If desired, hydrogen may be added during either of the polymerization reactions to alter the molecular weight of the polymer being produced. In at least one embodiment, hydrogen may be present in the first polymerization reaction and / or the second polymerization reaction at a partial pressure of about 0.001 psig to about 50 psig (0.007 kPa to 345 kPa), or about 0.01 psig to about 25 psig (0.07 kPa to 172 kPa), or about 0.1 psig and 10 psig (0.7 kPa to 70 kPa). When included, hydrogen may be included at an overall concentration of about 600 ppm or less, or about 500 ppm or less, or about 400 ppm or less, or about 300 ppm or less. In other embodiments, hydrogen may be included at an overall concentration of at least about 50 ppm, or at least about 100 ppm, or at least about 150 ppm.

[0155] The Cl symmetric metallocene used as the second polymerization catalyst in the second polymerization stage may also be utilized as the first polymerization catalyst in the firstpolymerization stage. That is, the first polymerization catalyst and the second polymerization catalyst may be the same. When also used as the first polymerization catalyst, the Cl symmetric metallocene may be present upon a support material (e.g., silica) and exposed to the first polymerization reaction conditions, wherein the metallocene (and support material, as well as any supported activators) becomes incorporated within particles of the matrix polypropylene. In this aspect, the first polymerization catalyst is provided to the polymerization reaction conditions and is subsequently provided to the second polymerization reaction conditions within the matrix polypropylene, thereby becoming the second polymerization catalyst, wherein the first polymerization catalyst (and subsequently the second polymerization catalyst) is disposed upon a support material, preferably in combination with at least one activator. Once exposed to the second polymerization reaction conditions, the metallocene may continue to exert its catalytic performance to promote formation of the copolymer phase within the matrix polypropylene. Typically, no additional Cl symmetric metallocene is added when forming the copolymer phase under the second polymerization reaction conditions. However, the introduction of an additional metallocene catalyst to the gas-phase polymerization reaction is not precluded in the disclosure herein.

[0156] In non-limiting examples, the matrix polypropylene produced under the first polymerization conditions may comprise an isotactic polypropylene (a propylene homopolymer) or a propyl ene / ethylene random copolymer. Suitable propyl ene / ethylene random copolymers may comprise predominantly propylene, such as about 95 wt% or greater propylene-derived monomer units, or about 97 wt% or greater propylene-derived monomer units, or about 99 wt% or greater propylene-derived monomer units, and a non-zero amount of ethylene-derived monomer units. Alternately, the matrix polypropylene may comprise a propyl ene / alpha olefin copolymer formed by copolymerizing predominantly propylene (about 90 wt% or greater propylene-derived monomer units, or about 90 wt% or greater propylene-derived monomer units) with a C4-C20 alpha olefin, optionally in further combination with ethylene.

[0157] The matrix polypropylene produced under the first polymerization reaction conditions may have a Mw value ranging from about 5,000 to about 500,000 and exhibit a wide molecular weight distribution (Mw / Mn). In non-limiting examples, the molecular weight distribution of the matrix polypropylene may be about 2 or more, or about 3 or more, or about 4 or more, or about 5or more, or about 6 or more, or about 7 or more, or about 8 or more, or about 9 or more, or about 10 or more.

[0158] In non-limiting examples, the copolymer phase produced under the second polymerization reaction conditions may be an elastomer and comprise an ethylene copolymer or a propylene copolymer, including terpolymers thereof. The copolymer phase may comprise a discrete phase within the matrix polypropylene, or the matrix phase may be at least partially dissolved in (miscible with) the matrix polypropylene. Suitable ethylene copolymers mays comprise predominantly ethylene-derived monomer units (e.g., about 70 wt% to about 97 wt% ethylene-derived monomer units, or about 70 wt% to about 90 wt% ethylene-derived units), with the balance of the monomer units comprising propylene-derived monomer units and / or C4 to C20 alpha olefin-derived monomer units, optionally further including monomer units derived from a diene monomer, such as butadiene, isoprene, dicyclopentadiene, or ethylidene norbomene. Suitable propylene copolymers may comprise predominantly propylene-derived monomer units (e.g, about 70 wt% to about 90 wt% propylene-derived monomer units), with the balance of the monomer units comprising ethylene-derived monomer units and / or C4 to C20 alpha olefin-derived monomer units, optionally further including monomer units derived from a diene monomer, such as butadiene, isoprene, dicyclopentadiene, or ethylidene norbornene. Suitable copolymer phases may therefore include C2 / C3 copolymers, C3 / C4 copolymers, C2 / C4 copolymers, C2 / C6 copolymers, C2 / C8 copolymers, C2 / C10 copolymers, C2 / C3 / C4 copolymers, C2 / C3 / C6 copolymers, C2 / C3 / C8 copolymers, C2 / C3 / C10 copolymers, and any combination thereof. Any of the foregoing copolymers may be elastomers or rubber compounds. In some examples, the copolymer phase may comprise or consist essentially of about 10 wt% to about 90 wt% ethylene and about 10 wt% to about 90 wt% propylene, each based on a total mass of the impact copolymer.

[0159] The copolymer phase produced under the second polymerization reaction conditions may have a Mw value that is higher than that of the matrix polypropylene produced under the first polymerization reaction conditions and exhibit a narrow molecular weight distribution (Mw / Mn). In non-limiting examples, the Mw value of the copolymer phase may be up to about 250,000, or up to about 1,000,000, or even up to about 5,000,000, such as about 50,000 to about 1,000,000, or about 100,000 to about 700,000, or about 200,000 to about 600,000. In non-limiting examples, the molecular weight distribution of the copolymer phase may be about 3 or less, or about 2.5 or less, or about 2 or less.

[0160] In non-limiting examples, the impact copolymers produced according to the disclosure herein may comprise about 60 wt% to about 95 wt% or about 65 wt% to about 95 wt% of the matrix polypropylene and about 5 wt% to about 40 wt% or about 5 wt% to about 35 wt% of the copolymer phase, each based on total mass of the impact copolymer. Depending on the ratio of the copolymer phase relative to the matrix polypropylene, the impact copolymer may comprise about 5 wt% to about 50 wt% non-propylene-derived monomer units. In a more specific example, the impact copolymer may comprise a total content of ethylene-derived monomer units ranging from about 5 wt% to about 40 wt%.

[0161] In any embodiment herein in which alpha olefins are used, suitable alpha olefins may include substituted or unsubstituted C2 to C40 alpha olefins, or C2 to C20 alpha-olefins, or C2 to C12 alpha olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecane, and isomers thereof. Where butene is used as an alpha olefin co-monomer, the butene source may be a mixed butene stream comprising various isomers of butene. In such a mixed stream, 1 -butene monomers are expected to be preferentially consumed by the polymerization process as compared to other butene monomers. Use of such mixed butene streams will provide an economic benefit, as these mixed streams are often waste streams from refining processes, for example, C4 raffinate streams, and can therefore be substantially less expensive than pure 1 -butene.

[0162] In non-limiting examples, the impact copolymer produced according to the disclosure herein may have a melting point ranging from about 50°C to about 140°C, or about 100°C to about 165°C. If the impact copolymers are semi-crystalline, there may be multiple melting points within the foregoing ranges.

[0163] In non-limiting examples, the impact copolymers produced according to the disclosure herein may have a Flexural Modulus, as measured by ASTM D790A, of about 400 MPa to about 2200 MPa, or about 600 MPa to about 1900 MPa. The foregoing values are measured with or without a nucleating agent being present.

[0164] In non-limiting examples, the impact copolymers produced according to the disclosure herein may have a room temperature Notched Izod Impact Strength, as measured by ASTM D256, of about 0.3 ft’lb / in or above. Values including no break under the test conditions are included within the foregoing range.Additional Embodiments

[0165] The present disclosure is further directed to the following non-limiting embodiments:

[0166] Embodiment 1. A method comprising: exposing a) propylene and optionally b) a C2or C4-C20alpha-olefin to first polymerization reaction conditions in the presence of a first polymerization catalyst and optionally hydrogen to form a matrix polypropylene; and exposing the matrix polypropylene and a) ethylene and a C3-C20alpha olefin and optionally a diene monomer, or b) propylene and a C2or C4-C20alpha olefin and optionally a diene monomer to second polymerization reaction conditions in the presence of a second polymerization catalyst and optionally hydrogen to form an impact copolymer comprising a copolymer phase dispersed within the matrix polypropylene; wherein the second polymerization reaction conditions comprise gas-phase polymerization reaction conditions, and the second polymerization catalyst comprises a Cl symmetric metallocene comprising a Group 4-6 metal.

[0167] Embodiment 2. The method of Embodiment 1, wherein the matrix polypropylene comprises an isotactic polypropylene homopolymer or a propyl ene / ethylene random copolymer.

[0168] Embodiment 3. The method of Embodiment 1 or Embodiment 2, wherein the first polymerization reaction conditions comprise slurry-phase polymerization reaction conditions or gas- phase polymerization reaction conditions.

[0169] Embodiment 4. The method of Embodiment 1 or Embodiment 2, wherein the first polymerization reaction conditions comprise slurry-phase polymerization reaction conditions.

[0170] Embodiment s. The method of any one of Embodiments 1-4, wherein the Cl symmetric metallocene comprises a Group 4 metal.

[0171] Embodiment 6. The method of any one of Embodiments 1-5, wherein the Cl symmetric metallocene has a structure represented bywherein:M is the Group 4 metal;T is a bridging group;Xi and X2 are each a univalent anionic ligand, or Xi and X2 are joined to form a metallocycle ring, a chelating ligand, a diene ligand, or an alkylidene;Ri is hydrogen, halogen, optionally substituted C1-C40alkyl, optionally substituted Cg- C14 aryl, optionally substituted C3-C13heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R"- SiR'3, wherein R" is C1-C10alkylene and R' is hydrogen, C1-C10alkyl, or C6-C10aryl;R2and R6are independently hydrogen, halogen, optionally substituted C1-C40alkyl, optionally substituted Cg-Ci4 aryl, optionally substituted C3-C13heteroaryl, -NR'2, -SR', -OR', - SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10alkylene and R' is hydrogen, C1-C10alkyl, or Ce-Cio aryl;R3is optionally substituted C1-C40alkyl or optionally substituted C6-C18aryl;R4and R5are independently H, R'", or OR'", wherein R'" is optionally substituted C1-C40alkyl, optionally substituted C6-C14aryl, optionally substituted C3-C13heteroaryl, or R4 and R5 are joined to form a C3-C62substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof; and R7, R8, R9, and R10are independently hydrogen, halogen, optionally substituted C1-C40alkyl, optionally substituted Cg-Ci4 aryl, optionally substituted C3-C13heteroaryl, -NR'2, -SR', - OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10alkylene and R' is hydrogen, C1-C10alkyl, or C6-C10aryl, or one or more of R5and Rg, Rg and R7, or R7and Rs are joined to form a C3- C62substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof.

[0172] Embodiment 7. The method of Embodiment 6, wherein the Group 4 metal is Hf or Zr.

[0173] Embodiment 8. The method of Embodiment 6 or Embodiment 7, wherein T is selected from the group consisting of CH2, CH2CH2, C(CH3)2, (Ph)2C, (p-(Et)3SiPh)2C, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4, and Si(CH2)4.

[0174] Embodiment 9. The method of any one of Embodiments 6-8, wherein Xi and X2 are independently halogen or C1-C6hydrocarbyl.

[0175] Embodiment 10. The method of any one of Embodiments 6-9, wherein R3is optionally substituted cyclohexyl, optionally substituted norbomanyl, optionally substituted adamantanyl, optionally substituted tert-butyl, or optionally substituted phenyl.

[0176] Embodiment 11. The method of any one of Embodiments 6-9, wherein R3is optionally substituted phenyl, optionally substituted naphthyl, or optionally substituted anthracenyl.

[0177] Embodiment 12. The method of any one of Embodiments 6-11, wherein R2and R6are hydrogen, and Ri is methyl.

[0178] Embodiment 13. The method of any one of Embodiments 6-12, wherein at least the second polymerization catalyst is disposed on a support material, optionally in combination with at least one activator.

[0179] Embodiment 14. The method of Embodiment 13, wherein the at least one activator is present and comprises at least one alumoxane.

[0180] Embodiment 15. The method of Embodiment 13, wherein the at least one activator is present and comprises at least one non-coordinating anion.

[0181] Embodiment 16. The method of any one of Embodiments 13-15, wherein the support material comprises silica.

[0182] Embodiment 17. The method of any one of Embodiments 1-16, wherein the first polymerization catalyst and the second polymerization catalyst are the same.

[0183] Embodiment 18. The method of Embodiment 17, wherein the first polymerization catalyst is provided to the first polymerization reaction conditions and is subsequently provided to the second polymerization reaction conditions within the matrix polypropylene, thereby becoming the second polymerization catalyst; wherein the second polymerization catalyst is disposed on a support material in combination with at least one activator.

[0184] Embodiment 19. The method of any one of Embodiments 1-18, wherein the first polymerization reaction conditions include a pressure higher than that of the second polymerization reaction conditions, and the second polymerization reaction conditions include a pressure of about 330 psi or below.

[0185] Embodiment 20. The method of any one of Embodiments 1-19, wherein the first polymerization reaction conditions and the second polymerization reaction conditions are conducted in a staged manner in a single reactor.

[0186] Embodiment 21. The method of any one of Embodiments 1-19, wherein the first polymerization reaction conditions and the second polymerization reaction conditions are conducted in a staged manner in separate reactors.

[0187] Embodiment 22. The method of any one of Embodiments 1-21, wherein the impact copolymer comprises about 60 wt% to about 95 wt% of the matrix polypropylene and about 5 wt% to about 40 wt% of the copolymer phase, each based on a total mass of the impact copolymer.

[0188] Embodiment 23. The method of any one of Embodiments 1-22, wherein the copolymer phase comprises about 10 wt% to about 90 wt% ethylene and about 10 wt% to about 90 wt% propylene, each based on a total mass of the impact copolymer.

[0189] Embodiment 24. The method of any one of Embodiments 1-23, wherein the impact copolymer comprises about 5 wt% to about 50 wt% non-propylene-derived monomer units.

[0190] Embodiment 25. The method of any one of Embodiments 1-24, wherein the matrix polypropylene comprises at least about 95 wt% propylene-derived monomer units.

[0191] Embodiment 26. The method of any one of Embodiments 1-25, wherein the copolymer phase has a polydispersity index of about 3 or less.

[0192] Embodiment 27. The method of any one of Embodiments 1-26, wherein the copolymer phase has an Mw value of about 250,000 or less.

[0193] To facilitate a better understanding of the embodiments of the present disclosure, the following examples of preferred or representative embodiments are given. In no way should the following examples be read to limit, or to define, the scope of the invention.EXAMPLES

[0194] Metallocene Catalysts. The following metallocenes were utilized for the polymerization reactions described further below. Activation of the metallocenes was performed by depositing the metallocenes on a silica support also containing a supported methylalumoxane.Metallocene AMetallocene C Metallocene D

[0195] Metallocene Syntheses. Metallocenes A-C were synthesized through introduction of the substituted phenyl group onto the 6-methyl-l,2,3,5-tetrahydro-s-indacene, 2-methyindene, or l,l,3,3,6-pentamethyl-l,2,3,5-tetrahydro-s-indacene parent ring system through Suzuki coupling of a phenylboronic acid to the corresponding brominated parent ring system, followed by lithiation, dimethylsilyl bridge introduction, and metallocene formation. Illustrative synthetic procedures may be found in U.S. Patent Application Publication 2022 / 0315680 and International Patent Application Publication WO 2023 / 034889. Metallocene D may be synthesized as described in International Patent Application Publication 2023 / 150480. Syntheses of Metallocenes C and D are provided below as representative examples.

[0196] Synthesis of Metallocene C. 4-(4-(tert-Butyl)phenyl)-l,l,3,3,6-pentamethyl-l,2,3,5- tetrahydro-s-indacene . 4-bromo- 1 , 1 ,3 ,3 ,6-pentam ethyl- 1 ,2,3 , 5-tetrahydro-s-indacene (0.98 g, 3.19 mmol), 4-tert-butylphenylboronic acid (0.57 g, 3.19 mmol), potassium carbonate (0.99 g, 7.03 mmol), bis(dibenzylideneacetone)palladium (0.02 g, 0.03 mmol), l,3,5,7-tetramethyl-6-phenyl- 2,4,8-troxa-6-phosphaadamantane (0.03 g, 0.10 mmol), tetrahydrofuran (15 mL), and nitrogen- purged water (3 mL) were combined in a tube. The tube was sealed, and the reaction was stirred and heated to 75°C for 16 hours. The reaction was then allowed to cool to room temperature. The reaction was concentrated in vacuo to remove tetrahydrofuran. The resulting residue was partitioned between water and hexane (50 mL). The hexane layer was collected, and the aqueous phase was washed once more with hexane (50 mL). The combined hexane extracts were washed with aqueous potassium carbonate and then brine. The hexane extract was dried over anhydrous magnesium sulfate then filtered. The filtrate was concentrated in vacuo to obtain the product as an orange solid (1.06 g, 92% yield).

[0197] Lithium 4-(4-(tert-butyl)phenyl)-2,5,5, 7, 7 -pentamethyl- 1,5, 6, 7-tetrahydro-s-indacenide. N-butyllithium (1.2 mL, 2.5 M in hexane) was combined with a precooled, stirred solution of 4-(4-tert-butyl)phenyl)-l,l,3,3,6-pentamethyl-l,2,5,5-tetrahydro-s-indacene (1.06 g) in 50 mL of diethyl ether. The reaction was stirred at room temperature for 5 hours, then concentrated under a stream of nitrogen and vacuum. The residue was stirred in 10 mL of pentane. The resulting suspension was fdtered over a plastic, fritted funnel. The filtered solid was washed further with two additions of pentane (5 mL). The solid was collected and concentrated under high vacuum to produce a light, white-pink solid (0.977 g, 90% yield).

[0198] ( 4-( 4-( tert-Bntyl)phenyl-2, 5, 5, 7, 7 -pentamethyl- 1, 5, 6, 7-tetrahydro-s-indacenyl)dimethyl- (2,3,4,5-tetramelhylcyclopenladienyl)silane. Lithium 4-(4-(tert-butyl)phenyl)-2,5,5,7,7- pentamethyl-l,5,6,7-tetrahydro-s-indacenide (0.98 g) was mixed with a solution of dimethyl(2,3,4,5-tetramethylcyclopentadienyl)silyl trifluoromethanesulfonate (0.88 g) in 20 mL of diethyl ether. The reaction was stirred at room temperature for 15 hours, then concentrated under a stream of nitrogen and vacuum. The residue was extracted twice with 20 mL of pentane filtered over CELITE®. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to produce an off-white foam (1.41 g, 97% yield).

[0199] Lithium 4-(4-(tert-biityl)phenyl)-l-(dimethyl(2,3,4,5- tetramethylcyclopentadieneidyl)silyl)-2, 5, 5, 7, 7-pentamethyl-l, 5, 6, 7-tetrahydro-s-indacenide. N- butyllithium (2.2 mL, 2.5 M in hexane) was added to a solution of (4-(4-(tert-butyl)phenyl)-2.5.5.7.7-pentamethyl-l, 5,6, 7-tetrahydro-s-indacenyl)dimethyl(2, 3,4,5- tetramethylcyclopentadienyl)silane (1.21 g) in 50 mL of diethyl ether. The reaction was stirred at room temperature, then concentrated under a stream of nitrogen and vacuum to produce a tan- brown solid (1.58 g, 98% yield) containing diethyl ether and pentane.

[0200] Dimethylsilyl (2, 5, 5, 7, 7-pentamethyl-4-( 4-tert-butyl-phenyl)-l, 5, 6, 7-tetrahydro-s- indacenyl)(2,3,4,5-tetramethyl-cyclopentadienyl) zirconium dichloride (Catalyst I2-Zr). A solution of zirconium chloride (0.345 g) in 10 mL of toluene was mixed with a precool solution of lithium 4-(4-(tert-butyl)phenyl)-l-(dimethyl(2,3,4,5-tetramethylcyclopentadienidyl)silyl)-2.5.5.7.7-pentamethyl-l, 5, 6, 7-tetrahydro-s-indacenide (0.89 g) in 30 mL of diethyl ether. The reaction was stirred at room temperature for 16 hours, then concentrated under a stream of nitrogen and vacuum. The residue was extracted twice with 20 mL of dicholoromethane and fdtered over CELITE®. The combined dichloromethane extracts were concentrated under a stream of nitrogen and vacuum to produce a brown solid. The solid was fdtered over a plastic, fritted funnel and wascombined with two 10 mL additions of hexane. The solid was collected and concentrated under high vacuum to yield a bright yellow solid (0.45 g, 43% yield).

[0201] Synthesis of Metallocene D. 5-tert-butyl-7-(4-tert-butylphenyl)-6-methoxy-2- methylindene. To a sealable flask were added 7-bromo-5-tert-butyl-6-methoxy-2-methylindene (0.791 g, 2.68 mmol), 4-tert-butylphenylboronic acid (0.480 g, 2.70 mmol, 1.01 equiv.), potassium carbonate (0.830 g, 6.01 mmol, 2.24 equiv.), bis(dibenzylideneacetone)palladium (0.020 g, 0.035 mmol, 0.013 equiv.), l,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (0.030 g, 0.10 mmol, 0.038 equiv.), and tetrahydrofuran (30 mL). Thereafter, nitrogen-bubbled water (10 mL) was added. The sealable flask was placed under a nitrogen atmosphere for 30 minutes, and then the flask was sealed, followed by stirring and heating at 75°C for 16 hours. The reaction mixture was then cooled to room temperature. The contents of the flask were transferred to a separate flask and concentrated in vacuo. The residue was partitioned between water (50 mL) and diethyl ether (50 mL). The organic phase was isolated, and the aqueous phase was further extracted with diethyl ether (50 mL). The combined diethyl ether extracts were washed with saturated aqueous potassium carbonate (50 mL) and then brine (50 mL). The organic extract was dried over anhydrous magnesium sulfate and filtered over a pad of silica, followed by washing of the magnesium sulfate pad with additional diethyl ether (3 x 50 mL). The diethyl ether filtrate was concentrated in vacuo to give a yellow solid. The yellow solid was then dissolved in pentane (50 mL) and again filtered through a pad of silica, followed by washing of the pad with additional pentane (3 * 50 mL). The pentane filtrate was concentrated in vacuo to afford the product as a white solid (0.544 g, 58% yield).JH NMR (400 MHz, C6D6): 8 7.47 (d, 2H, J = 8.4 Hz), 7.41- 7.33 (m, 3H), 6.43 (d, 1H, J = 2.2 Hz), 3.24 (s, 3H), 2.98 (s, 2H), 1.84 (s, 3H), 1.59 (s, 9H), 1.28 (s, 9H).

[0202] (6-(tert-butyl)-4-(4-(tert-butyl)phenyl)-5-methoxy-2-methyl-lH-inden-l- yl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl)silane. To a precooled, stirring solution of 5-tert-butyl-7-(4-tert-butylphenyl)-6-methoxy-2-methylindene (0.544 g, 1.56 mmol) in diethyl ether was added n-butyllithium (0.60 mL, 2.74 M in hexane, 1.6 mmol, 1.05 equiv.). The reaction mixture was stirred at room temperature for 16 hours and then concentrated under a stream of nitrogen and thereafter under high vacuum to afford white solid. The white solid was dissolved in diethyl ether (40 mL), and the resulting solution was then added to a stirring solution of tetramethylcyclopentadienyldimethylsilyl trifluoromethanesulfonate (0.425 g, 1.56 mmol, 1equiv.) in diethyl ether. The reaction mixture was stirred at room temperature for 1 hour, followed by concentration under a stream of nitrogen and then high vacuum. The residue was extracted with pentane (3 x 20 mL) and filtered over Celite. The combined pentane extracts were concentrated under a stream of nitrogen and then under high vacuum to afford the product as a white foam (0.615 g, 75% yield). ’H NMR (400 MHz, C6D6): 8 7.70 (d, 2H, J = 8.4 Hz), 7.61 (s, 1H), 7.43 (d, 2H, J = 8.4 Hz), 6.67 (s, 1H), 3.25 (s, 3H), 2.00 (s, 3H), 1.97 (s, 3H), 1.91 (s, 3H), 1.82 (s, 6H), 1.63 (s, 9H), 1.31 (s, 9H), -0.08 (s, 3H), -0.17 (s, 3H).

[0203] Lithium 6-( tert-bulyl)-4-( 4-( terl-butyl)phenyl)-l-(dimethyl( 2, 3, 4, 5-tetramethylcyclo penta-2,4-dien-l-ide-l-yl)silyl)-5-methoxy-2-methyl-lH-inden-l-ide. To a stirring solution of (6- (tert-butyl)-4-(4-(tert-butyl)phenyl)-5-methoxy-2-methyl-lH-inden-l-yl)dimethyl(2,3,4,5- tetramethylcyclopenta-2,4-dien-l-yl)silane (0.615 g, 1.17 mmol) in diethyl ether (50 mL), was added n-butyllithium (0.90 mL, 2.74 M in hexane, 2.5 mmol, 2.1 equiv.). The reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was then concentrated under a stream of nitrogen and then under high vacuum. The residue was washed with pentane (10 mL) and filtered through a plastic, fritted funnel. The solid was collected and dried under high vacuum to afford the product as a light orange solid (0.366 g, 58% yield). 'H NMR (400 MHz, THF-d8): 6 7.58 (d, 2H, J = 8.4 Hz), 7.49 (s, 1H), 7.37 (d, 2H, J = 8.4 Hz), 5.74 (s, 1H), 3.11 (s, 3H), 2.31 (s, 3H), 2.15 (s, 6H), 1.93 (s, 6H), 1.38 (s, 9H), 1.37 (s, 9H), 0.60 (s, 6H).

[0204] Dimethylsilyl (6-tert-butyl-4-(4-tert-butylphenyl)-5-methoxy-2-methylindenyl) (2, 3,4,5- tetramethylcyclopentadienyl) zirconium dichloride. To a stirring solution of lithium 6-(tert-butyl)- 4-(4-(tert-butyl)phenyl)-l-(dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-l-ide-l-yl)silyl)-5- methoxy-2-methyl-lH-inden-l-ide (0.366 g, 0.679 mmol) in diethyl ether (50 mL), was added zirconium dichloride (0.155 g, 0.665 mmol, 0.979 equiv.). Residual zirconium chloride was washed into the reaction mixture with toluene (5 mL). The reaction mixture was stirred at room temperature for 15 hours. The reaction mixture was then concentrated under a stream of nitrogen and followed by high vacuum. The residue was extracted with dichloromethane (2 x 20mL) and filtered over Celite. The combined dichloromethane extracts were concentrated under a stream of nitrogen and then under high vacuum to give a sticky orange foam (0.443 g). The foam was stirred in pentane (20 mL) for 1 hour, resulting in a yellow suspension. The suspension was filtered through a plastic, fritted funnel. The solid was collected and dried under high vacuum to afford the product as a yellow solid (0.253 g, 54% yield). 'H NMR (400 MHz, CD2C12): 8 7.60-7.52(m, 2H), 7.52-7.46 (m, 2H), 7.44 (s, 1H), 6.62 (s, 1H), 3.32 (s, 3H), 2.20 (s, 3H), 2.05 (s, 3H), 1 .98 (s, 3H), 1.90 (s, 3H), 1.89 (s, 3H), 1.37 (s, 9H), 1.35 (s, 9H), 1.19 (s, 3H), 1.08 (s, 3H).

[0205] Supported Methylalumoxane (SMAO) Preparation. Alumoxanes were deposited on two different silica supports by contacting the silica support with a methylalumoxane solution in toluene.

[0206] Supported Methylalumoxane 1 (SMAO-1). 12.8 g of PD 17062 silica particles (PQ Corporation, 512 m2 / g surface area, 1.43 mL / g pore volume, 66 pm average particle size, 111.7 A average pore diameter) was dehydrated at 600°C, slurried in 50 mb of toluene, and then cooled to -35°C. While stirring, 21.0 g of MAO solution (30 wt% solution in toluene) was slowly added to the silica slurry via pipette. The mixture was warmed to room temperature and stirred for 1 hour. After 1 hour, the mixture was heated to 100°C for an additional 2.5 hours. After 2.5 hours, the mixture was cooled to 55°C and fdtered while at this temperature. The collected solid was washed with toluene (2 x 30 mL) and pentane (2 x 30 mL) and dried in vacuo to afford 18.2 g of SMAO- 1 as a white free flowing powder.

[0207] Supported Methylalumoxane 2 (SMAO-2). 10.0 g of PD14024 silica particles (PQ Corporation, 611 m2 / g surface area, 1.41 mL / g pore volume, 66 pm average particle size, 91.7 A average pore diameter) was dehydrated at 200°C was suspended in -100 mL of dry toluene in a eelstir and cooled to -20 °C. While stirring, 22.0 g of MAO solution (30 wt% solution in toluene) was slowly added to the stirring silica slurry over 10 minutes. The mixture was stirred for 1.5 hours. After 1.5 hours, the temperature was raised to 100°C, and stirring was continued for an additional 3 hours. Upon cooling to room temperature, the slurry was filtered, and the collected solids were washed with toluene (2 x 50 mL) and pentane (2 x 50 mL) and were dried in vacuo for at least 2 hours to afford SMAO-2 as a free flowing white powder.

[0208] Supported Metallocene Preparation. Metallocenes A-D were supported on either SMAO-1 or SMAO-2 by the following procedure. 1.0 g of a given SMAO was slurried in 10 mL of toluene and placed on a shaker. While shaking, 0.514 mL of TIB AL (1 M in hexane) was then slowly added to the slurry. After 30 minutes, 20 pmol of the metallocene was added as a toluene solution. After an additional 2.5 hours of agitation, the slurry was filtered to collect the supported metallocene catalyst. The supported metallocene catalyst was washed with toluene (2 x 5 mL) and pentane (2 x 5 mL) and dried in vacuo. Thereafter, the supported metallocene catalysts were slurried in mineral oil for delivery to a polymerization reactor. Metallocenes A-D supported onthe silica support in combination with methylalumoxane are designated as Catalysts A-D in the tables and further description below, with the particular silica support being indicated in each instance.

[0209] General Procedure for Staged Slurry-Phase and Gas-Phase Polymerization. Slurry- Phase Polymerization Stage. A 2 L lab reactor was purged with nitrogen (N2) at 120°C for 1 hr to remove moisture therefrom. TIB AL (0.5-3 mL of 1 M solution in hexane) was added to the reactor, followed by hydrogen gas and / or ethylene and / or 1 -butene (depending of the polymer being synthesized). The hydrogen was introduced either via a mass flow meter (indicated in see units) or batch charged from a bomb pressurized to a known pressure (indicated in psi units) but was not further regulated during the slurry -phase polymerization stage. A metallocene catalyst (25-100 mg as a mineral oil slurry) and propylene were then added to the reactor to start the slurry-phase polymerization stage. The pressure was set at 400-470 psi to maintain the propylene in a liquid state at 70°C during the polymerization reaction. The polymerization temperatures, residence times, and other reaction conditions are specified in the tables below. When used, the amount of ethylene fed to the reactor was kept constant throughout the polymerization process by injecting a compensating amount of ethylene using a mass flow meter. When 1 -butene was used, the consumed 1 -butene was not replaced during the polymerization process. Gas-Phase Polymerization Stage. After the slurry-phase polymerization stage, the reactor was vented until a desired propylene pressure was reached, typically about 330 psi or less. Desired amounts of hydrogen gas and / or ethylene and / or 1 -butene were then added to the reactor to start the gas-phase polymerization. The polymerization temperatures, residence times, and other reaction conditions are specified in the tables below. The amounts of hydrogen gas and ethylene (if used) were kept constant throughout the gas-phase polymerization stage. When 1 -butene was used, the consumed 1 -butene was not replaced during the polymerization process. At the end of the gas-phase polymerization stage, the reaction was stopped by cooling and venting the reactor. The resulting impact copolymer was then collected and dried.

[0210] Polymer Characterization. The resulting polymers were characterized to determine molecular weights and thermal properties.

[0211] GPC-4D Analysis. Polymer molecular weights were determined by GPC-4D analysis, as detailed below and further described in U.S. Patent Application Publication 2018 / 0059076, which is incorporated herein by reference. The amount of copolymer phase and the C2content of thecopolymer phase in the matrix polypropylene was determined by fdtration and reinjection of the GPC eluent, followed by the further analyses described in U.S. Patent Application Publication 2018 / 0059076.

[0212] The distribution and the moments of molecular weight (Mw, Mn, Mz, Mw / Mn, etc.), the co-monomer content, and the branching index (g') were determined by using a high-temperature Gel Permeation Chromatography (Polymer Char GPC-IR) equipped with a multiple-channel bandfilter based infrared detector IR5 with a multiple-channel band filter based infrared detector ensemble IR5 with band region covering from about 2,700 cm’1to about 3,000 cm’1(representing saturated C-H stretching vibration), an 18-angle light scattering detector and a viscometer. Three Agilent PLgel 10-pm Mixed-B LS columns were used to provide polymer separation. Reagent grade 1,2,4-trichlorobenzene (TCB) (from Sigma-Aldrich) comprising -300 ppm antioxidant BHT can be used as the mobile phase at a nominal flow rate of -1.0 mL / min and a nominal injection volume of -200 pL. The whole system including transfer lines, columns, and detectors can be contained in an oven maintained at ~145°C. A given amount of sample can be weighed and sealed in a standard vial with -10 pL flow marker (heptane) added thereto. After loading the vial in the auto-sampler, the oligomer or polymer may automatically be dissolved in the instrument with -8 mb added TCB solvent at ~160°C with continuous shaking. The sample solution concentration can be from -0.2 to -2.0 mg / ml, with lower concentrations used for higher molecular weight samples. The concentration, c, at each point in the chromatogram can be calculated from the baseline-subtracted IR5 broadband signal, I, using the equation: c=al, where a is the mass constant determined with polyethylene or polypropylene standards. The mass recovery can be calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume. The conventional molecular weight (IR MW) is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to 10M gm / mole. The MW at each elution volume is calculated with Equation 1 :where the variables with subscript “PS” stand for polystyrene while those without a subscript are for the test samples. In this method, otps = 0.67 and Kps = 0.000175, a and K for other materials are calculated as described in the published literature (e.g., Sun, T., etal. (2001) Macromolecules, v.34, pg. 6812), except that for purposes of this present disclosure and claims thereto, a = 0.705 and K = 0.0000229 for ethylene-propylene copolymers and ethylene-propylene-diene terpolymers, a = 0.695 and K = 0.000579 for linear ethylene polymers, a = 0.705 and K = 0.0002288 for linear propylene polymers, and a = 0.695 and K = 0.000181 for linear butene polymers. 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.

[0213] The co-monomer 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 values are predetermined by NMR or FTIR. In particular, this provides the methyls per 1,000 total carbons (CH3 / IOOOTC) as a function of molecular weight. The shortchain branch (SCB) content per l,000TC (SCB / 1000TC) is then computed as a function of molecular weight by applying a chain-end correction to the CH3 / IOOOTC function, assuming each chain to be linear and terminated by a methyl group at each end. The weight % co-monomer is then obtained from Equation 2 in which f is 0.3, 0.4, 0.6, 0.8, and so on for C3, C4, Ce, Cs, and so on co-monomers, respectively: w2 = f * SCB / 1000TC .Equation 2

[0214] 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 in Equation 3 is obtainedThen 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 l,000TC (bulk CH3end / 1000TC) is obtained by weight-averaging the chain-end correction over the molecular- weight range. Then, Equations 4 and 5 applyw2b = f * bulk CH3 / 1000TCEquation 4 bulk SCB / 1000TC = bulk CH3 / 1000TC - bulk CH3end / 1000TCEquation 5 and bulk SCB / 1000TC is converted to bulk w2 in the same manner as described above.

[0215] 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.), as specified in Equation 6:Equation 6Here, AR(6) is the measured excess Rayleigh scattering intensity at scattering angle 6, c is the polymer concentration determined from the IR5 analysis, A2 is the second virial coefficient, P(0) is the form factor for a monodisperse random coil, and Kois the optical constant for the system, as specified in Equation 7:Equation 7 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 X = 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*(l-0.00126*w2) ml / mg and A2 = 0.0015 where w2 is weight percent butene comonomer.

[0216] 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, for the solution flowing through the viscometer is calculatedfrom their outputs. The intrinsic viscosity, at each point in the chromatogram is calculatedfrom the equation where c is concentration and is determined from the IR5 broadbandchannel output. The viscosity MW at each point is calculated as where αpsis 0.67 and Kpsis 0.000175.

[0217] The branching index (g'vis) 'scalculated using the output of the GPC-IR5-LS-VIS method as follows. The average intrinsic viscosity, °f the sample is calculated by Equation8:Equation 8 where the summations are over the chromatographic slices, i, between the integration limits.

[0218] The branching index g'vis is defined as Equation 9:Equation 9 where Mvis the viscosity-average molecular weight based on molecular weights determined by LS analysis and the K and oc are for the reference linear polymer, which are, for purposes of this present disclosure and claims thereto, α = 0.705 and K = 0.0000229 for ethylene-propylene copolymers and ethylene-propylene-diene terpolymers, oc = 0.695 and K = 0.000579 for linear ethylene polymers, α = 0.705 and K = 0.0002288 for linear propylene polymers, oc = 0.695 and K = 0.000181 for linear butene polymers. 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.

[0219] DSC Analysis. Thermal properties of the polymers were assayed by differential scanning calorimetry (DSC). In brief, peak melting point (Tm) and peak crystallization temperature (Tc) were determined by the following DSC procedure using a TA Instruments model DSC2500 device. Samples weighing approximately 5 to 10 mg were sealed in an aluminum hermetic sample pan and loaded into the instrument at about room temperature. The DSC data were recorded by first gradually heating the sample to about 200°C at a rate of about 10°C / minute. The sample was kept at about 200°C for 5 minutes, cooled to about -20°C at a rate of about 10°C / minute, followed byan isothermal hold for about 5 minutes, heating to about 200°C at about 10°C / minute, followed by an isothermal hold for about 5 minutes, and finally cooling to about 25°C at a rate of about 10°C / minute. Both the first and second cycle thermal events were recorded. The Tm and Tc values reported in the tables below were obtained during the second heating / cooling cycle unless otherwise noted.

[0220] HPLC-SEC procedure. The overall C2content of the impact copolymer was also assayed by high performance liquid chromatography-size exclusion chromatography (HPLC- SEC). In brief, a two-dimensional fractionation was carried out by gradient elution using 1- decanol and 1,2,4-trichlorobenzene as solvents from a graphitic column, followed by separation by size exclusion chromatography. Additional details can be found in U.S Patent 11,034,827, which is incorporated herein by reference.

[0221] MFR procedure. Melt flow rate was determined according to ASTM D-1238 condition L (2.16 kg, 230°C).

[0222] Flexural Modulus Procedure. The 1% secant flexural modulus, generally referred to as flexural modulus, was measured according to ASTM D 790 (A, 1.0 mm / min) using an injection molded ISO 37-Type 3 bar, a crosshead speed of 1 mm / min, and a support span of 30.0 mm.

[0223] Notched Izod Procedure. Notched Izod impact measurements were performed on notched, injection molded bars at the indicated temperature according to ASTM D256.

[0224] Example 1. Ethylene-Propylene Copolymer / iPP Impact Copolymers. Impact copolymers prepared using propylene only in the slurry-phase polymerization stage and ethylene / propylene in the gas-phase polymerization stage are characterized in Tables 1A, IB, 2 and 3 below. Table 1A summarizes the overall polymerization process under various run conditions, wherein hydrogen was not present during the slurry -phase polymerization stage. Table IB summarizes the overall polymerization process under various run conditions, wherein hydrogen was present during the slurry-phase polymerization stage. Table 2 summarizes the overall impact copolymer properties obtained under the various run conditions in Table 1A and selected run conditions in Table IB. Table 3 summarizes the properties of the ethylene-propylene copolymer phase extracted from the iPP phase for selected samples in Table 2. Extraction was performed by heating the impact copolymer in a solvent, filtering, and analyzing the solvent extract.Table 1ATable IBTable 2Table 3As shown, Catalysts C and D afforded the highest molecular weight values for the copolymer phase while still maintaining a relatively narrow molecular weight distribution (Mw / Mn) and high incorporation of ethylene. These parameters are desirable for the copolymer phase in impact copolymers. The C2values in Table 3 (GPC-4D values) are slightly lower than the overall C2values in Table 6 (see below, HPLC-SEC values), the differences for which are believed to arise from the different analysis procedures used in each case.

[0225] Example 2. Propylene-Butylene or Ethylene-Butylene Copolymer / iPP ImpactCopolymers. Impact copolymers prepared using propylene only in the slurry-phase polymerization stage and propylene / butylene or ethyl ene / butylene in the gas-phase polymerization stage were also prepared and characterized. Table 4 summarizes the overall polymerization process in various run conditions, wherein hydrogen was present during the slurry-phase polymerization stage.Table 4

[0226] Example 3. Ethylene-Propylene Copolymer / Ethylene-Propylene RandomCopolymer Matrix Impact Copolymers. Impact copolymers prepared using propylene / ethylene in the slurry- phase polymerization stage to produce a non-elastomeric random copolymer and ethylene / propylene in the gas-phase polymerization stage to produce an ethylene-propylene copolymer are characterized in Table 5 below. The ethylene-propylene copolymer contains a lower amount of ethylene monomer, such as 5 wt% to 30 wt% based on the ethylene-propylene copolymer. Table 5 summarizes the overall polymerization process in various run conditions, wherein hydrogen was present during the slurry- phase polymerization stage.Table 5

[0227] Additional Characterization Data. Selected additional characterization data for the impact copolymers produced in Entries 1-27 is provided in Table 6 below. Flexural modulus and Notched Izod Impact values for an iPP control are also provided.Table 6Significantly enhanced Notched Izod Impact values were realized in several instances. Atomic force microscopy (AFM) images (not shown) demonstrated that relatively large copolymer domains were formed using Catalyst C, whereas Catalyst A afforded more copolymer domains but of much smaller size. As further shown, a broad composition space with tunable stiffness / toughness balance may be realized. For example, impact copolymers having high MFR values (MFR>100 g / 10 min, 2.18 kg) with step-out toughness properties can be achieved.

[0228] All documents described herein are incorporated by reference herein for purposes of all jurisdictions where such practice is allowed, 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 disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the disclosure. Accordingly, it is not intended that the disclosure be limited thereby. For example, the compositions described herein may be free of any component, or composition not expressly recited or disclosed herein. Any method may lack any step not recited or disclosed herein. Likewise, the term “comprising” is considered synonymous with the term “including.” Whenever a method, composition, element or 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.

[0229] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the present specification and associated claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by one or more embodiments described herein. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claim, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0230] Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed. In particular, every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values. Also, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee. Moreover, the indefinite articles “a” or “an,” as used in the claims, are defined herein to mean one or more than one of the element that it introduces.

[0231] One or more illustrative embodiments are presented herein. Not all features of a physical implementation are described or shown in this application for the sake of clarity. It is understood that in the development of a physical embodiment of the present disclosure, numerous implementation-specific decisions must be made to achieve the developer's goals, such as compliance with system-related, business-related, government-related and other constraints, which vary by implementation and from time to time. While a developer's efforts might be timeconsuming, such efforts would be, nevertheless, a routine undertaking for one of ordinary skill in the art and having benefit of this disclosure.

[0232] Therefore, the present disclosure is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular embodiments disclosed above are illustrative only, as the present disclosure may be modified and practiced in different but equivalent manners apparent to one having ordinary skill in the art and having the benefit of the teachings herein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particularillustrative embodiments disclosed above may be altered, combined, or modified and all such variations are considered within the scope and spirit of the present disclosure. The embodiments illustratively disclosed herein suitably may be practiced in the absence of any element that is not specifically disclosed herein and / or any optional element disclosed herein.

Claims

CLAIMSThe invention claimed is:

1. A method comprising: exposing a) propylene and optionally b) a C2or C4-C20alpha-olefin to first polymerization reaction conditions in the presence of a first polymerization catalyst and optionally hydrogen to form a matrix polypropylene; and exposing the matrix polypropylene and a) ethylene and a C3-C20alpha olefin and optionally a diene monomer, or b) propylene and a C2or C4-C20alpha olefin and optionally a diene monomer to second polymerization reaction conditions in the presence of a second polymerization catalyst and optionally hydrogen to form an impact copolymer comprising a copolymer phase dispersed within the matrix polypropylene; wherein the second polymerization reaction conditions comprise gas-phase polymerization reaction conditions, and the second polymerization catalyst comprises a Cl symmetric metallocene comprising a Group 4-6 metal.

2. The method of claim 1, wherein the matrix polypropylene comprises an isotactic polypropylene homopolymer or a propylene / ethylene random copolymer.

3. The method of any preceding claim, wherein the first polymerization reaction conditions comprise slurry-phase polymerization reaction conditions or gas-phase polymerization reaction conditions.

4. The method of any preceding claim, wherein the C l symmetric metallocene has a structure represented bywherein:M is the Group 4 metal;T is a bridging group;X1and X2are each a univalent anionic ligand, or X1and X2are joined to form a metallocycle ring, a chelating ligand, a diene ligand, or an alkylidene;R1is hydrogen, halogen, optionally substituted C1-C40alkyl, optionally substituted C6-C14aryl, optionally substituted C3-C13heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10alkylene and R' is hydrogen, C1-C10alkyl, or C6-C10aryl;R2and R6are independently hydrogen, halogen, optionally substituted C1-C40alkyl, optionally substituted C6-C14aryl, optionally substituted C3-C 13 heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10alkylene and R' is hydrogen, C1-C10alkyl, or C6-C10aryl;R3is optionally substituted C1-C40alkyl or optionally substituted C6-C18aryl;R4and R5are independently H, R'", or OR'", wherein R'" is optionally substituted C1-C40alkyl, optionally substituted C6-C14aryl, optionally substituted C3-C13heteroaryl, or R4and R are joined to form a C3-C62 substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof; andR7, R8, R9, and R10are independently hydrogen, halogen, optionally substituted C1- C40alkyl, optionally substituted C6-C14aryl, optionally substituted C3-C13heteroaryl, -NR'2, -SR', - OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10alkylene and R' is hydrogen, C1-C10alkyl, or C6-C10aryl, or one or more of R5and R6, R6and R7, or R7and R8are joined to form a C3- C62substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof.

5. The method of claim 4, wherein a) the Group 4 metal is Hf or Zr; b) T is selected from the group consisting of CH2, CH2CH2, C(CH3)2, (Ph)2C, (p- (Et)3SiPh)2C, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4, and Si(CH2)4; c) X1and X2are independently halogen or C1-C6hydrocarbyl; d) R3is optionally substituted cyclohexyl, optionally substituted norbornanyl, optionally substituted adamantanyl, optionally substituted tert-butyl, or optionally substituted phenyl; e) wherein R2and R6are hydrogen, and R1is methyl or, f) any combination of a) through e).

6. The method of claim 4, wherein at least the second polymerization catalyst is disposed on a support material, optionally in combination with at least one activator.

7. The method of claim 6, wherein the at least one activator is present and comprises at least one alumoxane or at least one non-coordinating anion.

8. The method of any preceding claim, wherein the first polymerization catalyst and the second polymerization catalyst are the same.

9. The method of claim 8, wherein the first polymerization catalyst is provided to the first polymerization reaction conditions and is subsequently provided to the second polymerization reaction conditions within the matrix polypropylene, thereby becoming the second polymerization catalyst; wherein the second polymerization catalyst is disposed on a support material in combination with at least one activator.

10. The method of any preceding claim, wherein the first polymerization reaction conditions include a pressure higher than that of the second polymerization reaction conditions, and the second polymerization reaction conditions include a pressure of about 330 psi or below.11 . The method of any preceding claim, wherein the first polymerization reaction conditions and the second polymerization reaction conditions are conducted in a staged manner in either a single reactor or in separate reactors.

12. The method of any preceding claim, wherein the impact copolymer comprises about 60 wt% to about 95 wt% of the matrix polypropylene and about 5 wt% to about 40 wt% of the copolymer phase, each based on a total mass of the impact copolymer.

13. The method of any preceding claim, wherein the copolymer phase comprises about 10 wt% to about 90 wt% ethylene and about 10 wt% to about 90 wt% propylene, each based on a total mass of the impact copolymer.

14. The method of any preceding claim, wherein the impact copolymer comprises about 5 wt% to about 50 wt% non-propylene-derived monomer units.

15. The method of any preceding claim, wherein the matrix polypropylene comprises at least about 95 wt% propylene-derived monomer units.

16. The method of any preceding claim, wherein the copolymer phase has a polydispersity index of about 3 or less.

17. The method of any preceding claim, wherein the copolymer phase has an Mw value of about 250,000 or less.

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