WO2021262838A1 - Copolymers composed of ethylene, a-olefin, non-conjugated diene, and substituted styrene and articles therefrom - Google Patents

Abstract

This invention relates to a copolymer comprising units derived from ethylene, an α-olefin, a non- conjugated diene, and a substituted styrene compound.

Description

Title: Copolymers Composed of Ethylene, α-olefin, Non-conjugated Diene, and

Substituted Styrene and Articles Therefrom

INVENTORS: Tzu-Pin Lin, Jo Ann M. Canich, Brian J. Rohde, Carlos R. Lopez-Barron, Sarah J. Mattler, Peijun Jiang, John R. Hagadom

Cross-Reference to Related Applications

[0001] This application claims benefit of and priority to USSN 63/044748, filed June 26, 2020, the disclosure of which is incorporated herein by reference. [0002] This invention is related to concurrently filed USSN 63/044726, entitled

"Hexahydrocyclopenta[e]-as-indacen-l-yl and Octahydrobenzo[e]-as-indacen-1-yl based Catalyst Complexes and Process for Use Thereof and USSN 63/044757, entitled "Copolymers of Ethylene, α-olefin, Non-conjugated Diene, and Aryl-Substituted Cycloalkene, Methods to Produce, Blends, and Articles Therefrom". FIELD

[0003] This invention relates to copolymers having units derived from ethylene, an a- olefin, a non-conjugated diene, and a substituted styrene. More particularly, this invention relates to copolymers having units derived from ethylene, an a-olefin, anon-conjugated diene, and para-methylstyrene. BACKGROUND

[0004] Olefin-based elastomeric polymers can be produced by the copolymerization of ethylene, an α-olefin, and a diene monomer. The most common such elastomers are terpolymers of ethylene, propylene, and diene monomer (e.g., ethylidiene norbomene, hexadiene, octadiene, vinyl norbomene, and the like, which are generally referred to as EPDMs. While ordinary ethylene propylene (EP) elastomers (that typically lack a diene) can be cured through use of curatives such as organic peroxides. Curing with sulfur and sulfur- containing compounds often requires the presence of a pendant double bond. Hence, EPDM elastomers find use in numerous cured applications for which the EP copolymers are not suitable. [0005] EPDMs have many properties that make them desirable for applications that other types of elastomers are not as well suited. EPDMs have outstanding weather and acid resistance and high and low temperature performance properties. Such properties particularly suit EPDMs as an elastomer for use in hoses, gaskets, belts, bumpers; as blending components for plastics and for tire components, such as side walls; in the automotive industry and for roofing applications. Additionally, because of their electrical insulation properties, EPDMs are particularly well suited for use as wire and cable insulation. However, there is a need to improve both the melt processability and filler acceptance of EPDMs.

[0006] References of interest include: US 8,841,383; Chen, H. Y. et al. (1999) "Large Strain Stress Relaxation and Recovery Behavior of Amorphous Ethylene-Styrene Interpolymers," Macromolecules , v.32(22), pp. 7587-7593; D'Aniello, C. et al. (1995) "Correlation Between Microstructure and Physical Properties in Styrene-Ethylene Copolymers," Journal of Applied Polymer Science, v.58(10), pp. 1701-1706; Chen, H. et al. (1998) "Classification of Ethylene-Styrene Interpolymers Based on Comonomer Content," Journal of Applied Polymer Science, v.70(l), pp. 109-119; Oliva, L. et al. (1997) "Zirconocene- Based Catalysts for the Ethylene-Styrene Copolymerization: Reactivity Ratios and Reaction Mechanism," Macromolecules, v.30(19), pp. 5616-5619; Arriola, D. J. et al. (2007) "Penultimate Effect in Ethylene-Styrene Copolymerization and the Discovery of Highly Active Ethylene-Styrene Catalysts with Increased Styrene Reactivity, Journal of the American Chemical Society, v,129(22), pp. 7065-7076; Caporaso, L. et al. (1999) "Ethylene as Catalyst Reactivator in the Propene- Styrene Copolymerization," Macromolecules, v.32(21), pp. 7329- 7331; WO1997038019A1; JP08134140A; JP08216343A; EP0718323A2; and EP0083049A2. SUMMARY

[0007] Copolymers having units derived from ethylene, an α-olefin, a non-conjugated diene, and a substituted styrene are provided herein. In some examples, the copolymer can include ethylene, one or more α-olefins, one or more non-conjugated dienes, and one or more substituted styrene compounds.

[0008] In some examples, the process for producing the copolymer can include contacting ethylene, a C₃ to C₂₀ α-olefin monomer, a non-conjugated diene monomer, and a substituted styrene monomer with a catalyst system that can include a single site catalyst compound, an activator, and an optional support. A copolymer can be obtained that can include about 40 wt% to about 90 wt% of units derived from ethylene; about 9.8 wt% to about 59.8 wt% of units derived from the α-olefin; about 0.1 wt% to about 10 wt% of units derived from the non- conjugated diene; and about 0.1 wt% to about 15 wt% of units derived from the substituted styrene, based on a weight of the copolymer, where the copolymer has a strain hardening ratio of 2 or greater when an extensional viscosity is measured at a Hencky strain rate of 0.01 s^-1 to 10 s^-1 at a temperature of 190°C. [0009] In some examples, the process for producing the copolymer can include introducing an α-olefin monomer to a reaction vessel in an amount and under pressure sufficient to allow utilization of the α-olefin in a liquefied form as a polymerization diluent. A non-conjugated diene monomer and a substituted styrene monomer can be introduced to the diluent. Ethylene monomer can be added to the diluent to produce a mixture of the ethylene, the α-olefin, the substituted styrene, and the diene monomers. A catalyst system that can include a catalyst compound and an activator can be added to the diluent. The mixture can be reacted for a time sufficient to permit polymerization of the ethylene, the α-olefin, the substituted styrene, and the diene monomers to produce a copolymer that can include about 40 wt% to about 90 wt% of units derived from ethylene; about 9.8 wt% to about 59.8 wt% of units derived from the α-olefin; about 0.1 wt% to about 10 wt% of units derived from the non-conjugated diene; and about 0.1 wt% to about 15 wt% of units derived from the substituted styrene, based on the weight of the copolymer, where the copolymer can have a strain hardening ratio of 2 or greater when extensional viscosity is measured at a Hencky strain rate of 0.01 s^-1 to 10 s^-1 at a temperature of 190°C.

[0010] Elastomer compositions are also provided herein. In some examples, the elastomer composition can include a ethylene-propylene-diene-substituted styrene copolymer that can include 40 to 90 wt% propylene-derived units, 9.4 to 59.4 wt% ethylene-derived units, 0.3 to 10 wt% substituted styrene-derived units based on a total weight of the copolymer, wherein the copolymer has a strain hardening ratio of 2 or greater when an extensional viscosity is measured at a Hencky strain rate of 0.01 s^-1 to 10 s^-1 at a temperature of 190°C and a blend rubber that can include one or more elastomers where the one or more elastomers are not ethylene- propylene-diene-substituted styrene copolymers.

[0011] Tire sidewall compositions are also provided herein. In some examples, the tire sidewall composition can include from 10 to 30 phr of a ethylene-propylene-diene-substituted styrene copolymer that can include 40 to 90 wt% propylene-derived units, 9.4 to 59.4 wt% ethylene-derived units, 0.3 to 10 wt% substituted styrene-derived units, and 0.5 to 4 wt% diene- derived units selected from 5-ethylidene-2-norbomene, 5-vinyl-2-norbomene, dicyclopentadiene, and 1,4-hexadiene, based on the weight of the copolymer, wherein the copolymer has a strain hardening ratio of 2 or greater when extensional viscosity is measured at a Hencky strain rate of 0.01 s^-1 to 10 s^-1 at a temperature of 190°C. The tire sidewall composition can also include from 20 to 60 phr of a natural rubber and from 20 to 60 phr of a polybutadiene rubber. The tire sidewall composition can also include optional secondary blend rubber that can include polyisoprene rubber (IR), poly(styrene-co-butadiene) rubber (SBR), poly(isoprene-co-butadiene) rubber (IBR), styrene-isoprene-butadiene rubber (SIBR), butyl rubber, star branched butyl rubber, poly(isobutylene-coalkylstyrene), ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), and combinations thereof. The tire sidewall composition can also include a filler that can include carbon black, modified carbon black, silica, precipitated silica, and combinations thereof. The tire sidewall composition can also include an optional processing oil, resin, or combination thereof. The tire sidewall composition can also include a curing package.

BRIEF DESCRIPTION OF THE FIGURES [0012] So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.

[0013] Figures 1 A and IB (FIGs. 1A and IB) depict graphs of the rheological behaviors of

Sample 1.

[0014] Figure 2 (FIG. 2) depicts a graph of Stress-strain curves of a crosslinked Sample 1. The insets show Wide-angle X-ray scattering (WAXS) images at 0% and 500% strain. PET All ED DESCRIPTION

[0015] It is to be understood that the following disclosure describes several exemplary embodiments for implementing different features, structures, and/or functions of the invention. Exemplary embodiments of components, arrangements, and configurations are described below to simplify the present disclosure; however, these exemplary embodiments are provided merely as examples and are not intended to limit the scope of the invention. Additionally, the present disclosure may repeat reference numerals and/or letters in the various exemplary embodiments and across the Figures provided herein. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various exemplary embodiments and/or configurations discussed in the Figures. Moreover, the exemplary embodiments presented below can be combined in any combination of ways, i.e., any element from one exemplary embodiment can be used in any other exemplary embodiment, without departing from the scope of the disclosure.

Definitions [0016] For the purposes of this invention and the claims thereto, the new numbering scheme for the Periodic Table Groups is used as described in Chemical and Engineering News , v.63(5), pg. 27 (1985). Therefore, a “group 4 metal” is an element from group 4 of the Periodic Table, e.g. Hf, Ti, or Zr.

[0017] An “olefin,” alternatively referred to as an “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such polymer or copolymer is the polymerized from of the olefin. For example, when a copolymer is said to have an "ethylene" content of 35 wt% to 55 wt%, it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based on a weight of the copolymer. A “polymer” has two or more of the same or different mer units. A “homopolymer” is a polymer having mer units that are the same. A “copolymer” is a polymer having two or more mer units that are different from each other. For the purpose of this disclosure, a copolymer does not include graft copolymers. A “terpolymer” is a polymer having three mer units that are different from each other. A “tetrapolymer” is a polymer having four mer units that are different from each other. Accordingly, the definition of copolymer, as used herein, includes terpolymers, tetrapolymers and the like. “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.

[0018] The terms “alpha-olefin” and “α-olefin” are used interchangeably and refer to an olefin having a terminal carbon-to-carbon double bond in the structure thereof ((R¹R²)-C=CH₂, where R¹ and R² can independently be hydrogen or any hydrocarbyl group; preferably R¹ is hydrogen and R² is an alkyl group). A “linear alphα-olefin” is an alphα-olefin defined where R¹ is hydrogen and R² is hydrogen or a linear alkyl group. For the purposes of this disclosure, the term “α-olefin” includes C₂-C₂₀ olefins. Non-limiting examples of α-olefins include ethylene, propylene, 1 -butene, 1-pentene, 1 -hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1 -tricosene, 1 -tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene, 4-methyl- 1-pentene, 3-methyl-l-pentene, 5-methyl- 1-nonene, 3,5,5-trimethyl-l-hexene, vinylcyclohexene, and vinylnorbomane. Non-limiting examples of cyclic olefins and diolefins include cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, norbomene, 4-methylnorbomene, 2-methylcyclopentene, 4-methylcyclopentene, vinylcyclohexane, norbomadiene, dicyclopentadiene, 5-ethylidene-2-norbomene, vinylcyclohexene, 5-vinyl-2-norbomene,

1.3-divinylcyclopentane, 1,2-divinylcyclohexane, 1,3-divinylcyclohexane,

1.4-di vinylcyclohexane, 1,5-divinylcyclooctane, l-allyl-4-vinylcyclohexane,

1.4-diallylcyclohexane, l-allyl-5-vinylcyclooctane, and 1,5-diallylcyclooctane.

[0019] For purposes of this disclosure, ethylene is not considered an α-olefin.

[0020] As used herein, and unless otherwise specified, the term “C_n” means hydrocarbon(s) having n carbon atom(s) per molecule, where n is a positive integer. Likewise, a “C_m-C_y” group or compound refers to a group or compound comprising carbon atoms at a total number thereof in the range from m to y. Thus, a C₁-C₄ alkyl group refers to an alkyl group that includes carbon atoms at a total number thereof in the range of 1 to 4, e.g. , 1, 2, 3 and 4.

[0021] The terms “group,” “radical,” and “substituent” may be used interchangeably.

[0022] The terms “hydrocarbyl radical,” “hydrocarbyl group,” or “hydrocarbyl” may be used interchangeably and are defined to mean a group consisting of hydrogen and carbon atoms only. Preferred hydrocarbyls are C₁-C₁₀0 radicals that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic. Examples of such radicals include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, aryl groups, such as phenyl, benzyl naphthyl, and the like.

[0023] Unless otherwise indicated, (e.g., the definition of "substituted hydrocarbyl", "substituted styrene, "etc.), the term “substituted” means that at least one hydrogen atom has been replaced with at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, -(CH₂)q-SiR*3, and the like, where q is 1 to 10 and each R* is independently hydrogen, a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted completely saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within a hydrocarbyl ring.

[0024] The term "substituted hydrocarbyl" means a hydrocarbyl radical in which at least one hydrogen atom of the hydrocarbyl radical has been substituted with at least one heteroatom (such as halogen, e.g., Br, Cl, F or I) or heteroatom-containing group (such as a functional group, e g., -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, -(CH₂)q-SiR*3, and the like, where q is 1 to 10 and each R* is independently hydrogen, a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted completely saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within a hydrocarbyl ring.

[0025] The term "substituted styrene," means a styrene group having 1 or more hydrogen groups replaced by a hydrocarbyl group.

[0026] A heterocyclic ring is a ring having a heteroatom in the ring structure as opposed to a heteroatom substituted ring where a hydrogen on a ring atom is replaced with a heteroatom. For example, tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatom substituted ring. A substituted heterocyclic ring is a heterocyclic ring where a hydrogen of one of the ring atoms is substituted, e.g., replaced with a hydrocarbyl, or a heteroatom containing group (as further described in the definition of "substituted" herein). [0027] As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, and Mz is z average molecular weight, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD), also referred to as polydispersity index (PDI), is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units (e.g., Mw, Mn, Mz) are g/mol.

[0028] As used herein, a “catalyst” includes a single catalyst, or multiple catalysts. Catalysts can have isomeric forms such as conformational isomers or configurational isomers. Conformational isomers include, for example, conformers and rotamers. Configurational isomers include, for example, stereoisomers.

[0029] The term “complex,” may also be referred to as catalyst precursor, precatalyst, catalyst, catalyst compound, transition metal compound, or transition metal complex. These words are used interchangeably. Activator and cocatalyst are also used interchangeably. [0030] The following abbreviations may be used herein: Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is normal propyl, Bu is butyl, i-Bu is isobutyl, tBu is tertiary butyl, n-Bu is normal butyl, MAO is methylalumoxane, Bn is benzyl (i.e., CF₂Ph), RT is room temperature (and is 23°C unless otherwise indicated), CF₃SO_3- is triflate, and Cy is cyclohexyl. [0031] An “anionic ligand” is a negatively charged ligand that 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.

[0032] As used herein, a “catalyst system” includes at least one catalyst compound and an activator. A catalyst system of the present disclosure can further include a support material and an optional co-activator. For the purposes of this disclosure, when a catalyst is described as including neutral stable forms of the components, it is well understood by one of ordinary skill in the art, that the ionic form of the component is the form that reacts with the monomers to produce polymers. Furthermore, catalysts of the present disclosure represented by a Formula are intended to embrace ionic forms thereof of the compounds in addition to the neutral stable forms of the compounds. Furthermore, activators of the present disclosure are intended to embrace ionic/reaction product forms thereof of the activator in addition to ionic or neutral form.

[0033] An "anionic leaving group" is a negatively charged group that donates one or more pairs of electrons to a metal ion that can be displaced by monomer or activator.

[0034] A “scavenger” is a compound that can be added to a reactor to facilitate polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. A co-activator, that is not a scavenger, may also be used in conjunction with an activator in order to form an active catalyst. In at least one embodiment, a co-activator is pre-mixed with the transition metal compound to form an alkylated transition metal compound. Examples of scavengers include trialkylaluminums, methylalumoxanes, modified methylalumoxanes, MMAO-3 A (Akzo Nobel), bis(diisobutylaluminum)oxide (Akzo Nobel), tri(n-octyl)aluminum, triisobutylaluminum, and diisobutylaluminum hydride, and free- radical scavengers such as antioxidants (e.g., octadecyl 3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate also referred to as Irganox™ 1076, available from Ciba-Geigy). [0035] The term “alkenyl” means a straight-chain, branched-chain, or cyclic hydrocarbon radical having one or more double bonds. These alkenyl radicals may be optionally substituted. Examples of suitable alkenyl radicals include ethenyl, propenyl, allyl, 1,4-butadienyl cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, including their substituted analogues.

[0036] The term “alkoxy” or “alkoxide” means an alkyl ether radical wherein the term alkyl is as defined above. Examples of suitable alkyl ether radicals include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, and phenoxyl. [0037] The term “aryl” or “aryl group” includes a C₄-C₂₀ aromatic ring, such as a six carbon aromatic ring, and the substituted variants thereof, including phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise heteroaryl means an aryl group where a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, such as N, O, or S. As used herein, the term “aromatic” also refers to pseudoaromatic heterocycles which are heterocyclic substituents that have similar properties and structures (nearly planar) to aromatic heterocyclic ligands, but are not by definition aromatic; likewise the term aromatic also refers to substituted aromatics.

[0038] The terms “aryloxy” and “aryloxide” mean an aryl group bound to an oxygen atom, such as an aryl ether group/radical connected to an oxygen atom and can include those where the aryl group is a C₁ to C₁0 hydrocarbyl. Examples of suitable aryloxy radicals can include phenoxy, and the like.

[0039] The terms “hydrosilylcarbyl radical,” “hydrosilylcarbyl group,” or “hydrosilylcarbyl” interchangeably refers to a group consisting of hydrogen, carbon, and silicon atoms only. A hydrosilylcarbyl group can be saturated or unsaturated, linear or branched, cyclic or acyclic, aromatic or non-aromatic, and with the silicon atom being within and/or pendant to the cyclic/aromatic rings.

[0040] The term “silyl group,” refers to a group comprising silicon atoms, such as a hydrosilylcarbyl group. [0041] A “ring carbon atom” is a carbon atom that is part of a cyclic ring structure. By this definition, a benzyl group has six ring carbon atoms and para-methylstyrene also has six ring carbon atoms.

[0042] The term “ring atom” means an atom that is part of a cyclic ring structure. By this definition, a benzyl group has six ring atoms and tetrahydrofuran has 5 ring atoms. [0043] Where isomers of anamed alkyl, alkenyl, alkoxide, or aryl group exist (e.g., n-butyl, iso-butyl, iso-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).

[0044] For any particular compound disclosed herein, any general or specific structure presented also encompasses all conformational isomers, regio-isomers, and stereoisomers that may arise from a particular set of substituents, unless stated otherwise. Similarly, unless stated otherwise, the general or specific structure also encompasses all enantiomers, diastereomers, and other optical isomers whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as would be recognized by a skilled artisan.

[0045] The term “continuous” means a system that operates without interruption or cessation. For example a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn during a polymerization process.

[0046] Herein, “catalyst” and “catalyst complex” are used interchangeably.

Description

[0047] This invention relates to a copolymer comprising ethylene, α-olefin, non- conjugated diene, and substituted styrene units, which this disclosure will refer to as an EADS copolymer.

[0048] It has been surprisingly and unexpectedly discovered that an EADS copolymer that includes ethylene, α-olefin, non-conjugated diene, and substituted styrene units has excellent melt processability. Additionally, the substituted styrene units increase the ability of the EADS copolymer to accept a filler, which can improve stiffness, dimensional stability, tensile strength, and/or fire resistance of the EADS copolymer.

EADS Copolymer

[0049] In some examples, the EADS copolymer can be a copolymer that includes units derived from ethylene, C₃+α-olefin, non-conjugated diene, and substituted styrene. In some examples, the EADS copolymer can include at least 10 wt%, at least 20 wt%, at least 30 wt%, or at least 40 wt%, at least 50 wt%, at least 55 wt%, at least 60 wt%, at least 65 wt%, or at least 70 wt% of units derived from ethylene based on the weight of the EADS copolymer. In some examples, the EADS copolymer can include from about 5 to about 95 wt%, from about 25 wt% to about 95 wt%, from about 50 wt% to about 95 wt%, from about 5 wt% to about 75 wt%, from about 25 wt% to about 75 wt from about 50 to about 75 wt%, from about 60 wt% to about 75 wt%, or from about 65 wt% to about 75 wt% of units derived from ethylene based on the weight of the EADS copolymer.

[0050] In some examples, the EADS copolymer can include at least 10 wt%, at least 20 wt%, at least 30 wt%, or at least 40 wt%, at least 50 wt%, at least 55 wt%, at least 60 wt% , at least 65 wt%, or at least 70 wt% of units derived from a C₃+ α-olefin based on the weight of the EADS copolymer. In some examples, the EADS copolymer can include from about 5 wt% to about 95 wt%, from about 25 wt% to about 95 wt%, from about 50 wt% to about 95 wt%, from about 5 wt% to about 75 wt%, from about 25 to about 75 wt% from about 50 wt% to about 75 wt%, from about 60 wt% to about 75 wt%, or from about 65 wt% to about 75 wt% of units derived from a C₃+ α-olefin based on the weight of the EADS copolymer. In some examples, the units derived from the C₃+ α-olefin can be derived more C₃-C₂₀ α-olefins, including combinations of one or more C₃-C₂₀ a-oiefins. In some examples, the units derived from the C₃+ α-olefin can be derived from propylene, 1 -butene, isobutylene, 2-butene, cyclobutene, 1-pentene, 1 -hexene. 4-methyl- 1 -pen tens, 1-octene, 3-methyl- 1 -butene, 4-methyl-1-butene, cyclopentene, 1 -hexene, cyclohexene, 1-octene, 1-decene, 1-dodecene, or combinations thereof. In some examples, the units derived from an α-olefin can be derived from propylene. In some examples, the molar ratio of ethylene units to the α-olefin units is about 5/95 to about 95/5, about 40/60 to about 95/5, about 50/50 to about 95/5, or about 60/40 to about 95/5.

[0051] In some examples, the EADS copolymer can include less than or equal to 40 wt% units derived from a diene (or “diene”), less than or equal to 30 wt% diene, or less than or equal to 20 wt% diene, or less than or equal to 15 wt%, or less than or equal to 10 wt% diene, or less than or equal to 5 wt% diene, or less than or equal to 3 wt% diene based on the weight of the EADS copolymer. In some examples, the diene can be present from about 0.1 wt% to about 40 wt%, from about 0.1 wt% to about 30 wt%, from about 0.1 wt% to about 25 wt%, from about 0.1 wt% to about 15 wt%, from about 0.1 wt% to about 10 wt%, from about 0.1 wt% to about 5 wt%, from about 1 wt% to about 40 wt%, from about 1 wt% to about 30 wt%, from about 1 wt% to about 25 wt%, from about 1 wt% to about 15 wt%, from about 1 wt% to about 10 wt%, or from about 1 wt% to about 5 wt% based on the weight of the EADS copolymer. In some examples, the EADS copolymer can include the diene in an amount of from about 2.0 wt% to about 7.0 wt%, or from about 3.0 wt% to about 5.0 wt%, based on the weight of the EADS copolymer. The units derived from a diene can be derived from any hydrocarbon structure having at least two unsaturated bonds wherein at least one of the unsaturated bonds can be incorporated into a polymer.

[0052] Suitable non-conjugated dienes include straight or branched chain hydrocarbon di- olefins or cycloalkenyl-substituted alkenes, having about 6 to about 15 carbon atoms, such as for example:

(a) linear acyclic dienes, such as 1,4-hexadiene and 1,6-octadiene;

(b) branched acyclic dienes, such as 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6- octadiene, and 3,7-dimethyl-1,7-octadiene; (c) single ring dienes, such as 1,4-cyclohexadiene, 1,5-cyclo-octadiene and 1,7- cyclododecadiene;

(d) multi-ring fused and bridged ring dienes, such as tetrahydroindene, methyl- tetrahydroindene, dicyclopentadiene (DCPD), bicyclo-(2.2.1)-hepta-2, 5-diene (also referred to as "norbomadiene"), alkenyl-, alkylidene-, cycloalkenyl- and cycloalkybdene- norbomenes, such as 5-methylene-2-norbomene (MNB), 5-ethybdene-2-norbomene (ENB), 5-propenyl-2- norbomene, 5-isopropylidene-2-norbomene, 5-(4-cyclopentenyl)-2-norbomene,

5-cyclohexylidene-2-norbomene, and 5-vinyl-2-norbomene (VNB); and

(e) cycloalkenyl-substituted alkenes, such as vinyl cyclohexene, allyl cyclohexene, vinyl cyclooctene, 4-vinyl cyclohexene, allyl cyclodecene, and vinyl cyclododecene, divinyl benzene, and tetracyclo (A-11,12)-5,8-dodecene; and combinations thereof. In certain embodiments, the diene is 5-ethylidene-2-norbomene, 5-vinyl-2-norbomene, or divinyl benzene. Preferred non-conjugated dienes are 5-ethylidene-2-norbomene (ENB), 1,4-hexadiene, dicyclopentadiene (DCPD), norbomadiene, and 5 -vinyl-2 -norbomene (VNB), with ENB being most preferred. Preferably, the diene is 5 -ethylidene-2-norbomene. Note that throughout this application the terms " non-conjugated diene " and "diene" are used interchangeably.

[0053] In some examples, the EADS copolymer can include less than or equal to 15 wt% units derived from a substituted styrene compound (“substituted styrene”), or less than or equal to 30 wt% substituted styrene, or less than or equal to 20 wt% substituted styrene, or less than or equal to 15 wt% substituted styrene, or less than or equal to 10 wt% substituted styrene, or less than or equal to 5 wt% substituted styrene, or less than or equal to 3 wt% substituted styrene based on the weight of the EADS copolymer. In some examples, the substituted styrene can be present from 0.1 wt% to 40 wt%, from about 0.1 wt% to about 30 wt%, from about 0.1 wt% to about 25 wt%, from about 0.1 wt% to about 15 wt%, from about 0.1 wt% to about 10 wt%, or from about 0.1 wt% to about 5 wt%, from about 1 wt% to about 40 wt%, from about 1 wt% to about 30 wt%, from about 1 wt% to about 25 wt%, from about 1 wt% to about 15 wt%, from about 1 wt% to about 10 wt%, or from about 1 wt% to about 5 wt% based on the weight of the EADS copolymer. In some examples, the EADS copolymer can include substituted styrene in an amount of from about 2.0 wt% to about 7.0 wt%, or from about 3.0 wt% to about 5.0 wt%, based on the weight of the EADS copolymer. The units derived from a substituted styrene compound can be derived from any compound containing styrene. [0054] Preferred substituted styrene compounds include those represented by the Formula (I):

where x is 1, 2, 3, 4, or 5, typically 1 or 2, and each R is independently a hydrocarbyl group, such as a C₁ to C₂₀ hydrocarbyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl or an isomer thereof.

[0055] Particularly preferred substituted styrene compounds include those represented by the Formula (II):

where y is 1, 2 or 3, typically 3 x is 1, 2, 3, 4, or 5, typically 1 or 2, and each R¹ is independently hydrogen or a hydrocarbyl group, such as a C₁ to C₂₀ hydrocarbyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl or an isomer thereof. Preferably y is 3, each R¹ is hydrogen and x is 1, 2, or 3.

[0056] Additionally preferred substituted styrene compounds include those represented by the Formula (III):

where R², R³, R⁴, R⁵ and R⁶ is independently is hydrogen, or a hydrocarbyl group, such as a Ci to C₂₀ hydrocarbyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl or an isomer thereof, provided that at least one of R², R³, R⁴, R⁵ and R⁶ is not hydrogen, alternately 2, 3, 4, or 5 of R², R³, R⁴, R⁵ and R⁶ are not hydrogen.

[0057] In a preferred embodiment of the invention, R⁴ is not hydrogen.

[0058] In a preferred embodiment of the invention, R⁴ is a hydrocarbyl group, such as a Ci to C₂₀ hydrocarbyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl or an isomer thereof. [0059] In a preferred embodiment of the invention, R⁴ is a hydrocarbyl group, such as a Ci to C₂₀ hydrocarbyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl or an isomer thereof and R², R³, R⁵ and R⁶ are hydrogen.

[0060] Preferably the substituted styrene is a para-alkyl styrene, where the alkyl is a C₁ to C₄₀ alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl or an isomer thereof.

[0061] In some examples, the units derived from the substituted styrene compound are represented by the Formula (IV):

wherein R and R’ are independently selected from the group consisting of hydrogen and alkyl, typically C₁ to C₂₀ alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or an isomer thereof, preferably methyl, where at elast one of R and R is not hydrogen. In some examples, the units derived from a styrene compound are derived from para-alkylstyrenes, such as para-methylstyrene.

[0062] Preferably, the EADS comprises: 1) from 40 wt% to 80 wt% of ethylene-derived units (preferably from 40 wt% to 75 wt%), 2) from 0.3 wt% to 15 wt% of one or more non- conjugated diene-derived units (preferably from 0.3 wt% to 10.0 wt%, preferably from 0.3 wt% to 5 wt%), 3) from 0.3 wt% to 15 wt% of one or more substituted styrene derived units (preferably from 0.3 wt% to 10.0 wt%, preferably from 0.3 wt% to 5 wt%), and 4) where the balance of the EADS comprises C₃ to C₄₀ alpha-olefin (preferably propylene or butene, most preferably propylene)-derived units.

[0063] In embodiments of EADS copolymer:

1) the ethylene is present at 20 to 80 wt% (alternately 40 wt% to 80 wt%, alternately 40 wt% to 75 wt%),

2) the alpha-olefin (such as propylene) is present at 20 to 79.8 wt%, (alternately 30 wt% to 70 wt%, alternately 35 wt% to 60 wt%),

3) the non-conjugated diene is present at 0.1 to 20 wt% (alternately 0.3 wt% to 10 wt%, alternately 0.3 wt% to 5 wt%), and

4) the substituted styrene is present at 0.1 to 40 wt% (alternately 0.3 wt% to 10 wt%, alternately 0.3 wt% to 5 wt%), based upon the weight of the copolymer.

[0064] Note that the alpha olefin and the non-conjugated diene are not the same monomer. Preferably, the alpha olefin is a mono-olefin. Likewise, the non-conjugated diene is not a substituted styrene monomer.

Polymerization Process

[0065] In embodiments herein, the invention relates to polymerization processes where monomers comprising ethylene, alpha olefin comonomer, diene and substituted styrene are contacted with a catalyst system comprising an activator and at least one catalyst compound, as described herein. The catalyst compound and activator may be combined in any order, and are combined typically prior to contacting with the monomer.

[0066] For purposes of this invention and the claims thereto, a solution polymerization means a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert solvent or monomer(s) or their blends. A solution polymerization can be homogeneous. A homogeneous polymerization is one where the polymer product is dissolved in the polymerization medium. Such systems are not turbid as described in J. Vladimir Oliveira, C. Dariva and J. C. Pinto, Ind. Eng. Chem. Res., 2000, v.29, p. 4627.

[0067] For purposes of this invention and the claims thereto, a bulk polymerization means a polymerization process in which the monomers and/or comonomers being polymerized are used as a solvent or diluent using little or no inert solvent as a solvent or diluent. A small fraction of inert solvent might be used as a carrier for catalyst and scavenger. A bulk polymerization system contains less than about 25 wt% of inert solvent or diluent, such as less than about 10 wt%, such as less than about 1 wt%, such as about 0 wt%. [0068] Polymerization processes of this invention can be carried out in any manner known in the art. Any suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization process known in the art can be used. Such processes can be run in a batch, semi-batch, or continuous mode. Homogeneous polymerization processes and slurry processes are preferred. (A homogeneous polymerization process is preferably a process where at least 90 wt% of the product is soluble in the reaction media.) A bulk homogeneous process is particularly preferred. (A bulk process is preferably a process where monomer concentration in all feeds to the reactor is 70 volume % or more.) Alternately, no solvent or diluent is present or added in the reaction medium, (except for the small amounts used as the carrier for the catalyst system or other additives, or amounts typically found with the monomer; e.g., propane in propylene). In another embodiment, the process is a slurry process. As used herein the term “slurry polymerization process” means a polymerization process where a supported catalyst is employed and monomers are polymerized on the supported catalyst particles. At least 95 wt% of polymer products derived from the supported catalyst are in granular form as solid particles (not dissolved in the diluent).

[0069] Suitable diluents/solvents for polymerization include non-coordinating, inert liquids. Examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (Isopar™ fluids); perhalogenated hydrocarbons, such as perfluorinated C_{4- 10} alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene. Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1 -butene, 1 -hexene, 1-pentene, 3-methyl-l-pentene, 4-methyl- 1-pentene, 1-octene, 1-decene, and mixtures thereof. In a preferred embodiment, aliphatic hydrocarbon solvents are used as the solvent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In another embodiment, the solvent is not aromatic, preferably aromatics are present in the solvent at less than 1 wt%, preferably less than 0.5 wt%, preferably less than 0 wt% based upon the weight of the solvents. [0070] In a preferred embodiment, the feed concentration of the monomers and comonomers for the polymerization is 60 vol% solvent or less, preferably 40 vol% or less, or preferably 20 vol% or less, based on the total volume of the feedstream. Preferably the polymerization is run in a bulk process.

[0071] Preferred polymerizations can be run at any temperature and/or pressure suitable to obtain the desired ethylene polymers. Typical temperatures and/or pressures include a temperature in the range of from about 0°C to about 300°C, preferably about 20°C to about 200°C, preferably about 35°C to about 150°C, preferably from about 40°C to about 120°C, preferably from about 45°C to about 80°C; and at a pressure in the range of from about 0.35 MPa to about 10 MPa, preferably from about 0.45 MPa to about 6 MPa, or preferably from about 0.5 MPa to about 4 MPa.

[0072] In a typical polymerization, the run time of the reaction is up to 300 minutes, preferably in the range of from about 5 to 250 minutes, or preferably from about 10 to 120 minutes.

[0073] In some embodiments hydrogen is present in the polymerization reactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa), preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7 to 70 kPa).

[0074] In a preferred embodiment, little or no alumoxane is used in the process to produce the polymers. Preferably, alumoxane is present at zero mol%, alternately the alumoxane is present at a molar ratio of aluminum to transition metal less than 500:1, preferably less than 300:1, preferably less than 100:1, preferably less than 1:1.

[0075] In a preferred embodiment, little or no scavenger is used in the process to produce the ethylene polymer. Preferably, scavenger (such as tri alkyl aluminum) is present at zero mol%, alternately the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, preferably less than 50:1, preferably less than 15:1, preferably less than 10:1.

[0076] In a preferred embodiment, the polymerization:

1) is conducted at temperatures of 0 to 300°C (preferably 25 to 150°C, preferably 40 to 120°C, preferably 45 to 80°C);

2) is conducted at a pressure of atmospheric pressure to 10 MPa (preferably 0.35 to 10 MPa, preferably from 0.45 to 6 MPa, preferably from 0.5 to 4 MPa);

3) is conducted in an aliphatic hydrocarbon solvent (such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; preferably where aromatics are preferably present in the solvent at less than 1 wt%, preferably less than 0.5 wt%, preferably at 0 wt% based upon the weight of the solvents);

4) optionally, wherein the catalyst system used in the polymerization comprises less than 0.5 mol%, preferably 0 mol% alumoxane, alternately the alumoxane is present at a molar ratio of aluminum to transition metal less than 500: 1, preferably less than 300: 1, preferably less than 100:1, preferably less than 1:1;

5) the polymerization preferably occurs in one reaction zone;

6) the productivity of the catalyst compound is at least 80,000 g/mmol/hr (preferably at least 150,000 g/mmol/hr, preferably at least 200,000 g/mmol/hr, preferably at least 250,000 g/mmol/hr, preferably at least 300,000 g/mmol/hr);

7) optionally, scavengers (such as trialkyl aluminum compounds) are absent (e.g. present at zero mol%, alternately the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, preferably less than 50:1, preferably less than 15:1, preferably less than 10:1); and

8) optionally, hydrogen is present in the polymerization reactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa) (preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7 to 70 kPa)).

[0077] In a preferred embodiment, the catalyst system used in the polymerization comprises no more than one catalyst compound. A "reaction zone" also referred to as a "polymerization zone" is a vessel where polymerization takes place, for example a batch reactor. When multiple reactors are used in either series or parallel configuration, each reactor is considered as a separate polymerization zone. For a multi-stage polymerization in both a batch reactor and a continuous reactor, each polymerization stage is considered as a separate polymerization zone. In a preferred embodiment, the polymerization occurs in one reaction zone. Room temperature is 23°C unless otherwise noted.

[0078] Other additives may also be used in the polymerization, as desired, such as one or more scavengers, promoters, modifiers, reducing agents, oxidizing agents, hydrogen, aluminum alkyls, silanes, or chain transfer agents (such as alkylalumoxanes, a compound represented by the formula AIR₃ or ZnR₂ (where each R is, independently, a C₁-C₈ aliphatic radical, preferably methyl, ethyl, propyl, butyl, penyl, hexyl octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof). [0079] In some examples, the EADS copolymer can be produced in a high-pressure tubular reactor. The EADS copolymerization is not limited to any specific tubular reactor design, operating pressure, operating temperature, or initiator system. The reactor can be capable of injection of the reactants into the reaction stream at least two, at least three, or at least four locations along the reaction tube.

[0080] In some examples, the EADS copolymer can be produced by slurry polymerization utilizing α-olefin monomer, such as propylene, as the polymerization diluent in which a supported catalyst system is suspended, in an amount sufficient to yield a copolymer with the desired diene content, generally greater than or equal to 3 wt%. The concentration of diene in the reactor as a volume percentage of total diluent present can range from 0.1 to 25 vol%, 0.5 to 10 vol% or 1 to 5 vol%. Diene monomer can be supplied to the polymerization diluent. The concentration of styrene in the reactor as a volume percentage of total diluent present can range from 0.1 to 25 vol%, 0.5 to 10 vol% or 1 to 5 vol%. Styrene monomer can be supplied to the polymerization diluent. Ethylene can be added to the reaction vessel in an amount to maintain a differential pressure in excess of the combined vapor pressure of the α-olefin, diene, and styrene monomers. The ethylene content of the polymer can be determined by the ratio of ethylene differential pressure to the total reactor pressure. Generally the polymerization process can be carried out with a differential pressure of ethylene of from about 69 kPaa to about 6,900 kPaa or from about 275 kPaa to about 2,750 kPaa; and the polymerization diluent can be maintained at a temperature of from about -10°C to about 100°C; from about 10°C to about 70°C; or from about 20°C to about 60°C. Under the polymerization conditions as indicated above the ethylene, α-olefin, styrene and diene can polymerize to produce the EADS copolymer.

[0081] The polymerization can be carried out as a batchwise slurry polymerization or as a continuous slurry polymerization. The procedure of continuous process slurry polymerization is where ethylene, α-olefin, diene, styrene and catalyst are continuously supplied to the reaction zone.

[0082] In some examples, liquid propylene monomer can be introduced continuously together with styrene monomer, diene monomer and ethylene monomer. The reactor can contain a liquid phase composed substantially of liquid propylene and diene and styrene monomers together with dissolved ethylene gas, and a vapor phase containing vapors of all monomers. Feed ethylene gas can be introduced either into the vapor phase of the reactor, or sparged into the liquid phase as well known in the art. Catalyst and any additional cocatalyst and scavenger, if employed, can be introduced via nozzles in either the vapor or liquid phase, with polymerization occurring substantially in the liquid phase. The reactor temperature and pressure can be controlled via reflux of vaporizing α-olefin monomers (auto-refrigeration, as well as by cooling coils, jackets etc.) The polymerization rate can be controlled by the rate of catalyst addition. The ethylene content of the EADS copolymer can be determined by the ratio of ethylene to propylene in the reactor, which can be controlled by manipulating the respective feed rates of these components to the reactor. The molecular weight of the EADS copolymer can be controlled, optionally, by controlling other polymerization variables such as the temperature, or by a stream of hydrogen introduced to the gas or liquid phase of the reactor, as is well known in the art. The EADS copolymer which leaves the reactor can be recovered by flashing off gaseous ethylene and propylene at reduced pressure, and, if necessary, conducting further devolatilization to remove residual olefin, styrene and diene monomers in equipment such as a devolatilizing extruder. In a continuous process, the mean residence time of the catalyst and polymer in the reactor generally can be from about 20 minutes to 8 hours, 30 minutes to 6 hours, or 1 to 4 hours.

Catalyst Systems.

[0083] The EADS polymer described herein is prepared by contacting monomers and with a catalyst system comprising a single site transition metal compound and an activator. Transition Metal Compounds

[0084] Any single site transition metal compound capable of catalyzing a reaction, such as a polymerization reaction, upon activation with an activator as described above is suitable for use in polymerization processes of the present disclosure. Transition metal compounds known as metallocenes are exemplary catalyst compounds according to the present disclosure. Metallocene Catalyst Compounds

[0085] A "metallocene" catalyst compound is preferably a transition metal catalyst compound having one, two or three, typically one or two, substituted or unsubstituted cyclopentadienyl ligands bound to the transition metal Typically a metallocene catalyst is an organometallic compound containing at least one p-bound cyclopentadienyl moiety (or substituted cyclopentadienyl moiety). Substituted or unsubstituted cyclopentadienyl ligands include substituted or unsubstituted indenyl, fluorenyl, tetrahydro-s-indacenyl. tetrahydro-as- indacenyl, benz[f]indenyl, benz[e] indenyl. tetrahydrocyclopenta[b] naphthalene, tetrahydrocyclopenta[α]naphthalene, and the like. [0086] The metallocene catalyst compound of catalyst systems of the present disclosure may be unbridged metallocene catalyst compounds represented by the formula: Cp^ACp^BM'X'_n, wherein each Cp^A and Cp^B is independently selected from cyclopentadienyl ligands (for example, Cp, Ind, or Flu) and ligands isolobal to cyclopentadienyl, one or both Cp^A and Cp^B may contain heteroatoms, and one or both Cp^A and Cp^B may be substituted by one or more R" groups; M' is selected from Groups 3 through 12 atoms and lanthanide Group atoms; X' is an anionic leaving group; n is 0 or an integer from 1 to 4; each R" is independently selected from alkyl, substituted alkyl, heteroalkyl, alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, aryloxy, alkylthio, arylthio, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, a heteroatom-containing group, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, silyl, boryl, phosphino, phosphine, amino, amine, ether, and thioether.

[0087] In at least one embodiment, each Cp^A and Cp^B is independently selected from cyclopentadienyl, indenyl, fluorenyl, indacenyl, tetrahydroindenyl, cyclopentaphenanthreneyl, benzindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopent[a]acenaphthylenyl, 7-H-dibenzofluorenyl, indeno[l,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl, hydrogenated and substituted versions thereof. Each Cp^A and Cp^B may independently be indacenyl or tetrahydroindenyl.

[0088] The metallocene catalyst compound may be a bridged metallocene catalyst compound represented by the formula: Cp^A(T)Cp^BM'X'_n, wherein each Cp^A and Cp^B is independently selected from cyclopentadienyl ligands (for example, Cp, Ind, or Flu) and ligands isolobal to cyclopentadienyl, where onene or both Cp^A and Cp^B may contain heteroatoms, and one or both Cp^A and Cp^B may be substituted by one or more R" groups; M' is selected from Groups 3 through 12 atoms and lanthanide Group atoms, preferably Group 4; X' is an anionic leaving group; n is 0 or an integer from 1 to 4; (T) is a bridging group selected from divalent alkyl, divalent substituted alkyl, divalent heteroalkyl, divalent alkenyl, divalent substituted alkenyl, divalent heteroalkenyl, divalent alkynyl, divalent substituted alkynyl, divalent heteroalkynyl, divalent alkoxy, divalent aryloxy, divalent alkylthio, divalent arylthio, divalent aryl, divalent substituted aryl, divalent heteroaryl, divalent aralkyl, divalent aralkylene, divalent alkaryl, divalent alkarylene, divalent haloalkyl, divalent haloalkenyl, divalent haloalkynyl, divalent heteroalkyl, divalent heterocycle, divalent heteroaryl, a divalent heteroatom-containing group, divalent hydrocarbyl, divalent substituted hydrocarbyl, divalent heterohydrocarbyl, divalent silyl, divalent boryl, divalent phosphino, divalent phosphine, divalent amino, divalent amine, divalent ether, divalent thioether. R" is selected from alkyl, substituted alkyl, heteroalkyl, alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, aryloxy, alkylthio, arylthio, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, a heteroatom-containing group, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, silyl, boryl, phosphino, phosphine, amino, amine, germanium, ether, and thioether.

[0089] In at least one embodiment, each of Cp^A and Cp^B is independently selected from cyclopentadienyl, indenyl, fluorenyl, cyclopentaphenanthreneyl, benzindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopent[a] acenaphthylenyl,

7-H-dibenzofluorenyl, indeno[l,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl, hydrogenated, and substituted versions thereof, preferably cyclopentadienyl, n-propylcyclopentadienyl, indenyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, and n-butylcyclopentadienyl. Each Cp^A and Cp^B may independently be indacenyl or tetrahydroindenyl.

[0090] (T) is a bridging group containing at least one Group 13, 14, 15, or 16 element, in particular boron or a Group 14, 15 or 16 element , preferably (T) is O, S, NR', or SiR'2, where each R' is independently hydrogen or C₁-C₂₀ hydrocarbyl.

[0091] In another embodiment, the metallocene catalyst compound is represented by the formula:

T_yCp_mMG_nX_q where Cp is independently a substituted or unsubstituted cyclopentadienyl ligand (for example, substituted or unsubstituted Cp, Ind, or Flu) or substituted or unsubstituted ligand isolobal to cyclopentadienyl; M is a Group 4 transition metal; G is a heteroatom group represented by the formula JR*_Z where J is N, P, O or S, and R* is a linear, branched, or cyclic C₁-C₂₀ hydrocarbyl; z is 1 or 2; T is a bridging group as defined above; y is 0 or 1; X is a leaving group; m=l, n= 1, 2 or 3, q=0, 1, 2 or 3, and the sum of m+n+q is equal to the coordination number of the transition metal, typically 4. [0092] In at least one embodiment, J is N, and R* is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl or an isomer thereof.

[0093] In at least one embodiment, the catalyst compound is represented by Formula (V) or Formula (VI):

wherein in each of Formula (V) and Formula (VI): M is the metal center, and is a Group 4 metal, such as titanium, zirconium or hafnium, such as zirconium or hafnium when L₁ and L₂ are present and titanium when Z is present; n is 0 or 1 ;

T is an optional bridging group which, if present, is a bridging group containing at least one Group 13, 14, 15, or 16 element, in particular boron or a Group 14, 15 or 16 element (preferably T is selected from dialkylsilyl, diarylsilyl, dialkylmethyl, ethylenyl ( — CH₂ — CH₂ — ) or hydrocarbyl ethylenyl wherein one, two, three or four of the hydrogen atoms in ethylenyl are substituted by hydrocarbyl, where hydrocarbyl can be independently C₁ to C₁₆ alkyl or phenyl, tolyl, xylyl and the like), and when T is present, the catalyst represented can be in a racemic or a rneso form; Li and L2 are independently cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl, optionally substituted, that are each bonded to M, or L₁ and L₂ are independently cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl, which are optionally substituted, in which any two adjacent substituents on L¹ and L² are optionally joined to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent; Z is nitrogen, oxygen or phosphorus; q is 1 or 2;

R' is a cyclic, linear or branched C₁ to C₄₀ alkyl or substituted alkyl group (such as Z — R' form a eyclododecylamido group); Xi and X2 are, independently, hydrogen, halogen, hydride radicals, hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbyl radicals, substituted halocarbyl radicals, silylcarbyl radicals, substituted silylcarbyl radicals, germylcarbyl radicals, or substituted germylcarbyl radicals: or Xi and X2 are joined and bound to the metal atom to form a metallacycle ring containing from about 3 to about 20 carbon atoms; or both together can be an olefin, di olefin or aryne ligand.

[0094] Preferably, T in any formula herein is present and is a bridging group containing at least one Group 13, 14, 15, or 16 element, in particular a Group 14 element. Examples of suitable bridging groups include P(=S)R’, P(=Se)R’, P(=0)R’, 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, RECSiRE, RESiSiRE, RESiOSiRE, RECSiRECRE, R’₂SiCR’2SiR’2, R’C=CR’SiR’2, RECGeRE, R’₂GeGeR’2, RECGeRECRE, REGeCREGeRE, RESiGeRE, 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-CR’₂CR’2, REC-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’, REC-PR’-CRE, O, S, Se, Te, NR’, PR’, AsR’, SbR’, O-O, S-S, R’N-NR’, R’P-PR’, O-S, O-NR’, O-PR’, S-NR’, S-PR’, and R’N-PR’ where R’ is hydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl substituent and optionally two or more adjacent R’ may join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent. Preferred examples for the bridging group T include CEE, CH₂CH₂, SiMe2, SiPh2, SiMePh, Si(CH₂)₃, Si(CH₂)₄, O, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, Me₂SiOSiMe₂, and PBu.

[0095] In a preferred embodiment of the invention in any embodiment of any formula described herein, T is represented by the formula R^a2^J or (R^a2^J)₂, where J is C, Si, or Ge, and each R^a is, independently, hydrogen, halogen, C₁ to C₂₀ hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a C₁ to C₂₀ substituted hydrocarbyl, and two R^a can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system. Preferably, T is a bridging group comprising carbon or silica, such as dialkylsilyl, preferably T is selected from CH₂ , CH₂CH₂, C(CH₃ )2, SiMe₂, SiPh₂, SiMePh, silylcyclobutyl (Si(CH₂)₃), (Ph)₂C, (p-(Et)₃SiPh)₂C, Me₂SiOSiMe_2, and cyclopentasilylene (Si(CH₂)4). [0096] In at least one embodiment, the catalyst compound has a symmetry that is C₂ symmetrical.

[0097] Suitable metallocenes useful herein include, but are not limited to, the metallocenes disclosed in US Patents 6,309,997; 6,265,338; 7,179,876; 7,169,864; 7,157,531; 7,129,302; 6,995,109; 6,958,306; 6,884,748; 6,689,847; US Patent publication US2006/019925, US2007/0055028, and published PCT Applications WO 1997/022635; WO 2000/699022; WO 2001/030860; WO 2001/030861; WO 2002/046246; WO 2002/050088; WO 2004/026921; and WO 2006/019494, all fully incorporated herein by reference. Additional catalysts suitable for use herein those disclosed in the following articles: Chem Rev

2000, 100, 1253; Resconi; Chem Rev 2003, 103, 283; Chem Eur. J. 2006, 12, 7546 Mitsui; J Mol Catal A 2004, 213, 141; Macromol Chem Phys, 2005, 206, 1847; and J Am Chem Soc

2001, 123, 6847.

[0098] Exemplary metallocene compounds useful herein are include: bis(cyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dimethyl, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dimethyl, bis(pentamethylcyclopentadienyl)hafnium dichloride, bis(pentamethylcyclopentadienyl)zirconium dimethyl, bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride, bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl, bis(1-methyl-3-n-butylcyclopentadienyl)hafnium di chloride, bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl, bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dimethyl, bis(tetrahydro-1-indenyl)zirconium di chloride, bis(tetrahydro-1-indenyl)zirconium dimethyl,

(n-propyl cyclopentadienyl, pentamethyl cyclopentadienyl)zirconium dichloride, and (n-propyl cyclopentadienyl, pentamethyl cyclopentadienyl)zirconium dimethyl.

[0099] In at least one embodiment, the catalyst compound may be selected from: dimethylsilylbis(tetrahydroindenyl)MXn, dimethylsilyl bis(2-methylindenyl)MX_n, dimethylsilyl bis(2-methylfluorenyl)MX_n, dimethylsilyl bis(2 -methyl-5, 7-propylindenyl)MX_n, dimethylsilyl bis(2-methyl-4-phenylindenyl)MX_n, dimethylsilyl bis(2-ethyl-5-phenylindenyl)MX_n, dimethylsilyl bis(2-methyl-4-biphenylindenyl)MX_n, dimethylsilylene bis(2-methyl-4-carbazolylindenyl)MX_n, rac-dimelhylsilyl-bis-(5.6.7.8-tetrahydro-5.5.8.8-tetramelhyl-2-melhyl- 1 H- benz(f)indene)MXn, diphenylmethylene (cyclopentadienyl)(fluoreneyl)MX_n, bis(methylcyclopentadienyl)MXn, rac-dimethylsiylbis(2-methyl, 3-propyl indenyl)MX_n, dimethylsilylbis(indenyl)MXn,

Rac-meso-diphenylsilyl-bis(n-propylcyclopentadienyl)MX_n.

1, r-bis(4-triethylsilylphenyl)methylene-(cy cl opentadienyl)(3,8-di -tertiary -butyl-1- fluorenyl)MXn (bridge is considered the 1 position), bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(di-t-butylfluorenyl)MXn, bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(fluorenyl)MXn, bisphenylmethylene(cyclopentadienyl)(dimethylfluorenyl)MXn, bis(n-propylcyclopentadienyl)MXn, bis(n-butylcyclopentadienyl)MXn, bis(n-pentylcyclopentadienyl)MXn,

(n-propyl cyclopentadienyl)(n-butylcyclopentadienyl)MX_n, bis[(2-trimethylsilylethyl)cyclopentadienyl]MX_n, bis(trimethylsilyl cyclopentadienyl)MX_n, dimethylsilylbis(n-propylcyclopentadienyl)MXn, dimethylsilylbis(n-butylcyclopentadienyl)MXn, bis(1-n-propyl-2-methylcyclopentadienyl)MXn,

(n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)MXn, bis(l -methyl, 3-n-butyl cyclopentadienyl)MX_n, bis(indenyl)MXn, dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)MX_n, dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)MX_n, μ-(CH₃)₂Si(cyclopentadienyl)(l-adamantylamido)MXn, μ-(CH₃)₂Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)MXn, m-(CH₃)₂(tetramethylcyclopentadienyl)(1-adamantylamido)MXn, μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-adamantylamido)MXn, μ-(CH₃)₂C(tetramethylcyclopentadienyl)(1-adamantylamido)MXn, μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-tertbutylamido)MX_n, μ-(CH₃)₂Si(fluorenyl)(1-tertbutylamido)MXn, μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)MX_n, μ-(C6H5)2C(tetramethylcyclopentadienyl)(1-cyclododecylamido)MXn, μ-(CH₃)₂Si(n⁵-2, 6, 6-trimethyl- 1 ,5,6, 7-tetrahy dro-i'-indacen- 1 -yl)(tertbutylamido)MXn, where M is selected from Ti, Zr, and Hf; where X is selected from the group consisting of halogens, hydrides, C_1-12 alkyls, C_2-12 alkenyls, C_6-12 aryls, C_7-20 alkylaryls, C_1-12 alkoxys, C_6-16 aryloxys, C_7-18 alkylaryloxys, C_1-12 fluoroalkyls, C_6-12 fluoroaryls, and C_1-12 heteroatom- containing hydrocarbons, substituted derivatives thereof, and combinations thereof, and where n is zero or an integer from 1 to 4, preferably X is selected from halogens (such as bromide, fluoride, chloride), or C₁ to C₂₀ alkyls (such as methyl, ethyl, propyl, butyl, and pentyl) and n is 1 or 2, preferably 2.

[0100] In other embodiments of the invention, the catalyst is one or more of: bis(1-methyl, 3-n-butyl cyclopentadienyl) M(R)₂; dimethylsilyl bis(indenyl)M(R)2; bis(indenyl)M(R)2; dimethylsilyl bis(tetrahydroindenyl)M(R)2; bis(n-propylcyclopentadienyl)M(R)2; dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)M(R)2; dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)M(R)2; dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)M(R)2; dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)M(R)2; μ-(CH₃)₂Si(cyclopentadienyl)(l-adamantylamido)M(R)2; μ-(CH₃)₂Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)M(R)2; μ-(CH₃)₂(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)2; μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)2; μ-(CH₃)₂C(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)2; μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-tertbutylamido)M(R)2; μ-(CH₃)₂Si(fluorenyl)(1-tertbutylamido)M(R)2; μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)2; μ-(C₆H₅)₂C(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)2; μ-(CH₃)₂Si(n⁵-2.6.6-trimethyl- 1.5.6.7-tetrahydro-.v-indacen-1-yl)(tertbutylamido)M(R)₂: where M is selected from Ti, Zr, and Hf; and R is selected from halogen or C₁ to C₅ alkyl. [0101] In preferred embodiments of the invention, the catalyst compound is one or more of: dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl; dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl; dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium dimethyl; dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium dimethyl; μ-(CH₃)₂Si(cyclopentadienyl)(l-adamantylamido)titanium dimethyl; μ-(CH₃)₂Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)titanium dimethyl; μ-(CH₃)₂(tetramethylcyclopentadienyl)(1-adamantylamido)titanium dimethyl; μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-adamantylamido)titanium dimethyl; μ-(CH₃)₂C(tetramethylcyclopentadienyl)(1-adamantylamido)titanium dimethyl; μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-tertbutylamido)titanium dimethyl·: μ-(CH₃)₂Si(fluorenyl)(1-tertbutylamido)titanium dimethyl; μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)titanium dimethyl; μ-(C₆H₅)₂C(tetramethylcyclopentadienyl)( 1 -cyclododecylamido)titanium dimethyl; and/or μ-(CH₃)₂Si(n⁵-2, 6, 6-trimethyl- 1 ,5,6, 7-tetrahy dro-s-indacen- 1 -yl)(tertbutylamido)titanium dimethyl.

[0102] In at least one embodiment, the catalyst is rac-dimethylsilyl-bis(indenyl)hafnium dimethyl and or 1, l'-bis(4-tri ethylsilylphenyl)methylene-(cyclopentadienyl)(3,8-di -tertiary- butyl- 1 -fluorenyl)hafnium dimethyl.

[0103] In at least one embodiment, the catalyst compound is one or more of: bis(1-methyl, 3-n-butyl cyclopentadienyl)hafnium dimethyl, bis(1-methyl, 3-n-butyl cyclopentadienyl)zirconium dimethyl, dimethylsilyl bis(indenyl)zirconium dimethyl, dimethylsilyl bis(indenyl)hafnium dimethyl, bis(indenyl)zirconium dimethyl, bis(indenyl)hafnium dimethyl, dimethylsilyl bis(tetrahydroindenyl)zirconium dimethyl, bis(n-propylcyclopentadienyl)zirconium dimethyl, dimethylsilylbis(tetrahydroindenyl)hafnium dimethyl, dimethylsilyl bis(2-methylindenyl)zirconium dimethyl, dimethylsilyl bis(2-methylfluorenyl)zirconium dimethyl, dimethylsilyl bis(2-methylindenyl)hafnium dimethyl, dimethylsilyl bis(2-methylfluorenyl)hafnium dimethyl, dimethylsilyl bis(2-methyl-5,7-propylindenyl) zirconium dimethyl, dimethylsilyl bis(2-methyl-4-phenylindenyl) zirconium dimethyl, dimethylsilyl bis(2-ethyl-5-phenylindenyl) zirconium dimethyl, dimethylsilyl bis(2-methyl-4-biphenylindenyl) zirconium dimethyl, dimethylsilylene bis(2-methyl-4-carbazolylindenyl) zirconium dimethyl, rac-dimethylsilyl-bis-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-methyl-lH- benz(f)indene)hafnium dimethyl, diphenylmethylene (cyclopentadienyl)(fluoreneyl)hafnium dimethyl, bis(methylcyclopentadienyl)zirconium dimethyl, rac-dimethylsiylbis(2 -methyl, 3-propyl indenyl)hafhium dimethyl, dimethylsilylbis(indenyl)hafnium dimethyl, dimethylsilylbis(indenyl)zirconium dimethyl, dimethyl rac-dimethylsilyl-bis-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-methyl-lH- benz(f)indene)hafnium dimethyl, Rac-meso-diphenyl silyl-bis(n-propylcyclopentadienyl)hafni urn dimethyl,

1, r-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(3,8-di-tertiary-butyl-l- fluorenyl)hafnium X_n (bridge is considered the 1 position), bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(di-t-butylfluorenyl)hafnium dimethyl, bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(fluorenyl)hafnium dimethyl, bisphenylmethylene(cyclopentadienyl)(dimethylfluorenyl)hafnium dimethyl, bis(n-propylcyclopentadienyl)hafnium dimethyl, bis(n-butylcyclopentadienyl)hafnium dimethyl, bis(n-pentylcyclopentadienyl)hafnium dimethyl,

(n-propyl cyclopentadienyl)(n-butylcyclopentadienyl)hafnium dimethyl, bis[(2-trimethylsilylethyl)cyclopentadienyl]hafnium dimethyl, bis(trimethylsilyl cyclopentadienyl)hafnium dimethyl, dimethylsilylbis(n-propylcyclopentadienyl)hafnium dimethyl, dimethylsilylbis(n-butylcyclopentadienyl)hafnium dimethyl, bis(1-n-propyl-2-methylcyclopentadienyl)hafnium dimethyl, and (n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)hafnium dimethyl, bis(n-propylcyclopentadienyl)hafnium dimethyl, bis(n-butylcyclopentadienyl)hafnium dimethyl, bis(n-pentylcyclopentadienyl)hafnium dimethyl,

(n-propyl cyclopentadienyl)(n-butylcyclopentadienyl)hafnium dimethyl, bis[(2-trimethylsilylethyl)cyclopentadienyl]hafnium dimethyl, bis(trimethylsilyl cyclopentadienyl)hafnium dimethyl, dimethylsilylbis(n-propylcyclopentadienyl)hafnium dimethyl, dimethylsilylbis(n-butylcyclopentadienyl)hafnium dimethyl, bis(1-n-propyl-2-methylcyclopentadienyl)hafnium dimethyl, and (n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)hafnium dimethyl. Non-Metallocene Catalyst Compounds

[0104] Transition metal complexes for the polymerization processes described herein can include “non-metallocene complexes” that are defined to be transition metal complexes that do not feature a cyclopentadienyl anion or substituted cyclopentadienyl anion donors (e.g., cyclopentadienyl, fluorenyl, indenyl, methylcyclopentadienyl). Examples of families of non- metallocene complexes that may be suitable can include late transition metal pyridylbisimines (e.g., US 7,087,686), group 4 pyridyldiamidos (e.g., US 7,973,116), quinolinyldiamidos (e.g., US Pub. No. 2018/0002352 Al), pyridylamidos (e.g., US 7,087,690), phenoxyimines (e.g., Accounts of Chemical Research 2009, 42, 1532-1544), and bridged bi-aromatic complexes (e.g., US 7,091,292), the disclosures of which are incorporated herein by reference.

[0105] Particularly useful catalyst complexes that are suitable for use herein include: pyridyldiamido complexes; quinolinyldiamido complexes; phenoxyimine complexes; bisphenolate complexes; cyclopentadienyl-amidinate complexes; and iron pyridyl bis(imine) complexes or any combination thereof, including any combination with metallocene complexes.

[0106] The term “pyridyldiamido complex” or “pyridyldiamide complex” or “pyridyldiamido catalyst” or “pyridyldiamide catalyst” refers to a class of coordination complexes described in US Pat. No. 7,973,116B2, US 2012/0071616A1, US 2011/0224391 Al, US 2011/0301310A1, US 2015/0141601 Al, US 6,900,321 and US 8,592,615 that feature a dianionic tri dentate ligand that is coordinated to a metal center through one neutral Lewis basic donor atom (e.g., a pyridine group) and a pair of anionic amido or phosphido (i.e., deprotonated amine or phosphine) donors. In these complexes the pyridyldiamido ligand is coordinated to the metal with the formation of one five membered chelate ring and one seven membered chelate ring. It is possible for additional atoms of the pyridyldiamido ligand to be coordinated to the metal without affecting the catalyst function upon activation; an example of this could be a cyclometalated substituted aryl group that forms an additional bond to the metal center. [0107] The term “quinolinyldiamido complex” or “quinolinyldiamido catalyst” or “quinolinyldiamide complex” or “quinolinyldiamide catalyst” refers to a related class of pyridyldiamido complex/catalyst described in US 2018/0002352 where a quinolinyl moiety is present instead of a pyridyl moiety.

[0108] The term “phenoxyimine complex” or “phenoxyimine catalyst” refers to a class of coordination complexes described in EP 0874005 that feature a monoanionic bidentate ligand that is coordinated to a metal center through one neutral Lewis basic donor atom (e.g., an imine moiety) and an anionic aryloxy (i.e., deprotonated phenoxy) donor. Typically two of these bidentate phenoxyimine ligands are coordinated to a group 4 metal to form a complex that is useful as a catalyst component.

[0109] The term “bisphenolate complex” or “bisphenolate catalyst” refers to a class of coordination complexes described in US 6,841,502, WO 2017/004462, and WO 2006/020624 that feature a dianionic tetradentate ligand that is coordinated to a metal center through two neutral Lewis basic donor atoms (e.g., oxygen bridge moieties) and two anionic aryloxy (i.e., deprotonated phenoxy) donors. [0110] The term “cyclopentadienyl-amidinate complex” or “cyclopentadienyl-amidinate catalyst” refers to a class of coordination complexes described in US 8,188,200 that typically feature a group 4 metal bound to a cyclopentadienyl anion, a bidentate amidinate anion, and a couple of other anionic groups. [0111] The term “iron pyridyl bis(imine) complex” refers to a class of iron coordination complexes described in US 7,087,686 that typically feature an iron metal center coordinated to a neutral, tri dentate pyridyl bis(imine) ligand and two other anionic ligands.

[0112] Non-metallocene complexes can include iron complexes of tri dentate pyridylbisimine ligands, zirconium and hafnium complexes of pyridylamido ligands, zirconium and hafnium complexes of tridentate pyridyldiamido ligands, zirconium and hafnium complexes of tridentate quinolinyldiamido ligands, zirconium and hafnium complexes of bidentate phenoxyimine ligands, and zirconium and hafnium complexes of bridged bi- aromatic ligands.

[0113] Suitable non-metallocene complexes can include zirconium and hafnium non- metallocene complexes. In at least one embodiment, non-metallocene complexes for the present disclosure include group 4 non-metallocene complexes including two anionic donor atoms and one or two neutral donor atoms. Suitable non-metallocene complexes for the present disclosure include group 4 non-metallocene complexes including an anionic amido donor. Suitable non-metallocene complexes for the present disclosure include group 4 non- metallocene complexes including an anionic aryloxide donor atom. Suitable non-metallocene complexes for the present disclosure include group 4 non-metallocene complexes including two anionic aryloxide donor atoms and two additional neutral donor atoms.

[0114] Useful catalyst compounds can be a quinolinyldiamido (QDA) transition metal complex represented by Formula (BI), such as by Formula (BII), such as by Formula (Blll):

wherein:

M is a group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal, such as a group 4 metal;

J is group including a three-atom-length bridge between the quinoline and the amido nitrogen, such as a group containing up to 50 non-hydrogen atoms;

E is carbon, silicon, or germanium;

X is an anionic leaving group, (such as a hydrocarbyl group or a halogen);

L is a neutral Lewis base;

R¹ and R¹³ are independently selected from the group including of hydrocarbyls, substituted hydrocarbyls, and silyl groups;

R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R^10’, R¹¹, R^11’, R¹², and R¹⁴ are independently hydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyl, halogen, or phosphino; n is 1 or 2; m is 0, 1, or 2, where n+m is not greater than 4; and any two R groups (e.g., R¹ & R², R² & R³, R¹⁰ and R¹¹, etc.) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic, or unsubstituted heterocyclic, saturated or unsaturated ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings; any two X groups may be joined together to form a dianionic group; any two L groups may be joined together to form a bidentate Lewis base; and any X group may be joined to an L group to form a monoanionic bidentate group. [0115] In at least one embodiment, M is a group 4 metal, such as zirconium or hafnium, such as M is hafnium.

[0116] Representative non-metallocene transition metal compounds usable for forming poly(alphα-olefin)s of the present disclosure also include tetrabenzyl zirconium, tetra bis(trimethylsilymethyl) zirconium, oxotris(trimethlsilylmethyl) vanadium, tetrabenzyl hafnium, tetrabenzyl titanium, bis(hexamethyl disilazido)dimethyl titanium, tris(trimethyl silyl methyl) niobium dichloride, and tris(trimethylsilylmethyl) tantalum dichloride.

[0117] In at least one embodiment, J is an aromatic substituted or unsubstituted hydrocarbyl having from 3 to 30 non-hydrogen atoms, such as J is represented by the formula:

where R⁷, R⁸, R⁹, R¹⁰, R^10', R¹¹, R^11', R¹², R¹⁴ and E are as defined above, and any two R groups (e.g., R⁷ & R⁸, R⁸ & R⁹, R⁹ & R¹⁰, R¹⁰ & R¹¹, etc.) may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms (such as 5 or 6 atoms), and said ring may be saturated or unsaturated (such as partially unsaturated or aromatic), such as J is an arylalkyl (such as arylmethyl, etc.) or dihydro- lH-indenyl, or tetrahydronaphthalenyl group.

[0118] In at least one embodiment, J is selected from the following structures:

where indicates connection to the complex.

[0119] In at least one embodiment, E is carbon.

[0120] X may be an alkyl (such as alkyl groups having 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof), aryl, hydride, alkylsilane, fluoride, chloride, bromide, iodide, triflate, carboxylate, amido (such as NMe2), or alkylsulfonate.

[0121] In at least one embodiment, L is an ether, amine or thioether.

[0122] In at least one embodiment, R⁷ and R⁸ are joined to form a six-membered aromatic ring with the joined R⁷/R⁸ group being -CH=CHCH=CH-.

[0123] R¹⁰ and R¹¹ may be joined to form a five-membered ring with the joined R¹⁰R¹¹ group being -CH₂CH₂-.

[0124] In at least one embodiment, R¹⁰ and R¹¹ are joined to form a six-membered ring with the joined R¹⁰ R¹¹ group being -CH₂CH₂CH₂-. [0125] R¹ and R¹³ may be independently selected from phenyl groups that are variously substituted with between zero to five substituents that include F, Cl, Br, I, CF3, NO2, alkoxy, dialkylamino, aryl, and alkyl groups having 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof.

[0126] In at least one embodiment, the QDA transition metal complex represented by the Formula (BII) above where:

M is a group 4 metal (such hafnium);

E is selected from carbon, silicon, or germanium (such as carbon);

X is an alkyl, aryl, hydride, alkylsilane, fluoride, chloride, bromide, iodide, triflate, carboxylate, amido, alkoxo, or alkylsulfonate;

L is an ether, amine, or thioether;

R¹ and R¹³ are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups (such as aryl);

R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independently hydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino; n is 1 or 2; m is 0, 1, or 2; n+m is from 1 to 4; two X groups may be joined together to form a dianionic group; two L groups may be joined together to form a bi dentate Lewis base; an X group may be joined to an L group to form a monoanionic bidentate group;

R⁷ and R⁸ may be joined to form a ring (such as an aromatic ring, a six-membered aromatic ring with the joined R⁷R⁸ group being -CH=CHCH=CH-); and

R¹⁰ and R¹¹ may be joined to form a ring (such as a five-membered ring with the joined R¹⁰R¹¹ group being -CH₂CH₂-, a six-membered ring with the joined R¹⁰R¹¹ group being -CH₂CH₂CH₂-).

[0127] In at least one embodiment of Formula (BI), (BII), and (Blll), R⁴, R⁵, and R⁶ are independently selected from the group including hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, and wherein adjacent R groups (R⁴ and R⁵ and/or R⁵ and R⁶) are joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings. [0128] In at least one embodiment of Formula (BI), (BII), and (Blll), R⁷ _, R⁸ _, R⁹, and R¹⁰ are independently selected from the group including hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and wherein adjacent R groups (R⁷ and R⁸ and/or R⁹ and R¹⁰) may be joined to form a saturated, substituted hydrocarbyl, unsubstituted hydrocarbyl, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings.

[0129] In at least one embodiment of Formula (BI), (BII), and (Blll), R² and R³ are each, independently, selected from the group including hydrogen, hydrocarbyls, and substituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R² and R³ may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R² and R³ may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings.

[0130] In at least one embodiment of Formula (BI), (BII), and (Blll), R¹¹ and R¹² are each, independently, selected from the group including hydrogen, hydrocarbyls, and substituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R¹¹ and R¹² may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R¹¹ and R¹² may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings, or R¹¹ and R¹⁰ may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings.

[0131] In at least one embodiment of Formula (BI), (BII), and (Blll), R¹ and R¹³ are independently selected from phenyl groups that are variously substituted with between zero to five substituents that include F, Cl, Br, I, CF₃, NO₂, alkoxy, dialkylamino, aryl, and alkyl groups having 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof.

[0132] In at least one embodiment of Formula (BII), suitable R¹²-E-R¹¹ groups include CH₂, CMe₂, SiMe₂, SiEt₂, SiPr₂, SiBu₂, SiPh₂, Si(aryl)₂, Si(alkyl)₂, CH(aiyl), CH(Ph), CH(alkyl), and CH(2-isopropylphenyl), where alkyl is a C₁ to C₄₀ alkyl group (such as C₁ to C₂o alkyl, such as one or more of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and isomers thereof), aryl is a C₅ to C₄₀ aryl group (such as a Ce to C₂o aryl group, such as phenyl or substituted phenyl, such as phenyl, 2-isopropylphenyl, or 2-tertbutylphenyl). [0133] In at least one embodiment of Formula (Blll), R¹¹ _, R¹² _, R⁹, R¹⁴, and R¹⁰ are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and wherein adjacent R groups (R¹⁰ and R¹⁴, and/or R¹¹ and R¹⁴, and/or R⁹ and R¹⁰) may be joined to form a saturated, substituted hydrocarbyl, unsubstituted hydrocarbyl, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings.

[0134] The R groups above (i.e., any of R² to R¹⁴) and other R groups mentioned hereafter may contain from 1 to 30, such as 2 to 20 carbon atoms, such as from 6 to 20 carbon atoms. The R groups above (i.e., any of R² to R¹⁴) and other R groups mentioned hereafter, may be independently selected from the group including hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, trimethylsilyl, and -CH₂-Si(Me)3.

[0135] In at least one embodiment, the quinolinyldiamide complex is linked to one or more additional transition metal complex, such as a quinolinyldiamide complex or another suitable non-metallocene, through an R group in such a fashion as to make a bimetallic, trimetallic, or multimetallic complex that may be used as a catalyst component for olefin polymerization. The linker R-group in such a complex may contain 1 to 30 carbon atoms.

[0136] In at least one embodiment, E is carbon and R¹¹ and R¹² are independently selected from phenyl groups that are substituted with 0, 1, 2, 3, 4, or 5 substituents selected from the group consisting of F, Cl, Br, I, CF₃, NO2, alkoxy, dialkylamino, hydrocarbyl, and substituted hydrocarbyl groups with from one to ten carbons.

[0137] In at least one embodiment of Formula (BII) or (Blll), R¹¹ and R¹² are independently selected from hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, -CH₂- Si(Me)3, and trimethylsilyl.

[0138] In at least one embodiment of Formula (BII), and (Blll), R⁷, R⁸, R⁹, and R¹⁰ are independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy, -CH₂-Si(Me)₃, and trimethylsilyl.

[0139] In at least one embodiment of Formula (BI), (BII), and (Blll), R², R³, R⁴, R⁵, and R⁶ are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, substituted hydrocarbyls, and halogen.

[0140] In at least one embodiment of Formula (Blll), R¹⁰, R¹¹ and R¹⁴ are independently selected from hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, -CH₂-Si(Me)₃, and trimethylsilyl. [0141] In at least one embodiment of Formula (BI), (BII), and (Blll), each L is independently selected from Et₂0, MeOtBu, Et₃N, PhNMe2, MePh2N, tetrahydrofuran, and dimethylsulfide.

[0142] In at least one embodiment of Formula (BI), (BII), and (Blll), each X is independently selected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, dimethylamido, diethylamido, dipropylamido, and diisopropylamido.

[0143] In at least one embodiment of Formula (BI), (BII), and (Blll), R¹ is

2.6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2,6-diisopropyl-4-methylphenyl, 2,6-diethylphenyl, 2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl,

2.6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl.

[0144] In at least one embodiment of Formula (BI), (BII), and (Blll), R¹³ is phenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, 2-isopropylphenyl, 4-methylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorophenyl, 3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl.

[0145] In at least one embodiment of Formula (BII), J is dihydro- lH-indenyl and R¹ is

2.6-dialkylphenyl or 2, 4, 6-trialky lphenyl.

[0146] In at least one embodiment of Formula (BI), (BII), and (Blll), R¹ is

2.6-diisopropylphenyl and R¹³ is a hydrocarbyl group containing 1, 2, 3, 4, 5, 6, or 7 carbon atoms.

[0147] An exemplary catalyst used for polymerizations of the present disclosure is (QDA- l)HfMe₂, as described in US Pub. No. 2018/0002352 Al.

[0148] In at least one embodiment, the catalyst compound is a bis(phenolate) catalyst compound represented by Formula (Cl):

(Cl).

M is a Group 4 metal, such as Hf or Zr. X¹ and X² are independently a univalent C₁-C₂₀ hydrocarbyl, C₁-C₂₀ substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or X¹ and X² join together to form a C₄-C₆₂ cyclic or polycyclic ring structure. R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ is independently hydrogen, C₁-C₄₀ hydrocarbyl, C₁-C₄₀ substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or two or more of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, or R¹⁰ are j oined together to form a C₄-C₆₂ cyclic or polycyclic ring structure, or a combination thereof; Q is a neutral donor group; J is heterocycle, a substituted or unsubstituted C₇-C₆₀ fused polycyclic group, where at least one ring is aromatic and where at least one ring, which may or may not be aromatic, has at least five ring atoms' G is as defined for J or may be hydrogen, C₂-C₆₀ hydrocarbyl, C₁-C₆₀ substituted hydrocarbyl, or may independently form a C₄-C₆₀ cyclic or polycyclic ring structure with R⁶, R⁷, or R⁸ or a combination thereof; Y is divalent C₁-C₂₀ hydrocarbyl or divalent C₁-C₂₀ substituted hydrocarbyl or (-Q-Y-) together form a heterocycle; and heterocycle may be aromatic and/or may have multiple fused rings.

[0149] In at least one embodiment, the catalyst compound represented by Formula (Cl) is represented by Formula (CII) or Formula (CIII):

(CII), or

(CIII).

M is Hf, Zr, or Ti. X¹, X², R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and Y are as defined for Formula (Cl). R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ is independently a hydrogen, C₁-C₄₀ hydrocarbyl, C₁-C₄₀ substituted hydrocarbyl, a functional group comprising elements from Groups 13 to 17, or two or more of R¹, R², R³, R⁴, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶,

R²⁷, and R²⁸ may independently join together to form a C₄-C₆₂ cyclic or polycyclic ring structure, or a combination thereof; R¹¹ and R¹² may join together to form a five- to eight- membered heterocycle; Q* is a group 15 or 16 atom; z is 0 or 1 ; J* is CR" or N, and G* is CR" or N, where R" is C₁-C₂₀ hydrocarbyl or carbonyl-containing C₁-C₂₀ hydrocarbyl; and z = 0 if Q* is a group 16 atom, and z = 1 if Q* is a group 15 atom.

[0150] In at least one embodiment the catalyst is an iron complex represented by Formula (IV): wherein:

A is chlorine, bromine, iodine, -CF₃ or -OR¹¹; each of R¹ and R² is independently hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or five-, six- or seven-membered heterocyclyl comprising at least one atom selected from the group consisting of N, P, O and S; wherein each of R¹ and R² is optionally substituted by halogen, -NR¹¹2, -OR¹¹ or -SIR¹² ₃; wherein R¹ optionally bonds with R³, and R² optionally bonds with R⁵, in each case to independently form a five-, six- or seven-membered ring;

R⁷ is a C₁-C₂₀ alkyl; each of R³, R⁴, R⁵, R⁸, R⁹, R¹⁰, R¹⁵, R¹⁶, and R¹⁷ is independently hydrogen, C₁-C₂₂- alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, -NR¹¹2, -OR¹¹, halogen, -SiR¹² ₃ or five-, six- or seven- membered heterocyclyl comprising at least one atom selected from the group consisting of N, P, O, and S; wherein R³, R⁴, R⁵, R⁷, R⁸, R⁹, R¹⁰, R¹⁵, R¹⁶, and R¹⁷ are optionally substituted by halogen, -NR¹¹2, -OR¹¹ or -SiR¹² ₃; wherein R³ optionally bonds with R⁴, R⁴ optionally bonds with R⁵, R⁷ optionally bonds with R¹⁰, R¹⁰ optionally bonds with R⁹, R⁹ optionally bonds with R⁸, R¹⁷ optionally bonds with R¹⁶, and R¹⁶ optionally bonds with R¹⁵, in each case to independently form a five-, six- or seven-membered carbocyclic or heterocyclic ring, the heterocyclic ring comprising at least one atom from the group consisting of N, P, O and S;

R¹³ is C₁-C₂₀-alkyl bonded with the aryl ring via a primary or secondary carbon atom;

R¹⁴ is chlorine, bromine, iodine, -CF₃ or -OR¹¹, or C₁-C₂₀-alkyl bonded with the aryl ring; each R¹¹ is independently hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or -SiR¹² ₃, wherein R¹¹ is optionally substituted by halogen, or two R¹¹ radicals optionally bond to form a five- or six-membered ring; each R¹² is independently hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or two R¹² radicals optionally bond to form a five- or six-membered ring; each of E¹, E², and E³ is independently carbon, nitrogen or phosphorus; each u is independently 0 if E¹, E², and E³ is nitrogen or phosphorus and is 1 if E¹, E², and E³ is carbon; each X is independently fluorine, chlorine, bromine, iodine, hydrogen, C₁-C₂₀-alkyl, C₂-C₁₀-alkenyl, C₆-C₂₀-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, -NR¹⁸ ₂, -OR¹⁸, -SR¹⁸, -SO₃R¹⁸, -OC(O)R¹⁸, -CN, -SCN, b-diketonate, -CO, -BF4 . -PFr, or bulky non-coordinating anions, and the radicals X can be bonded with one another; each R¹⁸ is independently hydrogen, C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₆-C₂₀-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or -SiR¹⁹ ₃, wherein R¹⁸ can be substituted by halogen or nitrogen- or oxygen-containing groups and two R¹⁸ radicals optionally bond to form a five- or six-membered ring; each R¹⁹ is independently hydrogen, C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₆-C₂₀-aryl or arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, wherein R¹⁹ can be substituted by halogen or nitrogen- or oxygen-containing groups or two R¹⁹ radicals optionally bond to form a five- or six-membered ring; s is 1, 2, or 3;

D is a neutral donor; and t is 0 to 2. [0151] In another embodiment, the catalyst is a phenoxyimine compound represented by the Formula (VII):

wherein M represents a transition metal atom selected from the groups 3 to 11 metals in the periodic table; k is an integer of 1 to 6; m is an integer of 1 to 6; R^ato R^fmay be the same or different from one another and each represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, among which 2 or more groups may be bound to each other to form a ring; when k is 2 or more, R^a groups, R^b groups, R^c groups, R^d groups, R^e groups, or R^f groups may be the same or different from one another, one group of R^a to R^f contained in one ligand and one group of R^a to R^f contained in another ligand may form a linking group or a single bond, and a heteroatom contained in R^ato R^fmay coordinate with or bind to M; m is a number satisfying the valence of M; Q represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron- containing group, an aluminum-containing group, a phosphorus-containing group, a halogen- containing group, a heterocyclic compound residue, a silicon-containing group, a germanium- containing group or a tin-containing group; when m is 2 or more, a plurality of groups represented by Q may be the same or different from one another, and a plurality of groups represented by Q may be mutually bound to form a ring.

[0152] In another embodiment, the catalyst is a bis(imino)pyridyl of the Formula (VIII):

wherein:

M is Co or Fe; each X is an anion; n is 1, 2 or 3, so that the total number of negative charges on said anion or anions is equal to the oxidation state of a Fe or Co atom present in

(VIII);

R¹, R² and R³ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;

R⁴ and R⁵ are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;

R⁶ is Formula (IX):

R⁸ and R¹³ are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group;

R⁹, R¹⁰, R¹¹, R¹⁴, R¹⁵ and R¹⁶ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;

R¹² and R¹⁷ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and provided that any two of R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶ and R¹⁷ that are adjacent to one another, together may form a ring.

[0153] In at least one embodiment, the catalyst compound is represented by the Formula (XI):

(XI) ,

M¹ is selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten. In at least one embodiment, M¹ is zirconium. [0154] Each of Q¹, Q², Q³, and Q⁴ is independently oxygen or sulfur. In at least one embodiment, at least one of Q¹, Q², Q³, and Q⁴ is oxygen, alternately all of Q¹, Q², Q³, and Q⁴ are oxygen.

[0155] R¹ and R² are independently hydrogen, halogen, hydroxyl, hydrocarbyl, or substituted hydrocarbyl (such as C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy, C₆-C₂₀ aryl, C₆-C₁₀ aryloxy, C₂-C₁₀ alkenyl, C₂-C₄₀ alkenyl, C₇-C₄₀ arylalkyl, C₇-C₄₀ alkylaryl, C8-C₄₀ arylalkenyl, or conjugated diene which is optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl) silyl or tri(hydrocarbyl) silylhydrocarbyl, the diene having up to 30 atoms other than hydrogen). R¹ and R² can be a halogen selected from fluorine, chlorine, bromine, or iodine. Preferably, R¹ and R² are chlorine.

[0156] Alternatively, R¹ and R² may also be joined together to form an alkanediyl group or a conjugated C₄-C₄₀ diene ligand which is coordinated to M¹. R¹ and R² may also be identical or different conjugated dienes, optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl) silyl or tri(hydrocarbyl) silylhydrocarbyl, the dienes having up to 30 atoms not counting hydrogen and/or forming a p-complex with M¹.

[0157] Exemplary groups suitable for R¹ and or R² can include 1,4-diphenyl, 1,3-butadiene,

1.3-pentadiene, 2-methyl 1,3-pentadiene, 2,4-hexadiene, 1-phenyl, 1,3-pentadiene,

1.4-dibenzyl, 1,3-butadiene, 1 ,4-ditolyl- 1 , 3-butadiene, 1,4-bis (trimethylsilyl)-1, 3-butadiene, and 1,4-dinaphthyl-1, 3-butadiene. R¹ and R² can be identical and are C₁-C₃ alkyl or alkoxy, C₆-C₁₀ aryl or aryloxy, C₂-C₄ alkenyl, C₇-C₁₀ arylalkyl, C₇-C₁₂ alkylaryl, or halogen.

[0158] Each of R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ is independently hydrogen, halogen, C₁-C₄₀ hydrocarbyl or C₁-C₄₀ substituted hydrocarbyl (such as C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy, C₆-C₂₀ aryl, C₆-C₁₀ aryloxy, C₂-C₁₀ alkenyl, C₂-C₄₀ alkenyl, C₇-C₄₀ arylalkyl, C₇-C₄₀ alkylaryl, C8-C₄₀ arylalkenyl, or conjugated diene which is optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl) silyl or tri(hydrocarbyl) silylhydrocarbyl, the diene having up to 30 atoms other than hydrogen), -NR'₂, -SR', -OR, -OSiR'₃, -PR'₂, where each R is hydrogen, halogen, C₁-C₁₀ alkyl, or C₆-C₁₀ aryl, or one or more of R⁴ and R⁵, R⁵ and R⁶, R⁶ and R⁷, R⁸ and R⁹, R⁹ and R¹⁰, R¹⁰ and R¹¹, R¹² and R¹³, R¹³ and R¹⁴, R¹⁴ and R¹⁵, R¹⁶ and R¹⁷, R¹⁷ and R¹⁸, and R¹⁸ and R¹⁹ are joined to form a saturated ring, unsaturated ring, substituted saturated ring, or substituted unsaturated ring. In at least one embodiment, C₁-C₄₀ hydrocarbyl is selected from methyl, ethyl, propyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, n-pentyl, isopentyl, sec -pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl, and sec-decyl. Preferably, R¹¹ and R¹² are C₆-C₁₀ aryl such as phenyl or naphthyl optionally substituted with C₁-C₄₀ hydrocarbyl, such as C₁-C₁₀ hydrocarbyl. Preferably, R⁶ and R¹⁷ are C_1-40 alkyl, such as C₁-C₁₀ alkyl.

[0159] In at least one embodiment, each of R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ is independently hydrogen or C₁-C₄₀ hydrocarbyl. In at least one embodiment, C₁-C₄₀ hydrocarbyl is selected from methyl, ethyl, propyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, n-pentyl, isopentyl, sec -pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl, and sec-decyl. Preferably, each of R⁶ and R¹⁷ is C₁-C₄₀ hydrocarbyl and R⁴, R⁵, R⁷, R⁸, R⁹, R¹⁰, R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁸, and R¹⁹ is hydrogen. In at least one embodiment, C₁-C₄₀ hydrocarbyl is selected from methyl, ethyl, propyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl, and sec-decyl.

[0160] R³ is a C₁-C₄₀ unsaturated alkyl or substituted C₁-C₄₀ unsaturated alkyl (such as C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy, C₆-C₂₀ aryl, C₆-C₁₀ aryloxy, C₂-C₁₀ alkenyl, C₂-C₄₀ alkenyl, C₇-C₄₀ arylalkyl, C₇-C₄₀ alkylaryl, C₈-C₄₀ arylalkenyl, or conjugated diene which is optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl) silyl or tri(hydrocarbyl) silylhydrocarbyl, the diene having up to 30 atoms other than hydrogen).

[0161] Preferably, R³ is a hydrocarbyl comprising a vinyl moiety. As used herein, “vinyl” and “vinyl moiety” are used interchangeably and include a terminal alkene, e.g., represented by the structure

Hydrocarbyl of R³ may be further substituted (such as C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy, C₆-C₂₀ aryl, C₆-C₁₀ aryloxy, C₂-C₁₀ alkenyl, C₂-C₄₀ alkenyl, C₇-C₄₀ arylalkyl, C₇-C₄₀ alkylaryl, C₈-C₄₀ arylalkenyl, or conjugated diene which is optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl) silyl or tri(hydrocarbyl) silylhydrocarbyl, the diene having up to 30 atoms other than hydrogen). Preferably, R³ is C₁-C₄₀ unsaturated alkyl that is vinyl or substituted C₁-C₄₀ unsaturated alkyl that is vinyl. R³ can be represented by the structure -R’CH=CH₂ where R’ is C₁-C₄₀ hydrocarbyl or C₁-C₄₀ substituted hydrocarbyl (such as C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy, C₆-C₂₀ aryl, C₆-C₁₀ aryloxy, C₂-C₁₀ alkenyl, C₂-C₄₀ alkenyl, C₇-C₄₀ arylalkyl, C₇-C₄₀ alkylaryl, C₈-C₄₀ arylalkenyl, or conjugated diene which is optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl) silyl or tri(hydrocarbyl) silylhydrocarbyl, the diene having up to 30 atoms other than hydrogen). In at least one embodiment, C₁-C₄₀ hydrocarbyl is selected from methyl, ethyl, propyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, n-pentyl, isopentyl, sec -pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl, and sec-decyl. [0162] In at least one embodiment, R³ is 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl,

1-heptenyl, 1-octenyl, 1-nonenyl, or 1-decenyl.

[0163] In at least one embodiment, the catalyst is a Group 15-containing metal compound represented by Formulas (XII) or (XIII):

(XII) (XIII),

wherein M is a Group 3 to 12 transition metal or a Group 13 or 14 main group metal, a Group 4, 5, or 6 metal. In many embodiments, M is a Group 4 metal, such as zirconium, titanium, or hafnium. Each X is independently a leaving group, such as an anionic leaving group. The leaving group may include a hydrogen, a hydrocarbyl group, a heteroatom, a halogen, or an alkyl; y is 0 or 1 (when y is 0 group L' is absent). The term 'h' is the oxidation state of M. In various embodiments, n is +3, +4, or +5. In many embodiments, n is +4. The term 'm' represents the formal charge of the YZL or the YZL' ligand, and is 0, -1, -2 or -3 in various embodiments. In many embodiments, m is -2. L is a Group 15 or 16 element, such as nitrogen or oxygen; L' is a Group 15 or 16 element or Group 14 containing group, such as carbon, silicon or germanium. Y is a Group 15 element, such as nitrogen or phosphorus. In many embodiments, Y is nitrogen. Z is a Group 15 element, such as nitrogen or phosphorus. In many embodiments, Z is nitrogen. R¹ and R² are, independently, a C₁ to C₂₀ hydrocarbon group, a heteroatom containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, or phosphorus. In many embodiments, R¹ and R² are a C₂ to C₂₀ alkyl, aryl or aralkyl group, such as a C₂ to C₂₀ linear, branched or cyclic alkyl group, or a C₂ to C₂₀ hydrocarbon group. R¹ and R² may also be interconnected to each other. R³ may be absent or may be a hydrocarbon group, a hydrogen, a halogen, a heteroatom containing group. In many embodiments, R³ is absent, for example, if L is an oxygen, or a hydrogen, or a linear, cyclic, or branched alkyl group having 1 to 20 carbon atoms. R⁴ and R⁵ are independently an alkyl group, an aryl group, substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group, or multiple ring system, often having up to 20 carbon atoms. In many embodiments, R⁴ and R⁵ have between 3 and 10 carbon atoms, or are a C₁ to C₂₀ hydrocarbon group, a C₁ to C₂₀ aryl group or a C₁ to C₂₀ aralkyl group, or a heteroatom containing group. R⁴ and R⁵ may be interconnected to each other. R⁶ and R⁷ are independently absent, hydrogen, an alkyl group, halogen, heteroatom, or a hydrocarbyl group, such as a linear, cyclic or branched alkyl group having 1 to 20 carbon atoms. In many embodiments, R⁶ and R⁷ are absent. R* may be absent, or may be a hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group.

[0164] By "formal charge of the YZL or YZL' ligand," it is meant the charge of the entire ligand absent the metal and the leaving groups X. By "R¹ and R² may also be interconnected" it is meant that R¹ and R² may be directly bound to each other or may be bound to each other through other groups. By "R⁴ and R⁵ may also be interconnected" it is meant that R⁴ and R⁵ may be directly bound to each other or may be bound to each other through other groups. An alkyl group may be linear, branched alkyl radicals, alkenyl radicals, alkynyl radicals, cycloalkyl radicals, aryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- or dialkyl- carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, straight, branched or cyclic, alkylene radicals, or combination thereof. An aralkyl group is defined to be a substituted aryl group.

[0165] In one or more embodiments, R⁴ and R⁵ are independently a group represented by structure (XIV):

(XIV), wherein R⁸ to R¹² are each independently hydrogen, a C₁ to C₄₀ alkyl group, a halide, a heteroatom, a heteroatom containing group containing up to 40 carbon atoms. In many embodiments, R⁸ to R¹² are a C₁ to C₂₀ linear or branched alkyl group, such as a methyl, ethyl, propyl, or butyl group. Any two of the R groups may form a cyclic group and/or a heterocyclic group. The cyclic groups may be aromatic. In one embodiment R⁹, R¹⁰ and R¹² are independently a methyl, ethyl, propyl, or butyl group (including all isomers). In another embodiment, R⁹, R¹⁰ and R¹² are methyl groups, and R⁸ and R¹¹ are hydrogen.

[0166] In one or more embodiments, R⁴ and R⁵ are both a group represented by structure (XV):

(XV), wherein M is a Group 4 metal, such as zirconium, titanium, or hafnium. In at least one embodiment, M is zirconium. Each of L, Y, and Z may be a nitrogen. Each of R¹ and R² may be -CH₂-CH₂-. R³ may be hydrogen, and R⁶ and R⁷ may be absent.

[0167] In some examples, the catalyst compound is one or more of:

Catalyst 1 Catalyst 2 Catalyst 3 Catalyst 4

[0168] In some embodiments, a co-activator is combined with the catalyst compound (such as halogenated catalyst compounds described above) to form an alkylated catalyst compound. Organoaluminum compounds which may be utilized as co-activators include, for example, trialkyl aluminum compounds, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and the like, or alumoxanes. Alkylated catalyst compounds are often used in combination with non-coordinating anion containing activators.

[0169] In some embodiments, two or more different catalyst compounds are present in the catalyst system used herein. In some embodiments, two or more different catalyst compounds are present in the reaction zone where the process(es) described herein occur. When two transition metal compound based catalysts are used in one reactor as a mixed catalyst system, the two transition metal compounds are preferably chosen such that the two are compatible. A simple screening method such as by ¹H or ¹³C NMR, known to those of ordinary skill in the art, can be used to determine which transition metal compounds are compatible. It is preferable to use the same activator for the transition metal compounds, however, two different activators can be used in combination. If one or more transition metal compounds contain an anionic ligand as a leaving group which is not a hydride, hydrocarbyl, or substituted hydrocarbyl, then the alumoxane or other alkyl aluminum is typically contacted with the transition metal compounds prior to addition of the non-coordinating anion activator.

[0170] The two transition metal compounds (pre-catalysts) may be used in any ratio. Preferred molar ratios of (A) transition metal compound to (B) transition metal compound fall within the range of (A:B) 1:1000 to 1000:1, alternatively 1:100 to 500:1, alternatively 1:10 to 200:1, alternatively 1:1 to 100:1, and alternatively 1:1 to 75:1, and alternatively 5:1 to 50:1. The particular ratio chosen will depend on the exact pre-catalysts chosen, the method of activation, and the end product desired. In a particular embodiment, when using the two pre- catalysts, where both are activated with the same activator, useful mole percents, based upon the molecular weight of the pre-catalysts, are 10 to 99.9% A to 0.1 to 90%B, alternatively 25 to 99% A to 0.5 to 50% B, alternatively 50 to 99% A to 1 to 25% B, and alternatively 75 to 99% A to 1 to 10%B.

Activators

[0171] The terms “cocatalyst” and “activator” are used herein interchangeably and are defined to be a compound which can activate one or more of the catalyst compounds described above by converting the neutral catalyst compound to a catalytically active catalyst compound cation.

[0172] After the complexes have been synthesized, catalyst systems may be formed by combining the complexes with activators in any suitable manner including by supporting them for use in slurry or gas phase polymerization. The catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in the monomer). Suitable catalyst system may include a complex as described above and an activator such as alumoxane or a non-coordinating anion.

[0173] Non-limiting activators, for example, include alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and other suitable cocatalysts. Suitable activators may include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract a reactive, s-bound, metal ligand making the metal complex cationic and providing a charge-balancing non-coordinating or weakly coordinating anion.

Alumoxane Activators

[0174] In at least one embodiment, alumoxane activators are utilized as an activator in the catalyst system. The alkylalumoxane may be used with another activator. Alumoxanes are generally oligomeric compounds containing -Al(R¹)-O- sub-units, where R¹ 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 may also be used. In at least one embodiment, a visually clear methylalumoxane can be used. A cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution. Suitable alumoxane can be a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, covered under US 5,041,584).

[0175] Another suitable alumoxane is solid polymethylaluminoxane as described in US 9,340,630; US 8,404,880; and US 8,975,209.

[0176] When the activator is an alumoxane (modified or unmodified), embodiments may include the maximum amount of activator such as at up to about a 5,000-fold molar excess Al/M over the catalyst compound (per metal catalytic site). The minimum activator-to- catalyst-compound is about a 1 : 1 molar ratio. Alternate suitable ranges include from about 1 : 1 to about 500:1, alternately from about 1:1 to about 200:1, alternately from about 1:1 to about 100:1, or alternately from about 1:1 to about 50:1. In an alternate embodiment, little or no alumoxane is used in the polymerization processes described herein. In at least one embodiment, alumoxane is present at about zero mole%, alternately the alumoxane is present at a molar ratio of aluminum to catalyst compound transition metal less than about 500: 1, such as less than about 300:1, such as less than about 100:1, such as less than about 1:1. Non-Coordinating Anion Activators

[0177] A non-coordinating anion (NCA) is defined to mean an anion either that does not coordinate to the catalyst metal cation or that does coordinate to the metal cation, but only weakly. The term NCA is also defined to include multicomponent NCA-containing activators, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, that contain an acidic cationic group and the non-coordinating anion. The term NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, that can react with a catalyst to form an activated species by abstraction of an anionic group. An NCA coordinates weakly enough that a neutral Lewis base, such as an olefmically or acetylenically unsaturated monomer can displace it from the catalyst center. Any suitable metal or metalloid that can form a compatible, weakly coordinating complex may be used or contained in the non-coordinating anion. Suitable metals include aluminum, gold, and platinum. Suitable metalloids include boron, aluminum, phosphorus, and silicon.

[0178] “Compatible” non-coordinating anions can be those which are not degraded to neutrality when the initially formed complex decomposes, and the anion does 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 this 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. [0179] It is within the scope of the present disclosure to use an ionizing activator, neutral or ionic, such as tri(n-butyl) ammonium tetrakis(pentafluorophenyl)borate, a tris perfluorophenyl boron metalloid precursor or a tris perfluoronaphthyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 1998/043983), boric acid (US 5,942,459), or 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.

[0180] The catalyst systems of the present disclosure can include at least one non- coordinating anion (NCA) activator.

[0181] In at least one embodiment, boron containing NCA activators represented by the formula below is used:

Z_d ⁺(A^d-) where: Z is (L-H) or a reducible Lewis acid; L is a neutral Lewis base; H is hydrogen; (L-H)⁺ is a Bronsted acid; A^d- is a non-coordinating anion, for example a boron containing non- coordinating anion having the charge d-; and d is 1, 2, or 3. [0182] The cation component, Z_d ⁺ may include Bronsted acids such as protons or protonated Lewis bases or reducible Lewis acids capable of protonating or abstracting a moiety, such as an alkyl or aryl, from the bulky ligand containing transition metal catalyst precursor, resulting in a cationic transition metal species. [0183] The activating cation Z_d ⁺ may also be a moiety such as silver, tropylium, carbenium, ferroceniums and mixtures, such as carbeniums and ferroceniums, such as Z_d ⁺ is triphenyl carbenium. Suitable reducible Lewis acids can be a triaryl carbenium (where the aryl can be substituted or unsubstituted, such as those represented by the formula: (Ar3C⁺), where Ar is aryl substituted with a C₁ to C₄₀ hydrocarbyl or with a substituted C₁ to C₄₀ hydrocarbyl, or a heteroaryl substituted with a C₁ to C₄₀ hydrocarbyl, or with a substituted C₁ to C₄₀ hydrocarbyl; such as the reducible Lewis acids in “Z” include those represented by the formula: (Ph₃C), where Ph is a substituted or unsubstituted phenyl, such as substituted with Ci to C₄₀ hydrocarbyls or substituted a C₁ to C₄₀ hydrocarbyls, such as C₁ to C₂₀ alkyls or aromatics or substituted C₁ to C₂₀ alkyls or aromatics, such as Z is a triphenylcarbenium.

[0184] When Z_d ⁺ is the activating cation (L-H)_d ⁺, such as a Bronsted acid, capable of donating a proton to the transition metal catalytic precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof, such as ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethyl amine, 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.

[0185] The anion component A^d- includes those having the formula [M^k+Q_n]^d- wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (such as 1, 2, 3, or 4); n - k = d; M is an element selected from Group 13 of the Periodic Table of the Elements, such as boron or aluminum, and Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted- hydrocarbyl radicals, said Q having up to 20 carbon atoms with the proviso that in not more than 1 occurrence is Q a halide. In at least one embodiment, each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, such as each Q is a fluorinated aryl group, such as each Q is a pentafluoryl aryl group. Examples of suitable A^d' also include diboron compounds as disclosed in US 5,447,895, which is fully incorporated herein by reference.

[0186] Examples of boron compounds which may be used as an activating cocatalyst include the compounds described as (and particularly those specifically listed as) activators in US 8,658,556, which is incorporated by reference herein.

[0187] Bulky activators are also useful herein as NCAs. “Bulky activator” as used herein refers to anionic activators represented by the formula:

wherein: each R¹ is, independently, a halide, such as a fluoride;

Ar is a substituted or unsubstituted aryl group (such as a substituted or unsubstituted phenyl), such as substituted with C₁ to C₄₀ hydrocarbyls, such as C₁ to C₂₀ alkyls or aromatics; each R² is, independently, a halide, a G, to C₂₀ substituted aromatic hydrocarbyl group or a siloxy group of the formula -O-Si-R^a, where Ra is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (such as R2 is a fluoride or a perfluorinated phenyl group); each R³ is a halide, G, to C₂₀ substituted aromatic hydrocarbyl group or a siloxy group of the formula -O-Si-Ra, where Ra is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (such as R3 is a fluoride or a Ce perfluorinated aromatic hydrocarbyl group); wherein R2 and R3 can form one or more saturated or unsaturated, substituted or unsubstituted rings (such as R2 and R3 form a perfluorinated phenyl ring);

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; and wherein at least three of the substituents on the B atom each have a molecular volume of greater than 250 cubic A, alternately greater than 300 cubic A, or alternately greater than 500 cubic A.

[0188] Suitable (Ar3C)d+ is (Ph3C)d+, where Ph is a substituted or unsubstituted phenyl, such as substituted with C₁ to C₄₀ hydrocarbyls or substituted C₁ to C₄₀ hydrocarbyls, such as C₁ to C₂₀ alkyls or aromatics or substituted C₁ to C₂₀ alkyls or aromatics.

[0189] “Molecular volume” is used herein as an approximation of spatial steric bulk of an activator molecule in solution. Comparison of substituents with differing molecular volumes allows the substituent with the smaller molecular volume to be considered “less bulky” in comparison to the substituent with the larger molecular volume. Conversely, a substituent with a larger molecular volume may be considered “more bulky” than a substituent with a smaller molecular volume.

[0190] 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, v.71(ll), November 1994, pp. 962-964. Molecular volume (MV), in units of cubic A, is calculated using the formula: MV = 8.3Vs, where Vs is the scaled volume. Vs is the sum of the relative volumes of the constituent atoms, and is calculated from the molecular formula of the substituent using the following table of relative volumes. For fused rings, the Vs is decreased by 7.5% per fused ring.

[0191] For a list of particularly useful Bulky activators as described in US 8,658,556, which is incorporated by reference herein.

[0192] In at least one embodiment, one or more of the NCA activators is chosen from the activators described in US 6,211,105.

[0193] Suitable activators, such as ionic activators Z_d ⁺ (A^d_). may include, but are not limited to, one or more of triaryl carbenium (such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2, 3,4,6- tetrafluorophenyl)borate), trialkyl ammonium tetrakis(pentafluorophenyl)borate, N,N- dialkylanilinium tetrakis(pentafluorophenyl)borate, N,N-dialkyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis-(2, 3,4,6- tetrafluorophenyl)borate, N,N-dialkylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate, N,N-dialkylanilinium tetrakis(perfluoronaphthyl)borate, trialkylammonium tetrakis(perfluorobiphenyl)borate, N,N- dialkylanilinium tetrakis(perfluorobiphenyl)borate, trialkylammonium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, N,N-dialkylanilinium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, N,N-dialkyl-(2,4,6-trimethylanilinium) tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, dialkylammonium tetrakis(pentafluorophenyl)borate, (where alkyl is methyl, ethyl, propyl, n-butyl, iso-butyl, or t-butyl). In at least one embodiment, the ionic activator Z_d ⁺ (A^d-) is one or more of N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Me3NH⁺] [B(C₆F₅)₄-], 1 -(4-(tris(pentafluorophenyl)borate)-2, 3,5,6- tetrafluorophenyl)pynOlidinium, 4-(tris(pentafluorophenyl)borate)-2, 3,5,6- tetrafluoropyridine, 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, trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammonium tetrakis(perfluoronaphthyl)borate, tripropylammonium tetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate, tri (t-butyl /ammonium tetrakis(perfluoronaphthyl)borate, N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(perfluoronaphthyl)borate, and tropillium tetrakis(perfluoronaphthyl)borate.

[0194] Suitable activator-to-catalyst ratio, e.g., all NCA activators-to-catalyst ratio is about a ril molar ratio. Alternate suitable ranges include from about 0.1 : 1 to about 100: 1, alternately from about 0.5:1 to about 200:1, alternately from about 1:1 to about 500:1, alternately from about 1:1 to about 1000:1. A particularly useful range is from about 0.5:1 to about 10:1, such as about 1 : 1 to about 5:1.

[0195] It is also within the scope of the present disclosure that the catalyst compounds can be combined with combinations of alumoxanes and NCA’s (see for example, US 5,153,157; US 5,453,410; EP 0 573 120 Bl; WO 1994/007928; and WO 1995/014044 which discuss the use of an alumoxane in combination with an ionizing activator).

[0196] Alternately, a co-activator, such as a group 1, 2, or 13 organometallic species (e.g., an alkyl aluminum compound such as tri-n-octyl aluminum), may also be used in the catalyst system herein. The complex-to-co-activator molar ratio is from 1:100 to 100:1; 1:75 to 75:1; 1:50 to 50:1; 1:25 to 25:1; 1:15 to 15:1; 1:10 to 10:1; 1:5 to 5:1; 1:2 to 2:1; 1:100 to 1:1; 1:75 to 1:1; 1:50 to 1:1; 1:25 to 1:1; 1:15 to 1:1; 1:10 to 1:1; 1:5 to 1:1; 1:2 to 1:1; 1:10 to 2:1. [0197] In at least one embodiment, the activator is N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate.

[0198] In at least one embodiment, the activator is N,N-dimethylanilinium tetrakis(heptafluoronaphthyl)borate.

Optional Scavengers, Co- Activators, Chain Transfer Agents

[0199] In addition to activator compounds, scavengers or co-activators may be used. Aluminum alkyl or organoaluminum compounds which may be utilized as scavengers or co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethyl zinc.

[0200] Chain transfer agents may be used in the compositions and or processes described herein. Useful chain transfer agents are typically alkylalumoxanes, a compound represented by the formula AIR₃, ZnR₂ (where each R is, independently, a C₁-C₈ aliphatic radical, preferably methyl, ethyl, propyl, butyl, penyl, hexyl octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof. Optional Support Materials

[0201] In embodiments herein, the catalyst system may comprise an inert support material. Preferably the supported material is a porous support material, for example, talc, and inorganic oxides. Other support materials include zeolites, clays, organoclays, or any other organic or inorganic support material and the like, or mixtures thereof. [0202] Preferably, the support material is an inorganic oxide in a finely divided form.

Suitable inorganic oxide materials for use in catalyst systems herein include Groups 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides that may be employed either alone or in combination with the silica, or alumina are magnesia, titania, zirconia, and the like. Other suitable support materials, however, can be employed, for example, finely divided functionalized polyolefins, such as finely divided polyethylene. Particularly useful supports include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, and the like. Also, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica-titania, and the like. Preferred support materials include AI2O₃ , Zr02, S1O2, and combinations thereof, more preferably S1O2, AI2O₃ , or S1O2/AI2O_{3 .}

[0203] It is preferred that the support material, most preferably an inorganic oxide, has a surface area in the range of from about 10 to about 700 m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g and average particle size in the range of from about 5 to about 500 pm. More preferably, the surface area of the support material is in the range of from about 50 to about 500 m^/g, pore volume of from about 0.5 to about 3.5 cc/g and average particle size of from about 10 to about 200 pm. Most preferably the surface area of the support material is in the range is from about 100 to about 400 m²/g, pore volume from about 0.8 to about 3.0 cc/g and average particle size is from about 5 to about 100 pm. The average pore size of the support material useful in the invention is in the range of from 10 to 1,000 A, preferably 50 to about 500 A, and most preferably 75 to about 350 A. In some embodiments, the support material is a high surface area, amorphous silica (surface area=300 m Agm; pore volume of 1.65 cm-Vgm). Preferred silicas are marketed under the tradenames of DAVISON™ 952 or DAVISON™ 955 by the Davison Chemical Division of W.R. Grace and Company. In other embodiments DAVISON™ 948 is used.

[0204] The support material should be dry, that is, free of absorbed water. Drying of the support material can be effected by heating or calcining at about 100°C to about 1,000°C, preferably at least about 600°C. When the support material is silica, it is heated to at least 200°C, preferably about 200°C to about 850°C, and most preferably at about 600°C; and for a time of about 1 minute to about 100 hours, from about 12 hours to about 72 hours, or from about 24 hours to about 60 hours. The calcined support material must have at least some reactive hydroxyl (OH) groups to produce supported catalyst systems of this invention. The calcined support material is then contacted with at least one polymerization catalyst comprising at least one catalyst compound and an activator.

[0205] The support material, having reactive surface groups, typically hydroxyl groups, is slurried in a non-polar solvent and the resulting slurry is contacted with a solution of a catalyst compound and an activator. In some embodiments, the slurry of the support material is first contacted with the activator for a period of time in the range of from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours. The solution of the catalyst compound is then contacted with the isolated support/activator. In some embodiments, the supported catalyst system is generated in situ. In alternate embodiment, the slurry of the support material is first contacted with the catalyst compound for a period of time in the range of from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours. The slurry of the supported catalyst compound is then contacted with the activator solution.

[0206] The mixture of the catalyst, activator and support is heated to about 0°C to about 70°C, preferably to about 23°C to about 60°C, preferably at room temperature. Contact times typically range from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.

[0207] Suitable non-polar solvents are materials in which all of the reactants used herein, i.e., the activator, and the catalyst compound, 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, aromatics, such as benzene, toluene, and ethylbenzene, may also be employed. EADS Copolymer Properties

[0208] The EADS copolymer can have a melt flow rate (“MFR”, ASTM D1238-13, 2.16 kg, 230°C) of greater than or equal to 0.2 g/10 min, or greater than or equal to 0.5 g/10 min. In some examples, the EADS copolymer can have an MFR of 0.5 g/10 min to 50 g/10 min, 1 g/10 min to 40 g/10 min, 2 g/10 min to 35 g/10 min, or 2 g/10 min to 30 g/10 min. In some examples, the EADS copolymer can have an MFR of 0.5 to 50 g/10 min, 2 g/10 min to 10 g/10 min, 2 g/10 min to 8 g/10 min, or 3 g/10 min to 5 g/10 min. In some examples, the MFR of the EADS can be less than 15 g/10 min, less than 10 g/10 min, less than 5 g/10 min, less than 4 g/10 min, less than 3 g/10 min, less than 2 g/10 min, or less than 1.5 less g/10 min.

[0209] The EADS copolymer can have a heat of fusion (“H_f”), as determined by the Differential Scanning Calorimetry (“DSC”) procedure described herein, of greater than or equal to 0.5 J/g, or 1 J/g, or 5 J/g, and is less than or equal to 75 J/g, or preferably less than or equal to 70 J/g, or 50 J/g, or less than or equal to 35 J/g. In some examples, the H_f value can be from a low value of 1.0 J/g, 1.5 J/g, 3.0 J/g, 4.0 J/g, 6.0 J/g, or 7.0 J/g to a high value of 30 J/g, 35 J/g, 40 J/g, 50 J/g, 60 J/g, 70 J/g, or 75 J/g.

[0210] The EADS copolymer can have a percent crystallinity of 0 to 40%, 0.5% to 40%, 1% to 30%, or 5% to 35%, wherein “percent crystallinity” is determined according to the DSC procedure described herein. In some examples, the EADS copolymer can have a crystallinity less than 40% or 0.25% to 25% or 0.5% to 22%.

[0211] The procedure for DSC determinations is as follows. 0.5 grams of polymer is weighed and pressed to a thickness of 15 to 20 mils (about 381-508 microns) at 140°C-150°C, using a “DSC mold” and MYLAR™ film as a backing sheet. The pressed polymer sample is allowed to cool to ambient temperatures by hanging in air (the MYLAR™ film backing sheet is not removed). The pressed polymer sample is then annealed at room temperature (about 23°C-25°C). A 15-20 mg disc is removed from the pressed polymer sample using a punch die and is placed in a 10 microliter aluminum sample pan. The disc sample is then placed in a DSC (Perkin Elmer Pyris 1 Thermal Analysis System) and is cooled to -100°C. The sample is heated at 10°C/min to attain a final temperature of 165°C. The thermal output, recorded as the area under the melting peak of the disc sample, is a measure of the heat of fusion and can be expressed in Joules per gram (J/g) of polymer and is automatically calculated by the Perkin Elmer system. Under these conditions, the melting profile shows two (2) maxims, the maxima at the highest temperature is taken as the melting point within the range of melting of the disc sample relative to a baseline measurement for the increasing heat capacity of the polymer as a function of temperature. The percent crystallinity (X%) is calculated using the formula: [area under the curve (in J/g) / H° (in J/g)] * 100, where H° is the heat of fusion for the homopolymer of the maj or monomer component. The values for H° are to be obtained from the Polymer Handbook, Fourth Edition, published by John Wiley and Sons, New York 1999, except that a value of 290 J/g is used as the equilibrium heat of fusion (H°) for 100% crystalline polyethylene, a value of 140 J/g is used as the equilibrium heat of fusion (H°) for 100% crystalline polybutene, and a value of 207 J/g (H°) is used as the heat of fusion for a 100% crystalline polypropylene.

[0212] The EADS copolymer can have a single peak melting transition as determined by DSC. In some examples, the EADS copolymer can have a primary peak transition of less than 90°C, with a broad end-of-melt transition of greater than 110°C. The peak “melting point” (“Tm”) is defined as the temperature of the greatest heat absorption within the range of melting of the sample. However, the EADS copolymer can show secondary melting peaks adjacent to the principal peak, and/or at the end-of-melt transition, however for the purposes herein, such secondary melting peaks are considered together as a single melting point, with the highest of these peaks being considered the Tm of the EADS copolymer. The EADS copolymer can have a Tm of less than or equal to 110°C, less than or equal to 100°C , less than or equal to 90°C , less than or equal to 80°C , less than or equal to 70°C, 25°C to 100°C, 25°C to 85°C , 25°C to 75°C, 25°C to 65°C, 30°C to 80°C, or 30°C to 70°C.

[0213] The EADS copolymer can have a weight average molecular weight (“Mw”), as determined by GPC-4D, of 5,000 g/mole to 5,000,000 g/mole, 10,000 g/mole to 1,000,000 g/mole, or 50,000 g/mole to 400,000 g/mole. In some examples, the EADS copolymer can have a Mw greater than 10,000 g/mole, greater than 15,000 g/mole, greater than 20,000 g/mole, or greater than 80,000 g/mole. In some examples, the EADS copolymer can have a Mw less than 5,000,000 g/mole, less than 1,000,000 g/mole, or less than 500,000 g/mole.

[0214] The EADS copolymer can have a number average molecular weight (“Mn”), as determined by GPC-4D, of 2,500 g/mole to 2,500,00 g/mole, 10,000 g/mole to 250,000 g/mole, or, 000 g/mole to 200,000 g/mole. The EADS copolymer can have z average molecular weight, ("Mz"), as determined by GPC-4D, of 10,000 g/mole to 7,000,000 g/mole, 80,000 g/mole to 700,000 g/mole, or 85,000 g/mole to 500,000 g/mole.

[0215] The EADS copolymer can have a molecular weight distribution (“MWD’j (Mw/Mn) of 1.5 to 20, 1.5 to 15, 1.5 to 5, 1.8 to 5, or 1.8 to 3 or 4. In some examples, the EADS copolymer can have a MWD of 1.5, 1.8, or 2.0 to 4.5, 5, 10, or 20.

[0216] GPC-4D is used to determine the molecular weight (Mn, Mw, and Mz) and MWD of EADS copolymer, as described in the Experimental section below. [0217] In some examples, the EADS copolymer can possess an Elongation at Break (ASTM D-412-16 at 23°C) of less than 2,000%, or less than 1,000%, or less than 900%. [0218] In some examples, the EADS copolymer can have a melt strength of less than 5 cN, less than 4 cN, less than 3 cN, less than 2 cN, less than 1 cN, less than 0.5 cN, or less than 0.1 cN at 190°C. For purposes herein, the “Melt Strength” of a polymer at a particular temperature, e.g., 190°C, can be determined with a Gottfert Rheotens Melt Strength Apparatus (e.g., Gottfert Rheotens 71.97). The measurement was accomplished by grasping the extrudate from a capillary rheometer (e.g., a Gottfert Rheograph 2002 capillary rheometer), or from an extruder equipped with a capillary die, after the extrudate has been extruded 100 mm using variable speed gears and increasing the gear speed at a constant acceleration (12 mm/s2, starting from an initial, zero-force calibration velocity of 10 mm/s) until the molten polymer strand breaks. The force in the strand can be measured with a balance beam in conjunction with a linear variable displacement transducer. The force required to extend and then break the extrudate is defined as the Melt Strength. The force can be measured in centinewtons (cN). A typical plot of force as a function of wheel velocity is known in the art to include a “resonate” immediately before the strand breaks. In such cases, the plateau force can be approximated by the midline between the oscillations.

[0219] In some examples, the EADS copolymer can have a g'_vis branching index of less than 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, or 1 as measured by the method described herein. [0220] Strain hardening can be observed as a sudden, abrupt upswing of the extensional viscosity in the transient extensional viscosity vs. time plot. This abrupt upswing, away from the linear viscoelastic behavior, was reported in the 1960s for LDPP and LDPE (reference: J. Meissner, Rheol. Acta., v.8, 78, 1969) and was attributed to the presence of long branches in the polymer. The strain-hardening ratio (SHR) is defined as the ratio of the maximum transient extensional viscosity at certain strain rate over the respective value of the linear viscoelasticity envelop (LVE):

where linear viscoelasticity envelop is computed as following:

with parameters and obtained by fitting storage and loss moduli:

[0221] In some examples, the EADS copolymer can have strain hardening in the material. In some examples, the strain hardening ratio can be 2 or greater, 5 or greater, 10 or greater, 15 or greater, greater than 1 to 15, or greater than 1 to 10 when extensional viscosity is measured at a Hencky strain rate of 0.01 s^-1 to 10 s^-1, e.g., 0.01 s^-1, 0.1 s-1, 1 s^-1, 2 s^-1, 3 s^-1, 4 s^-1, 5 s^-1, 6 s^-1, 7 s^-1, 8 s^-1, 9 s^-1, 10 s^-1, and at a temperature of 190°C.

[0222] The EADS copolymers described herein have good shear thinning. Shear thinning is determined by fitting complex viscosity versus radial frequency curve with Carreau-Yasuda model. Shear thinning can be also characterized using a shear thinning index. Shear thinning is characterized by the decrease of the complex viscosity with increasing angular frequency. [0223] The term "shear thinning index" is determined using plots of the logarithm of the complex viscosity versus frequency. The slope is the ratio of complex viscosity at a frequency of 100 rad/s and at a frequency of 0.1 rad/s. These plots are exemplary output of small amplitude oscillatory shear (SAOS) experiments. For purposes of the present disclosure, the SAOS test temperature is 190°C for propylene polymers and blends thereof. Polymer viscosity is conveniently measured in Pascal. seconds (Pa.s) as function of radial frequencies within a range of from 0.1 to 628 rad/s and at 190°C under a nitrogen atmosphere using a dynamic mechanical spectrometer such as the TA Instruments Advanced Rheometrics Expansion System (ARES-G2). Generally, a low value of shear thinning index indicates that the copolymer is highly shear-thinning and that it is readily processable in high shear processes, for example by injection molding. The more negative this slope, the faster the complex viscosity decreases as the frequency increases.

[0224] In some examples, the EADS copolymer can have a shear thinning index of at least 0.03, 0.09, 0.10, 0.15, or 0.2. In some examples, the EADS copolymer can have a shear thinning index of about 0.03, about 0.05, about 0.07, about 0.09, about 0.10 to about 0.15, about 0.18, about 0.20, about 0.25, about 0.30, about 0.35, or about 0.40.

[0225] In some examples, the EADS copolymer can have a Flex modulus (Secant 1%) as determined by ASTM D790-17 of about 300 MPa, about 500 MPa, about 700 MPa, about 800 MPa, or about 900 MPa to about 1,000 MPa, about 1,500 MPa, about 2,000 MPa, about 2,500 MPa, or about 3,000 MPa. [0226] In some examples, the EADS copolymer can have a tensile stress at break as determined by ASTM D638-14 of about 5 MPa, about 8 MPa, about 10 MPa, about 12 MPa, or about 15 MPa to about 25 MPa, about 30 MPa, about 35 MPa, about 40 MPa, about 45 MPa, about 50 MPa, or about 55 MPa.

[0227] In some examples, the EADS copolymer can have a tensile strain at break as determined by ASTM D638-14 of about 10%, about 15%, about 20%, about 25%, about 30%, or about 35%, to about 500%, about 600%, about 700%, about 800%, about 900%, about 1,000%, or about 1,500%.

[0228] In a particular embodiment, the EADS copolymer can have a Mooney viscosity ML (1+4) at 125°C of from 0.5 to 100, or from 5 to 40, or from 10 to 40. (Mooney viscosity is measured as ML (1+4) @ 125°C according to ASTM D-1646).

Blends and End Use Applications

[0229] Rubber refers to any polymer or composition of polymers consistent with the ASTM D1566 definition: “a material that is capable of recovering from large deformations, and can be, or already is, modified to a state in which it is essentially insoluble (but can swell) in boiling solvent... ” Elastomer is a term that may be used interchangeably with the term rubber.

[0230] Elastomeric composition refers to any composition comprising at least one elastomer as defined above.

[0231] A vulcanized rubber compound by ASTM D1566 definition refers to “a crossbnked elastic material compounded from an elastomer, susceptible to large deformations by a small force capable of rapid, forceful recovery to approximately its original dimensions and shape upon removal of the deforming force.” A cured elastomeric composition refers to any elastomeric composition that has undergone a curing process and/or comprises or is produced using an effective amount of a curative or cure package, and is a term used interchangeably with the term vulcanized rubber compound.

[0232] The term phr is parts per hundred rubber by weight or “parts,” and is a measure common in the art wherein components of a composition are measured relative to a total of all of the elastomer components. The total phr or parts for all rubber components, whether one, two, three, or more different rubber components is present in a given recipe is always defined as 100 phr. All other non-rubber components are ratioed against the 100 parts of rubber and are expressed in phr. This way one can easily compare, for example, the levels of curatives or filler loadings, etc., between different compositions based on the same relative proportion of rubber without the need to recalculate percents for every component after adjusting levels of only one, or more, component(s). For purposes of this specification, when phr is used with respect to the presence of the ethylene-propylene-diene-substituted styrene copolymer, the reference is made with respect to the total amount of both copolymer and all blend rubber components (one or more than one). Thus, for example, if an elastomer composition is composed of 40 phr ethylene-propylene-diene-substituted styrene copolymer then there would be a total of 100 - 40 = 60 parts by weight of additional elastomer available to complete the elastomer composition. The additional 60 parts being composed of blend rubber or other rubber constituents added to the elastomer composition.

[0233] Isoolefin refers to any olefin monomer having at least one carbon having two substitutions on that carbon.

[0234] Multiolefin or polyene refers to any monomer having two or more double bonds. In a preferred embodiment, when present in isobutylene polymers, the multiolefm employed is any monomer comprising two conjugated double bonds such as a conjugated diene like isoprene.

[0235] Isobutylene based elastomer or polymer refers to elastomers or polymers comprising at least 70 mol % repeat units from isobutylene.

[0236] Solubility in refluxing xylene is determined as described in US 8,841,383.

[0237] A thermoplastic elastomer by ASTM D1566 definition refers to a rubber-like material “that repeatedly can be softened by heating and hardened by cooling through a temperature range characteristic of the polymer, and in the softened state can be shaped into articles.” Thermoplastic elastomers are microphase separated systems of at least two polymers. One phase is the hard polymer that does not flow at room temperature, but becomes fluid when heated, that gives thermoplastic elastomers its strength. The other phase is a soft rubbery polymer that gives thermoplastic elastomers their elasticity. The hard phase is typically the major or continuous phase, also referred to as the matrix.

[0238] A thermoplastic vulcanizate by ASTM D1566 definition refers to “a thermoplastic elastomer with a chemically cross-linked rubbery phase, produced by dynamic vulcanization.” Dynamic vulcanization is “the process of intimate melt mixing of a thermoplastic polymer and a suitable reactive rubbery polymer to generate a thermoplastic elastomer with a chemically cross-linked rubbery phase... ” The rubbery phase, whether or not cross-linked, is typically the minor or dispersed phase.

[0239] This invention further provides an elastomer composition (also referred to as a rubber blend) comprising EADS copolymer compounded with a blend rubber and optional additives. Typically 5 to 40 phr of the copolymer, more preferably from 10 to 30 phr copolymer is present in the elastomer composition.

[0240] The blend rubber can include one or more than one rubber (the second or more rubber being referred to as “secondary rubbers”) selected from natural rubbers (“NR”), polyisoprene rubber (“IR”), poly(styrene-co-butadiene) rubber (“SBR”), polybutadiene rubber (“BR”), poly(isoprene-co-butadiene) rubber (“IBR”), styrene-isoprene-butadiene rubber (“SIBR”), butyl rubber, star branched butyl rubber (“SBBR”), poly(isobutylene-co- alkylstyrene), polychloroprene rubber, nitrile rubber, ethylene-propylene rubber (“EPM”), ethylene-propylene-diene rubber (“EPDM”), mixtures thereof and the like. In an embodiment, the blend rubber can include a mixture of at least two of these elastomers. In an embodiment, the blend rubber(s) can contain halogen either by halogenation of the polymer or polymerization of halogen-containing monomers, e.g., polychloroprene, chlorobutyl rubber, bromobutyl rubber, brominated or chlorinated star branched butyl rubber, etc.

[0241] In embodiments, the blend rubber can comprise a mixture of natural rubber and polybutadiene rubber. The natural rubber being present at from 5 to 80 phr and the polybutadiene rubber at from 5 to 80 phr.

[0242] In embodiments, the elastomer composition can further comprise a filler, for example, selected from carbon black, modified carbon black, silica, precipitated silica, and the like, and blends thereof. In an embodiment, the elastomer composition can further comprise a chemical protectant, for example, selected from waxes, antioxidants, antiozonants, and the like, and combinations thereof. In an embodiment, the elastomer composition can further comprise a processing oil, resin, or the like, and combinations thereof. In an embodiment, the elastomer composition can further comprise a curing package.

[0243] Another embodiment of the invention provides the vulcanizate obtained by curing the elastomer composition described above. The vulcanizate can be substantially free of staining as determined in accordance with ASTM D-925. The vulcanizate in one embodiment can have a reduced level, be substantially free of or be free of N,N’-disubstituted-para- phenyldiamines.

[0244] In another embodiment, the invention provides an article comprising the vulcanizate. The article can be a tire sidewall, for example, or a tire made with the sidewall comprising the vulcanizate. The tire can further include retreads. In various embodiments, the tire can be a bias truck tire, an off-road tire, or a luxury passenger automobile tire. Alternately or additionally, the article can be a tire tread or a tire made with the tire tread comprising the vulcanizate. [0245] Another embodiment of the invention provides a process for making a molded article. The process comprises melt mixing the elastomeric composition described above, shaping the mixture into an article, and curing the shaped article to co-vulcanize the EADS copolymer and the blend rubber.

[0246] Another embodiment of the invention provides a process for making a tire. The process comprises melt mixing the elastomeric composition described above, shaping the mixture into a sidewall in a tire build comprising a carcass and a tread, and curing the build to form the tire. In an embodiment, the process can include retreading the tire.

[0247] A further embodiment provides a tire sidewall composition comprising a curable composition or vulcanizate of from 10 to 30 phr EADS copolymer; from 20 to 60 phr natural rubber; from 20 to 60 phr polybutadiene rubber; an optional secondary blend rubber selected from IR, SBR, IBR, SIBR, butyl rubber, SBBR, poly(isobutylene-co-alkylstyrene), EPM, EPDM and mixtures thereof; a filler selected from carbon black, modified carbon black, silica, precipitated silica, and blends thereof; a chemical protectant selected from waxes, antioxidants, antiozonants and combinations thereof; an optional processing oil, resin, or combination thereof; and a curing package.

Blend Rubbers

[0248] The blend rubber can be any other elastomer, such as, for example, a general purpose rubber in one embodiment. A general purpose rubber, often referred to as a commodity rubber, may be any rubber that usually provides high strength and good abrasion along with low hysteresis and high resilience. These elastomers require antidegradants in the mixed compound because they generally have poor resistance to both heat and ozone.

[0249] Examples of general purpose rubbers include NR, IR, SBR, polybutadiene rubber (“BR”), IBR, and SIBR, and mixtures thereof. EPM and EPDM and their mixtures, often are also referred to as general purpose elastomers.

[0250] In one embodiment, the blend rubber is selected NR, IR, SBR, BR, IBR, SIBR, butyl rubber, SBBR, poly(isobutylene-co-alkylstyrene), EPM, EPDM, and the like, preferably NR. In an embodiment, the blend rubber can include a mixture of at least two of these elastomers, preferably a mixture of NR and BR.

[0251] Natural rubbers are described in detail by Subramaniam in Rubber Technology, p. 179-208 (Morton, ed., Chapman & Hall, 1995). Desirable embodiments of the natural rubbers of the present invention are selected from Malaysian rubber such as SMR CV, SMR 5, SMR 10, SMR 20, and SMR 50 and mixtures thereof, wherein the natural rubbers have a Mooney viscosity at 100°C (ML 1+4) of from 30 to 120, more preferably from 40 to 65. The Mooney viscosity test referred to herein is in accordance with ASTM D1646.

[0252] In another embodiment, the elastomeric composition may also comprise a BR. The Mooney viscosity of the BR as measured at 100°C (ML 1+4) may range from 35 to 70, from 40 to about 65 in another embodiment, and from 45 to 60 in yet another embodiment. Commercial examples of these synthetic rubbers useful in the present invention are sold under the trade name BUDENE™ (Goodyear Chemical Company, Akron, OH), BUNA™ (Lanxess Inc., Samia, Ontario, Canada), and Diene™ (Firestone Polymers LLC, Akron, OH). An example is high cis-polybutadiene (cis-BR). By "cis-polybutadiene" or "high cis- poly butadiene," it is meant that 1,4-cis polybutadiene is used, wherein the amount of cis component is at least 95%. A particular example of high cis-polybutadiene commercial products used in the composition BUDENE™ 1207 or BUNA™ CB 23.

[0253] In another embodiment, the elastomeric composition may also comprise an IR. The Mooney viscosity of the polyisoprene rubber as measured at 100°C (ML 1+4) may range from 35 to 70, from 40 to about 65 in another embodiment, and from 45 to 60 in yet another embodiment. A commercial example of these synthetic rubbers useful in the present invention is NATSYN™ 2200 (Goodyear Chemical Company, Akron, OH).

[0254] In another embodiment, the elastomeric composition may also comprise rubbers of ethylene and propylene derived units such as EPM and EPDM as suitable additional rubbers. Examples of suitable comonomers in making EPDM are ethylidene norbomene, 1,4-hexadiene, dicyclopentadiene, as well as others. A suitable ethylene-propylene rubber is commercially available under the tradename VISTALON™ from ExxonMobil Chemical Company, Houston, TX.

[0255] In another embodiment, the blend rubber can include special purpose elastomers such as isobutylene-based homopolymers or copolymers known as butyl rubbers. These polymers can be described as random copolymers of a C₄ to C₇ isomonoolefm derived unit, such as isobutylene derived unit, and at least one other polymerizable unit. Butyl rubbers can be prepared by reacting a mixture of monomers, the mixture having at least (1) a C₄ to C₇ isoolefm monomer component such as isobutylene with (2) a multiolefm, monomer component. The isoolefm is in a range from 70 to 99.5 wt% by weight of the total monomer mixture in one embodiment, and 85 to 99.5 wt% in another embodiment. The multiolefm component is present in the monomer mixture from 30 to 0.5 wt% in one embodiment, and from 15 to 0.5 wt% in another embodiment. In yet another embodiment, from 8 to 0.5 wt% of the monomer mixture is multiolefm. [0256] The isoolefin is a C₄ to C₇ compound, non-limiting examples of which are compounds such as isobutylene, isobutene, 2-methyl- 1 -butene, 3 -methyl- 1 -butene, 2-methyl- 2-butene, 1 -butene, 2-butene, methyl vinyl ether, indene, vinyltrimethylsilane, hexene, and 4-methyl- 1-pentene. The multi olefin is a C₄ to C₁₄ multiolefm such as isoprene, butadiene, 2, 3-dimethyl-1, 3-butadiene, myrcene, 6,6-dimethyl-fulvene, hexadiene, cyclopentadiene, and piperylene, and other monomers such as disclosed in US 5,162,425. Other polymerizable monomers such as styrene and dichlorostyrene are also suitable for homopolymerization or copolymerization in butyl rubbers. One embodiment of the butyl rubber polymer can be obtained by reacting 95 to 99.5 wt% of isobutylene with 0.5 to 8 wt% isoprene, or from 0.5 wt% to 5.0 wt% isoprene in yet another embodiment. Butyl rubbers and methods of their production are described in detail in, for example, US 2,356,128, 3,968,076, 4,474,924, 4,068,051 and 5,532,312. See, also, WO 2004/058828, WO 2004/058827, WO 2004/058835, WO 2004/058836, WO 2004/058825, WO 2004/067577 and WO 2004/058829.

[0257] A commercial example of a desirable butyl rubber is EXXON™ BUTYL Grades of poly(isobutylene-co-isoprene), having a Mooney viscosity of from 32 ± 2 to 51 ± 5 (ML 1 + 8 at 125°C) (ExxonMobil Chemical Company, Houston, TX). Another commercial example of a desirable butyl-type rubber is VISTANEX™ polyisobutylene rubber having a molecular weight viscosity average of from 0.9 ± 0.15 x 10⁶ to 2.11 ± 0.23 x 10⁶ (ExxonMobil Chemical Company, Houston, TX).

[0258] Another embodiment of a blend rubber useful in the invention is a branched or star- branched butyl rubber. These rubbers are described in, for example, EP 0 678 529 Bl, US 5,182,333 and US 5,071,913. In one embodiment, the SBBR is a composition of a butyl rubber, either halogenated or not, and a polydiene or block copolymer, either halogenated or not. The invention is not limited by the method of forming the SBBR. The polydienes/block copolymer, or branching agents (hereinafter "polydienes"), are typically cationically reactive and are present during the polymerization of the butyl or halogenated butyl rubber, or can be blended with the butyl rubber to form the SBBR. The branching agent or poly diene can be any suitable branching agent, and the invention is not limited to the type of poly diene used to make the SBBR.

[0259] In one embodiment, the SBBR can be a composition of the butyl or halogenated butyl rubber as described above and a copolymer of a poly diene and a partially hydrogenated polydiene selected from the group including styrene, poly butadiene, polyisoprene, polypiperylene, natural rubber, styrene-butadiene rubber, EPDM, EPR, styrene-butadiene- styrene and styrene-isoprene-styrene block copolymers. These polydienes are present, based on the monomer wt%, greater than 0.3 wt% in one embodiment, and from 0.3 to 3 wt% in another embodiment, and from 0.4 to 2.7 wt% in yet another embodiment. A commercial embodiment of the SBBR of the present invention is SB Butyl 4266 (ExxonMobil Chemical Company, Houston, TX), having a Mooney viscosity (ML 1+8 at 125°C, ASTM D 1646) of from 34 to 44. Further, cure characteristics of SB Butyl 4266 are as follows: MH is 69 ± 6 dN m, ML is 11.5 ± 4.5 dN m (ASTM D2084).

[0260] In an embodiment, the blend rubber can include halogenated butyl rubber. Halogenated butyl rubber is produced by the halogenation of the butyl rubber product described above. Halogenation can be carried out by any means, and the invention is not herein limited by the halogenation process. Methods of halogenating polymers such as butyl polymers are disclosed in US 2,631,984, 3,099,644, 4,554,326, 4,681,921, 4,650,831, 4,384,072, 4,513,116 and 5,681,901. In one embodiment, the butyl rubber is halogenated in hexane diluent at from 4°C to 60°C using bromine (Br₂) or chlorine (Cl₂) as the halogenation agent. The halogenated butyl rubber has a Mooney Viscosity of from 20 to 70 (ML 1+8 at 125°C) in one embodiment, and from 25 to 55 in another embodiment. The halogen wt% is from 0.1 to 10 wt% based in on the weight of the halogenated butyl rubber in one embodiment, and from 0.5 to 5 wt% in another embodiment. In yet another embodiment, the halogen wt% of the halogenated butyl rubber is from 1 to 2.5 wt%.

[0261] A commercial embodiment of a halogenated butyl rubber is Bromobutyl 2222 (ExxonMobil Chemical Company, Houston, TX). Its Mooney viscosity is from 27 to 37 (ML 1+8 at 125°C, ASTM 1646, modified), and the bromine content is from 1.8 to 2.2 wt% relative to the Bromobutyl 2222. Further, cure characteristics of Bromobutyl 2222 are as follows: MH is from 28 to 40 dN m, ML is from 7 to 18 dN m (ASTM D2084). Another commercial embodiment of the halogenated butyl rubber is Bromobutyl 2255 (ExxonMobil Chemical Company, Houston, TX). Its Mooney viscosity is from 41 to 51 (ML 1+8 at 125°C, ASTM D1646), and the bromine content is from 1.8 to 2.2 wt%. Further, cure characteristics of Bromobutyl 2255 are as follows: MH is from 34 to 48 dN m, ML is from 11 to 21 dN m (ASTM D2084).

[0262] The blend rubbers in the present invention may also comprise at least one random copolymer comprising a C₄ to C₇ isomonoolefms, such as isobutylene and an alkylstyrene comonomer, such as para-methylstyrene, containing at least 80%, more alternatively at least 90% by weight of the para-isomer and optionally include functionalized interpolymers wherein at least one or more of the alkyl substituents groups present in the styrene monomer units contain benzybc halogen or some other functional group. In another embodiment, the polymer may be a random elastomeric copolymer of ethylene or a C₃ to C₆ α-olefin and an alkylstyrene comonomer, such as para-methylstyrene containing at least 80%, alternatively at least 90% by weight of the para-isomer and optionally include functionalized interpolymers wherein at least one or more of the alkyl substituents groups present in the styrene monomer units contain benzylic halogen or some other functional group. Exemplary materials may be characterized as polymers containing the following monomer units randomly spaced along the polymer chain:

wherein R and R¹ are independently hydrogen, lower alkyl, such as a C₁ to C₇ alkyl and primary or secondary alkyl halides and X is a functional group such as halogen. In an embodiment, R and R¹ are each hydrogen. Up to 60 mol% of the para-substituted styrene present in the random polymer structure may be the functionalized structure (2) above in one embodiment, and in another embodiment from 0.1 to 5 mol%. In yet another embodiment, the amount of functionalized structure (2) is from 0.2 to 3 mol%. [0263] The functional group X may be halogen or some other functional group which may be incorporated by nucleophilic substitution of benzylic halogen with other groups such as carboxylic acids; carboxy salts; carboxy esters, amides and imides; hydroxy; alkoxide; phenoxide; thiolate; thioether; xanthate; cyanide; cyanate; amino and mixtures thereof. These functionalized isomonoolefm copolymers, their method of preparation, methods of functionalization, and cure are more particularly disclosed in US 5, 162,445. In an embodiment, the elastomer comprises random polymers of isobutylene and para-methylstyrene containing from 0.5 to 20 mol% para-methylstyrene wherein up to 60 mol% of the methyl substituent groups present on the benzyl ring contain a bromine or chlorine atom, such as a bromine atom (para-(bromomethylstyrene)), as well as acid or ester functionalized versions thereof. In another embodiment, the functionality is selected such that it can react or form polar bonds with functional groups present in the matrix polymer, for example, acid, amino or hydroxyl functional groups, when the polymer components are mixed at high temperatures. [0264] In certain embodiments, the random copolymers have a substantially homogeneous compositional distribution such that at least 95% by weight of the polymer has a para- alky lstyrene content within 10% of the average para-alkylstyrene content of the polymer. Exemplary polymers are characterized by a narrow MWD (M_w/M_n) of less than 5, alternatively less than 2.5, an exemplary viscosity average molecular weight (“M_v”) in the range of from 200,000 up to 2,000,000 and an exemplary M_n in the range of from 25,000 to 750,000 as determined by GPC.

[0265] The random copolymer may be prepared by a slurry polymerization, typically in a diluent comprising a halogenated hydrocarbon(s) such as a chlorinated hydrocarbon and/or a fluorinated hydrocarbon including mixtures thereof, (see e.g.. WO 2004/058828, WO 2004/058827, WO 2004/058835, WO 2004/058836, WO 2004/058825, WO 2004/067577, and WO 2004/058829), of the monomer mixture using a Lewis acid catalyst, followed by halogenation, preferably bromination, in solution in the presence of halogen and a radical initiator such as heat and/or light and/or a chemical initiator and, optionally, followed by electrophilic substitution of bromine with a different functional moiety. [0266] In an embodiment, brominated poly(isobutylene-cr;-/;-methylstyrene) ("BIMSM") polymers generally contain from 0.1 to 5% mole of bromomethylstyrene groups relative to the total amount of monomer derived units in the copolymer. In another embodiment, the amount of bromomethyl groups is from 0.2 to 3.0 mol%, and from 0.3 to 2.8 mol% in yet another embodiment, and from 0.4 to 2.5 mol% in yet another embodiment, and from 0.3 to 2.0 in yet another embodiment, wherein a desirable range may be any combination of any upper limit with any lower limit. Expressed another way, exemplary copolymers contain from 0.2 to 10 wt% of bromine, based on the weight of the polymer, from 0.4 to 6 wt% bromine in another embodiment, and from 0.6 to 5.6 wt% in another embodiment, are substantially free of ring halogen or halogen in the polymer backbone chain. In one embodiment, the random polymer is a copolymer of C₄ to C₇ isoolefm derived units (or isomonoolefm), para-methylstyrene derived units and para-(halomethylstyrene) derived units, wherein the para- (halomethylstyrene) units are present in the polymer from 0.4 to 3.0 mol% based on the total number of para-methylstyrene, and wherein the para-methylstyrene derived units are present from 3 to 15 wt% based on the total weight of the polymer in one embodiment, and from 4 to 10 wt% in another embodiment. In another embodiment, the para-(halomethylstyrene) is para- (bromomethylstyrene).

[0267] A commercial embodiment of the halogenated isobutylene-p-methylstyrene rubber of the present invention is EXXPRO™ elastomers (ExxonMobil Chemical Company, Houston, TX), having a Mooney viscosity (ML 1+8 at 125°C, ASTM D1646) of from 30 to 50, a p-methylstyrene content of from 4 to 8.5 wt%, and a bromine content of from 0.7 to 2.2 wt% relative to the halogenated isobutylene-p-methylstyrene rubber.

[0268] In one embodiment, the blend rubber can also include a specialty rubber containing a polar functional group such as butadiene-acrylonitrile rubber (NBR, or nitrile rubber), a copolymer of 2-propenenitrile and 1,3-butadiene. Nitrile rubber can have an acrylonitrile content of from 10 to 50 wt% in one embodiment, from 15 to 40 wt% in another embodiment, and from 18 to 35 wt% in yet another embodiment. The Mooney viscosity may range from 30 to 90 in one embodiment (1+4, 100°C, ASTM D-1646), and from 30 to 75 in another embodiment. These rubbers are common in the art, and described in, for example, Handbook of Plastics, Elastomers, and Composites 1.41-1.49 (Harper, ed., McGraw-Hill, Inc. 1992). Commercial examples of these synthetic rubbers useful in the present invention are sold under the trade names BREON™, NIPOL™, SIVIC™ and ZETPOL™ (Zeon Chemicals, Louisville, KY), EUROPRENE™ N (Polimeri Europa Americas, Houston, TX), and KRYNAC™, PERBUNAN™ and THERBAN™ (Lanxess Corporation, Akron, OH).

[0269] In another embodiment, the blend rubber can include a derivative of NBR such as hydrogenated or carboxylated or styrenated nitrile rubbers. Butadiene-acrylonitrile-styrene rubber, a copolymer of 2-propenenitrile, 1,3-butadiene and styrene, can have an acrylonitrile content of from 10 to 40 wt% in one embodiment, from 15 to 30 wt% in another embodiment, and from 18 to 30 wt% in yet another embodiment. The styrene content of the SNBR copolymer may range from 15 wt% to 40 wt% in one embodiment, and from 18 wt% to 30 wt% in another embodiment, and from 20 to 25 wt% in yet another embodiment. The Mooney viscosity may range from 30 to 60 in one embodiment (1+4, 100°C, ASTM D1646), and from 30 to 55 in another embodiment. These rubbers are common in the art, and described in, for example, Handbook of Plastics, Elastomers, and Composites 1.41-1.49 (Harper, ed., McGraw- Hill, Inc. 1992). A commercial example of this synthetic rubber useful in the present invention is sold under the trade name KRYNAC™ (Lanxess Corporation, Akron, OH).

[0270] In yet another embodiment, the blend rubber can include a specialty rubber containing a halogen group such as polychloroprene (“CR” or “chloroprene rubber”), a homopolymer of 2-chloro-1, 3-butadiene. The Mooney viscosity may range from 30 to 110 in one embodiment (1+4, 100°C, ASTM D-1646), and from 35 to 75 in another embodiment. These rubbers are common in the art, and described in, for example, Handbook of Plastics, Elastomers, and Composites 1.41-1.49 (Harper, ed., McGraw-Hill, Inc. 1992). Commercial examples of these synthetic rubbers useful in the present invention are sold under the trade names NEOPRENE™ (DuPont Dow Elastomers, Wilmington, DE), BUTACLOR™ (Polimeri Europa Americas, Houston, TX) and BAYPREN™ (Lanxess Corporation, Akron, OH).

[0271] In another embodiment, the elastomeric compositions may comprise at least one thermoplastic resin. Thermoplastic resins suitable for practice of the present invention may be used singly or in combination and are resins containing nitrogen, oxygen, halogen, sulfur or other groups capable of interacting with an aromatic functional groups such as halogen or acidic groups. The resins are present in the nanocomposite from 30 to 90 wt% of the nanocomposite in one embodiment, and from 40 to 80 wt% in another embodiment, and from 50 to 70 wt% in yet another embodiment. In yet another embodiment, the resin is present at a level of greater than 40 wt% of the nanocomposite, and greater than 60 wt% in another embodiment.

[0272] Suitable thermoplastic resins include resins selected from the group consisting or polyamides, polyimides, polycarbonates, polyesters, polysulfones, polylactones, polyacetals, acrylonitrile-butadiene-styrene resins (“ABS”), polyphenyleneoxide (“PPO”), polyphenylene sulfide (“PPS”), polystyrene, styrene-acrylonitrile resins (“SAN”), styrene maleic anhydride resins (“SMA”), aromatic polyketones (“PEEK,” “PED,” and “PEKK”) and mixtures thereof. [0273] Suitable thermoplastic polyamides (nylons) comprise crystalline or resinous, high molecular weight solid polymers including copolymers and terpolymers having recurring amide units within the polymer chain. Polyamides may be prepared by polymerization of one or more epsilon lactams such as caprolactam, pyrrolidione, lauryllactam and aminoundecanoic lactam, or amino acid, or by condensation of dibasic acids and diamines. Both fiber-forming and molding grade nylons are suitable. Examples of such polyamides are polycaprolactam (nylon-6), polylauryllactam (nylon-12), polyhexamethyleneadipamide (nylon-6,6) polyhexamethyleneazelamide (nylon-6,9), polyhexamethylenesebacamide (nylon-6,10), polyhexamethylene-isophthalamide (nylon-6, IP) and the condensation product of 11 -amino- undecanoic acid (nylon-11) and the like. Commercially available thermoplastic polyamides (especially those having a softening point below 275°C) may be advantageously used in the practice of this invention, with linear crystalline polyamides having a softening point or melting point between 160 and 260°C being preferred.

[0274] Suitable thermoplastic polyesters which may be employed include the polymer reaction products of one or a mixture of aliphatic or aromatic polycarboxylic acids esters of anhydrides and one or a mixture of diols. Examples of satisfactory polyesters include poly (trans-1, 4-cyclohexylene C₂-6 alkane dicarboxylates such as poly (trans- 1,4-cyclohexylene succinate) and poly (trans- 1,4-cyclohexylene adipate); poly (cis or trans-1, 4- cyclohexanedimethylene) alkanedicarboxylates such as poly(cis-1,4-cyclohexanedimethylene) oxalate and poly-(cis-1,4-cyclohexanedimethylene) succinate, poly (C₂₄ alkylene terephthalates) such as polyethyleneterephthalate and polytetramethylene-terephthalate, poly (C₂₄ alkylene isophthalates such as polyethyleneisophthalate and polytetramethylene- isophthalate and like materials. Preferred polyesters are derived from aromatic dicarboxylic acids such as naphthalenic or phthalic acids and C₂ to C₄ diols, such as polyethylene terephthalate and polybutylene terephthalate. Preferred polyesters will have a melting point in the range of 160°C to 260°C.

[0275] Poly(phenylene ether) (“PPE”) thermoplastic resins which may be used in accordance with this invention are well known, commercially available materials produced by the oxidative coupling polymerization of alkyl substituted phenols. They are generally linear, amorphous polymers having a glass transition temperature in the range of 190°C to 235°C. These polymers, their method of preparation and compositions with polystyrene are further described in US 3,383,435.

[0276] Other thermoplastic resins which may be used include the polycarbonate analogs of the polyesters described above such as segmented poly (ether co-phthalates); polycaprolactone polymers; styrene resins such as copolymers of styrene with less than 50 mol% of acrylonitrile (“SAN”) and ABS; sulfone polymers such as polyphenyl sulfone; copolymers and homopolymers of ethylene and C₂ to C₈ α-olefins, in one embodiment a homopolymer of propylene derived units, and in another embodiment a random copolymer or block copolymer of ethylene derived units and propylene derived units, and like thermoplastic resins as are known in the art.

[0277] The total amount of blend rubber present in the elastomeric composition can range from a lower limit of 40, 50, 60, 65, 70 or 75 phr to an upper limit of 85, 90, 95, or 99 phr. In one embodiment, the blend rubber can comprise NR in a proportion from a lower limit of 10, 20, 30, 40, or 45 percent by weight to an upper limit of 55, 60, 70, 80, 90, 95, or 100 percent by weight of the total blend rubber. In an embodiment, the blend rubber can be a mixture of NR and another blend rubber such as BR, wherein the NR and BR can each be independently present in the elastomeric composition from a lower limit of 5, 10, 20, 25, 30, or 35 phr to an upper limit of 40, 45, 50, or 60 phr.

Other Components

[0278] The elastomeric compositions may also include a variety of other components and may be optionally cured to form cured elastomeric compositions that ultimately are fabricated into end use articles. For example, the elastomeric compositions may optionally comprise: a) at least one filler, for example, calcium carbonate, clay, mica, silica, silicates, talc, titanium dioxide, starch, wood flower, carbon black, or mixtures thereof; b) at least one clay, for example, montmorillonite, nontronite, beidelbte, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, stevensite, vermiculite, halloysite, aluminate oxides, hydrotalcite, or mixtures thereof, optionally, treated with modifying agents; c) at least one processing oil, for example, aromatic oil, naphthenic oil, paraffinic oil, or mixtures thereof; d) at least one processing aid, for example, plastomer, polybutene, polyalphaolefm oils, or mixtures thereof; e) at least one cure package or curative or wherein the composition has undergone at least one process to produce a cured composition; f) any combination of a-e. [0279] Plastomers suitable for use in the present invention in certain embodiments can be described as polyolefin copolymers having a density of from 0.85 to 0.915 g/cm³ and a melt index (MI) between 0.10 and 30 dg/min. In one embodiment, the plastomers are copolymers of ethylene derived units and at least one of C₃ to C₁₀ α-olefin derived units, the copolymers having a density in the range of less than 0.915 g/cm³. The amount of comonomer (C₃ to C₁₀ α-olefin derived units) present in the plastomer can range from 2 wt% to 35 wt% in one embodiment, and from 5 wt% to 30 wt% in another embodiment, and from 15 wt% to 25 wt% in yet another embodiment, and from 20 wt% to 30 wt% in yet another embodiment.

[0280] The plastomer may have a MI@190°C of between 0.10 and 20 dg/min in one embodiment, and from 0.2 to 10 dg/min in another embodiment, and from 0.3 to 8 dg/min in yet another embodiment. The average molecular weight of the plastomers can range from 10,000 to 800,000 in one embodiment, and from 20,000 to 700,000 in another embodiment. The 1% secant flexural modulus (ASTM D-790) of the plastomers can range from 10 MPa to 150 MPa in one embodiment, and from 20 MPa to 100 MPa in another embodiment. Further, the plastomer can have a Tm of from 50°C to 62°C (first melt peak) and from 65°C to 85°C (second melt peak) in one embodiment, and from 52°C to 60°C (first melt peak) and from 70°C to 80°C (second melt peak) in another embodiment.

[0281] Plastomers can be metallocene catalyzed copolymers of ethylene derived units and higher α-olefin derived units such as propylene, 1 -butene, 1 -hexene and 1-octene, and which contain enough of one or more of these comonomer units to yield a density between 0.860 and 0.900 g/cm³ in one embodiment. The MWD (M_w/M_n) of desirable plastomers can range from 2 to 5 in one embodiment, and from 2.2 to 4 in another embodiment. Examples of commercially available plastomers are EXACT™ 4150, a copolymer of ethylene and 1-hexene, the 1 -hexene derived units making up from 18 to 22 wt% of the plastomer and having a density of 0.895 g/cm³ and MI of 3.5 dg/min (ExxonMobil Chemical Company, Houston, TX); and EXACT™ 8201, a copolymer of ethylene and 1-octene, the 1-octene derived units making up from 26 to 30 wt% of the plastomer, and having a density of 0.882 g/cm³ and MI of 1.0 dg/min (ExxonMobil Chemical Company, Houston, TX).

[0282] In one embodiment, a polybutene processing oil may be present in the composition. In one embodiment, the polybutene processing oil can be a low molecular weight (less than 15,000 M_n) homopolymer or copolymer of olefin derived units having from 3 to 8 carbon atoms in one embodiment, preferably from 4 to 6 carbon atoms in another embodiment. In yet another embodiment, the polybutene is a homopolymer or copolymer of a C₄ raffinate. An embodiment of such low molecular weight polymers termed "polybutene" polymers is described in, for example, Synthetic Lubricants and High-Performance Functional Fluids, pp. 357-392 (Rudnick & Shubkin, ed., Marcel Dekker 1999) (hereinafter "polybutene processing oil" or "polybutene").

[0283] In one embodiment of the invention, the polybutene processing oil is a copolymer of at least isobutylene derived units, 1 -butene derived units, and 2-butene derived units. In one embodiment, the polybutene is a homopolymer, copolymer, or terpolymer of the three units, wherein the isobutylene derived units are from 40 to 100 wt% of the copolymer, the 1 -butene derived units are from 0 to 40 wt% of the copolymer, and the 2-butene derived units are from 0 to 40 wt% of the copolymer. In another embodiment, the polybutene is a copolymer or terpolymer of the three units, wherein the isobutylene derived units are from 40 to 99 wt% of the copolymer, the 1 -butene derived units are from 2 to 40 wt% of the copolymer, and the 2-butene derived units are from 0 to 30 wt% of the copolymer. In yet another embodiment, the polybutene is a terpolymer of the three units, wherein the isobutylene derived units are from 40 to 96 wt% of the copolymer, the 1 -butene derived units are from 2 to 40 wt% of the copolymer, and the 2-butene derived units are from 2 to 20 wt% of the copolymer. In yet another embodiment, the polybutene is a homopolymer or copolymer of isobutylene and 1 -butene, wherein the isobutylene derived units are from 65 to 100 wt% of the homopolymer or copolymer, and the 1 -butene derived units are from 0 to 35 wt% of the copolymer.

[0284] Polybutene processing oils can have a M_n of less than 10,000 in one embodiment, less than 8,000 in another embodiment, and less than 6,000 in yet another embodiment. In one embodiment, the polybutene oil has a M_n of greater than 400, and greater than 700 in another embodiment, and greater than 900 in yet another embodiment. A preferred embodiment can be a combination of any lower molecular weight limit with any upper molecular weight limit herein. For example, in one embodiment of the polybutene of the invention, the polybutene has a M_n of from 400 to 10,000, and from 700 to 8,000 in another embodiment, and from 900 to 3,000 in yet another embodiment. Useful viscosities of the polybutene processing oil ranges from 10 to 6,000 cSt (centiStokes) at 100°C in one embodiment, and from 35 to 5,000 cSt at 100°C in another embodiment, and is greater than 35 cSt at 100°C in yet another embodiment, and greater than 100 cSt at 100°C in yet another embodiment.

[0285] Commercial examples of such a processing oil are the PARAPOL™ Series of processing oils (ExxonMobil Chemical Company, Houston, TX), such as PARAPOL™ 450, 700, 950, 1300, 2400 and 2500. The commercially available PARAPOL™ Series of polybutene processing oils are synthetic liquid polybutenes, each individual formulation having a certain molecular weight, all formulations of which can be used in the composition of the invention. The molecular weights of the PARAPOL™ oils are from 420 Mn (PARAPOL™ 450) to 2700 Mn (PARAPOL™ 2500) as determined by GPC. The MWD of the PARAPOL™ oils range from 1.8 to 3 in one embodiment, and from 2 to 2.8 in another embodiment.

[0286] The elastomeric composition of the invention may include one or more types of polybutene as a mixture, blended with addition of the EADS copolymer to blend rubber, or preblended with either the EADS copolymer or blend rubber. The amount and identity (e.g., viscosity, Mn, etc.) of the poly butene processing oil mixture can be varied in this manner. Thus, PARAPOL™ 450 can be used when low viscosity is desired in the composition, while PARAPOL™ 2500 can be used when a higher viscosity is desired, or compositions thereof to achieve some other viscosity or molecular weight. In this manner, the physical properties of the composition can be controlled. More particularly, the phrases "polybutene processing oil," or "polybutene processing oil" include a single oil or a composition of two or more oils used to obtain any viscosity or molecular weight (or other property) desired, as specified in the ranges disclosed herein.

[0287] The polybutene processing oil or oils are present in the elastomeric composition of the invention from 1 to 60 phr in one embodiment, and from 2 to 40 phr in another embodiment, from 4 to 35 phr in another embodiment, and from 5 to 30 phr in yet another embodiment, and from 2 to 10 phr in yet another embodiment, and from 5 to 25 phr in yet another embodiment, and from 2 to 20 phr in yet another embodiment, wherein a desirable range of polybutene may be any upper phr limit combined with any lower phr limit described herein. Preferably, the polybutene processing oil does not contain aromatic groups or unsaturation.

[0288] Processing aids can also be selected from commercially available compounds such as so called isoparaffins, polyalphaolefms (“PAOs”) and polybutenes (a subgroup of PAOs). These three classes of compounds can be described as paraffins which can include branched, cyclic, and normal structures, and blends thereof. These processing aids can be described as comprising G, to C₂₀₀ paraffins in one embodiment, and G to C₁₀₀ paraffins in another embodiment.

[0289] Other processing aids can include esters, polyethers, and polyalkylene glycols. Other processing aids may be present or used in the manufacture of the elastomeric compositions of the invention. Processing aids include, but are not limited to, plasticizers, tackifiers, extenders, chemical conditioners, homogenizing agents and peptizers such as mercaptans, petroleum and vulcanized vegetable oils, mineral oils, paraffinic oils, polybutene aids, naphthenic oils, aromatic oils, waxes, resins, rosins, and the like.

[0290] The processing aid is typically present or used in the manufacturing process from 1 to 70 phr in one embodiment, from 3 to 60 phr in another embodiment, and from 5 to 50 phr in yet another embodiment.

[0291] The elastomeric composition may have one or more filler components such as, for example, calcium carbonate, silica, clay and other silicates which may or may not be exfoliated, talc, titanium dioxide, and carbon black. The fillers may be any size and typically range, for example, from about 0.0001 pm to about 100 pm. As used herein, silica is meant to refer to any type or particle size silica or another silicic acid derivative, or silicic acid, processed by solution, pyrogenic or the like methods and having a surface area, including untreated, precipitated silica, crystalline silica, colloidal silica, aluminum or calcium silicates, fumed silica, and the like.

[0292] In one embodiment, the filler can be carbon black or modified carbon black, and combinations of any of these. In another embodiment, the filler can be a blend of carbon black and silica. The preferred filler for such articles as tire treads and sidewalls is reinforcing grade carbon black present at a level of from 10 to 100 phr of the blend, more preferably from 30 to 80 phr in another embodiment, and from 50 to 80 phr in yet another embodiment. Useful grades of carbon black, as described in Rubber Technology, p. 59-85, range from N110 to N990. More desirably, embodiments of the carbon black useful in, for example, tire treads are N229, N351, N339, N220, N234 and NllO provided in ASTM (D3037, D1510, and D3765). Embodiments of the carbon black useful in, for example, sidewalls in tires are N326, N330, N347, N351, N550, N660, and N762. Carbon blacks suitable for innerliners and other air barriers include N550, N660, N650, N762, N990 and REGAL™ 85.

[0293] The layered filler may comprise a layered clay, optionally, treated or pre-treated with a modifying agent such as organic molecules. The elastomeric compositions may incorporate a clay, optionally, treated or pre-treated with a modifying agent, to form a nanocomposite or nanocomposite composition. Nanocomposites may include at least one elastomer as described above and at least one modified layered filler. The modified layered filler may be produced by the process comprising contacting at least one layered filler such as at least one layered clay with at least one modifying agent. The modified layered filler may be produced by methods and using equipment well within the skill in the art. For example, see US 4,569,923, 5,663,111, 6,036,765 and 6,787,592.

[0294] In an embodiment, the layered filler such as a layered clay may comprise at least one silicate. In certain embodiments, the silicate may comprise at least one "smectite" or "smectite-type clay" referring to the general class of clay minerals with expanding crystal lattices. For example, this may include the dioctahedral smectites which consist of montmorillonite, beidellite, and nontronite, and the trioctahedral smectites, which includes saponite, hectorite, and sauconite. Also encompassed are smectite-clays prepared synthetically, e.g., by hydrothermal processes as disclosed in US 3,252,757, 3,586,468, 3,666,407, 3,671,190, 3,844,978, 3,844,979, 3,852,405 and 3,855,147. In other embodiments, the at least one silicate may comprise natural or synthetic phyllosilicates, such as montmorillonite, nontronite, beidellite, bentonite, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, stevensite and the like, as well as vermiculite, halloysite, aluminate oxides, hydrotalcite, and the like. Combinations of any of the previous embodiments are also contemplated.

[0295] The layered filler such as the layered clays described above may be modified such as intercalated or exfoliated by treatment with at least one modifying agent or swelling agent or exfoliating agent or additive capable of undergoing ion exchange reactions with the cations present at the interlayer surfaces of the layered filler. Modifying agents are also known as swelling or exfoliating agents. Generally, they are additives capable of undergoing ion exchange reactions with the cations present at the interlayer surfaces of the layered filler. Suitable exfoliating additives include cationic surfactants such as ammonium, alkylamines or alkylammonium (primary, secondary, tertiary and quaternary), phosphonium or sulfonium derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines and sulfides.

[0296] For example, amine compounds (or the corresponding ammonium ion) are those with the structure R²R³R⁴N, wherein R², R³, and R⁴ are C₁ to C₃₀ alkyls or alkenes in one embodiment, C₁ to C₂₀ alkyls or alkenes in another embodiment, which may be the same or different. In one embodiment, the exfoliating agent is a so-called long chain tertiary amine, wherein at least R² is a C₁₄ to C₂₀ alkyl or alkene. In other embodiments, a class of exfoliating additives can include those which can be covalently bonded to the interlayer surfaces. These include polysilanes of the structure -Si(R⁵)2R⁶ where R⁵ is the same or different at each occurrence and is selected from alkyl, alkoxy or oxysilane and R⁶ is an organic radical compatible with the matrix polymer of the composite. Other suitable exfoliating additives can include protonated amino acids and salts thereof containing 2-30 carbon atoms such as 12-aminododecanoic acid, epsilon-caprolactam and like materials. Suitable swelling agents and processes for intercalating layered silicates are disclosed in US 4,472,538, 4,810,734 and 4,889,885 as well as WO 1992/002582.

[0297] Examples of some commercial products are Cloisites produced by Southern Clay Products, Inc. in Gonzales, TX. For example, Cloisite Na⁺, Cloisite 30B, Cloisite 10A, Cloisite 25 A, Cloisite 93 A, Cloisite 20A, Cloisite 15 A, and Cloisite 6A. They are also available as SOMASIF™ and LUCENTITE™ clays produced by CO-OP Chemical Co., LTD. In Tokyo, Japan. For example, SOMASIF™ MAE, SOMASIF™ MEE, SOMASIF™ MPE, SOMASIF™ MTE, SOMASIF™ ME- 100, LUCENTITE™ SPN, and LUCENTITE™ (SWN).

[0298] The amount of clay or exfoliated clay incorporated in the nanocomposites in accordance with an embodiment of the invention is sufficient to develop an improvement in the mechanical properties or barrier properties of the nanocomposite, for example, tensile strength or oxygen permeability. Amounts generally will range from 0.5 to 10 wt% in one embodiment, and from 1 to 5 wt% in another embodiment, based on the polymer content of the nanocomposite. Expressed in parts per hundred rubber, the clay or exfoliated clay may be present from 1 to 30 phr in one embodiment, and from 5 to 20 phr in another embodiment. [0299] In certain embodiments, the elastomeric compositions and the articles made from those compositions may comprise or be manufactured with the aid of at least one cure package, at least one curative, at least one crosslinking agent, and/or undergo a process to cure the elastomeric composition. As used herein, at least one curative package refers to any material or method capable of imparting cured properties to a rubber as commonly understood in the industry. At least one curative package may include any and at least one of sulfur, zinc oxide, and fatty acids. Peroxide cure systems or resin cure systems may also be used. Further, heat or radiation- induced crosslinking of polymers may be used.

[0300] One or more crosslinking agents are preferably used in the elastomeric compositions of the present invention, especially when silica is the primary filler, or is present in combination with another filler. More preferably, the coupling agent may be a bifunctional organosilane crosslinking agent. An "organosilane crosslinking agent" is any silane coupled filler and/or crosslinking activator and/or silane reinforcing agent known to those skilled in the art including, but not limited to, vinyl triethoxysilane, vinyl-tris-(beta-methoxyethoxy)silane, methacryloylpropyltrimethoxysilane, gamma-amino-propyl triethoxysilane (sold commercially as All 00 by Witco), gamma-mercaptopropyltrimethoxysilane (A189 by Witco) and the like, and mixtures thereof. In one embodiment, bis-(3-tri ethoxy silypropyl)tetrasulfide (known commercially as "Si69") is employed.

[0301] Generally, polymer blends, for example, those used to produce tires, are crosslinked to thereby improve the polymer’ s mechanical properties. It is known that the physical properties, performance characteristics, and durability of vulcanized rubber compounds are directly related to the number (crosslink density) and type of crosslinks formed during the vulcanization reaction. Sulphur is the most common chemical vulcanizing agent for diene-containing elastomers. It exists as a rhombic 8-member ring or in amorphous polymeric forms. The sulphur vulcanization system also consists of the accelerator to activate the sulphur, an activator, and a retarder to help control the induction time. Accelerators serve to control the induction time and rate of vulcanization, and the number and type of sulphur crosslinks that are formed. These factors play a significant role in determining the performance properties of the vulcanizate. [0302] Activators are chemicals that increase the rate of vulcanization by reacting first with the accelerators to form rubber-soluble complexes which then react with the sulphur to form sulphurating agents. General classes of accelerators include amines, diamines, guanidines, thioureas, thiazoles, thiurams, sulfenamides, sulfenimides, thiocarbamates, xanthates, and the like.

[0303] Retarders may be used to increase the cure induction time to allow sufficient time to process the unvulcanized rubber.

[0304] Halogen-containing elastomers such as halogenated star-branched butyl rubber, brominated butyl rubber, chlorinated butyl rubber, star-branched brominated butyl (polyisobutylene/isoprene copolymer) rubber, halogenated poly(isobutylene-co-p- methylstyrene), polychloroprene, and chlorosulfonated polyethylene may be crosslinked by their reaction with metal oxides. The metal oxide is thought to react with halogen groups in the polymer to produce an active intermediate which then reacts further to produce carbon-carbon bonds. Zinc halide is liberated as a by-product and it serves as an autocatalyst for this reaction.

[0305] Generally, polymer blends may be crosslinked by adding curative molecules, for example sulphur, metal oxides, organometallic compounds, radical initiators, etc., followed by hearing. In particular, the following metal oxides are common curatives that will function in the present invention: ZnO, CaO, MgO, AI₂O₃, C₁O₃ , FeO, Fe₂O₃, and NiO. These metal oxides can be used alone or in conjunction with the corresponding metal fatty acid complex (e.g., zinc stearate, calcium stearate, etc.), or with the organic and fatty acids added alone, such as stearic acid, and optionally other curatives such as sulphur or a sulphur compound, an alkylperoxide compound, diamines or derivatives thereof (e.g., DIAK™ products from E.I. du Pont de Nemours and Co.). This method of curing elastomers may be accelerated and is often used for the vulcani- zation of elastomer blends.

[0306] The acceleration of the cure process is accomplished in the present invention by adding to the composition an amount of an accelerant, often an organic compound. The mechanism for accelerated vulcanization of natural rubber involves complex interactions between the curative, accelerator, activators and polymers. Ideally, the entire available curative is consumed in the formation of effective crosslinks which join together two polymer chains and enhance the overall strength of the polymer matrix. Numerous accelerators are known in the art and include, but are not limited to, the following: stearic acid, diphenyl guanidine (“DPG”), tetramethylthiuram disulfide (“TMTD”), 4,4'-dithiodimorpholine (“DTDM”), tetrabutylthiuram disulfide (“TBTD”), benzothiazyl disulfide (“MBTS”), hexamethylene-1,6-bisthiosulfate disodium salt dihydrate (sold commercially as DURALINK™ HTS by Flexsys), 2-morpholinothio benzothiazole (“MBS” or “MOR”), blends of 90% MOR and 10% MBTS (MOR 90), N-tertiarybutyl-2-benzothiazole sulfenamide (“TBBS”), and N-oxydiethylene thiocarbamyl-N-oxydiethylene sulfonamide (“OTOS”), zinc 2-ethyl hexanoate (“ZEH”), and "thioureas."

[0307] The compositions produced in accordance with the present invention typically contain other components and additives customarily used in rubber mixes, such as effective amounts of other nondiscolored and nondiscoloring processing aids, pigments, antioxidants, and/or antiozonants.

Processing

[0308] Blends of elastomers may be reactor blends and/or melt mixes. Mixing of the components may be carried out by combining the polymer components, filler and any clay in the form of an intercalate in any suitable mixing device such as a two-roll open mill, BRABENDER™ internal mixer, BANBURY™ internal mixer with tangential rotors, KR.UPP™ internal mixer with intermeshing rotors, or preferably a mixer/extruder, by techniques known in the art. Mixing is performed at temperatures in the range from up to the melting point of the elastomer and/or secondary rubber used in the composition in one embodiment, from 40°C up to 250°C in another embodiment, and from 100°C to 200°C in yet another embodiment, under conditions of shear sufficient to allow the clay intercalate to exfoliate and become uniformly dispersed within the polymer to form the nanocomposite. [0309] Typically, from 70% to 100% of the elastomer or elastomers is first mixed for 20 to 90 seconds, or until the temperature reaches from 40°C to 75°C. Then, three quarters of the filler, and the remaining amount of elastomer, if any, are typically added to the mixer, and mixing continues until the temperature reaches from 90°C to 150°C. Next, the remaining filler is added, as well as the processing oil, and mixing continues until the temperature reaches from 140°C to 190°C. The masterbatch mixture is then finished by sheeting on an open mill and allowed to cool, for example, to from 60°C to 100°C when the curatives are added.

[0310] Mixing with clays is performed by techniques known to those skilled in the art, wherein the clay is added to the polymer at the same time as the carbon black in one embodiment. The polybutene processing oil is typically added later in the mixing cycle after the carbon black and clay have achieved adequate dispersion in the elastomeric matrix. [0311] The cured compositions of the invention can include various elastomers and fillers with the polybutene processing oil. The compositions of the invention typically include isobutylene-based elastomers such as halogenated poly(isobutylene-co-p-methylstyrene), butyl rubber, or halogenated star-branched butyl rubber (“HSBBR”) either alone, or some combination with one another, with the polybutene processing oil being present from 5 to 30 phr in one embodiment.

[0312] The elastomeric compositions of the invention may be extruded, compression molded, blow molded, injection molded, and laminated into various shaped articles including fibers, films, laminates, layers, industrial parts such as automotive parts, appliance housings, consumer products, packaging, and the like. [0313] In particular, the elastomeric compositions are useful in articles for a variety of tire applications such as truck tires, bus tires, automobile tires, motorcycle tires, off-road tires, aircraft tires, and the like. The elastomeric compositions may either be fabricated into a finished article or a component of a finished article such as a tread or sidewall for a tire. Additionally, the elastomeric compositions may also be used as adhesives, caulks, sealants, and glazing compounds. They are also useful as plasticizers in rubber formulations; as components to compositions that are manufactured into stretch-wrap films; as dispersants for lubricants; and in potting and electrical cable filling materials.

[0314] In yet other applications, the elastomer(s) or elastomeric compositions of the invention are also useful in medical applications such as pharmaceutical stoppers and closures, coatings for medical devices, and in paint rollers.

[0315] This invention also relates to a tire sidewall composition comprising: from 10 to 30 phr EADS copolymer, preferably having a strain hardening ratio of 2 or greater when extensional viscosity is measured at a Hencky strain rate of 0.01 s^-1 to 10 s^-1 at a temperature of 190°C; from 20 to 60 phr natural rubber; from 20 to 60 phr polybutadiene rubber; an optional secondary blend rubber selected from polyisoprene rubber (IR), poly(styrene-co-butadiene) rubber (SBR), poly(isoprene-co-butadiene) rubber (IBR), styrene- isoprene-butadiene rubber (SIBR), butyl rubber, star branched butyl rubber, poly(isobutylene- co-alkylstyrene), ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), and mixtures thereof; a filler selected from carbon black, modified carbon black, silica, precipitated silica, and blends thereof; a chemical protectant selected from waxes, antioxidants, antiozonants and combinations thereof; an optional processing oil, resin, or combination thereof; and a curing package.

[0316] This invention also relates to a process for making a tire, comprising:

(a) compounding to form a green mixture: from 10 to 30 phr of EADS copolymer having a strain hardening ratio of 2 or greater when extensional viscosity is measured at a Hencky strain rate of 0.01 s^-1 to 10 s^-1 at a temperature of 190°C; from 20 to 60 phr natural rubber; from 20 to 60 phr polybutadiene rubber; an optional secondary blend rubber selected from polyisoprene rubber, poly(styrene- co-butadiene) rubber, poly(isoprene-co-butadiene) rubber, styrene-isoprene-butadiene rubber, butyl rubber, star branched butyl rubber, poly(isobutylene-co-alkylstyrene), ethylene- propylene rubber, ethylene-propylene-diene rubber and mixtures thereof; a filler selected from carbon black, modified carbon black, silica, precipitated silica, and blends thereof; a chemical protectant selected from waxes, antioxidants, antiozonants and combinations thereof; an optional processing oil, resin, or combination thereof; and a curing package;

(b) forming the green mixture into a sidewall in a tire build comprising a carcass and a tread; and

(c) curing the build to form the tire, and optionally

(d) retreading the tire. [0317] This invention further relates to:

1. A copolymer comprising units derived from ethylene, one or more α-olefins, one or more non-conjugated dienes, and one or more substituted styrene compounds.

2. The copolymer of paragraph 1, wherein the copolymer is a random copolymer. 3. The copolymer of paragraph 1 or paragraph 2, wherein the α-olefin is propylene.

4. The copolymer of any of paragraphs 1 to 3, wherein the substituted styrene compound is represented by the formula:

wherein each R², R³, R⁴, R⁵ and R⁶ is independently hydrogen or a C₁ to C₂₀ hydrocarbyl group, wherein at least one of R², R³, R⁴, R⁵ and R⁶ is not hydrogen.

5. The copolymer of any of paragraphs 1 to 4, wherein the substituted styrene compound is para-alkylstyrene.

6. The copolymer of any of paragraphs 1 to 5, wherein a molar ratio of ethylene derived units to α-olefin derived units is about 5/95 to about 95/5. 7. The copolymer of any of paragraphs 1 to 6, wherein the copolymer comprises about

0.01 wt% to about 40 wt% of the non-conjugated diene units based on a weight of the copolymer.

8. The copolymer of any of paragraphs 1 to 7, wherein the copolymer comprises about 0.1 wt% to about 40 wt% of the styrene compound units based on a weight of the copolymer. 9. A composition comprising the copolymer of any of paragraphs 1 to 8 and an inorganic filler.

10. The copolymer of any of paragraphs 1 to 9, wherein the non-conjugated diene is ethylidene norbomene.

11. The copolymer of any of paragraphs 1 to 10, wherein the copolymer comprises: about 40 wt% to about 90 wt% of units derived from ethylene; about 9.8 wt% to about 59.8 wt% of units derived from the α-olefin; about 0.1 wt% to about 10 wt% of units derived from the non-conjugated diene; and about 0.1 wt% to about 15 wt% of units derived from the substituted styrene, based on a weight of the copolymer. 12. The copolymer of paragraph 11, wherein the α-olefin is propylene and the substituted styrene is para-alkylstyrene.

13. The copolymer of paragraph 11 or paragraph 12, wherein the α-olefin is propylene, the non-conjugated diene is ethylidene norborene or vinyl norbomene, and the substituted styrene is para-alkylstyrene.

14. A composition comprising the copolymer of any of paragraphs 11 to 13 and an inorganic filler.

15. The composition of paragraph 14, wherein the composition has about 25 wt% to about 60 wt% of the inorganic filler based on a combined weight of the inorganic filler and the copolymer.

16. The copolymer of any of paragraphs 1 to 15, wherein the non-conjugated diene is ethylidene norbomene.

17. A process for producing a copolymer, comprising: contacting ethylene, a C₃ to C₂₀ α-olefin monomer, a non-conjugated diene monomer, and a substituted styrene monomer with a catalyst system comprising a single site catalyst compound, an activator, and an optional support; obtaining a copolymer comprising about 40 wt% to about 90 wt% of units derived from ethylene; about 9.8 wt% to about 59.8 wt% of units derived from the C₃ to C₂₀ α-olefin; about 0.1 wt% to about 10 wt% of units derived from the non-conjugated diene; and about 0.1 wt% to about 15 wt% of units derived from the substituted styrene, based on a weight of the copolymer, wherein the copolymer has a strain hardening ratio of 2 or greater when an extensional viscosity is measured at a Hencky strain rate of 0.01 s^-1 to 10 s^-1 at a temperature of 190°C.

18. The process of paragraph 17, wherein the C₃ to C₂₀ α-olefin is one or more of propylene, butene butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, or an isomer thereof; and the substituted styrene is represented by the formula:

wherein each R², R³, R⁴, R⁵ and R⁶ is independently hydrogen, or a C₁ to C₂₀ hydrocarbyl group, wherein at least one of R², R³, R⁴, R⁵ and R⁶ is not hydrogen; and the non-conjugated diene is selected from the group consisting of: 5-ethylidene-2-norbomene (ENB), 1,4-hexadiene, dicyclopentadiene (DCPD), norbomadiene, and 5-vinyl-2-norbomene, and combinations thereof.

19. The process of paragraph 17 or paragraph 18 wherein the single site catalyst compound is selected from the group consisting of: pyridyldiamido complexes, quinolinyldiamido complexes, phenoxyimine complexes, bisphenolate complexes, cyclopentadienyl-amidinate complexes, iron pyridyl bis(imine) complexes, and combinations thereof.

20. The process of any of paragraphs 17 to 19 wherein the single site catalyst compound is a metallocene catalyst.

21. A process for producing a copolymer, comprising: introducing an α-olefin monomer to a reaction vessel in an amount and under pressure sufficient to allow utilization of the α-olefin in a liquefied form as a polymerization diluent; introducing a non-conjugated diene monomer and a substituted styrene monomer to the diluent; adding ethylene monomer to the diluent to produce a mixture of the ethylene, the a- olefin, the substituted styrene, and the diene monomers; and, adding a catalyst system comprising a catalyst compound and an activator to the diluent; reacting the mixture for a time sufficient to permit polymerization of the ethylene, the α-olefin, the substituted styrene, and the diene monomers to produce a copolymer comprising about 40 wt% to about 90 wt% of units derived from ethylene; about 9.8 wt% to about 59.8 wt% of units derived from the α-olefin; about 0.1 wt% to about 10 wt% of units derived from the non- conjugated diene; and about 0.1 wt% to about 15 wt% of units derived from the substituted styrene, based on the weight of the copolymer, wherein the copolymer has a strain hardening ratio of 2 or greater when extensional viscosity is measured at a Hencky strain rate of 0.01 s^-1 to 10 s^-1 at a temperature of 190°C.

22. The process of paragraph 21, wherein the α-olefin monomer is propylene and the non- conjugated diene monomer is ethylidene norbomene.

23. The process of paragraph 21 or paragraph 22, wherein the catalyst compound is selected from the group consisting of: pyridyldiamido complexes, quinolinyldiamido complexes, phenoxyimine complexes, bisphenolate complexes, cyclopentadienyl-amidinate complexes, iron pyridyl bis(imine) complexes, and combinations thereof.

24. The process of any of paragraphs 21 to 23, wherein the catalyst compound is a metallocene catalyst.

25. An elastomer composition comprising a blend of: a ethylene-propylene-diene-substituted styrene copolymer comprising: 40 to 90 wt% propylene-derived units,

9.4 to 59.4 wt% ethylene-derived units,

0.3 to 10 wt% diene-derived units, and 0.3 to 10 wt% substituted styrene-derived units, based on a total weight of the copolymer, wherein the copolymer has a strain hardening ratio of 2 or greater when an extensional viscosity is measured at a Hencky strain rate of 0.01 s^-1 to 10 s^-1 at a temperature of 190°C.; and a blend rubber comprising one or more elastomers wherein the one or more elastomers are not ethylene-propylene-diene-substituted styrene copolymer.

26. The elastomer composition of paragraph 25, wherein the blend comprises from 5 to 40 phr of the copolymer.

27. The elastomer composition of paragraph 25 or paragraph 26, wherein the one or more elastomers is selected from the group consisting of: natural rubbers, polyisoprene rubber, poly(styrene-co-butadiene) rubber, polybutadiene rubber, poly(isoprene-co-butadiene) rubber, styrene-isoprene-butadiene rubber, butyl rubber, star branched butyl rubber, poly(isobutylene- co-alkylstyrene), polychloroprene rubber, nitrile rubber, ethylene-propylene rubber, ethylene- propylene-diene rubber and combinations thereof.

28. The elastomer composition of any of paragraphs 25 to 27, wherein the one or more elastomers comprises 5 to 80 phr of a natural rubber and 5 to 80 phr of a polybutadiene rubber.

29. The elastomer composition of paragraphs 25 to 28, further comprising one or more of the following: a filler selected from the group consisting of: carbon black, modified carbon black, silica, precipitated silica and blends thereof; a chemical protectant selected from the group consisting of: waxes, antioxidants, antiozonants, and combinations thereof; a processing oil, resin or a combination thereof; and a curing package.

30. A vulcanizate obtained by curing the elastomer composition of paragraph 29 wherein the curing package is present.

31. An article comprising the vulcanizate of paragraph 30 selected from the group consisting of: a tire sidewall, a tire tread, a tire, a retreaded tire, a bias truck tire, an off-road tire, and a passenger automobile tire. 32. An article comprising the copolymer of any of paragraphs 11 to 13 selected from the group consisting of: a tire sidewall, a tire tread, a tire, a retreaded tire, a bias truck tire, an off- road tire, and a passenger automobile tire.

33. A tire sidewall composition comprising: from 10 to 30 phr of a ethylene-propylene-diene-substituted styrene copolymer, comprising,

40 to 90 wt% propylene-derived units,

9.4 to 59.4 wt% ethylene-derived units;

0.3 to 10 wt% substituted styrene-derived units, and

0.5 to 4 wt% diene-derived units selected from 5-ethylidene-2-norbomene, 5-vinyl-2-norbomene, dicyclopentadiene, and 1,4-hexadiene, based on the weight of the copolymer, wherein the copolymer has a strain hardening ratio of 2 or greater when extensional viscosity is measured at a Hencky strain rate of 0.01 s^-1 to 10 s^-1 at a temperature of 190°C; from 20 to 60 phr of a natural rubber; from 20 to 60 phr of a polybutadiene rubber; an optional secondary blend rubber selected from the group consisting of: polyisoprene rubber (IR), poly(styrene-co-butadiene) rubber (SBR), poly(isoprene-co-butadiene) rubber (IBR), styrene-isoprene-butadiene rubber (SIBR), butyl rubber, star branched butyl rubber, poly(isobutylene-co-alkylstyrene), ethylene-propylene rubber (EPM), ethylene-propylene- diene rubber (EPDM), and combinations thereof; a filler selected from the group consisting of: carbon black, modified carbon black, silica, precipitated silica, and combinations thereof; a chemical protectant selected from the group consisting of: waxes, antioxidants, antiozonants, and combinations thereof; an optional processing oil, resin, or combination thereof; and a curing package.

EXPERIMENTAL

[0318] The foregoing discussion can be further described with reference to the following non-limiting examples.

GPC-4D

[0319] Unless otherwise indicated, the distribution and the moments of molecular weight (Mw, Mn, Mz, Mw/Mn, etc.), the comonomer content and the branching index (gVis) are determined by using a high temperature Gel Permeation Chromatography (Polymer Char GPC- IR) equipped with a multiple-channel band-filter based Infrared detector IR5 with a multiple- channel band filter based infrared detector ensemble IR5 with band region covering from about 2,700 cm^-1 to about 3,000 cm^-1 (representing saturated C-H stretching vibration), an 18-angle light scattering detector and a viscometer. Three Agilent PLgel 10-pm Mixed-B LS columns are used to provide polymer separation. Reagent grade 1, 2, 4-tri chlorobenzene (TCB) (from Sigma-Aldrich) comprising -300 ppm antioxidant butylated hydroxytoluene (BHT) can be used as the mobile phase at anominal flow rate of -1.0 mL/min and anominal injection volume of -200 pL. The whole system including transfer lines, columns, and detectors can be contained in an oven maintained at ~145°C. A given amount of sample can be weighed and sealed in a standard vial with -10 pL flow marker (heptane) added thereto. After loading the vial in the auto-sampler, the oligomer or polymer may automatically be dissolved in the instrument with -8 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, /, using the equation: c=al, where a is the mass constant determined with polyethylene or polypropylene standards. The mass recovery can be calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre- determined concentration multiplied by injection loop volume. The conventional molecular weight (IR MW) is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to lOM gm/mole. The MW at each elution volume is calculated with following equation:

where the variables with subscript “PS” stand for polystyrene while those without a subscript are for the test samples. In this method, aps = 0.67 and Kps = 0.000175, a and K for other materials are as calculated and published in literature (Sun, T. et al. Macromolecules 2001, v.34, pg. 6812), except that for purposes of this invention and claims thereto, a = 0.695+(0.01*(wt. fraction propylene)) and K = 0.000579-(0.0003502*(wt. fraction propylene)) for ethylene-propylene copolymers and EADS copolymers, a = 0.695 and K = 0.000579 for linear ethylene polymers, a = 0.705 and K = 0.0002288 for linear propylene 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. [0320] The comonomer composition is determined by the ratio of the IR5 detector intensity corresponding to CH₂ and CH₃ channel calibrated with a series of PE and PP homo/copolymer standards whose nominal value are predetermined by NMR or FTIR. In particular, this provides the methyls per 1,000 total carbons (CH₃/IOOOTC) 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/IOOOTC function, assuming each chain to be linear and terminated by a methyl group at each end. The weight % comonomer is then obtained from the following expression in which f is 0.3, 0.4, 0.6, 0.8, and so on for C₃, C₄, C₆, C₈, and so on co-monomers, respectively: w2 = f * SCB/1000TC

[0321] The bulk composition of the polymer from the GPC-IR and GPC-4D analyses is obtained by considering the entire signals of the CH₃ and CH₂ channels between the integration limits of the concentration chromatogram. First, the following ratio is obtained

[0322] Then the same calibration of the CH₃ and CH₂ signal ratio, as mentioned previously in obtaining the CH₃/1000TC as a function of molecular weight, is applied to obtain the bulk CH₃/1000TC. A bulk methyl chain ends per 1000TC (bulk CH₃end/1000TC) is obtained by weight-averaging the chain-end correction over the molecular-weight range. Then w2b = f * bulk CH₃/1000TC bulk SCB/1000TC = bulk CH₃/1000TC - bulk CH₃end/1000TC and bulk SCB/1000TC is converted to bulk w2 in the same manner as described above.

[0323] The LS detector is the 18-angle Wyatt Technology High Temperature DAWN HELEOSII. The LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering ( Light Scattering from Polymer Solutions; Huglin, M. B., Ed.; Academic Press, 1972.):

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity at scattering angle θ, c is the polymer concentration determined from the IR5 analysis, A2 is the second virial coefficient, R(q) is the form factor for a monodisperse random coil, and K₀ is the optical constant for the system:

where is Avogadro's number, and (dn/dc) is the refractive index increment for the system. The refractive index, n = 1.500 for TCB at 145°C and l = 665 nm. For analyzing polyethylene homopolymers, ethylene-hexene copolymers, and ethylene-octene copolymers, dn/dc = 0.1048 ml/mg and A2 = 0.0015; for analyzing ethylene-butene copolymers, dn/dc = 0.1048*(1-0.00126*w2) ml/mg and A2 = 0.0015 where w2 is weight percent butene comonomer.

[0324] A high temperature Agilent (or Viscotek Corporation) viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity, h_s, for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [h], at each point in the chromatogram is calculated from the equation [n]= n_s/c. where c is concentration and is determined from the IR5 broadband channel output. The viscosity MW at each point is calculated as M = K_PSM^αPS+1 /[N] , where α_ps is 0.67 and K_ps is 0.000175.

[0325] The branching index (g'vis) is calculated using the output of the GPC-IR5-LS-VIS method as follows. The average intrinsic viscosity, |n |_avg. of the sample is calculated by:

where the summations are over the chromatographic slices, i, between the integration limits.

The branching index g'_vis is defined as where M_v is the viscosity-average

molecular weight based on molecular weights determined by LS analysis and the K and a are for the reference linear polymer, which are, for purposes of this invention and claims thereto, a = 0.695+(0.01*(wt. fraction propylene)) and K = 0.000579-(0.0003502*(wt. fraction propylene) for ethylene-propylene copolymers, and EADS copolymers, a = 0.695 and K = 0.000579 for linear ethylene polymers, a = 0.705 and K = 0.0002288 for linear propylene 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. Viscosity

[0326] The transient extensional viscosity was measured at 190°C using a SER2P testing Platform available from Xpansion Instruments LLC, Tallmadge, Ohio, USA. The SER Testing Platform was used on a MCR501 rheometer available from Anton Paar. The SER Testing Platform is described in US 6,578,413 and US 6,691,569. A general description of transient uniaxial extensional viscosity measurements is provided, for example, in “Measuring the transient extensional rheology of polyethylene melts using the SER universal testing platform”, The Society of Rheology, Inc., J. Rheol. v.49(3), pp. 585-606 (2005). Strain hardening occurs when a polymer is subjected to elongational flow and the transient extensional viscosity increases with respect to the linear viscoelasticity envelop (LVE). Strain hardening is observed as abrupt upswing of the extensional viscosity in the transient extensional viscosity vs. time plot. A strain hardening ratio (SHR) is used to characterize the upswing in extensional viscosity and is defined as the ratio of the maximum transient extensional viscosity at certain strain rate over the respective value of the LVE. Strain hardening is present in the material when the ratio is greater than 1.

Shear

[0327] Dynamic shear melt rheological data 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 a temperature of about 190°C for at least 30 minutes before inserting compression-molded sample of resin onto the parallel plates. To determine the viscoelastic behavior of the samples, frequency sweeps from 0.01 rad/s to 628 rad/s were carried out at a temperature of about 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 cross-linking during the experiments. All the samples were compression molded at about 190°C. A sinusoidal shear strain is applied to the material if the strain amplitude is sufficiently small the material behaves linearly. It can be shown that the resulting steady-state stress will also oscillate 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. Flexural Properties

[0328] For mechanical testing the pelletized material was used to prepare dog bones shaped samples (ISO 37 Type 3 bars) using injection molding machine BOY XS at temperatures ~195-200°C. All the data is plotted based on mean value from 5 measurements. The Flex Test was based on ASTM D790-17 has the following characteristics: specimens that are ISO 37 Type 3 bars; a span on the test fixture of 30 mm; a test speed of 1 mm/min; and a deflection of the specimens to 1.2% that captures the 1% Secant Modulus. The Tensile Test based on ASTM D638 has the following characteristics: specimens that are ISO 37 Type 3 bars; a test speed of 508 mm/min (20”/min); and a contact extensometer that attaches to specimen when elongating and detaches when the specimen breaks.

Differential Scanning Calorimetry (DSC)

[0329] The procedure for DSC determinations is as follows. 0.5 grams of polymer is weighed and pressed to a thickness of 15 to 20 mils (about 381-508 microns) at 140°C-150°C, using a “DSC mold” and MYLAR™ film as a backing sheet. The pressed polymer sample is allowed to cool to ambient temperatures by hanging in air (the MYLAR™ film backing sheet is not removed). The pressed polymer sample is then annealed at room temperature (about 23°C-25°C). A 15-20 mg disc is removed from the pressed polymer sample using a punch die and is placed in a 10 microliter aluminum sample pan. The disc sample is then placed in a DSC (Perkin Elmer Pyris 1 Thermal Analysis System) and is cooled to -100°C. The sample is heated at 10°C/min to attain a final temperature of 165°C. The thermal output, recorded as the area under the melting peak of the disc sample, is a measure of the heat of fusion and is expressed in Joules per gram (J/g) of polymer and is automatically calculated by the Perkin Elmer system. Under these conditions, the melting profile shows two (2) maxims, the maxima at the highest temperature is taken as the melting point within the range of melting of the disc sample relative to a baseline measurement for the increasing heat capacity of the polymer as a function of temperature. The percent crystallinity (X%) is calculated using the formula: [area under the curve (in J/g) / H° (in J/g)] * 100, where H° is the heat of fusion for the homopolymer of the maj or monomer component. The values for H° are to be obtained from the Polymer Handbook, Fourth Edition, published by John Wiley and Sons, New York 1999, except that a value of 290 J/g is used as the equilibrium heat of fusion (H°) for 100% crystalline polyethylene, a value of 140 J/g is used as the equilibrium heat of fusion (H°) for 100% crystalline polybutene, and a value of 207 J/g (H°) is used as the heat of fusion for a 100% crystalline polypropylene.

[0330] Unless otherwise noted all melting points (T_m) are DSC second melt. Example 1

Catalyst 1 Catalyst 2 Catalyst 3 Catalyst 4

[0331] Synthesis and the rheological properties of EPDM-PMS tetrapolymers. Sample 1 was prepared in a continuous stirred-tank reactor with a total pressure of 350 psi, a temperature of 100°C. Ethylene gas was added at rate of 6 standard liter per minute. Ethylidene norbomene (ENB) was added at a rate of 2 g/min, para-methylstyrene was added at a rate of 4 mL/min, isohexane was added at a rate of 42.7 g/min, catalyst 2 was added at a rate of 6.61 * 10^-7 mol/min, [ PhNMe₂H] [ B(C₆F₅)₄] was added at a rate of 6.61 * 10^-7 mol/min, and a scavenger (TnOAl) was added at a rate of 3.70 * 10^-6 mol/min. The reaction proceeded for 40 minutes under those conditions and Sample 1 was recovered from the reactor. The properties of Sample 1 and commercial grades of EPDM are compared in Table 1.

Table 1

V2504 is Vistalon™2504 elastomer, available from ExxonMobil Chemical Company, Baytown Texas.

V7001 is Vistalon™7001 elastomer, available from ExxonMobil Chemical Company, Baytown Texas.

[0332] Sample 1 exhibits characteristics of long-chain branching, as suggested by the Small-Amplitude Oscillatory Shear (SAOS) as shown on the left graph of Figure 1 and extensional rheology as shown on the right graph of Figure 1. The strain-hardening behavior is desirable for melt fabrication.

[0333] To examine the mechanical properties of the crosslinked rubber, sample 1 was cured using the following formulation at 74°C: polymer (100 phr), 388 Super Fine™ Sulfur (1 phr), diphenyl guanidine (0.2 phr), n-cyclohexyl-2-benzothiazolesulfenamide (0.2 phr), zinc stearate (0.5 phr). For comparison, commercial EPDM, Vistalon™ 2504 elastomer (C₂ = 58.0 wt%, C₃ = 37.3 wt%, ENB = 4.7 wt%) and Vistalon™ 7001 elastomer (C₂ = 73.0 wt%, C₃ = 22.0 wt%, ENB = 5.0 wt%) were compounded using the same formulation.

[0334] Sample 1 shows elastomeric behavior after crosslinking, as shown in Figure 2. Sample 1 shows strain-induced crystallization (SIC) during stretching, as evidenced by the 2D- WAXS patterns. SIC enhances the strength and fatigue properties desired in many applications (e.g., tires).

[0335] Filler acceptance is of significance in many commercial applications and can add stiffness, dimensional stability, upper service temperatures, tensile strength, damping characteristics, and fire resistance. To this end, sample 1 was blended with 10/20/30/40/50 wt% of fillers (carbons, silica, CaC03). Vistalon™ elastomer grades V2504 and V7001 were subjected to the same blending formulation for benchmarking.

[0336] Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It should be appreciated that ranges including the combination of any two values, e.g., the combination of any lower value with any upper value, the combination of any two lower values, and/or the combination of any two upper values are contemplated unless otherwise indicated. Certain lower limits, upper limits and ranges appear in one or more claims below. All numerical values are "about" or "approximately" the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art. [0337] Various terms have been defined above. To the extent a term used in a claim is not defined above, it should be given the broadest definition persons in the pertinent art have given that term as reflected in at least one printed publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.

[0338] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims

CLAIMS: What is claimed is:

1. A copolymer comprising units derived from ethylene, one or more α-olefins, one or more non-conjugated dienes, and one or more substituted styrene compounds.

2. The copolymer of claim 1 , wherein the copolymer is a random copolymer.

3. The copolymer of claim 1 or 2, wherein the α-olefin is propylene.

4. The copolymer of any preceding claim, wherein the substituted styrene compound is represented by the formula:

wherein each R², R³, R⁴, R⁵ and R⁶ is independently hydrogen or a C₁ to C₂₀ hydrocarbyl group, wherein at least one of R², R³, R⁴, R⁵ and R⁶ is not hydrogen.

5. The copolymer of any preceding claim, wherein the substituted styrene compound is para-alkylstyrene.

6. The copolymer of any preceding claim, wherein a molar ratio of ethylene derived units to the α-olefin derived units is about 5/95 to about 95/5.

7. The copolymer of any preceding claim, wherein the copolymer comprises about 0.01 wt% to about 40 wt% of the non-conjugated diene units based on a weight of the copolymer.

8. The copolymer of any preceding claim, wherein the copolymer comprises about 0.1 wt% to about 40 wt% of the styrene compound units based on a weight of the copolymer.

9. A composition comprising the copolymer of any preceding claim and an inorganic filler.

10. The copolymer of any preceding claim, wherein the non-conjugated diene is ethylidene norbomene.

11. The copolymer of any preceding claim, wherein the copolymer comprises: about 40 wt% to about 90 wt% of units derived from ethylene; about 9.8 wt% to about 59.8 wt% of units derived from the α-olefin; about 0.1 wt% to about 10 wt% of units derived from the non-conjugated diene; and about 0.1 wt% to about 15 wt% of units derived from the substituted styrene, based on a weight of the copolymer.

12. The copolymer of claim 11, wherein the α-olefin is propylene and the substituted styrene is a para-alkylstyrene.

13. The copolymer of claim 11, wherein the α-olefin is propylene, the non-conjugated diene is ethylidene norborene or vinyl norbomene, and the substituted styrene is para-alkylstyrene.

14. A composition comprising the copolymer of claim 11 and an inorganic filler.

15. The composition of claim 14, wherein the composition has about 25 wt% to about 60 wt% of the inorganic filler based on a combined weight of the inorganic filler and the copolymer.

16. The copolymer of any preceding claim, wherein the non-conjugated diene is ethylidene norbomene.

17. A process for producing a copolymer, comprising: contacting ethylene, a C₃ to C₂₀ α-olefin monomer, a non-conjugated diene monomer, and a substituted styrene monomer with a catalyst system comprising a single site catalyst compound, an activator, and an optional support; obtaining a copolymer comprising about 40 wt% to about 90 wt% of units derived from ethylene; about 9.8 wt% to about 59.8 wt% of units derived from the α-olefin; about 0.1 wt% to about 10 wt% of units derived from the non-conjugated diene; and about 0.1 wt% to about 15 wt% of units derived from the substituted styrene, based on a weight of the copolymer, wherein the copolymer has a strain hardening ratio of 2 or greater when an extensional viscosity is measured at a Hencky strain rate of 0.01 s^-1 to 10 s^-1 at a temperature of 190°C.

18. The process of claim 17, wherein the α-olefin is one or more of propylene, butene butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, or an isomer thereof; the substituted styrene is represented by the formula:

wherein each R², R³, R⁴, R⁵ and R⁶ is independently hydrogen or a C₁ to C₂₀ hydrocarbyl group, wherein at least one of R², R³, R⁴, R⁵ and R⁶ is not hydrogen; and the non-conjugated diene is selected from the group consisting of: 5-ethylidene-2-norbomene, 1,4-hexadiene, dicyclopentadiene, norbomadiene, 5-vinyl-2-norbomene, and combinations thereof.

19. The process of claim 17 or 18 wherein the single site catalyst compound is selected from the group consisting of: pyridyldiamido complexes, quinolinyldiamido complexes, phenoxyimine complexes, bisphenolate complexes, cyclopentadienyl-amidinate complexes, iron pyridyl bis(imine) complexes, and combinations thereof.

20. The process of claim 17, 18, or 19 wherein the single site catalyst compound is a metallocene catalyst.

21. A process for producing a copolymer, comprising: introducing an α-olefin monomer to a reaction vessel in an amount and under pressure sufficient to allow utilization of the α-olefin in a liquefied form as a polymerization diluent; introducing a non-conjugated diene monomer and a substituted styrene monomer to the diluent; adding ethylene monomer to the diluent to produce a mixture of the ethylene, the α-olefin, the substituted styrene, and the diene monomers; and, adding a catalyst system comprising a catalyst compound and an activator to the diluent; reacting the mixture for a time sufficient to permit polymerization of the ethylene, the α-olefin, the substituted styrene, and the diene monomers to produce a copolymer comprising about 40 wt% to about 90 wt% of units derived from ethylene; about 9.8 wt% to about 59.8 wt% of units derived from the α-olefin; about 0.1 wt% to about 10 wt% of units derived from the non-conjugated diene; and about 0.1 wt% to about 15 wt% of units derived from the substituted styrene, based on the weight of the copolymer, wherein the copolymer has a strain hardening ratio of 2 or greater when extensional viscosity is measured at a Hencky strain rate of 0.01 s^-1 to 10 s^-1 at a temperature of 190°C.

22. The process of claim 21, wherein the α-olefin monomer is propylene and the non- conjugated diene monomer is ethylidene norbomene.

23. The process of claim 21 or 22, wherein the catalyst compound is selected from the group consisting of: pyridyldiamido complexes, quinolinyldiamido complexes, phenoxyimine complexes, bisphenolate complexes, cyclopentadienyl-amidinate complexes, and iron pyridyl bis(imine) complexes, and combinations thereof.

24. The process of claim 21 or 22, wherein the catalyst compound is a metallocene catalyst.

25. An elastomer composition comprising a blend of: a ethylene-propylene-diene-substituted styrene copolymer comprising:

40 to 90 wt% propylene-derived units,

9.4 to 59.4 wt% ethylene-derived units,

0.3 to 10 wt% diene-derived units, and 0.3 to 10 wt% substituted styrene-derived units, based on a total weight of the copolymer, wherein the copolymer has a strain hardening ratio of 2 or greater when an extensional viscosity is measured at a Hencky strain rate of 0.01 s^-1 to 10 s^-1 at a temperature of 190°C; and a blend rubber comprising one or more elastomers wherein the one or more elastomers are not ethylene-propylene-diene-substituted styrene copolymers.

26. The elastomer composition of claim 25, wherein the blend comprises from 5 to 40 phr of the copolymer.

27. The elastomer composition of claim 25 or 26, wherein the one or more elastomers are selected from natural rubbers, polyisoprene rubber, poly(styrene-co-butadiene) rubber, polybutadiene rubber, poly(isoprene-co-butadiene) rubber, styrene-isoprene-butadiene rubber, butyl rubber, star branched butyl rubber, poly(isobutylene-co-alkylstyrene), polychloroprene rubber, nitrile rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, and combinations thereof.

28. The elastomer composition of claim 25 or 26, wherein the one or more elastomers comprise a natural rubber and a polybutadiene rubber, wherein the one or more elastomers comprises 5 to 80 phr of a natural rubber and 5 to 80 phr of a polybutadiene rubber.

29. The elastomer composition of claim 25, 26, 27, or 28, further comprising one or more of the following: a filler selected from the group consisting of: carbon black, modified carbon black, silica, precipitated silica, and combinations thereof; a chemical protectant selected from the group consisting of: waxes, antioxidants, antiozonants, and combinations thereof; a processing oil, resin or a combination thereof; and a curing package.