Methods for producing impact copolymers using dianionic complexes containing eight-membered chelate rings

Abstract

Impact copolymers may be prepared using a dianionic complex having 8-membered chelate rings. Methods for forming impact copolymers comprise: exposing a) propylene and optionally b) a C2 or C4-C20 alpha-olefin and / or a a,w'- diene 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, or b) propylene and a C2 or C4-C20 alpha olefin 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 dianionic complex of a Group 3-6 metal, the dianionic complex omprising two eight-membered chelate rings containing the Group 3-6 metal.

Description

METHODS FOR PRODUCING IMPACT COPOLYMERS USING DIANIONIC COMPLEXES CONTAINING EIGHT-MEMBERED CHELATE RINGS FIELD

[0001] The present disclosure relates to impact copolymers and, more particularly, productionof impact copolymers using metal complexes. BACKGROUND

[0002] Impact copolymers (ICPs) are specialty polymers containing a crystalline phase, typicallyan 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 acopolymer phase having both a high molecular weight and narrow molecular weight distribution (polydispersity 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 conventional polymerization processes and polymerization catalysts. In addition, it may be difficult to form ICPs having balanced toughness and stiffness using conventional polymerization processes and polymerization catalysts.

[0004] ICPs may be prepared by compounding a copolymer phase within a crystalline phase, orby 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 multi- site catalysts in a staged slurry / gas-phase polymerization processes, wherein the crystalline phaseis 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, including the choice of monomer(s) to undergo polymerization. Ziegler-Natta catalysts may be advantageous in regard to the foregoing, since they may maintain high polymerization activity throughout both polymerization stages. A disadvantage of Ziegler-Natta catalysts when forming impact copolymers is that the multi-site nature of these types of catalysts tends to afford copolymer phases having an undesirably broad molecular weight distribution and relatively low molecular weights, thereby compromising the impact properties. While metallocene catalysts may sometimes be utilized as an alternative to Ziegler-Natta catalysts for impact copolymer formation, many metallocene catalysts are expensive and exhibit considerably lower polymerization activities than do Ziegler-Natta catalysts, particularly during the second polymerization stage, thereby resulting in incomplete filling of the crystalline phase with the copolymer phase. SUMMARY

[0005] In various aspects, the present disclosure provides methods for forming impactcopolymers, comprising: exposing a) propylene and optionally b) a C2or C4-C20alpha-olefin and / or a diene to first polymerization reaction conditions in the presence of a firstpolymerization catalyst and optionally hydrogen to form a matrix polypropylene; and exposing the matrix polypropylene and a) ethylene and a C3-C20 alpha olefin, or b) propylene and a C2 or C4- C20alpha olefin 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 dianionic complex of a Group 3-6 metal, the dianionic complex comprising two eight-membered chelate rings containing the Group 3-6 metal.

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

[0007] To assist those of ordinary skill in the relevant art in making and using the subject matterhereof, reference is made to the appended drawings. The following figures are included to illustrate certain aspects of the disclosure, and should not be viewed as exclusive configurations. The subject matter disclosed is capable of considerable modifications, alterations, combinations, and equivalents in form and function, as will occur to those skilled in the art and having the benefit of this disclosure.

[0008] FIG. 1 is a graph of flexural modulus as a function of Notched Izod value for samplesfrom Examples 2-4.

[0009] FIG. 2 is a plot of small-amplitude oscillatory shear of samples from Example 4 incomparison to a similar sample lacking long-chain branching.

[0010] FIG. 3 is a plot of extensional viscosity of samples from Example 4 in comparison to asimilar sample lacking long-chain branching. DETAILED DESCRIPTION

[0011] The present disclosure relates to impact copolymers and, more particularly, productionof impact copolymers using metal complexes.

[0012] The present disclosure provides polymerization methods for producing impactcopolymers having desirable properties, in which a dianionic complex of a Group 3-6 metal, such as a bis(phenolate) complex or similar complex containing two eight-membered chelate rings, 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 dianionic complexes 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 ofincompatibilities between the first and second polymerization catalysts and their associated polymerization reaction conditions may be substantially averted. Nevertheless, it may sometimes be advantageous to combine the dianionic complexes described herein with another type of catalyst, such as a metallocene, to provide desired polymerization performance.

[0013] Bis(phenolate) complexes and similar dianionic complexes may be well-suited forforming impact copolymers in staged polymerization processes. Such complexes are readily compatible with both slurry and gas-phase polymerization reaction conditions, as well as capable of facilitating extended catalyst production with high catalytic activities under both types of polymerization reaction conditions. Bis(phenolate) complexes and similar dianionic complexes also may provide a highly crystalline, predominantly isotactic polypropylene matrix and a copolymer phase having a high molecular weight. In contrast to some other types of Ziegler-Natta catalysts having multiple catalytic sites, bis(phenolate) complexes and similar dianionic complexes may afford polymers having a relatively limited molecular weight distribution (polydispersity index, Mw / Mn). Bis(phenolate) complexes and similar dianionic complexes are relatively simple to prepare and are typically isolated as a single isomer, which greatly simplifies their purification. By contrast, many metallocene catalysts used in polypropylene production are isolated as mixtures of diastereomers, thus leading to complicated isolation and purification processes. Therefore, the combination of properties attainable with bis(phenolate) and similar dianionic complexes may be particularly advantageous for producing impact copolymers according to the present disclosure.

[0014] As a further advantage, polymerization reactions mediated by the foregoing complexesmay utilize higher alpha olefins and / or ^^^-dienes as co-monomers in addition to propylene. Incorporation of such co-monomers may allow tailoring of the properties of the resulting impact copolymers to be realized. For example, incorporation of ^^^-diene monomers (e.g., 1,7- octadiene or similar long-chain hydrocarbyl groups having terminal unsaturation at both ends of the hydrocarbyl chain) into an impact copolymer may be advantageous, particularly within the matrix polypropylene. The resulting matrix polypropylene has long-chain branching and may still be effectively filled with a copolymer phase during the second polymerization stage. More importantly and surprisingly, introduction of long-chain branching in the matrix polypropylene may result in greater balancing of the stiffness and toughness of the resulting impact copolymers.

[0015] As a still further advantage, the bis(phenolate) complexes and similar dianioniccomplexes may be utilized in combination with metallocene catalysts in the course of forming impact copolymers according to the present disclosure. The metallocene catalysts may allow further tailoring of the properties of the impact copolymer to be realized. For example, vast differences in hydrogen response and starting molecular weight capability between bis(phenolate) catalysts and metallocenes can allow for ready tailoring of the resulting molecular weight distribution. Due to this functionality, it may be possible to prepare bimodal and multimodal polymers in a single reactor while using two catalysts on a single support. In addition, the inherently different activity of bis(phenolate) catalysts and metallocenes to various co-monomers may allow for compositional fine-tuning to take place across a given molecular weight distribution, especially in the dispersed (internal) phase of an impact copolymer. Thus, the present disclosure may allow impact copolymers having step-out performance with balanced stiffness and toughness to be realized.

[0016] In particular, it may be advantageous to pair a bis(phenolate) complex or similar dianioniccomplex with a metallocene having C1 symmetry in the course of forming impact copolymers according to the present disclosure. Metallocenes having C1 symmetry are asymmetric, meaning the metallocenes have no planes of symmetry about any axis. Advantageously, metallocenes having C1 symmetry may be effective for forming both isotactic polypropylene as a matrix polypropylene and elastomeric polymers as a copolymer phase under appropriate polymerization reaction conditions, as well as provide a balance between a sufficiently broad molecular weight distribution of the isotactic polypropylene and a sufficiently narrow molecular weight distribution and high molecular weight of the copolymer phase therein to afford a good impact copolymer performance. As such, metallocenes having C1 symmetry may further aid in tailoring the performance of impact copolymers when used in combination with bis(phenolates) and similar anionic complexes, such as promoting a balance between toughness and impact resistance.

[0017] As a final advantage, bis(phenolate) complexes and similar dianionic complexes may bereadily incorporated upon a support material for facilitating both slurry polymerization and gas- phase polymerization reaction processes. While located upon the support material, activation of such complexes may be realized using various types of activators, such as supported alumoxanes, acidic clays, and more discrete support-bound activators containing tethered aluminum or boron compounds. The latter supported activator may be particularly advantageous in avoiding use ofcostly methylalumoxane as an external activator, which is highly reactive and also prone to gelation. Definitions

[0018] For the purposes of the present disclosure, the new numbering scheme for groups of thePeriodic 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.

[0019] As used herein, Mn is number average molecular weight, Mw is weight averagemolecular weight, and Mz is z average molecular weight, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD), also referred to as polydispersity 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).

[0020] For purposes of this disclosure, when a polymer, copolymer, or oligomer, particularly apolyolefin, 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 arepresent 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 three mer 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 higherpolymers (or oligomers). A "decene polymer" or "decene copolymer," for example, is a polymer or copolymer comprising at least 50 mol% decene-derived units.

[0021] The term “independently,” when referenced to selection of multiple items from within agiven 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.

[0022] The terms “group,” “radical,” and “substituent” may be used interchangeably herein.

[0023] 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 “Cn” 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.

[0024] The terms “hydrocarbyl radical,” “hydrocarbyl,” and “hydrocarbyl group” may be usedinterchangeably 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 C1-C100 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- butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, including their substituted analogues.

[0025] Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom of thehydrocarbyl 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 atleast 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 join together to form a substituted or unsubstituted, saturated, unsaturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure.

[0026] The term “substituted” refers to replacement of at least one hydrogen atom or carbonatom 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.

[0027] The term “optionally substituted” means that a hydrocarbon or hydrocarbyl group can beunsubstituted 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.

[0028] The term “saturated hydrocarbon” means a hydrocarbon that contains zero carbon-carbondouble 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.

[0029] The term “alkyl” means a straight-chain, branched-chain, or cyclic hydrocarbon radicalhaving 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.

[0030] The term “alkylene” means a divalent alkyl radical. For example, a methylene group isa divalent alkylene radical.

[0031] The term “olefin” (alternately referred to as “alkene”) means a linear, branched, or cycliccompound of carbon and hydrogen having at least one double carbon-carbon bond.

[0032] The term “alkenyl” means a straight-chain, branched-chain, or cyclic hydrocarbon radicalhaving 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.

[0033] The term “diene” refers to an alkene having two carbon-carbon double bonds. The term“^^^-diene” refers to an alkene having an unsaturated carbon-carbon double bond at each end of a carbon chain.

[0034] The term “aromatic” means a hydrocarbyl compound or group containing a planarunsaturated 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 Hückel Rule and contain a cyclic cloud of 4n+2 π- electrons, where n is a positive integer.

[0035] The term “aryl” or “aryl group” means a carbon-containing aromatic ring or substitutedvariants 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.

[0036] A substituted aryl is an aryl group where at least one hydrogen atom of the aryl radicalhas 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*, -GeR*3, -SnR*, -SnR*3, -PbR*3, 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.

[0037] 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 heteroatom- containing group, such as halogen (e.g., F, Cl, Br, 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*, -GeR*3, -SnR*, -SnR*3, -PbR*3, and the like, where each R* is independently hydrogen, a hydrocarbyl, halogen, 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.

[0038] The term “heterocyclic” means a cyclic group where a ring carbon atom (or two or threering 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.

[0039] The term “substituted heterocyclic” means a heterocyclic group where at least onehydrogen 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 as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*, -SiR*3, -GeR*, -GeR*3, -SnR*, -SnR*3, -PbR*3, and the like, where each R* is independently hydrogen, a hydrocarbyl or halocarbyl radical.

[0040] The term “ring atom” means an atom that is part of a cyclic ring structure. By thisdefinition, a benzyl group has 6 ring atoms and tetrahydrofuran has five ring atoms.

[0041] 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).

[0042] 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).

[0043] The term “catalyst system” refers to a combination of at least one catalyst compound(e.g., at least one bis(phenolate) complex or similar dianionic complex and optionally, at least one metallocene, such as a C1 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.

[0044] In the present disclosure, a “catalyst” may be described as any of a catalyst precursor, apre-catalyst compound, catalyst compound, a catalyst, or a transition metal compound or complex, 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.

[0045] The term “alkoxide” means entities containing a C1 to C40 hydrocarbyl group bound tooxygen. The hydrocarbyl group may be straight-chain, branched, or cyclic, and be saturated orunsaturated, 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.

[0046] The term “complex” means molecules in which an ancillary ligand is coordinated to acentral 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.

[0047] The term “metallocene” means an organometallic compound with at least one ^-boundcyclopentadienyl moiety or substituted cyclopentadienyl moiety (such as substituted or unsubstituted cyclopentadienyl (Cp) and / or indenyl (Ind)) and more frequently two (or three) ^- bound cyclopentadienyl moieties or substituted cyclopentadienyl moieties. The terms “metallocene” and “metallocene catalyst” may be used interchangeably herein.

[0048] The term “phenolate” means a complex in which at least one phenol anion forms acovalent bond to metal ion. A “bis(phenolate)” refers to a complex in which two phenol anions form covalent bonds to a metal ion. Optionally, the two phenol anions may be joined together by a linker group to create a chelate ring of a desired size.

[0049] The term “scavenger” refers to a compound that may be added to a catalyst system tofacilitate 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.

[0050] The term “continuous” means a system that operates without interruption or cessation fora 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.

[0051] The term “bulk polymerization” or “slurry-phase polymerization” means apolymerization process in which the monomers and / or co-monomers being polymerized are usedas 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 carrier for 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.

[0052] The term “gas-phase polymerization” refers to a polymerization process in whichmonomers and / or co-monomers are present in a gaseous state and supported catalyst particles are fluidized within a reactor.

[0053] When used in the present disclosure, the following abbreviations may be used: dme is1,2-dimethoxyethane, Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is normal propyl, cPr is cyclopropyl, Bu is butyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu is para- tertiary butyl, nBu is normal butyl, sBu is sec-butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOAL is tri(n-octyl)aluminum, MAO is methylalumoxane, sMAO is supported methylalumoxane, Bn is benzyl (i.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. Dianionic Complexes

[0054] Suitable dianionic complexes, such as bis(phenolate) complexes, effective for promotingformation 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 preferably Zr. More generally, when suitably activated, the dianionic complexes 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 dianionic complexes are disposed upon a support material in combination with at least one activator. The dianionic complexes may be further effective to promote polymerization of at least one alpha olefin (e.g., propylene), optionally in combination with ethylene) in further combination with at least one ^^^-diene monomer to introduce long-chain branching within at least one of the matrix polypropylene and / or the copolymer phase of the impact copolymer. Further details regarding activation of the dianionic complexes and polymerization therewith is provided hereinbelow.

[0055] Bis(phenolate) complexes suitable for use in the present disclosure may have a structurerepresented by Formula 1.Formula 1 wherein:

[0056] M is a Group 3-6 metal, preferably a Group 4 metal;

[0057] E and E' are independently O, S, or NR9, wherein each R9 is independentlyhydrogen, a C1-C40optionally substituted hydrocarbyl, or a heteroatom-containing group;

[0058] Z is a Group 14-16 atom forming a dative bond to M;

[0059] A1ZA1’ is part of a heterocyclic Lewis base, designated as B, containing 4 to 40non-hydrogen atoms that links A2to A2’via a 3-atom bridge, with Z being the central atom of the 3-atom bridge;

[0060] A1 and A1' are independently C, N, or CR22, wherein each R22 is hydrogen oroptionally substituted C1-C20hydrocarbyl, such as optionally substituted C1-C20alkyl;

[0061] s a divalent group, optionally part of an optionally substitutedhydrocarbyl ring or optionally substituted heterocyclic ring, containing 2 to 40 non-hydrogen atoms that links A1to a first aryl group via a 2-atom bridge, the first aryl having E bonded thereto;

[0062] is a divalent group, optionally part of an optionally substitutedhydrocarbyl ring or optionally substituted heterocyclic ring, containing 2 to 40 non-hydrogen atoms that links A1'to a second aryl group via a 2-atom bridge, the second aryl group having E’ bonded thereto;

[0063] each L is a Lewis base;

[0064] each X is an anionic ligand;

[0065] n is 1, 2, or 3;

[0066] m is 0, 1, or 2;

[0067] n+m is not greater than 4; and

[0068] R1, R2, R3, R4, R1', R2', R3', and R4' are independently hydrogen, optionallysubstituted C1-C40 hydrocarbyl, a heteroatom, or a heteroatom-containing group, or one or more of R1and R2, R2and R3, R3and R4, R1'and R2', R2’and R3', or R3'and R4'are joined to form one or more optionally substituted hydrocarbyl rings or optionally substituted heterocyclic rings, each ring having 5, 6, 7, or 8 ring atoms, and optionally wherein the optionally substituted hydrocarbyl rings or optionally substituted heterocyclic rings are fused to one or more additional rings;

[0069] wherein:

[0070] when m is 2, any two L groups are optionally joined together to form a bidentateLewis base; or

[0071] an X is optionally joined to an L to form a monoanionic bidentate ligand bound toM; or

[0072] when n is 2 or 3, any two X are optionally joined together to form a dianionic ligandbound to M.

[0073] In more specific examples, the dianionic complex comprises a Group 4 metal. Preferably,the Group 4 metal M is zirconium.

[0074] Preferably, E and E’ are each O. As such, preferred dianionic complexes of the presentdisclosure may be bis(phenolate) complexes. When E and E’ are S or NR9, the complexes may be referred to as bis(phenothiolate) or bis(anilide) complexes.

[0075] When E or E’ is NR9, R9 is independently hydrogen, C1-C40 optionally substitutedhydrocarbyl, or a heteroatom-containing group. Preferably, R9is a C1-C20alkyl group or a C6-C10aryl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, phenyl, naphthyl, or the like, any of which may be optionally substituted.

[0076] Preferably, the heterocyclic Lewis base is a 5- or 6-membered heteroaromatic ring.Examples of such heterocyclic Lewis bases may include, for example, pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, and furan, any of which may be optionally substituted or fused to another ring. More preferably, Z of the heterocyclic Lewis base is N. Still more preferably, the heterocyclic Lewis base may be an optionally substituted pyridine.

[0077] In more specific examples, the heterocyclic Lewis base is a 2,6-disubstituted pyridinering, whereinare bonded to the 2- and 6-positions of the pyridine ring, respectively, and the nitrogen atom of the pyridine ring (Z in A1ZA1’) forms the dative bond to M.

[0078] and are each preferably a two-atom linker group, wherein the two-atom portion of the linker group refers to the number of atoms linking the heterocyclic Lewis base to an aryl group bearing E or E’. Example two-atom linker groups from which and may be independently selected include optionally substituted arylene, optionally substituted heteroarylene, or optionally substituted vinylene. Other examples of suitable two-atom linker groups may include non-aromatic groups, such as optionally substituted ethylene, optionally substituted cycloalkylene, optionally substituted heterocyclene, and the like.

[0079] In some examples, and may each be an optionally substitutedphenylene (e.g., an optionally substituted o-phenylene), an optionally substituted cycloalkylene, or an optionally substituted heteroarylene, any of which may be optionally fused to additional aromatic or non-aromatic rings. For example, in one or more embodiments, and may be independently selected from an optionally substituted o-phenylene, an optionally substituted 1,2-thienyl group, or an optionally substituted 1,2-furanyl group, any of which may be fused to an additional aromatic or non-aromatic ring. Preferably, and are the same.

[0080] In some examples, R2, R4, R2’, and R4’ are each hydrogen.

[0081] In some examples, R3 and R3’ are independently hydrogen, an optionally substituted C1-C40 hydrocarbyl group, or a halogen (e.g., F). More preferably, R3and R3’may be independently selected from an optionally substituted C1-C10 alkyl group, a halogen, or any combination thereof. R3and R3’may be the same or different, but preferably R3and R3’are the same. Examples of suitable hydrocarbyl groups for R3and R3’include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, adamantyl, 2-phenylisopropyl (^^^-dimethylbenzyl), 1,1,3,3- tetramethylbutyl, and the like.

[0082] In some examples, R1 and R1’ are independently selected from among optionallysubstituted C1-C40hydrocarbyl groups, more preferably optionally substituted C4-C16hydrocarbyl groups or optionally substituted C6-C16 hydrocarbyl groups. Still more preferably, R1and R1’may each be an optionally substituted bulky alkyl group (inclusive of tertiary alkyl groups), such as optionally substituted t-butyl, optionally substituted cyclohexyl, optionally substituted 1- methylcyclohexyl, optionally substituted norbornanyl, optionally substituted adamantanyl,optionally substituted 1,1,3,3-tetramethylbutyl, 2-phenylisopropyl, and the like. More preferably, R1and R1’are each independently an optionally substituted tertiary alkyl group, such as an optionally substituted adamantyl group or an optionally substituted t-butyl group. Optionally substituted adamantyl groups include 1-adamantyl and 2-adamantyl, such as 3,5-dimethyl-1- adamantyl or 3,5,7-tiimethyl-1-adamantyl. R1and R1’may be the same or different, but preferably R1and R1’are the same.

[0083] Non-limiting examples of X include, but are not limited to, an optionally substituted C1-C40 hydrocarbyl (such as an optionally substituted C1-C20 hydrocarbyl), an optionally substituted C4-C62 aryl, an optionally substituted C4-C62 heteroaryl, hydride, amide, alkoxide, sulfide, phosphide, halide, or a combination thereof. For example, each X may be independently a halide or a C1-C6hydrocarbyl or a C1-C10hydrocarbyl, such as methyl or benzyl, either of which may be further optionally substituted. In some embodiments, each X may be independently selected from chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl. In some embodiments of the present disclosure, one or more X may form a part of a fused ring or a ring system when combined with another X or with L.

[0084] In some examples, n is 2. In some or other examples, m is 0.

[0085] Accordingly, in more specific examples, suitable dianionic complexes for use in thepresent disclosure may be bis(phenolate) complexes (E=E’=O) having a structure represented by any of Formulas 2A-2E belowFormula 2Ewherein:

[0086] R1, R1’, R3, R3’, R22, X, and M are defined as above, Q is optional substitution at any openring position, and further optionally two Q may be joined to define a carbocyclic, heterocyclic, aromatic, or heteroaromatic ring fused to the phenyl, thienyl, furanyl, pyrrolyl, or cyclohexyl ring system of Formulas 2A-2E. Variable r is 0, 1, 2, 3, or 4 for the phenyl rings of Formula 2A; 0, 1, or 2 for the thienyl, furanyl, and pyrrolyl rings of Formulas 2B-2D; and 0, 1, 2, 3, 4, 5, 6, 7, or 8 for the cyclohexenyl ring system of Formula 2E. Variable q is 0, 1, 2, or 3, preferably 0 or 1. When present, Q is optionally substituted C1-C40 hydrocarbyl, a heteroatom, or a heteroatom-containing group or one, or two or more Q are joined to define the above-referenced carbocyclic, heterocyclic, aromatic, or heteroaromatic rings, wherein such rings may have 5, 6, 7, or 8 ring atoms and may be optionally fused to one or more additional rings.

[0087] More preferably, R1 and R1’ are each independently selected from a tertiary alkyl groupor a tertiary alkylaryl group, such as an adamantyl group (e.g., an optionally substituted 1- adamantyl group), an optionally substituted t-butyl group, an optionally substituted 2- phenylisopropyl group, or an optionally substituted 1,1,3,3-tetramethylbutyl group; R3and R3’are each selected from among a C1-C10 alkyl group, a C1-C10 alkylaryl group, or a halogen (e.g., F); and M is a Group 4 metal, preferably Zr. In more specific examples, R1and R1’are each independently an optionally substituted 1-adamantyl group or an optionally substituted t-butyl group, R3and R3’are independently an optionally substituted C1-C10 alkyl group or F; and M is a Group 4 metal, preferably Zr. Preferably, R1and R1’are the same, and R3and R3’are the same.

[0088] Illustrative examples of bis(phenolate) complexes having a structure represented byFormulas 2A-2E (M = Zr of Hg) may include, but are not limited to:

[0089] Any of the foregoing dianionic complexes may be incorporated in catalyst systemscomprising 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 dianionic complex. The activator and optional co-activator may convert the dianionic complex into a form effective for promoting olefin polymerization under suitable polymerization reaction conditions to form an impact copolymer, as described in further detail hereinbelow. Metallocene Complexes

[0090] The foregoing dianionic complexes, including bis(phenolate) complexes, of the presentdisclosure may be utilized in combination with a metallocene upon a support material to define a catalyst system containing both types of catalysts. Although any metallocene having suitable polymerization activity may be used, the metallocene may preferably have C1 symmetry. Additional description of suitable metallocenes having C1 symmetry follows. It should be noted that in the metallocenes represented by the formulas below, variable definitions are exclusive to the metallocenes in this section. For example, the definition for R1specified for the dianionic complexes described above and the definition for R1specified for the metallocene complexes below are mutually exclusive of one another.

[0091] Suitable metallocenes having C1 symmetry and effective for promoting formation ofimpact copolymers according to the disclosure herein may comprise a Group 3-6 metal, preferably a Group 4 metal (e.g., Ti, Zr, or Hf). When suitably activated, the metallocenes may likewise be effective for promoting polymerization of ethylenically unsaturated compounds, in combination at least one dianionic complex, such as a bis(phenolate) complex, as discussed above. The C1symmetric metallocenes may likewise be disposed upon a support material in combination with the at least one dianionic complex.

[0092] Metallocenes having C1 symmetry and suitable for use in the present disclosure may havea structure represented by Formula 3Formula 3 wherein in the C1 symmetric metallocene:

[0093] M is a transition metal of Group 3, 4, or 5 of the Periodic Table of Elements, such as aGroup 4 metal, for example, Zr, Hf, or Ti;

[0094] T is a bridging group;

[0095] X1 and X2 are each a univalent anionic ligand, or X1 and X2 are joined to form ametallocycle ring, a chelating ligand, a diene ligand, or an alkylidene;

[0096] R1 is hydrogen, halogen, optionally substituted C1-C40 alkyl, 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-C10 alkylene and each R' is hydrogen, C1-C10 alkyl, or C6-C10aryl; preferably, R1is C1-C10 alkyl, and more preferably, R1is methyl;

[0097] R2 and R6 are independently hydrogen, halogen, optionally substituted C1-C40 alkyl,optionally substituted C6-C14 aryl, an optionally substituted C3-C13heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R''-SiR'3, wherein R'' is C1-C10 alkylene and each R' is hydrogen, C1-C10 alkyl, or C6-C10aryl; preferably, at least one of R2and R6are hydrogen, and more preferably, R2and R6are both hydrogen;

[0098] R3 is an optionally substituted C1-C40 alkyl, an optionally substituted C6-C18 aryl, or anoptionally substituted C3-C13heteroaryl; more preferably R3is a bulky alkyl group, such as optionally substituted cyclohexyl, optionally substituted norbornanyl, optionally substituted adamantanyl, or optionally substituted tert-butyl, such as cyclohexyl, 1-adamantyl, 2-adamantyl, (1s,4s)-bicyclo[2.2.1]heptan-7-ide, (1R,4S)-bicyclo[2.2.1]heptan-2-ide, or (1s,4s)-bicyclo[2.2.1]heptan-1-ide; or R3 is an optionally substituted aryl group, more preferably anoptionally substituted phenyl group; even more preferably, R3is an optionally substituted phenyl group, an optionally substituted naphthyl group, or an optionally substituted anthracenyl group;

[0099] R4 and R5 are independently H, R''', or OR''', wherein R''' is an optionally substituted C1-C40 alkyl, 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

[0100] R7, R8, R9, and R10 are independently hydrogen, halogen, optionally substituted C1-C40alkyl, optionally substituted C6-C14 aryl, optionally substituted C3-C13heteroaryl, -NR'2, -SR', - OR', -SiR'3, -OSiR'3, -PR'2, or -R''-SiR'3, wherein R'' is C1-C10 alkylene and R' is hydrogen, C1-C10alkyl, or C6-C10 aryl, or one or more of R5 and R6, R6 and R7, or R7 and R8 are joined to form a C3-C62 substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or acombination thereof; preferably R7, R8, R9, and R10are methyl.

[0101] As a non-limiting illustration, in Formula 3 when R4 and R5 are joined to form apolycyclic 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[f]indenyl ligand contains such a 6-membered carbocyclic ring.The 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 suchsubstituents may be present. Example ligands in which R4and R5are fused to form a carbocyclic ring include those having structures represented by Formulas 4-6:Formula 4 Formula 5 Formula 6 where the wavy lines indicate a connection to M in Formula 3 (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, an optionally substituted naphthyl group, or an optionally substituted anthracenyl group.

[0102] When R4 and R5 are not joined to form a polycyclic ring structure, preferably both R4 andR5may be hydrogen, or R4may be OR''' and R5may be R''', wherein each R''' is independently selected. In specific examples, R4may be OR''', preferably OCH3and R5may be hydrogen.

[0103] In some embodiments of the present disclosure, X1 and X2 are each independently anoptionally substituted C1-C40 hydrocarbyl (such as an optionally substituted C2-C20 hydrocarbyl), 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-C6 hydrocarbyl or a C1-C10 hydrocarbyl, 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.

[0104] 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. In some 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, R'2CGeR'2, R'2GeGeR'2, R'2CGeR'2CR'2, R'2GeCR'2GeR'2, R'2SiGeR'2, 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, R'2C–NR'–CR'2CR'2, R'2C–NR'–CR'=CR', R'2CR'2C–NR'–CR'2CR'2, R'2C–P=CR', or R'2C–PR'– CR'2 where each R' is independently hydrogen or an optionally substituted C1-C20 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or phenyl), a C1-C20 halocarbyl, 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 CH2 or SiMe2, and more preferably SiMe2 or SiPh2.

[0105] Suitable alkyl groups in any selection herein may be optionally substituted andindependently 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.

[0106] Suitable aryl groups in any selection herein may be optionally substituted andindependently 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- isopropylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 3,5-di-isopropylphenyl, 2,5-di- isopropylphenyl, 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.

[0107] Suitable cycloalkyl groups in any selection herein may be optionally substituted andindependently chosen from, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, norbornanyl, adamantyl and the like.

[0108] In more specific examples, metallocenes suitable for forming an impact copolymeraccording to the disclosure herein may have a structure represented by Formula 3 and having bulky alkyl substitution at R3may include variables defined in accordance with the following:

[0109] M is a Group 4 metal; preferably, zirconium or hafnium;

[0110] T is a bridging group; preferably, CR11R12 or SiR11R12, wherein R11 and R12 areindependently hydrogen, an optionally substituted C1-C40hydrocarbyl, or an optionally substituted C6-C62 aryl, or R11and R12are joined to form a substituted or unsubstituted C4-C62 saturated 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 CH2 or SiMe2 or more preferably, T is SiMe2 or SiPh2;

[0111] X1 and X2 are each a univalent anionic ligand, or X1 and X2 are joined to form ametallocycle ring, a chelating ligand, a diene ligand, or an alkylidene, preferably X1and X2areindependently a halide (F, Cl, Br, I) or a C1-C6hydrocarbyl, such as a C1-C6alkyl or phenyl, more preferably methyl;

[0112] R1 is hydrogen, a halogen, an optionally substituted C1-C40 hydrocarbyl, an optionallysubstituted 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-C10 alkylene and R' is hydrogen, C1-C10 alkyl, or C6- C10 aryl; preferably, R1is C1-C10 alkyl; more preferably, R1is methyl;

[0113] R2 and R6 are independently hydrogen, a halogen, 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-C10 alkylene 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;

[0114] R3 is a bulky alkyl group; preferably R3 is an optionally substituted cyclohexyl, optionallysubstituted norbornanyl, optionally substituted adamantyl (e.g., 1-adamantyl, 2-adamantyl, (1s,4s)-bicyclo[2.2.1]heptan-7-yl, (1R,4S)-bicyclo[2.2.1]heptan-2-yl, (1s,4s)- bicyclo[2.2.1]heptan-1-yl) , or optionally substituted t-butyl;

[0115] R4 and R5 are 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; and

[0116] R7, R8, R9, and R10 are 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' ishydrogen, C1-C10 alkyl, or C6-C10 aryl, or one or more of R5 and R6, R6 and R7, or R7 and R8 arejoined 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.

[0117] If R4 and R5 are not joined to form a cyclic or polycyclic ring structure, preferably bothR4and R5may be hydrogen, or R4may be OR''' and R5may be R''', wherein each R''' is independently selected. In specific examples, R4may be OR''', preferably OCH3, and R5may be hydrogen, or R4may be OR''', preferably OCH3, and R5may be an alkyl group, preferably t-butyl.

[0118] Accordingly, in some embodiments, suitable metallocenes having C1 symmetry and abulky alkyl group at R3may have a structure represented by Formula 7Formula 7 wherein:

[0119] M is a Group 4 metal, preferably Zr or Hf, more preferably Hf;

[0120] X1 and X2 are independently a halide (F, Cl, Br, I) or a C1-C6 alkyl; preferably X1 and X2are each chloride or methyl;

[0121] R1 is C1-C10 alkyl group, preferably methyl;

[0122] R3 is a bulky alkyl group, preferably optionally substituted cyclohexyl, optionallysubstituted norbornanyl, optionally substituted adamantyl, or optionally substituted t-butyl; preferable groups include 1-adamantyl, 2-adamantyl, (1s,4s)-bicyclo[2.2.1]heptan-7-ide, (1R,4S)- bicyclo[2.2.1]heptan-2-ide, or (1s,4s)-bicyclo[2.2.1]heptan-1-ide;

[0123] R4 and R5 are 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;

[0124] R6 is hydrogen, halogen, optionally substituted C1-C40 alkyl, 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-C10 alkylene and each R' is hydrogen, C1-C10 alkyl, or C6-C10aryl; preferably R6is hydrogen or optionally substituted phenyl;

[0125] R7, R8, R9, and R10 are 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-C10 alkylene and R' ishydrogen, C1-C10 alkyl, or C6-C10 aryl, or one or more of R5 and R6, R6 and R7, or R7 and R8 arejoined to form a substituted or unsubstituted C4-C62saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof; preferably R5, R6, R7, and R8are each C1-C10 alkyl; more preferably R5, R6, R7, and R8are each methyl; and

[0126] R11 and R12 are independently optionally substituted C1-C10 alkyl, or optionallysubstituted 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.

[0127] In some examples, R4 and R5 may form a 5-membered carbocyclic ring. Specificexamples 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 8A, preferably wherein R6is hydrogen or optionally substituted phenyl, and more preferably wherein R6is hydrogen. The metallocene represented by Formula 8B lacks the 5-membered carbocyclic ring fused to the indenyl group.Formula 8A Formula 8B wherein in Formula 8A:

[0128] Q is an optional C1-C6 alkyl 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.

[0129] Illustrative examples of metallocenes having a structure represented by Formulas 7, 8A,and 8B may include, but are not limited to:M

[0130] In other specific examples, metallocenes suitable for forming an impact copolymeraccording to the disclosure herein may have a structure represented by Formula 3 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.

[0131] M is a Group 4 metal; preferably, zirconium or hafnium;

[0132] T is a bridging group; preferably, CR11R12 or SiR11R12, wherein R11 and R12 areindependently hydrogen, an optionally substituted C1-C40hydrocarbyl, or 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 SiMe2and more preferably, T is SiMe2or SiPh2;

[0133] X1 and X2 are each a univalent anionic ligand, or X1 and X2 are joined to form ametallocycle ring, a chelating ligand, a diene ligand, or an alkylidene, preferably X1and X2areindependently a halide (F, Cl, Br, I) or a C1-C6hydrocarbyl, such as a C1-C6alkyl or phenyl, more preferably methyl;

[0134] R1 is hydrogen, a halogen, an optionally substituted C1-C40 hydrocarbyl, an optionallysubstituted 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-C10 alkylene and R' is hydrogen, C1-C10 alkyl, or C6- C10 aryl; preferably, R1is C1-C10 alkyl; more preferably, R1is methyl;

[0135] R2 and R6 are independently hydrogen, a halogen, 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-C10 alkylene 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;

[0136] R3 is optionally substituted phenyl, optionally substituted naphthyl, or optionallysubstituted anthracenyl;

[0137] R4 and R5 are independently H, R''', or OR''', wherein R''' is an optionally substituted C1-C40 alkyl, 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

[0138] R7, R8, R9, and R10 are independently hydrogen, a halogen, an optionally substituted C1-C40 hydrocarbyl, 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-C10 alkylene and R' ishydrogen, C1-C10 alkyl, or C6-C10 aryl, or one or more of R5 and R6, R6 and R7, or R7 and R8 arejoined to form a substituted or unsubstituted C4-C62saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof; preferably R5, R6, R7, and R8are each C1-C10 alkyl; more preferably R5, R6, R7, and R8are each methyl.

[0139] Accordingly, in some embodiments, suitable metallocenes having C1 symmetry and anoptionally substituted phenyl group at R3may have a structure represented by Formula 9Formula 9 wherein:

[0140] R13-R17 are independently hydrogen, an optionally substituted C1-C40 hydrocarbyl, anoptionally 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-C10 alkyl, or C6-C10aryl, or R13and R14, R14and R15, R15and 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;

[0141] M is a Group 4 metal, preferably Zr or Hf;

[0142] X1 and X2 are independently a halide (F, Cl, Br, I) or a C1-C6 alkyl; preferably X1 and X2are each chloride or methyl;

[0143] R1 is C1-C10 alkyl group, preferably methyl;

[0144] R4 and R5 are independently H, R''', or OR''', wherein R''' is an optionally substituted C1-C40 alkyl, or R4and R5are joined to form a C3-C62 substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof;

[0145] R6 is hydrogen, halogen, optionally substituted C1-C40 alkyl, optionally substituted C6-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 each R' is hydrogen, C1-C10alkyl, or C6-C10aryl; preferably R6is hydrogen or optionally substituted phenyl;

[0146] R7, R8, R9, and R10 are 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' ishydrogen, C1-C10 alkyl, or C6-C10 aryl, or one or more of R5 and R6, R6 and R7, or R7 and R8 arejoined to form a substituted or unsubstituted C4-C62 saturated or unsaturated cyclic or polycyclicring structure, or a combination thereof; preferably R5, R6, R7, and R8are each C1-C10alkyl; more preferably R5, R6, R7, and R8are each methyl; and

[0147] R11 and R12 are independently optionally substituted C1-C10 alkyl, or optionallysubstituted 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.

[0148] In some examples, R4 and R5 may form a 5-membered carbocyclic ring. Specificexamples 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 10A, preferably wherein R6is hydrogen or optionally substituted phenyl, and more preferably wherein R6is hydrogen. The metallocene represented by Formula 10B lacks the 5-membered carbocyclic ring fused to the indenyl group.wherein in Formula 10A:

[0149] Q is an optional C1-C6 alkyl 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.

[0150] Illustrative examples of metallocenes having a structure represented by Formulas 9, 10A,or 10B may include, but are not limited to:Hf may replace Zr in any of the foregoing metallocenes.

[0151] 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.

[0152] Also for clarity, the following ring structures are substituted indenyl groups, wheresubstitutions 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.

[0153] Any of the foregoing metallocenes may be incorporated in catalyst systems containing adianionic complex described herein and 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 and the dianionic complex. The activator and optional co-activator may convert the metallocene into a form effective for promoting olefin polymerization under suitable polymerization reaction conditions to form an impact copolymer, as described in further detail hereinbelow. Support Materials

[0154] In conducting polymerization reactions to form an impact copolymer according to thepresent disclosure, the dianionic complex, such as a bis(phenolate) complex, and the optional 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 dianionic complex and the 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.Further, the activator may be covalently bonded to the support material and / or otherwise chemically modify the support material. Additional activator details are provided below.

[0155] 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 dianionic complexes and optional 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 Al2O3, 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.

[0156] The support material may be optionally treated with an electron-withdrawing anion. Theelectron-withdrawing anion may increase the Lewis or Brønsted 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.

[0157] The support material may be optionally fluorided by introducing a fluoride-containinganion. 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, SO2ClF, F2, SiF4, SF6, ClF3, ClF5, BrF5, IF7, NF3, HF, BF3, NHF2, NH4HF2, and combinations thereof.

[0158] Non-limiting examples of cations suitable for use in the present disclosure in combinationwith the electron-withdrawing anion include ammonium, trialkylammonium, tetraalkylammonium, tetraalkylphosphonium, H+, [H(OEt2)2]+, [HNR3]+(R is a C1-C20 hydrocarbyl group, which may be the same or different and optionally substituted), or combinations thereof.

[0159] The method by which the support material is contacted with the electron-withdrawinganion, 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.

[0160] The support material, such as an inorganic oxide and more preferably silica, may have asurface 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.

[0161] The support material, such as an inorganic oxide and more preferably silica, may have apore 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 / g to about 4 cc / g. The average pore size of the support material may be about 10 Å to about 1000 Å, or about 10 Å to about 500 Å, or about 10 Å to about 100 Å, or about 100 Å to about 1000 Å, or about 100 Å to about 500 Å, or about 500 Å to about 1000 Å.

[0162] The support material, such as an inorganic oxide and more preferably silica, may have anaverage particle size of about 5 µm to about 500 µm, or about 5 µm to about 100 µm, or about 5µm to about 50 µm, or about 50 µm to about 500 µm, or about 50 µm to about 100 µm, or about 100 µm to about 500 µm.

[0163] Before employing the support material in a polymerization reaction or before disposinga dianionic complex 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 dianionic complex and optionally an activator to produce a catalyst system.

[0164] To accomplish the foregoing, the support material may be slurried in a non-polar solventand contacted with a solution of the dianionic complex, optionally a metallocene, and optionally 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 dianionic complex thereon. Alternately, the slurry of the support material may first be contacted with the dianionic complex 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.

[0165] Suitable non-polar solvents for loading the dianionic complex, the optional metallocene,and the optional activator upon the support material may include those in which the dianionic complex, the optional metallocene, and the optional 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 materials including cycloalkanes, such as cyclohexane. Aromatic hydrocarbons, such as benzene, toluene, and ethylbenzene, may also be employed. Activators

[0166] In most cases, at least one activator is present upon the support material in combinationwith the dianionic complex and the optional metallocene. Suitable activators may include, forexample, alumoxanes (e.g., methylalumoxane-MAO), non-coordinating anions, or any combination thereof.

[0167] Alumoxanes are generally oligomeric compounds containing-Al(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 3A, 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.

[0168] When the activator is an alumoxane (modified or unmodified), some embodiments mayselect 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.

[0169] 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(C10F7)4]-.

[0170] The term “non-coordinating anion” (NCA) means an anion which either does notcoordinate to a cation or which is only weakly coordinated to a cation thereby remaining sufficiently 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 byabstraction 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.

[0171] “Compatible” non-coordinating anions are those which are not degraded to neutralitywhen 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.

[0172] It is within the scope of the present disclosure to use an ionizing, neutral, or ionicactivator, such as tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, a tris perfluorophenylboron metalloid precursor or a trisperfluoronaphthylboron metalloid precursor, polyhalogenated 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.

[0173] In preferred embodiments, boron-containing NCA activators represented by Formula 11below may be used,Formula 11where Z is (L-H) or a reducible Lewis acid; L is a neutral Lewis base; H is hydrogen; (L-H) is aBronsted acid; Ad-is a boron-containing non-coordinating anion having the charge d-; and d is 1, 2, or 3.

[0174] The cation component Zd+ may include Bronsted acids such as protons or protonatedLewis bases or reducible Lewis acids capable of protonating or abstracting a moiety from the metal-ligand complexes to afford a cationic metal-ligand complex.

[0175] 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 C1 to C40 hydrocarbyl, or a substituted C1 to C40 hydrocarbyl). Preferably, the reducible Lewis acids in Formula 9 above defined as "Z" include those represented by the formula: (Ph3C), 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 C1 to C20 alkyls or aromatics, and preferably Zd+is triphenylcarbonium.

[0176] When Zd+ is the activating cation (L-H)d+, it is preferably a Bronsted acid, capable ofdonating 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 triethylphosphine, 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.

[0177] 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.

[0178] Illustrative but not limiting examples of boron compounds which may be used as anactivator 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.

[0179] Most preferably, the activator Zd+ (Ad-) is one or more of N,N-dimethylaniliniumtetra(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-], 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl) pyrrolidinium; [Me3NH+][B(C6F5)4-], 1-(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.

[0180] Bulky activators are also useful herein as NCAs. "Bulky activator" as used herein refersto anionic activators represented by Formulas 12 or 13 below.Formula 12 Formula 13 In Formulas 12 and 13, each R1ais, independently, a halide, preferably a fluoride; Ar is a substituted or unsubstituted aryl group (preferably a substituted or unsubstituted phenyl), preferably substituted with C1to C40hydrocarbyls, preferably C1to 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 C1to C20hydrocarbyl or hydrocarbylsilyl 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 C1to 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 Å, greater than 300 cubic Å, or greater than 500 cubic Å, as specified below.

[0181] Preferably, (Ar3C)d+ is (Ph3C)d+, where Ph is a substituted or unsubstituted phenyl,preferably substituted with C1to C40hydrocarbyls or substituted C1to C40hydrocarbyls, preferably C1 to C20 alkyls or aromatics or substituted C1 to C20 alkyls or aromatics.

[0182] In some or other examples, activation may take place with an organoaluminum compoundhaving haloaryl groups, such as a pentafluorophenyl group, and a cationic group (in neutral form) may be introduced with the support material at a molar ratio of about 0.01:1 to about 1:1, based on the molar concentration of, respectively, the organoaluminum compound having haloaryl groups or the cationic group (in neutral form) relative to a molar concentration of hydroxyl groups upon the support material. Within this range, a molar ratio of less than or equal to about 1:1 can be employed, such as less than or equal to about 0.5:1, or less than or equal to about 0.25:1. The amount of hydroxyl groups upon the support material may be determined, for example, by Attenuated Total Reflectance Infrared Spectroscopy (ATRIR), X-ray Photoelectron Spectroscopy (XPS), NMR, or Secondary Ion Mass Spectroscopy (SIMS).

[0183] The organoaluminum compound having haloaryl groups may be substantially dispersedover the total surface area of the support material, wherein an amount of coverage upon the supportmaterial may be at least about 75%, or at least about 90% of the total surface area of the support material.

[0184] After the organoaluminum compound has been introduced to the support material, theremay be remaining hydroxyl groups on the support material, which may be detrimental to overall catalyst activity. To prevent catalyst deactivation, the remaining hydroxyl groups can be treated with a second aluminum compound having a formula of Al(R1)(R2)(R3), wherein R1is C1-C40 alkyl, a substituted or unsubstituted C6-C40aryl, or hydride, and R2and R3are independently, C1- C40 alkyl, alkoxy, heteroalkyl, or a substituted or unsubstituted C6-C40 aryloxy or heteroaryl group.

[0185] The second aluminum compound may contain simple components, such as an alkylaluminum, and phenolic derivatives, such as BHT. A protonolysis reaction between an aluminum alkyl or aluminum hydride and surface hydroxyl groups results in deactivation of the hydroxyl groups via release of hydrocarbon or hydrogen, and leads to anchoring of the second aluminum compound on the support material. This effectively reduces or eliminates the possibility of active protons interfering with the catalyst activity.

[0186] The second aluminum compound may be introduced to the activator-bound support at amolar ratio of about 0.1:1 to about 10:1, based on the molar concentration of, respectively, the antioxidant (BHT) relative to the molar concentration of hydroxyl groups on the support material before treatment with the organoaluminum compound containing haloaryl groups. Within this range, a molar ratio of less than or equal to about 5:1 can be employed, such as less than or equal to about 2:1, and most preferably less than or equal to about 1:1. In some embodiments within these ranges, a molar ratio of the second aluminum compound relative to hydroxyl groups can be less than or equal to about 0.9:1, or less than or equal to about 0.8:1, or less than or equal to 0.5:1, or less than or equal to about 0.25:1.

[0187] In more specific examples, the non-coordinating anion activator may be formed in situupon a support material as a reaction product of an organoaluminum compound containing electron-withdrawing substituents, preferably three electron-withdrawing substituents, preferably one or more haloaryl groups (e.g., pentafluorophenyl), and a tertiary arylamine (e.g., N,N- diethylaniline or similar amines). The reaction product may further complex surface hydroxyl groups or a portion thereof upon the support material. Tris(pentafluorophenyl)aluminum may be a suitable organoaluminum compound for accomplishing the foregoing. Tris(pentafluorophenyl)aluminum or similar organoaluminum compounds may complex surfacehydroxyl groups via the aluminum atom to form an oxyanion, with the negative charge being balanced by the resulting protonated tertiary arylamine. Remaining surface hydroxyl groups may be blocked using a second organoaluminum compound lacking electron-withdrawing substituents, such as (BHT)2AlEt or a similar second organoaluminum compound as specified above, wherein the remaining surface hydroxyl groups are blocked with a (BHT)2Al complex.

[0188] "Molecular volume" is used herein as an approximation of spatial steric bulk of anactivator 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 Å, 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 Å3, and the Calculated Total MV for tetrakis(perfluorophenyl)borate is four times 183 Å3, or 732 Å3.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.

[0189] 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.

[0190] It is also within the scope of this disclosure that the dianionic complex may be activatedwith combinations of alumoxanes and NCAs (see for example, U.S. Patents 5,153,157 and 5,453,410; EP 0573120 B1, 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.

[0191] In addition to activators, scavengers or co-activators can be used. Aluminum alkyl ororganoaluminum compounds which may be utilized as scavengers or co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n- octylaluminum, ethylaluminum dichloride, diethylaluminum chloride, and diethyl zinc.

[0192] Chain transfer agents can also be used in the compositions and / or processes describedherein. Useful chain transfer agents are typically alkylalumoxanes, a compound represented by the formula AlR3, ZnR2(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.

[0193] In any embodiment, an alumoxane, such as MAO, may be mixed in an inert solvent, suchas 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 60oC, including room temperature deposition, may also be effective. NCAs may be deposited upon the support material in a similar manner. Catalyst Systems

[0194] The present disclosure further provides catalyst systems comprising a support material; adianionic complex, such as a bis(phenolate) complex; and an optional metallocene disposed upon the support material; and an activator selected from an alumoxane or NCA also disposed upon the support material. Preferably, the activator may be an NCA formed fromtris(pentafluorophenyl)aluminum or a similar Lewis acid. The dianionic complex, the optional 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 dianionic complex and / or the optional metallocene include the Al:M ratios specified above. Polymerization Methods

[0195] Polymerization methods for producing impact copolymers according to the presentdisclosure may comprise: exposing a) propylene and optionally a C2or C4-C20alpha olefin and / or a diene 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, or b) propylene and a C2 or C4-C20 alpha olefin 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 at least the second polymerization catalyst comprises a dianionic complex comprising a Group 3-6 metal, in which the dianionic complex comprises two eight-membered chelated rings containing the Group 3-6 metal. Suitable dianionic complexes are discussed in more detail above. Preferably, the dianionic complex comprises a Group 4 metal, more preferably Zr, as described in more detail above. The dianionic complex may be present upon a support material, preferably in combination with an activator, to define a catalyst system. Optionally, a metallocene, such as a metallocene having C1 symmetry, may also be present in the catalyst system.

[0196] The first polymerization reaction conditions may comprise slurry-phase polymerizationreaction 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.

[0197] As indicated above, when producing impact copolymers according to the presentdisclosure, the matrix polypropylene may be formed under first polymerization reaction conditions involving slurry-phase polymerization, and the copolymer phase may be grown in the matrixpolypropylene 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 a 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.

[0198] Accordingly, in various examples, the first polymerization reaction conditions and thesecond 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 conditions to produce the copolymer phase within the matrix polypropylene.

[0199] Both slurry-phase polymerizations and gas-phase polymerizations may be conducted inthe 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.

[0200] 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 temperature ranging 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 be separated from the polymer and recycled, optionally after a distillation, to the reactor, or these components may be conveyed directly to a reactor forming a 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.

[0201] Gas-phase polymerization processes may operate by circulating one or more gaseousmonomers 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 contacting the 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 even 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.

[0202] The first polymerization reaction conditions may include a pressure that is higher thanthat of the second polymerization reaction conditions. In non-limiting examples, the pressure under the second polymerization reaction conditions (i.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.

[0203] Slurry-phase polymerization reactions and gas-phase polymerization reactions may beconducted in the presence or absence of one or more scavengers. Typical scavengers include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, diethyl zinc, or excess alumoxane activator.

[0204] If desired, hydrogen may be added during either of the polymerization reactions to alterthe 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.

[0205] The dianionic complex that is the second polymerization catalyst in the secondpolymerization stage may also be utilized as the first polymerization catalyst in the first polymerization 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 dianionic complex may be present upon a support material (e.g., silica) and exposed to the first polymerization reaction conditions, wherein the dianionic complex (and support material, as well as the supported activators) becomes incorporated within particles of the matrix polypropylene. In this aspect, the first polymerization catalyst is provided to the first polymerization reaction conditions (e.g., within a catalyst system) 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 dianioniccomplex and the optional metallocene may continue to promote formation of the copolymer phase within the matrix polypropylene.

[0206] In non-limiting examples, the matrix polypropylene produced under the firstpolymerization conditions may comprise an isotactic polypropylene or a propylene / ethylene random copolymer, which is also primarily isotactic. The polypropylene may be a propylene homopolymer or copolymer. In still another example, a ^^^-diene may be present in the first polymerization reaction conditions in combination with propylene to produce a long-chain branched polypropylene. Long-chain branches within the long-chain branched polypropylene are sufficiently long to induce polymer entanglement and may have a molecular weight of about 500 or more, or about 750 or more, or about 1000 or more, or about 1500 or more, or about 2000 or more, or about 2500 or more, or about 3000 or more, or about 4000 or more, or about 5000 or more. A ^^^-diene may provide a reactive site remote from the main polymer chain from which the long-chain branch may continue to grow. When used, the ^^^-diene may be present in the matrix polypropylene in an amount up to about 10 wt% relative to a total mass of the matrix polypropylene. In some embodiments, the non-zero amount of the at least one ^^^-diene may range from about 0.001 wt% to about 10 wt%, or about 0.01 wt% to about 9.99 wt%, or about 0.1 wt% to about 9.9 wt%, or about 0.5 wt% to about 99.5 wt%, or about 0.1 wt% to about 10 wt%, or any subrange thereof.

[0207] Suitable ^^^-dienes that may be utilized to introduce long-chain branching include, butare not limited to 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, 2- methyl-1,6-heptadiene, 2-methyl-1,7-octadiene, 2-methyl-1,8-nonadiene, 2-methyl-1,9- decadiene, 2-methyl-1,10-undecadiene, 2-methyl-1,11-dodecadiene, 2-methyl-1,12-tridecadiene, 2-methyl-1,13-tetradecadiene, and vinylnorbornene.

[0208] Suitable propylene / ethylene random copolymers within the matrix polypropylene maycomprise 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 propylene / alpha olefin copolymer formed by copolymerizing predominantly propylene (about 90 wt% or greater, or 95 wt% or greaterpropylene-derived monomer units) with a C4-C20 alpha olefin, optionally in further combination with ethylene. Up to about 10 wt% ^^^-diene may be additionally present in any of the foregoing.

[0209] The matrix polypropylene produced under the first polymerization reaction conditionsmay have a Mw value ranging from about 5,000 to about 500,000 and exhibit a relatively 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 5 or more, or about 6 or more, such as about 2 to about 5, or about 3 to about 6.

[0210] In non-limiting examples, the copolymer phase produced under the secondpolymerization 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 norbornene. 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.

[0211] The copolymer phase produced under the second polymerization reaction conditions mayhave 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 5 or less, or about 4 or less, or about 3 or less.

[0212] In non-limiting examples, the impact copolymers produced according to the disclosureherein may comprise about 65 wt% to about 95 wt% of the matrix polypropylene and 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%.

[0213] In any embodiment herein in which alpha olefins are used, suitable alpha olefins mayinclude 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, C4raffinate streams, and can therefore be substantially less expensive than pure 1-butene.

[0214] In non-limiting examples, the impact copolymer produced according to the disclosureherein 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.

[0215] In non-limiting examples, the impact copolymers produced according to the disclosureherein may have a Flexural Modulus, as measured by ASTM D790A, of about 400 MPa to about 2200 MPa, or about 600 MPa to about 1600 MPa. The foregoing values are measured with or without a nucleating agent being present.

[0216] In non-limiting examples, the impact copolymers produced according to the disclosureherein 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

[0217] The present disclosure is further directed to the following non-limiting embodiments:

[0218] Embodiment 1. A method comprising:exposing a) propylene and optionally b) a C2 or C4-C20 alpha-olefin and / or a ^^^’- diene 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 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 dianionic complex of a Group 3-6 metal, the dianionic complex comprising two eight-membered chelate rings containing the Group 3-6 metal.

[0219] Embodiment 2. The method of Embodiment 1, wherein the matrix polypropylenecomprises an isotactic polypropylene having a melting point of about 140°C to about 165°C.

[0220] Embodiment 3. The method of Embodiment 1 or Embodiment 2, wherein the ^^^-diene is present, and the matrix polypropylene has a g’vis value of about 0.6 to about 0.95, as determined by GPC-4D.

[0221] Embodiment 4. The method of any one of Embodiments 1-3, wherein the firstpolymerization reaction conditions comprise slurry-phase polymerization reaction conditions or gas-phase polymerization reaction conditions.

[0222] Embodiment 5. The method of any one of Embodiments 1-3, wherein the firstpolymerization reaction conditions comprise slurry-phase polymerization reaction conditions.

[0223] Embodiment 6. The method of any one of Embodiments 1-5, wherein the dianioniccomplex comprises a Group 4 metal.

[0224] Embodiment 7. The method of any one of Embodiments 1-5, wherein the dianioniccomplex has a structure represented bywherein: M is a Group 4 metal; E and E' are independently O, S, or NR9, wherein each R9is independently hydrogen, a C1-C40 optionally substituted hydrocarbyl, or a heteroatom-containing group; Z is a Group 14-16 atom forming a dative bond to M; A1ZA1’is part of a heterocyclic Lewis base, designated as B, containing 4 to 40 non- hydrogen atoms that links A2to A2’via a 3-atom bridge, with Z being the central atom of the 3- atom bridge; A1and A1'are independently C, N, or CR22, wherein each R22is independently hydrogen or optionally substituted C1-C20 hydrocarbyl; is a divalent group, optionally part of an optionally substituted hydrocarbyl ring or optionally substituted heterocyclic ring, containing 2 to 40 non-hydrogen atoms that links A1to a first aryl group via a 2-atom bridge, the first aryl having E bonded thereto; is a divalent group, optionally part of an optionally substituted hydrocarbyl ring or optionally substituted heterocyclic ring, containing 2 to 40 non-hydrogen atoms that links A1'to a second aryl group via a 2-atom bridge, the second aryl group having E’ bonded thereto; each L is a Lewis base; each X is an anionic ligand; n is 1, 2, or 3; m is 0, 1, or 2; n+m is not greater than 4; and R1, R2, R3, R4, R1', R2', R3', and R4'are independently hydrogen, optionally substituted C1- C40hydrocarbyl, a heteroatom, or a heteroatom-containing group or one or more of R1and R2, R2and R3, R3and R4, R1'and R2', R2’and R3', or R3'and R4'are joined to form one or more optionally substituted hydrocarbyl rings or optionally substituted heterocyclic rings, each ring having 5, 6, 7, or 8 ring atoms, and optionally wherein the optionally substituted hydrocarbyl rings or the optionally substituted heterocyclic rings are fused to one or more additional rings; and wherein: when m is 2, any two L are optionally joined together to form a bidentate Lewis base; or an X is optionally joined to an L to form a monoanionic bidentate ligand bound to M; or when n is 2 or 3, any two X are optionally joined together to form a dianionic ligand bound to M.

[0225] Embodiment 8. The method of Embodiment 7, wherein the Group 4 metal compriseszirconium.

[0226] Embodiment 9. The method of Embodiment 7 or Embodiment 8, wherein E and E’are each O.

[0227] Embodiment 10. The method of any one of Embodiments 7-9, wherein R1 and R1’ areindependently a tertiary alkyl group or a tertiary alkylaryl group.

[0228] Embodiment 11. The method of Embodiment 10, wherein the tertiary alkyl groupcomprises an optionally substituted adamantyl group.

[0229] Embodiment 12. The method of any one of Embodiments 7-11, whereinand are independently an optionally substituted arylene, an optionally substituted heteroarylene, or an optionally substituted vinylene.

[0230] Embodiment 13. The method of any one of Embodiments 7-11, whereinand are each an optionally substituted phenylene or an optionally substituted heteroarylene.

[0231] Embodiment 14. The method of any one of Embodiments 7-13, wherein theheterocyclic Lewis base is a 5- or 6-membered heteroaromatic ring.

[0232] Embodiment 15. The method of any one of Embodiments 7-14, Z of the heterocyclicLewis base is N.

[0233] Embodiment 16. The method of any one of Embodiments 7-15, wherein theheterocyclic Lewis base is an optionally substituted pyridine.

[0234] Embodiment 17. The method of any one of Embodiments 1-16, wherein at least thesecond polymerization catalyst is disposed upon a support material, optionally in combination with at least one activator, to form a catalyst system.

[0235] Embodiment 18. The method of Embodiment 17, wherein a metallocene comprisinga Group 4 metal is also disposed upon the support material.

[0236] Embodiment 19. The method of Embodiment 18, wherein the metallocene is a C1symmetric metallocene.

[0237] Embodiment 20. The method of Embodiment 19, wherein the C1 symmetricmetallocene 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-C40 alkyl, 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-C10 alkylene and R' is hydrogen, C1-C10 alkyl, or C6-C10 aryl; R2and R6are independently hydrogen, halogen, optionally substituted C1-C40 alkyl, 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-C10 alkylene and R' is hydrogen, C1- C10 alkyl, or C6-C10 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-C14 aryl, optionally substituted C3-C13heteroaryl, or R4and R5arejoined 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-C40 alkyl, 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-C10 alkylene and R' is hydrogen, C1-C10alkyl, or C6-C10 aryl, or one or more of R5 and R6, R6 and R7, or R7 and R8 are joined to form a C3-C62 substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or acombination thereof.

[0238] Embodiment 21. The method of Embodiment 20, wherein the Group 4 metal is Hf orZr; 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; X1and X2are independently halogen or C1-C6 hydrocarbyl; R3is optionally substituted phenyl, optionally substituted naphthyl, or optionally substituted anthracenyl; R2and R6are hydrogen; and R1is methyl.

[0239] Embodiment 22. The method of any one of Embodiments 17-21, wherein the at leastone activator is present and comprises at least one alumoxane.

[0240] Embodiment 23. The method of any one of Embodiments 17-21, wherein the at leastone activator is present and comprises at least one non-coordinating anion.

[0241] Embodiment 24. The method of Embodiment 23, wherein the non-coordinating anionis surface bound to the support material as a reaction product of surface hydroxyl group and a non- coordinating anion precursor, the non-coordinating anion precursor comprising an organoaluminum compound having a haloaryl group.

[0242] Embodiment 25. The method of any one of Embodiments 17-24, wherein the supportmaterial comprises silica.

[0243] Embodiment 26. The method of any one of Embodiments 1-25, wherein the firstpolymerization 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.

[0244] Embodiment 27. The method of any one of Embodiments 1-26, wherein the firstpolymerization 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.

[0245] Embodiment 28. The method of any one of Embodiments 1-27, wherein the impactcopolymer comprises about 65 wt% to about 95 wt% of the matrix polypropylene and about 5 wt% to about 35 wt% of the copolymer phase, each based on a total mass of the impact copolymer.

[0246] Embodiment 29. The method of any one of Embodiments 1-28, wherein thecopolymer 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.

[0247] To facilitate a better understanding of the embodiments of the present disclosure, thefollowing 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

[0248] Bis(phenolate) Complexes. The following bis(phenolate) complexes were synthesizedin a manner similar to that described in U.S. Patents 11,254,763 and 11,225,539, each of which are incorporated herein by reference. The bis(phenolate) complexes were utilized in the polymerization reactions described further below.I1 I2 I3 I4

[0249] Metallocene Catalysts. The following metallocenes were utilized for the polymerizationreactions described further below.Metallocene A Metallocene B (MCA) (MCB)

[0250] Metallocene A was synthesized through introduction of the substituted phenyl group onto6-methyl-1,2,3,5-tetrahydro-s-indacene via Suzuki coupling of 4-t-butylphenylboronic acid to the corresponding brominated parent ring system, followed by lithiation, dimethylsilyl bridge introduction, and metallocene formation. Illustrative synthetic procedures for Metallocene A may be found in U.S. Patent Application Publication 2022 / 0315680 and International Patent Application Publication WO 2023 / 034889, each of which is incorporated herein by reference. Illustrative synthetic procedures for Metallocene B may be found in U.S. Patent 9,458,254, which is incorporated herein by reference.

[0251] Supported Activator Preparation. Non-coordinating anion activators were prepared insitu and deposited upon a silica support. 0.21 g (2.85 mmol) of AlMe3in toluene (~5 mL) was slowly added to a stirred slurry of 1.46 g (2.85 mmol) of tris(pentafluorophenyl)boron in toluene or pentane (~30 mL). Upon completion, the mixture became homogenous and was stirred uncapped for 1 hour at room temperature, during which time BMe3 was removed as a gas. While stirring, the resulting Al(C6F5)3solution was transferred to 10 g of silica (PD17062, Ecovyst), followed by addition of N,N-diethylaniline (0.425 g, 2.85 mmol) in minimal toluene. The silica slurry was further stirred for an additional 30 minutes.

[0252] In a separate flask, 0.975 g of triethylaluminum (8.55 mmol) was suspended in toluene(30 mL) and cooled in a freezer. While stirring, a solution of 3.77 g (17.1 mmol) of BHT (butylated hydroxytoluene) in toluene (10 mL) was slowly added to the triethylaluminum suspension. After 30 minutes, the resulting triethylaluminum:BHT complex was slowly added at room temperature to the silica slurry prepared above. The combined reaction mixture was then stirred overnight. After 18 hours, the reaction mixture was filtered, and the solid was washed with toluene (2 x 50 mL) and pentane (2 x 50 mL). After drying in vacuo, the support material was obtained as white powder.

[0253] Supported Catalyst Preparation. The bis(phenolate) complexes and metalloceneslisted above were supported by contacting a toluene solution of the catalyst compound(s) with the supported activator prepared as above. In brief, a toluene solution of the catalyst compound(s) (~17-38 ^mol) was slowly added to 1.2 g of the supported activators slurried in 1 mL toluene. After shaking for 4 hours, the solids were collected on a glass frit, washed with toluene (2 x 10 mL) and pentane (2 x 10 mL). After drying in vacuo, the supported catalyst was slurried in mineral oil to make a 5 wt% slurry for dispensation to a polymerization reactor.

[0254] General Procedure for Staged Slurry-Phase and Gas-Phase Polymerization. Slurry-Phase Polymerization Stage. A 2 L autoclave reactor equipped with a mechanical stirrer was used for polymer preparation. Prior to the run, the reactor was placed under nitrogen purge at 90°C for 30 minutes. Upon cooling to ambient temperature, propylene (600 mL), scavenger (0.4 mL of 1 M TIBAL, triisobutylaluminum), an optional diene co-monomer, and optionally hydrogen (charged from a 50 mL bomb at a desired pressure) were introduced to the reactor and mixed for 5 minutes. A desired amount of supported catalyst prepared as above (typically 12.5 – 25.0 mg) was then introduced to the reactor by flushing a pre-determined amount of the 5 wt% catalyst slurry from a catalyst tube with 200 mL of liquid propylene. The reactor was kept at room temperature for 5 minutes (pre-polymerization stage), before raising the temperature to 70°C for a desired time period (typically 20-30 min). The propylene was maintained in a liquid state throughout the polymerization process. Additional polymerization details are specified in the tables below. Gas-Phase Polymerization Stage. After the slurry-phase polymerization, the reactor was vented to a desired propylene pressure (typically 40-160 psi). Once at the desired propylene pressure, ethylene gas was introduced (typically 80 – 220 psi) and optionally, hydrogen gas, and the reaction as allowed to proceed for typically 10-20 minutes. Upon completion, the reactor was vented and the polymer collected and dried in air overnight. Additional polymerization details are specified in the tables below.

[0255] Polymer Characterization. The resulting polymers were characterized to determinemolecular weights and thermal properties.

[0256] GPC-4D Analysis. Polymer molecular weights and co-monomer contents weredetermined 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 C2 content of the copolymer phase in the matrix polypropylene were determined by filtration and reinjection of the GPC eluent, followed by the further analyses described in U.S. Patent Application Publication 2018 / 0059076.

[0257] The distribution and the moments of molecular weight (Mw, Mn, Mz, Mw / Mn, etc.), theco-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 band- filter based infrared detector IR5 with a multiple-channel band filter based infrared detector ensemble IR5 with band region covering from about 2,700 cm-1to about 3,000 cm-1(representingsaturated C-H stretching vibration), an 18-angle light scattering detector and a viscometer. Three Agilent PLgel 10-µm 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 μL. The whole system including transfer lines, columns, and detectors can be contained in an oven maintained at ~145°C. A given amount of sample can be weighed and sealed in a standard vial with ~10 μL flow marker (heptane) added thereto. After loading the vial in the auto-sampler, the oligomer or polymer may automatically be dissolved in the instrument with ~8 mL added TCB solvent at ~160°C with continuous shaking. The sample solution concentration can be from ~0.2 to ~2.0 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=αI, where α is the mass constant determined with polyethylene or polypropylene standards. The mass recovery can be calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume. The conventional molecular weight (IR MW) is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to 10M gm / mole. The MW at each elution volume is calculated with Equation 1: ^^ ^^^^lEquation 1 where the variables with subscript “PS” stand for polystyrene while those without a subscript are for the test samples. In this method, αPS = 0.67 and KPS = 0.000175, α and K for other materials are calculated as described in the published literature (e.g., Sun, T., et al. (2001) Macromolecules, v.34, pg.6812), except that for purposes of this present disclosure and claims thereto, ^ = 0.705 and K = 0.0000229 for ethylene-propylene copolymers and ethylene-propylene-diene terpolymers, ^ = 0.695 and K = 0.000579 for linear ethylene polymers, ^ = 0.705 and K = 0.0002288 for linear propylene polymers, and ^ = 0.695 and K = 0.000181 for linear butene polymers. Concentrationsare 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.

[0258] The co-monomer composition is determined by the ratio of the IR5 detector intensitycorresponding to CH2and CH3channel 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 / 1000TC) as a function of molecular weight. The short- chain branch (SCB) content per 1,000TC (SCB / 1000TC) is then computed as a function of molecular weight by applying a chain-end correction to the CH3 / 1000TC function, assuming each chain to be linear and terminated by a methyl group at each end. The weight % co-monomer is then obtained from Equation 2 in which ^^ is 0.3, 0.4, 0.6, 0.8, and so on for C3, C4, C6, C8, and so on co-monomers, respectively:

[0259] The bulk composition of the polymer from the GPC-IR and GPC-4D analyses is obtainedby 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 CH3and CH2signal ratio, as mentioned previously in obtaining the CH3 / 1000TC as a function of molecular weight, is applied to obtain the bulk CH3 / 1000TC. A bulk methyl chain ends per 1,000TC (bulk CH3end / 1000TC) is obtained by weight-averaging the chain-end correction over the molecular-weight range. Then, Equations 4 and 5 applybulk SCB / 1000TC = bulk CH3 / 1000TC − bulk CH3end / 1000TCEquation 5 and bulk SCB / 1000TC is converted to bulk ^^2 in the same manner as described above.

[0260] The LS detector is the 18-angle Wyatt Technology High Temperature DAWNHELEOSII. The LS molecular weight (M) at each point in the chromatogram is determined byanalyzing 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 6 Here, ΔR(θ) is the measured excess Rayleigh scattering intensity at scattering angle ^, c is the polymer concentration determined from the IR5 analysis, A2 is the second virial coefficient, P(θ) is the form factor for a monodisperse random coil, and Kois the optical constant for the system, as specified in Equation 7:Equation 7 where NAis Avogadro’s number, and (dn / dc) is the refractive index increment for the system. The refractive index, n = 1.500 for TCB at 145°C and λ = 665 nm. For analyzing polyethylene homopolymers, ethylene-hexene copolymers, and ethylene-octene copolymers, dn / dc = 0.1048 ml / mg and A2 = 0.0015; for analyzing ethylene-butene copolymers, dn / dc = 0.1048*(1-0.00126*w2) ml / mg and A2= 0.0015 where w2 is weight percent butene co- monomer.

[0261] A high-temperature Agilent (or Viscotek Corporation) viscometer, which has fourcapillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity, ηs, for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [η], at each point in the chromatogram is calculated from the equation [η]=ηs / c, where c is concentration and is determined from the IR5 broadband channel output. The viscosity MW at each point is calculated as where is 0.67 and Kps is 0.000175.

[0262] The branching index (g'vis) is calculated using the output of the GPC-IR5-LS-VISmethod as follows. The average intrinsic viscosity, [η]avg, of the sample is calculated by Equation 8:where the summations are over the chromatographic slices, i, between the integration limits.

[0263] The branching index g'vis is defined as Equation 9:where Mvis the viscosity-average molecular weight based on molecular weights determined by LS analysis and the K and α are for the reference linear polymer, which are, for purposes of this present disclosure and claims thereto, ^ = 0.705 and K = 0.0000229 for ethylene-propylene copolymers and ethylene-propylene-diene terpolymers, ^ = 0.695 and K = 0.000579 for linear ethylene polymers, ^ = 0.705 and K = 0.0002288 for linear propylene polymers, ^ = 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.

[0264] DSC Analysis. Thermal properties of the polymers were assayed by differential scanningcalorimetry (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 -50°C at a rate of about 10°C / minute, followed by an 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.

[0265] Tensile Properties. Tensile properties (ultimate tensile strength, elongation at break,tensile yield, and elongation at yield) were determined according to ISO 37 (2005) or ASTM D638 (30 mm grip separation and 50.8 mm / min at a temperature of 70°F).

[0266] MFR procedure. Melt flow rate was determined according to ASTM D-1238 conditionL (2.16 kg, 230°C).

[0267] Flexural Modulus Procedure. The 1% secant flexural modulus, generally referred to asflexural 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.

[0268] Notched Izod Procedure. Notched Izod impact measurements were performed onnotched, injection molded bars at the indicated temperature according to ASTM D256.

[0269] Small Amplitude Oscillatory Shear (SAOS) Test: Dynamic shear melt rheologicaldata were measured with an Advanced Rheometrics Expansion System (ARES-G2) from TA Instruments using parallel plates (diameter = 25 mm) in a dynamic mode under nitrogen atmosphere. For all experiments, the rheometer was thermally stable at 190°C for at least 30 minutes before inserting a compression-molded sample of resin onto the parallel plates. To determine viscoelastic behavior, frequency sweeps in the range from 0.01 to 628 rad / s were carried out at a temperature of 190°C under constant strain. Depending on the molecular weight and temperature, strains in the linear deformation range verified by strain sweep test were used. A nitrogen stream was circulated through the sample oven to minimize chain extension or crosslinking during the experiments. All the samples were compression molded at 190°C. A sinusoidal shear strain was applied to the material if the strain amplitude was sufficiently small for the material to behave linearly. It can be shown that the resulting steady- state stress also oscillates sinusoidally at the same frequency but will be shifted by a phase angle d with respect to the strain wave. The stress leads the strain by d. For purely elastic materials d=0° (stress is in phase with strain) and for purely viscous materials, d=90° (stress leads the strain by 90°, although the stress is in phase with the strain rate). For viscoelastic materials, 0 < d < 90.

[0270] Extensional Flow measurements. Samples were thermally equilibrated for 10-15minutes before the test. The SER Testing Platform from Advanced Rheometrics Expansion System (ARES-G2) from TA Instruments was used for the analyses, as described in U.S. Patents 6,578,413 and 6,691,569, which are incorporated herein by reference. A general description of transient uniaxial extensional viscosity measurements is provided, for example, in “Measuring the transientextensional rheology of polyethylene melts using the SER universal testing platform”, The Society of Rheology, Inc., J. Rheol. v.49(3), 585-606 (2005). Strain hardening can happen when a polymer is subjected to elongational flow and the transient extensional viscosity increases with respect to the linear viscoelasticity envelop (EVE) or subjected to extensional viscosity at higher rates at Hencky strains of 1.0 or lower, where Hencky strain is calculated as product of Hencky strain rate and time. Strain hardening is observed as an abrupt upswing of the extensional viscosity in the transient extensional viscosity versus time plot. Strain hardening ratio (SHR) is used to characterize the upswing in extensional viscosity and is the ratio discussed above. Strain hardening is present in the material when the ratio is greater than 1.

[0271] Example 1. Propylene Homopolymers. Propylene homopolymers were prepared usingpropylene only in the slurry-phase polymerization stage and conducting only the slurry-phase polymerization (first stage) of the polymerization process. Characterization data and additional polymerization details are set forth in Table 1 below. Table 1As shown, the bis(phenolate) complexes alone (I3 and I4, Entries 3 and 4) afforded comparable Mw values to the tested metallocene catalysts alone (MCA and MCB, Entries 1 and 2), but with a surprisingly smaller polydispersity index (Mw / Mn). Small changes in Tm and Tc were also observed when using the bis(phenolate) complexes. Using a bis(phenolate) complex and a metallocene in combination with one another (Entries 5-8) increased the polydispersity index compared to a bis(phenolate) complex alone, and the Mw value increased significantly, except in the case of Entry 8. The broadening of the polydispersity index is believed to arise from thedifferent polymer molecular weights that may be produced by the two catalysts. As further shown, the bis(phenolate) complexes maintained high activity values in all cases.

[0272] Example 2. Ethylene-Propylene Impact Copolymers at Fixed Ethylene Pressure.Ethylene-propylene impact copolymers were prepared using propylene only in the slurry-phase polymerization stage (first stage) and propylene and ethylene in the gas-phase polymerization stage (second stage) of the polymerization process, with a fixed amount of ethylene being used in the gas- phase polymerization. Characterization data and additional polymerization details are set forth in Tables 2A-2D below. Table 2ATable 2BTable 2C= no break Table 2D

[0273] As shown above, the catalysts produced primarily an isotactic polypropylene matrix andprimarily an ethylene-propylene copolymer phase in most cases. Narrow polydispersity values for the copolymer phase were realized in most cases, and no break occurred during notched Izod testing in most cases as well.

[0274] Example 3. Ethylene-Propylene Impact Copolymers at Variable Ethylene Pressure.Ethylene-propylene impact copolymers were prepared using propylene only in the slurry-phase polymerization stage (first stage) and propylene and ethylene in the gas-phase polymerization stage (second stage) of the polymerization process, with a variable amount of ethylene being used in the gas-phase polymerization. Characterization data and additional polymerization details are set forth in Tables 3A-3D below. Table 3ATable 3BTable 3C= no break Table 3D

[0275] As shown above, narrow polydispersity indices were realized for both the overall impactcopolymer and the ethylene-propylene copolymer phase, and no break occurred during notched Izod testing in some cases as well. Increased ethylene incorporation occurred when the ethylene partial pressure was higher. Because of their greater ethylene incorporation in the copolymerphase, a slight improvement in stiffness and toughness was also realized in comparison to the samples of Example 2.

[0276] Example 4. Ethylene-Propylene Impact Copolymers with Long-Chain Branchingin Matrix Polypropylene. Ethylene-propylene impact copolymers were prepared using propylene and 1,7-octadiene in the slurry-phase polymerization stage (first stage) and propylene and ethylene in the gas-phase polymerization stage (second stage) of the polymerization process. Characterization data and additional polymerization details are set forth in Tables 4A-4D below. Table 4ATable 4BTable 4C= no break Table 4D

[0277] As shown, the overall polydispersity indices broadened somewhat when copolymerizing1,7-octadiene with propylene, and the MFR values were lowered. These results are consistent with the introduction of long-chain branches resulting from introduction of 1,7-octadiene into the matrix polypropylene.

[0278] This group of impact copolymers was also relatively insensitive to the copolymer phasecomposition and amount, thereby allowing tunable stiffness and toughness to be realized. FIG.1 is a graph of flexural modulus as a function of Notched Izod value for samples from Examples 2- 4. As shown, the samples lacking long-chain branching tended to exhibit decreased flexural modulus as the Notched Izod value increased (Examples 2 and 3), whereas the flexural modulus of samples having long-chain branching exhibited little decrease with increasing Notched Izod values (Example 4). Therefore, the ability of the bis(phenolate) complexes to introduce long-chainbranching into the matrix polypropylene may allow impact copolymers having balanced stiffness and toughness to be realized.

[0279] Additional rheological data for the long-chain branched samples (Example 4) wascollected and compared against a similar sample containing no long-chain branching (Entry 15, Example 2). Small-amplitude oscillatory shear was measured using an ARES-G2 rheometer (TA Instruments) with an 8 mm parallel plate geometry and a shear strain of 1%. FIG.2 is a plot of small-amplitude oscillatory shear of samples from Example 4 in comparison to a similar sample lacking long-chain branching. The plot displays complex viscosity as a function of angular frequency. Complex viscosity plots were constructed by time-temperature superposition (tTs) of individual measurements performed at temperatures ranging from 150°C to 250°C. As shown, a progressively increasing amount of 1,7-octadiene in the slurry-phase polymerization resulted in improved processability by virtue of increased shear thinning behavior. A typical low-frequency plateau characterizing the so-called zero-shear viscosity was observed for the sample of Entry 12, whereas the other samples showed an increasingly strong viscosity upturn at low frequencies, reflective of their high melt strength resulting from long-chain branching.

[0280] FIG. 3 is a plot of extensional viscosity of samples from Example 4 in comparison to asimilar sample lacking long-chain branching. In FIG. 3, dashed lines represent the linear viscoelastic envelope (LVE) viscosity (L) measured by start-up shear at a shear rate of 0.0001 s-1. The difference in the long-time viscosity reflects the higher melt strength of samples containing long-chain branching (Entries 28-32, Example 4). Strain hardening can happen when a polymer is subjected to elongational flow and the transient extensional viscosity increases with respect to the LVE or the polymer is subjected to extensional viscosity at higher rates at Hencky strains of 1.0 or lower, where Hencky strain is calculated as the product of Hencky strain rate and time. Strain hardening is observed as an abrupt upswing of the extensional viscosity in the transient extensional viscosity versus time plot. Strain hardening ratio (SHR) is used to characterize the upswing in extensional viscosity and is the ratio discussed above. Strain hardening is present when the ratio is greater than 1. The strain hardening ratio was negligible for the impact copolymer containing the linear matrix polypropylene (Entry 15), whereas remarkably large values were observed for the long-chain branched samples (Entries 28-32).

[0281] All documents described herein are incorporated by reference herein for purposes of alljurisdictions where such practice is allowed, including any priority documents and / or testingprocedures 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.

[0282] Unless otherwise indicated, all numbers expressing quantities of ingredients, propertiessuch 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.

[0283] Whenever a numerical range with a lower limit and an upper limit is disclosed, anynumber 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.

[0284] One or more illustrative embodiments are presented herein. Not all features of a physicalimplementation are described or shown in this application for the sake of clarity. It is understoodthat 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 time- consuming, such efforts would be, nevertheless, a routine undertaking for one of ordinary skill in the art and having benefit of this disclosure.

[0285] Therefore, the present disclosure is well adapted to attain the ends and advantagesmentioned 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 particular illustrative 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

CLAIMS The invention claimed is:

1. A method comprising: exposing a) propylene and optionally b) a C2 or C4-C20 alpha-olefin and / or a ^^^’- diene 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 C2 or C4-C20 alpha olefin 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 dianionic complex of a Group 3-6 metal, the dianionic complex comprising two eight-membered chelate rings containing the Group 3-6 metal.

2. The method of claim 1, wherein a) the matrix polypropylene comprises an isotactic polypropylene having a melting point of about 140°C to about 165°C b) the ^^^-diene is present, and the matrix polypropylene has a g’visvalue of about 0.6 to about 0.95, as determined by GPC-4D; or, c) both a) and b).

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 first polymerization reaction conditions comprise slurry-phase polymerization reaction conditions. - 91 -5. The method of any preceding claim, wherein the dianionic complex has a structure represented bywherein: M is a Group 4 metal; E and E' are independently O, S, or NR9, wherein each R9is independently hydrogen, a C1- C40 optionally substituted hydrocarbyl, or a heteroatom-containing group; Z is a Group 14-16 atom forming a dative bond to M; A1ZA1’is part of a heterocyclic Lewis base, designated as B, containing 4 to 40 non- hydrogen atoms that links A2to A2’via a 3-atom bridge, with Z being the central atom of the 3- atom bridge; A1and A1'are independently C, N, or CR22, wherein each R22is independently hydrogen or optionally substituted C1-C20 hydrocarbyl; is a divalent group, optionally part of an optionally substituted hydrocarbyl ring or optionally substituted heterocyclic ring, containing 2 to 40 non-hydrogen atoms that links A1to a first aryl group via a 2-atom bridge, the first aryl having E bonded thereto; is a divalent group, optionally part of an optionally substituted hydrocarbyl ring or optionally substituted heterocyclic ring, containing 2 to 40 non-hydrogen atoms that links A1'to a second aryl group via a 2-atom bridge, the second aryl group having E’ bonded thereto; each L is a Lewis base; each X is an anionic ligand; n is 1, 2, or 3; m is 0, 1, or 2; n+m is not greater than 4; and R1, R2, R3, R4, R1', R2', R3', and R4'are independently hydrogen, optionally substituted C1-C40hydrocarbyl, a heteroatom, or a heteroatom-containing group or one or more of R1and R2, R2andR3, R3and R4, R1'and R2', R2’and R3', or R3'and R4'are joined to form one or more optionally substituted hydrocarbyl rings or optionally substituted heterocyclic rings, each ring having 5, 6, 7, or 8 ring atoms, and optionally wherein the optionally substituted hydrocarbyl rings or the optionally substituted heterocyclic rings are fused to one or more additional rings; and wherein: when m is 2, any two L are optionally joined together to form a bidentate Lewis base; or an X is optionally joined to an L to form a monoanionic bidentate ligand bound to M; or when n is 2 or 3, any two X are optionally joined together to form a dianionic ligand bound to M.

6. The method of claim 5, wherein the Group 4 metal comprises zirconium.

7. The method of claim 5, wherein E and E’ are each O.

8. The method of claim 5, wherein R1and R1’are independently a tertiary alkyl group or a tertiary alkylaryl group.

9. The method of claim 8, wherein the tertiary alkyl group comprises an optionally substituted adamantyl group.

10. The method of claim 5, wherein and are independently an optionally substituted arylene, an optionally substituted heteroarylene, an optionally substituted phenylene, or an optionally substituted vinylene.

11. The method of claim 5, wherein the heterocyclic Lewis base is a 5- or 6-membered heteroaromatic ring.

12. The method of claim 11, Z of the heterocyclic Lewis base is optionally substituted pyridine.

13. The method of any preceding claim, wherein at least the second polymerization catalyst is disposed upon a support material, optionally in combination with at least one activator, to form a catalyst system.

14. The method of claim 13, wherein a C1 symmetric metallocene comprising a Group 4 metal is also disposed upon the support material.

15. The method of claim 14, wherein the C1 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-C14 aryl, optionally substituted C3-C13heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R''-SiR'3, wherein R'' is C1-C10 alkylene and R' is hydrogen, C1-C10 alkyl, or C6-C10aryl; R2and R6are independently hydrogen, halogen, optionally substituted C1-C40alkyl, optionally substituted C6-C14 aryl, optionally substituted C3-C13heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R''-SiR'3, wherein R'' is C1-C10 alkylene and R' is hydrogen, C1-C10 alkyl, 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-C40 alkyl, optionally substituted C6-C14 aryl, optionally substituted C3-C13heteroaryl, or R4and R5arejoined 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 C6-C14aryl, optionally substituted C3-C13heteroaryl, -NR'2, -SR', - OR', -SiR'3, -OSiR'3, -PR'2, or -R''-SiR'3, wherein R'' is C1-C10 alkylene and R' is hydrogen, C1-C10alkyl, or C6-C10 aryl, or one or more of R5 and R6, R6 and R7, or R7 and R8 are joined to form a C3-C62 substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or acombination thereof.

16. The method of claim 15, wherein the Group 4 metal is Hf or Zr; 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; X1and X2are independently halogen or C1-C6 hydrocarbyl; R3is optionally substituted phenyl, optionally substituted naphthyl, or optionally substituted anthracenyl; R2and R6are hydrogen; and R1is methyl.

17. 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.

18. The method of any preceding claim, wherein the impact copolymer comprises about 65 wt% to about 95 wt% of the matrix polypropylene and about 5 wt% to about 35 wt% of the copolymer phase, each based on a total mass of the impact copolymer.

19. 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.

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