Polypropylene copolymers and processes for production thereof

Abstract

The present disclosure relates to polypropylene polymer compositions prepared using catalyst compounds comprising group 4 metal bis(phenolate) complexes, compositions comprising such polypropylene polymers, and processes to prepare such polymers. In some embodiments, a polymerization process comprising introducing into a first reactor, in a homogeneous phase, a solvent feed, a monomer feed comprising a propylene feed and ethylene feed wherein the ratio of propylene feed (kg / hr) to ethylene feed (kg / hr) is from about 5 to about 40 (kg / kg), and a catalyst system comprising an activator and a bis(phenolate) Lewis base catalyst compound, and obtaining a first copolymer effluent from the first reactor ("the first reactor effluent"); providing to the second reactor in a homogeneous phase, a solvent feed, a second monomer feed comprising propylene feed and ethylene feed wherein the ratio of propylene feed (kg / hr) to ethylene feed (kg / hr) is from about 10 to about 50 (kg / kg), and a catalyst system comprising an activator and a bis(phenolate) Lewis base catalyst compound (represented by Formula (I)), and obtaining a second copolymer effluent from the second reactor ("the second reactor effluent"); introducing the first reactor effluent into the second reactor, or combining the first reactor effluent with a second reactor effluent post reactor.

Description

Polypropylene Copolymers and Processes For Production Thereof PRIORITY CLAIM

[0001] This application claims the benefit of U.S. Provisional application Number 63 / 702,219, filed October 2, 2024, entitled “Polypropylene Copolymers and Processes For Production Thereof”, the entirety of which is incorporated by reference herein. CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This invention is related to: 1) U.S. Provisional Application Number 63 / 702,205, filed October 2, 2024; 2) U.S. Provisional Application Number 63 / 702,209, filed October 2, 2024; 3) U.S. Provisional Application Number 63 / 702,214, filed October 2, 2024; 4) U.S. Provisional Application Number 63 / 702,223, filed October 2, 2024; 5) concurrently filed PCT Application Number PCT / US2025 / ___, entitled “Polypropylene Copolymer Blends and Roofing Membranes Thereof” (attorney docket number 2024EM121- WO) 6) concurrently filed PCT Application Number PCT / US2025 / ___, entitled “Polypropylene Copolymers and Processes for Production Thereof” (attorney docket number 2024EM122-WO); 7) concurrently filed PCT Application Number PCT / US2025 / ___, entitled “High Melt Strength Propylene Based Elastomers Compositions for Elastic Blown or Cast Films” (attorney docket number 2024EM123-WO); and 8) concurrently filed PCT Application Number PCT / US2025 / ___, entitled “Polypropylene Copolymer Compositions and Films Thereof” (attorney docket number 2024EM125-WO). FIELD

[0003] The present disclosure relates to polypropylene copolymers prepared using catalyst compounds comprising group 4 metal bis(phenolate) complexes, compositions comprising suchpolypropylene copolymers, and processes to prepare such copolymers.BACKGROUND

[0004] Polypropylene copolymers are one of the well-known elastomer types and have received substantial commercial acceptance. Many of these copolymers are intermolecularly heterogeneous in terms of tacticity, composition (weight percent comonomers) or both. Alternatively, they can also be compositionally heterogeneous within a polymer chain (i.e. blocky). Polypropylene copolymers are known to have good properties such as weatherability, ozone resistance, and thermal stability. And the polymers have accepted wide utilities in automotive applications, as construction materials, and as carpet backing, among others. Theproperties of these polymers can be tailored for specific applications by means of control over molecular weight, molecular weight distribution, composition distribution, as well intermolecular structures.

[0005] Some polypropylene copolymers have been used in various applications because of their excellent elastomeric properties, easy processability, and good compatibility with a wide variety of materials. Such copolymers can have about 15-20 wt% ethylene to provide balance of crystallinity, softness / flexability, and elasticity. However, there is still a need to improve pellet stability at higher temperatures, without compromising the low temperature polymer properties such as temperature of glass transition (Tg). The pellet stability challenge is typically addressed by increasing the crystallinity of the polymers with a higher propylene content, which also results in an undesirable higher Tg, or by introducing a minor component of random copolymer (RCP) with a higher crystallinity and melt temperature. The added RCP has a low amount of ethylene content (e.g., about 4-10 wt%). Addition of RCP may add to the cost and reduces throughput of the overall polymer product (composition). In some cases, addition of RCP is needed in amounts of greater than 10 wt% of the overall polymer composition in order to obtain adequate pellet stability.

[0006] In WO 2021 / 162745, polypropylene polymers made by group 4 metal bis(phenolate) catalysts were disclosed. However, only monomodal polymers were disclosed.

[0007] There is a need for in-reactor processes to provide polypropylene polymers having pellet stability at high temperatures without compromising low temperature polymer properties (such as low glass transition temperature).

[0008] References for citing in an Information Disclosure Statement (37 C.F.R.1.97(h)): WO 2021 / 162745; U.S. Patent Nos.8,710,148, 8,013,069, 8,247,495. SUMMARY

[0009] The present disclosure relates to polypropylene copolymers prepared using catalyst compounds comprising group 4 metal bis(phenolate) complexes, compositions comprising such polypropylene copolymers, and processes to prepare such copolymers.

[0010] In some embodiments, a polymerization process includes introducing into a first reactor, in a homogeneous phase, a solvent feed, a monomer feed comprising a propylene feed and ethylene feed wherein the ratio of propylene feed (kg / hr) to ethylene feed (kg / hr) is from about 3 to about 30 (kg / kg). The process also includes introducing a catalyst system having an activator and a bis(phenolate) Lewis base catalyst compound and obtaining a first copolymer effluent from the first reactor (“the first reactor effluent”). The polymerization process includes providing to the second reactor in a homogeneous phase, a solvent feed, a second monomer feed comprisingpropylene feed and ethylene feed where the ratio of propylene feed (kg / hr) to ethylene feed (kg / hr) is from about 5 to about 65 (kg / kg), and a catalyst system having an activator and a bis(phenolate) Lewis base catalyst compound, and obtaining a second copolymer effluent from the second reactor (“the second reactor effluent”). The polymerization process includes introducing the first reactor effluent into the second reactor or combining the first reactor effluent with a second reactor effluent post reactor. The polymerization process includes obtaining a polymer comprising a first copolymer having from about 5 to about 30 wt% ethylene and about 70 to about 95 wt% propylene, and a second copolymer having an ethylene content at least about 3 wt% less than the ethylene content of the first copolymer, and where the second copolymer is from about 2 to about 40 wt% of the total polymer composition.

[0011] In some embodiments, a polypropylene polymer composition includes a first copolymer comprising about 5 to about 30 wt% ethylene units and about 70 to about 95 wt% propylene units. The first copolymer includes a mm triad tacticity of about 95% or greater, a r1r2of about 1 to about 3, a second copolymer having an ethylene content at least about 3 wt% less than the ethylene content of the first copolymer, where the second copolymer has a weight average molecular weight (Mw(LS)) that is less than the weight average molecular weight of the first copolymer, and where the composition of the second copolymer is 2 - 40 wt% of the total polymer composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] FIG.1 is a plant and process flow for polymerization, according to an embodiment.

[0013] FIG.2A is a pellet mill, according to an embodiment.

[0014] FIG.2B is a detailed depiction of the pelleting and cutting portion of the press of FIG. 2A, according to an embodiment. DETAILED DESCRIPTION

[0015] The present disclosure relates to polypropylene copolymers prepared using catalyst compounds comprising group 4 metal bis(phenolate) complexes, compositions comprising such polypropylene copolymers, and processes to prepare such copolymers.

[0016] The present disclosure relates to solution processes for polypropylene copolymers prepared using a catalyst family comprising transition metal complexes of a dianionic, tridentate ligand that features a central neutral donor group and two phenolate donors, where the tridentate ligands coordinate to the metal center to form two eight-membered rings. In complexes of this type, it is advantageous for the central neutral donor to be a heterocyclic group. It is particularly advantageous for the heterocyclic group to lack hydrogens in the position alpha to the heteroatom. In complexes of this type, it can also be advantageous for the phenolates to be substituted withone or more cyclic tertiary alkyl substituents.

[0017] It has been discovered that polypropylene polymers having bimodal composition distribution can be provided by polymerizations under various process conditions, such as (1) catalyst used, (2) concentration of ethylene and propylene (after introduced into the reactor), (3) molar ratio of propylene to ethylene in the reactor, and (4) reactor temperature.

[0018] Polypropylene polymers of the present disclosure can have improved pellet stability, good high and low temperature properties, such as melting temperature (Tm) and glass transition temperature (Tg), respectively, and softness as compared to conventional monomodal polypropylene polymers made by the bis(phenolate) Lewis base catalysts and bimodal polymers made by metallocene catalysts. For example, polypropylene polymers of the present disclosure can have low glass transition temperature (e.g., provided by higher ethylene content) for good low temperature performance. The higher ethylene content also provides softness, which would need to be balanced with pellet stability, which is provided by the RCP made by the catalysts of the present disclosure with higher crystallinity at the same ethylene conent than those made by metallocene catalysts. Other physical properties of polypropylene copolymers of the present disclosure can be comparable to those of the comparative polymers. Definitions

[0019] For the purposes of the present disclosure and the claims thereto, the following definitions shall be used:

[0020] 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.

[0021] “Catalyst productivity” is a measure of the mass of polymer produced using a known quantity of polymerization catalyst. Typically, “catalyst productivity” is expressed in units of (g of polymer) / (g of catalyst) or (g of polymer) / (mmols of catalyst) or the like. If units are not specified, then the “catalyst productivity” is in units of (g of polymer) / (grams of catalyst). For calculating catalyst productivity, only the weight of the transition metal component of the catalyst is used (i.e. the activator and / or co-catalyst is omitted). "Catalyst activity" is a measure of the mass of polymer produced using a known quantity of polymerization catalyst per unit time for batch and semi-batch polymerizations. For calculating catalyst productivity, only the weight of the transition metal component of the catalyst is used (i.e. the activator and / or co-catalyst is omitted). Typically, “catalyst activity” is expressed in units of (g of polymer) / (mmol of catalyst) / hour or (kg of polymer) / (mmols of catalyst) / hour or the like. If units are not specified, then the “catalyst activity” is in units of (g of polymer) / (mmol of catalyst) / hour.

[0022] "Conversion" is the percentage of a monomer that is converted to polymer product in a polymerization and is reported as % and is calculated based on the polymer yield, the polymer composition, and the amount of monomer fed into the reactor.

[0023] An “olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an "ethylene" content of 35 wt% to 55 wt%, it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer. A “polymer” has two or more of the same or different mer units. A “homopolymer” is a polymer having mer units that are the same. A “copolymer” is a polymer having two or more mer units that are different from each other. A “terpolymer” is a polymer having three mer units that are different from each other. Accordingly, the definition of copolymer, as used herein, includes terpolymers 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. An "ethylene polymer" or "ethylene copolymer" or “polyethylene copolymer” is a polymer or copolymer comprising at least 50 mole% ethylene derived units, a "propylene polymer" or "propylene copolymer" or “polypropylene copolymer” is a polymer or copolymer comprising at least 50 mole% propylene derived units, and so on. The terms “propylene polymer”, “propylene polymer composition”, “polypropylene polymer”, “polypropylene polymer compostition”, “propylene based polymer”, “propylene based polymer composition”, “polypropylene based polymer”, “polypropylene based polymer composition”, “polypropylene copolymer”, “polypropylene copolymer composition”, “propylene copolymer”, and “propylene copolymer composition” are used interchangeable.

[0024] Ethylene shall be considered an α-olefin.

[0025] Unless otherwise specified, the term “Cn” means hydrocarbon(s) having n carbon atom(s) per molecule, wherein n is a positive integer.

[0026] The term “hydrocarbon” means a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and / or unsaturated), including mixtures of hydrocarbon compounds having different values of n. Likewise, a “Cm-Cy” group or compound refers to a group or compound comprising carbon atoms at a total number thereof in the range from m to y. Thus, a C1-C50alkyl group refers to an alkyl group comprisingcarbon atoms at a total number thereof in the range from 1 to 50.

[0027] The terms “group,” “radical,” and “substituent” may be used interchangeably.

[0028] 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. Hydrocarbyls can be C1-C100radicals 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 naphthalenyl, and the like.

[0029] Unless otherwise indicated, (e.g., the definition of "substituted hydrocarbyl", 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 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.

[0030] 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.

[0031] The term "aryl" or "aryl group" means an aromatic ring (typically made of 6 carbon atoms) and the substituted variants thereof, such as phenyl, 2-methyl-phenyl, xylyl, 4-bromo- xylyl. Likewise, heteroaryl means an aryl group where a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, such as N, O, or S. As used herein, the term "aromatic" also refers to pseudoaromatic heterocycles which are heterocyclic substituents that have similar properties and structures (nearly planar) to aromatic heterocyclic ligands but are not by definition aromatic.

[0032] The term "substituted aromatic," means an aromatic group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group.

[0033] A "substituted phenolate" is a phenolate group where at least one, two, three, four or five hydrogen atoms in the 2, 3, 4, 5, and / or 6 positions has been replaced with at least one non- hydrogen group, such as a hydrocarbyl group, a heteroatom or 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), where the 1 position is the phenolate group (Ph-O-, Ph-S-, and Ph-N(R^)- groups, where R^ is hydrogen, C1-C40 hydrocarbyl, C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group). For example, a "substituted phenolate" group in the catalyst compounds described herein can be represented by the formula:where R18is hydrogen, C1-C40hydrocarbyl (such as C1-C40alkyl) or C1-C40substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, E17is oxygen, sulfur, or NR17, and each of R17, R19, R20, and R21is independently selected from hydrogen, C1-C40hydrocarbyl (such as C1-C40 alkyl) or C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or two or more of R18, R19, R20, and R21are joined together to form a C4-C62cyclic or polycyclic ring structure, or a combination thereof, and the wavy lines show where the substituted phenolate group forms bonds to the rest of the catalyst compound.

[0034] An "alkyl substituted phenolate" is a phenolate group where at least one, two, three, four or five hydrogen atoms in the 2, 3, 4, 5, and / or 6 positions has been replaced with at least one alkyl group, such as a C1 to C40, alternately C2 to C20, alternately C3 to C12 alkyl, such as methyl, ethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantanyl and the like including their substituted analogues.

[0035] An "aryl substituted phenolate" is a phenolate group where at least one, two, three,four or five hydrogen atoms in the 2, 3, 4, 5, and / or 6 positions has been replaced with at least one aryl group, such as a C1 to C40, alternately C2 to C20, alternately C3 to C12 aryl group, such as phenyl, 4-fluorophenyl, 2-methylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, mesityl, 2-ethylphenyl, naphthalenyl and the like including their substituted analogues.

[0036] 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.

[0037] A heterocyclic ring, also referred to as a heterocyclic, 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 means a heterocyclic ring having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group.

[0038] A substituted hydrocarbyl ring means a ring comprised of carbon and hydrogen atoms having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group.

[0039] For purposes of the present disclosure, in relation to catalyst compounds (e.g., substituted bis(phenolate) catalyst compounds), the term “substituted” means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom or 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.

[0040] A tertiary hydrocarbyl group possesses a carbon atom bonded to three other carbon atoms. When the hydrocarbyl group is an alkyl group, tertiary hydrocarbyl groups are also referred to as tertiary alkyl groups. Examples of tertiary hydrocarbyl groups include tert-butyl, 2- methylbutan-2-yl, 2-methylhexan-2-yl, 2-phenylpropan-2-yl, 2-cyclohexylpropan-2-yl, 1-methylcyclohexyl, 1-adamantyl, bicyclo[2.2.1]heptan-1-yl and the like. Tertiary hydrocarbyl groups can be illustrated by formula A:,wherein RA, RBand RCare hydrocarbyl groups or substituted hydrocarbyl groups that may optionally be bonded to one another, and the wavy line shows where the tertiary hydrocarbyl group forms bonds to other groups.

[0041] A cyclic tertiary hydrocarbyl group is defined as a tertiary hydrocarbyl group that forms at least one alicyclic (non-aromatic) ring. Cyclic tertiary hydrocarbyl groups are also referred to as alicyclic tertiary hydrocarbyl groups. When the hydrocarbyl group is an alkyl group, cyclic tertiary hydrocarbyl groups are also referred to as cyclic tertiary alkyl groups or alicyclic tertiary alkyl groups. Examples of cyclic tertiary hydrocarbyl groups include 1-adamantanyl, 1-methylcyclohexyl, 1-methylcyclopentyl, 1-methylcyclooctyl, 1-methylcyclodecyl, 1-methylcyclododecyl, bicyclo[3.3.1]nonan-1-yl, bicyclo[2.2.1]heptan-1-yl, bicyclo[2.3.3]hexan-1-yl, bicycle[1.1.1]pentan-1-yl, bicycle[2.2.2]octan-1-yl, and the like. Cyclic tertiary hydrocarbyl groups can be illustrated by formula B:, wherein RAis a hydrocarbyl group or substituted hydrocarbyl group, each RDis independently hydrogen or a hydrocarbyl group or substituted hydrocarbyl group, w is an integer from 1 to about 30, and RA, and one or more RD, and or two or more RDmay optionally be bonded to one another to form additional rings.

[0042] When a cyclic tertiary hydrocarbyl group contains more than one alicyclic ring, it can be referred to as polycyclic tertiary hydrocarbyl group or if the hydrocarbyl group is an alkyl group, it may be referred to as a polycyclic tertiary alkyl group.

[0043] The terms “alkyl radical,” and “alkyl” are used interchangeably throughout this disclosure. For purposes of this disclosure, "alkyl radical" is defined to be C1-C100 alkyls that may be linear, branched, or cyclic. Examples of such radicals can include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like including their substituted analogues. Substituted alkyl radicals are radicals in which at least one hydrogen atom of the alkyl radical has been substituted with at least a non-hydrogen group, such as a hydrocarbyl group, a heteroatom or 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.

[0044] Where isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl) reference to one member of the group (e.g., n-butyl) shall expressly disclose the remaining isomers (e.g., iso-butyl, sec-butyl, and tert-butyl) in the family. Likewise, reference to an alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer (e.g., butyl) expressly discloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, and tert- butyl).

[0045] 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 (g mol-1).

[0046] The following abbreviations may be used herein: Me is methyl, Et is ethyl, Pr is propyl, cPr is cyclopropyl, nPr is n-propyl, iPr is isopropyl, Bu is butyl, nBu is normal butyl, iBu is isobutyl, sBu is sec-butyl, tBu is tert-butyl, Oct is octyl, Ph is phenyl, MAO is methylalumoxane, dme is 1,2-dimethoxyethane, p-tBu is para-tertiary butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOA and TNOAL are tri(n-octyl)aluminum, p-Me is para-methyl, Bn is benzyl (i.e., CH2Ph), THF (also referred to as thf) is tetrahydrofuran, RT is room temperature (and is 23°C unless otherwise indicated), tol is toluene, EtOAc is ethyl acetate, Cbz is Carbazole, and Cy is cyclohexyl.

[0047] A “catalyst system” is a combination comprising at least one catalyst compound and at least one activator. When "catalyst system" is used to describe such a pair before activation, it means the unactivated catalyst complex (precatalyst) together with an activator and, optionally, a co-activator. When it is used to describe such a pair after activation, it means the activated complex and the activator or other charge-balancing moiety. The transition metal compound may be neutral as in a precatalyst, or a charged species with a counter ion as in an activated catalyst system. For the purposes of the present disclosure and the claims thereto, when catalyst systems are described as comprising neutral stable forms of the components, it is well understood by one of ordinary skill in the art, that the ionic form of the component is the form that reacts with the monomers to produce polymers. A polymerization catalyst system is a catalyst system that canpolymerize monomers to polymer.

[0048] In the description herein, the catalyst may be described as a catalyst, a catalyst precursor, a pre-catalyst compound, catalyst compound or a transition metal compound, and these terms are used interchangeably.

[0049] An “anionic ligand” is a negatively charged ligand which donates one or more pairs of electrons to a metal ion. The term “anionic donor” is used interchangeably with “anionic ligand”. Examples of anionic donors in the context of the present disclosure include, but are not limited to, methyl, chloride, fluoride, alkoxide, aryloxide, alkyl, alkenyl, thiolate, carboxylate, amido, methyl, benzyl, hydrido, amidinate, amidate, and phenyl. Two anionic donors may be joined to form a dianionic group.

[0050] A “neutral Lewis base or “neutral donor group” is an uncharged (i.e. neutral) group which donates one or more pairs of electrons to a metal ion. Non-limiting examples of neutral Lewis bases include ethers, thioethers, amines, phosphines, ethyl ether, tetrahydrofuran, dimethylsulfide, triethylamine, pyridine, alkenes, alkynes, allenes, and carbenes. Lewis bases may be joined together to form bidentate or tridentate Lewis bases.

[0051] For purposes of the present disclosure and the claims thereto, phenolate donors include Ph-O-, Ph-S-, and Ph-N(R^)- groups, where R^ is hydrogen, C1-C40hydrocarbyl, C1-C40substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, and Ph is optionally substituted phenyl.

[0052] The term “multimodal,” when used to describe a polymer or polymer composition, means “multimodal molecular weight distribution,” which is understood to mean that the Gel Permeation Chromatography (GPC) trace, plotted as Absorbance versus Retention Time (seconds), has more than one peak or at least one inflection points and / or “multimodal ethylene content distribution” which is understood to mean that the Solvent Gradient Interactive Chromatography (SGIC) trace, plotted as concentration versus elution volume, has more than one peak or at least one inflection points. An “inflection point” is that point where the second derivative of the curve changes in sign (e.g., from negative to positive or vice versa). For example, a polyolefin composition that includes a first lower molecular weight polymer and / or ethylene content component and a second higher molecular weight polymer and / or ethylene content component can be considered to be a “bimodal” polyolefin composition if an inflection point is observed. For example, the Mw values of the high molecular weight polymer and low molecular weight polymer differ by at least 5%, relative to each other, such as by at least 10%, such as by at least 20%, such as at least 50%, such as by at least 100%, such as by a least 200%, which can be indicated by a lower MFR of the high molecular weight polymer than that of the low molecularweight polymer. For example, the ethylene content values of the high ethylene content polymer and low ethylene content polymer differ by at least 2 wt%, such as by at least 4 wt%, such as at least 6 wt%, such as by at least 8 wt%, such as by a least 10 wt%.

[0053] The term “mole fraction” should be considered as “mol%” / 100, e.g., 0.01 mole fraction is 1 mol%. Polymerization Processes

[0054] Solution polymerization processes can be used to carry out polymerizations of the present disclosure in any suitable manner known to one having ordinary skill in the art. In some embodiments, the polymerization processes may be carried out in continuous polymerization processes. The term “batch” refers to processes in which the complete reaction mixture is withdrawn from the polymerization reactor vessel at the conclusion of the polymerization reaction. In contrast, in a continuous polymerization process, one or more reactants are introduced continuously to the reactor vessel and a solution comprising the polymer product is withdrawn concurrently or near concurrently. 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 is typically homogeneous. A homogeneous polymerization is one where the polymer product is dissolved in the polymerization medium. Such systems are preferably not turbid as described in J. Vladimir Oliveira, et al. (2000) Ind. Eng. Chem. Res., v.29, pgs.4627.

[0055] In a typical solution process, catalyst components, solvent, monomers and hydrogen (when used) are fed under pressure to one or more reactors. Catalyst components may be pre- mixed prior to entering the reactor, or the pre-catalyst and the activator may be fed into the reactor separately. Temperature control in the reactor can generally be obtained by balancing the heat of polymerization and with reactor cooling by reactor jackets or cooling coils to cool the contents of the reactor, auto refrigeration, pre-chilled feeds, vaporization of liquid medium (diluent, monomers or solvent) or combinations of all three. Adiabatic reactors with pre-chilled feeds can also be used. The monomers are dissolved / dispersed in the solvent either prior to being fed to the first reactor or dissolve in the reaction mixture. The solvent and monomers are generally purified to remove potential catalyst poisons prior entering the reactor. The feedstock may be heated or cooled prior to feeding to the first reactor. Additional monomers and solvent may be added to the second reactor, and it may be heated or cooled. The catalysts / activators can be fed in the first reactor or split between two reactors. In solution polymerization, polymer produced is soluble and remains dissolved in the solvent under reactor conditions, forming a polymer solution (also referred as to effluent).

[0056] A solution polymerization process of the present disclosure can use a stirred tank reactor system including one or more stirred polymerization reactors. Generally, the reactors should be operated under conditions to achieve a thorough mixing of the reactants. In a multiple reactor system, in some embodiments, the first polymerization reactor can operate at a lower temperature than the second reactor. In some embodiments, the first polymerization reactor can operate at a higher temperature than the second reactor. The residence time in each reactor will depend on the design and the capacity of the reactor. The catalysts / activators can be fed into the first reactor only or split between two reactors.

[0057] In some embodiments, a multiple reactor system can include loop reactors or plug flow reactors. For example, Figure 1 shows a schematic lay-out of a plant according to the invention and a process flow according to the invention. A feed for polymerization is passed through conduit (2) by a centrifugal pump (3). The feed contains A) hexane as solvent, B) monomer, generally the predominant monomer is ethylene or propylene, and C) comonomer which may be any copolymerizable alpha-olefin, and D) a diene or other polyene or cyclic copolymerizable material. The feed is passed through a chiller 6 in which the feed is optionally chilled to a low temperature for subsequent adiabatic polymerization in the two continuous reactors 8 which may be operated in parallel or in series (only one of which reactors is shown in the drawings). Activator and metallocene catalyst may be premixed and added at (5) and / or (7) to one or both reactors (8). Tri-Octyl aluminum is added at (4) to minimize the impact of poisons in the feed and in the reactor on the catalyst activity. The solution, containing polymer, which emerges from the reactors (8) through a conduit (11), is first treated with a catalyst killer, preferably water, added at (10) in a molecular solution in hexane solvent to terminate the polymerization reaction. A heat exchanger (12) is arranged as part of a heat integrating arrangement and heated by a lean phase merging from an upper layer (20) in a liquid phase separator (14), and provides an initial increase in the temperature of the polymer solution in the conduit (11). A trim heat exchanger (16), operating by using steam, hot oil or other high temperature fluid, further increases the temperature to a level suitable for liquid phase separation. The solution then passes through a let down valve (18) where a pressure drop is created which causes the separation of the polymer solution and settlement into the lean phase (20) and a polymer rich phase (22) below it. It is important to note that no energy consuming pump is required to provide a pressure increase in the conduit (11) between the reactors (8) and the separator (14) as the polymer containing solution is propelled by the pressure from the pump (3).The lean phase (20), after being cooled by the heat exchanger (12), aforementioned, is cooled further by a cooling device (24), passed through a surge tank (26) and then submitted to in-line chemical analysis at to determine the concentration of monomer and comonomer in the solvent. This cooled lean phase (22) is combined with fresh feed of solvent and monomer at (30) to provide in combination the desired concentrations and then passed through a drier (32) which serves to remove any unreacted water used as the catalyst killer or present in the fresh feed supplied or any impurity in the recycled solvent and monomer.

[0058] A polymer can be recovered from the effluent of either reactor or the combined effluent, by separating the polymer from other constituents of the effluent. Conventional separation means may be employed. For example, polymer can be recovered from effluent by coagulation with a non-solvent such as isopropyl alcohol, acetone, or n-butyl alcohol, or the polymer can be recovered by heat and vacuum stripping the solvent or other media with heat or steam. One or more conventional additives such as antioxidants can be incorporated in the polymer during the recovery procedure. The methods of recovery envisioned is by the use of lower critical solution temperature (LCST) followed by devolatilization .

[0059] Suitable diluents / solvents for conducting the polymerization reaction include non- coordinating, inert liquids. In particular embodiments, the reaction mixture for the solution polymerization reactions disclosed herein may include at least one hydrocarbon solvent. 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™); halogenated and perhalogenated hydrocarbons, such as perfluorinated C4-C10alkanes, chlorobenzene, and mixtures thereof; and aromatic and alkyl-substituted aromatic compounds, such as benzene, toluene, mesitylene, ethylbenzene, xylene, and mixtures thereof. Mixtures of any of the foregoing hydrocarbon solvents may also be used. Suitable solvents also include liquid olefins which may act as monomers or co-monomers including ethylene, propylene, 1-butene, 1- hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In another embodiment, the solvent is not aromatic, such as aromatics are present in the solvent at less than 1 wt%, such as less than 0.5 wt%, such as less than 0 wt% based upon the weight of the solvents.

[0060] Any olefinic feed can be polymerized using polymerization methods and solution polymerization conditions disclosed herein. Suitable olefinic feeds may include any C2-C40 alkene, which may be straight chain or branched, cyclic or acyclic, and terminal or non-terminal,optionally containing heteroatom substitution. In more specific embodiments, the olefinic feed may comprise a C2-C20 alkene, particularly linear alpha olefins, such as, for example, ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, or 1-dodecene. Other suitable olefinic monomers may include ethylenically unsaturated monomers, vinyl monomers and cyclic olefins. Non-limiting olefinic monomers may also include norbornene, isobutylene, isoprene, vinylbenzocyclobutane, styrene, alkyl substituted styrene, cyclopentene, and cyclohexene. Any single olefinic monomer or any mixture of olefinic monomers may undergo polymerization according to the disclosure herein. Alternately, diene is absent from the olefinic feed used herein.

[0061] In more particular embodiments, the one or more olefinic monomers present in the reaction mixtures disclosed herein comprise at least ethylene and propylene.

[0062] Polymerizations can be run at any temperature and / or pressure suitable to obtain the desired polymers. Solution polymerization conditions suitable for use in the polymerization processes disclosed herein include temperatures ranging from about 0°C to about 300°C, or from about 20°C to about 200°C, or from about 35°C to about 180°C or from about 70°C to about 140°C. Pressures may range from about 0.1 MPa to about 15 MPa, or from about 0.2 MPa to about 12 MPa, or from about 0.5 MPa to about 10 MPa, or from about 1 MPa to about 7 MPa. Polymerization run times (residence time) may range up to about 300 minutes, particularly in a range from about 5 minutes to about 250 minutes, or from about 10 minutes to about 120 minutes.

[0063] Small amounts of hydrogen, for example 1-5,000 parts per million (ppm) by weight, based on the total solution fed to the reactor may be added to one or more of the feed streams of the reactor system in order to improve control of the melt index and / or molecular weight distribution. In some embodiments, hydrogen may be included in the reactor vessel in the solution polymerization processes. According to various embodiments, the concentration of hydrogen gas in the reaction mixture may range up to about 5,000 ppm, or up to about 4,000 ppm, or up to about 3,000 ppm, or up to about 2,000 ppm, or up to about 1,000 ppm, or up to about 500 ppm, or up to about 400 ppm, or up to about 300 ppm, or up to about 200 ppm, or up to about 100 ppm, or up to about 50 ppm, or up to about 10 ppm, or up to about 1 ppm. In some or other embodiments, hydrogen gas may be present in the reactor vessel at a partial pressure of about 0.007 to 345 kPa, or about 0.07 to 172 kPa, or about 0.7 to 70 kPa.

[0064] In at least one embodiment, the catalyst productivity for the polypropylene copolymer in the polymerization process is 100,000 kg polymer per kg of catalyst or more, 200,000 kg polymer per kg of catalyst or more, 300,000 kg polymer per kg of catalyst or more, 400,000 kg polymer per kg of catalyst or more, 500,000 kg polymer per kg of catalyst or more.

[0065] The ethylene concentration in the first reactor can be 2 mole / liter or less, or 1.5mole / liter or less, or 1.0 mole / liter or less, 0.5 mole / liter or less, or 0.03 mole / liter or more, or 0.05 mole / liter or more, or 0.07 mole / liter or more, or 0.09 mole / liter or more, such as about 0.05 mole / liter to about 2 mole / liter, such as about 0.09 mole / liter to about 0.5 mole / liter. The propylene concentration in the first reactor can be 3 mole / liter or less, or 2.9 mole / liter or less, or 2.8 mole / liter or less, or 0.2 mole / liter or more, or 0.4 mole / liter or more, or 0.6 mole / liter or more, or 0.75 mole / liter or more, such as about 0.5 mole / liter to about 3 mole / liter, such as about 0.75 mole / liter to about 2.8 mole / liter. In some embodiments, a flow ratio of propylene feed (kg / hr) to ethylene feed (kg / hr) of the first reactor is about 3 to about 30, such as about 4 to about 25, such as about 5 to about 20, such as about 6 to about 10, such as about 6.2 to about 9.

[0066] The ethylene concentration in the second reactor can be 1 mole / liter or less, or 0.7 mole / liter or less, or 0.5 mole / liter or less, or 0.4 mole / liter or less, or 0.31 mole / liter or less, or 0.01 mole / liter or more, or 0.02 mole / liter or more, or 0.024 mole / liter or more, such as about 0.005 mole / liter to about 1 mole / liter, such as about 0.024 mole / liter to about 0.31 mole / liter. The propylene concentration in the second reactor can be 3 mole / liter or less, or 2.8 mole / liter or less, or 2.6 mole / liter or less, or 2.4 mole / liter or less, or 0.2 mole / liter or more, or 0.5 mole / liter or more, or 0.8 mole / liter or more, or 1 mole / liter or more, or 1.2 mole / liter or more, or 1.3 mole / liter or more, such as about 0.25 to about 3 mole / liter, such as about 1.3 mole / liter to about 2.4 mole / liter. In some embodiments, a flow rate ratio of propylene feed (kg / hr) to ethylene feed (kg / hr) of the second reactor is about 5 to about 65, such as about 8 to about 50, such as about 10 to about 40, such as about 12 to about 38, such as about 14 to about 36.

[0067] The feed temperature of the first reactor and the second reactor can be about -20 ⁰C to about 50 ⁰C, or about -10 ⁰C to about 40 ⁰C, or about 0 ⁰C to about 35 ⁰C, or about 8 ⁰C to about 31 ⁰C.

[0068] The reactor pressure can be about 500 psig to about 2000 psig, or about 1000 psig to about 1900 psig, or about 1300 psig to about 1800 psig, or about 1500 psig to about 1700 psig,

[0069] The H2 / C3 feed ratio of the first reactor can be about 0 to about 3 (g / kg), or about 0 to about 2 (g / kg), or about 0 to about 1 (g / kg), or about 0 to about 0.5 (g / kg), or about 0 to about 0.1 (g / kg). The H2 / C3 feed ratio of the second reactor can be about 0 to about 5 (g / kg), or about 0.2 to about 4 (g / kg), or about 0.4 to about 3 (g / kg), or about 0.5 to about 2 (g / kg), or about 0.6 to about 1 (g / kg), or about 0.63 to about 0.9 (g / kg). The H2 concentration in the first reactor can be about 0 to about 0.05 mole / L, or about 0 to about 0.02 mole / L, or about 0 to about 0.01 mole / L. The H2 concentration in the second reactor can be about 0 to about 0.4 mole / L, or about 0 to about 0.2 mole / L, or about 0 to about 0.1 mole / L, or about 0 to about 0.05 mole / L, or about 0 to about 0.01 mole / L.

[0070] In some embodiments, the molar ratio of propylene to ethylene in the first reactor is about 2 to about 20, such as about 3 to about 17, such as about 3.5 to about 15, such as about 3.8 to about 12, such as about 4 to about 10.

[0071] In some embodiments, the molar ratio of propylene to ethylene in the second reactor is about 4 to about 70, such as about 4.5 to about 60, such as about 4 to about 50.

[0072] In some embodiments, a reactor temperature of the first reactor is about 60oC to about 140oC, such as about 65oC to about 120oC, such as about 65oC to about 95oC, such as about 70oC to about 85oC, such as about 70oC to about 83oC.

[0073] In some embodiments, a reactor temperature of the second reactor is about 60oC to about 110oC, such as about 70oC to about 95oC, such as about 73oC to about 80oC, such as about 74oC to about 77oC, such as about 75oC. Alternatively, a reactor temperature of the second reactor is about 120oC to about 150oC, such as about 130oC to about 145oC, such as about 130oC to about 140oC, such as about 133oC to about 137oC, such as about 135oC.

[0074] In at least one embodiment, monomer conversion of the first reactor is 25% or more, or 30% or more, or 36% or more, or 40% or more. In some embodiments, ethylene conversion of the first reactor is about 40% to about 95%, such as about 50% to about 90%, such as about 55% to about 80%, such as about 57% to about 70%, such as about 58% to about 66%. In some embodiments, propylene conversion of the first reactor is about 25% to about 85%, such as about 25% to about 75%, such as about 25% to about 65% such as about 30% to about 60%, such as about 32% to about 50%, such as about 33% to about 40%.

[0075] In at least one embodiment, monomer conversion of the second reactor is 25% or more, or 35% or more, or 45% or more, or 50% or more, or 25 wt% to about 75%, or 41% to about 55%. In some embodiments, ethylene conversion of the second reactor is about 45% to about 95%, such as about 50% to about 85%, such as about 55% to about 80%. In some embodiments, propylene conversion of the second reactor is about 25% to about 75%, such as about 37% to about 70%, such as about 39% to about 60%, such as about 41% to about 54%.

[0076] It was discovered that the catalyst has the capability of producing high molecular weight and high tacticity polypropylene copolymer at high polymerization temperatures. In at least one embodiment, the polymerization temperatures in the polymerization process is 65°C or higher, 80°C or higher. Molecular weight of the polypropylene copolymer decreases with polymerization temperature and increases with monomer concentration in the reaction media.

[0077] In some embodiments, the polymerization of the first reactor: 1) is conducted at temperatures of 65°C or higher, such as about 70oC to about 82oC 2) ethylene concentration of about 0.09 mole / liter to about 0.48 mole / liter; 3) propylene concentration of about 0.75 mole / literto about 2.85 mole / liter; 4) molar ratio of propylene to ethylene of about 4.4 to about 4.9; 5) a flow rate ratio of propylene feed to ethylene feed of about 6.2 to about 8.9; 6) is conducted at a pressure of atmospheric pressure to 15 MPa (such as about 0.35 to about 12 MPa, such as about 0.45 to about 10 MPa, such as about 0.5 to about 10 MPa); 7) is conducted in an aliphatic hydrocarbon solvent (such as, isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; such as where aromatics (such as toluene) are present in the solvent at less than 1 wt%, such as less than 0.5 wt%, such as at 0 wt% based upon the weight of the solvents); 8) the polymerization occurs in one reaction zone; 9) a monomer conversion of of about 36% to about 44%

[0078] In some embodiments, the polymerization of the second reactor: 1) is conducted at temperatures of about 70oC to about 80oC, such as about 75C, or about 130oC to about 140oC, such as about 135oC; 2) ethylene concentration of about 0.02 mole / liter to about 0.14 mole / liter; 3) propylene concentration of about 1.3 mole / liter to about 2.5 mole / liter; 4) molar ratio of propylene to ethylene of about 9.5 to about 24; 5) a flow rate ratio of propylene feed to ethylene feed of about 14 to about 36; 6) is conducted at a pressure of atmospheric pressure to 15 MPa (such as about 0.35 to about 12 MPa, such as about 0.45 to about 10 MPa, such as about 0.5 to about 10 MPa); 7) is conducted in an aliphatic hydrocarbon solvent (such as, isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; such as where aromatics (such as toluene) are present in the solvent at less than 1 wt%, such as less than 0.5 wt%, such as at 0 wt% based upon the weight of the solvents); 8) the polymerization occurs in one reaction zone; 9) a monomer conversion of about 41% to about 55%.

[0079] In embodiments herein, processes relate to homogeneous polymerization processes where monomers (such as propylene), and optionally comonomer, are contacted with a catalyst system comprising an activator and at least one catalyst compound, as described above. The catalyst compound and activator may be combined in any order and may or may not be combined prior to contacting with the monomers in the reactor.

[0080] In at least one embodiment, the catalyst and the activator can be fed into the polymerization reactor in a form of dry powder or slurry without the need of preparing a homogenous catalyst solution by dissolving the catalyst into a carrying solvent. Catalyst and activator can be mixed prior to entering the reactor or contacted in the reactor. Separate solutions of catalyst and activator may be each be fed into the reactor.

[0081] A "reaction zone" also referred to as a "polymerization zone" is a vessel where polymerization takes place, for example a batch reactor. When multiple reactors are used in either series or parallel configuration, each reactor is considered as a separate polymerization zone. For a multi-stage polymerization in both a batch reactor and a continuous reactor, each polymerization stage is considered as a separate polymerization zone. In at least one embodiment, the polymerization occurs in one reaction zone. Alternatively, two reactors in either series or parallel configuration can be used for polymerization of polypropylene copolymers.

[0082] In at least one embodiment, the polymerization process includes two or more reactors in parallel configuration. In this configuration, the polymer effluent from each reactor meets post reactor to form a combined effluent stream. The polypropylene copolymers produced from each reactor have different molecular weight and composition. In some embodiments, one reactor is used to produce polypropylene copolymer with lower ethylene content and lower molecular weight than that produced from the second reactor. The mixture of the two reactor products has bimodal composition distribution. For example, the effluent from the two reactors are mixed or blended together and form a single stream for product recovery and finishing.

[0083] In at least one embodiment, the polymerization process includes two or more reactors in series configuration. In this configuration, the polymer effluent from the first reactor flows into the second reactor. In at least one embodiement, the polymerization process includes two or more reactors in parallel configuration. In this configuration, the polymer effluent from the first reactor and the polymer effluent from the second reactor combine downstream of both reactors. In some embodiments, the catalyst may be fed into the first reactor only. Alternatively, the catalyst feed is split between the reactors. Alternatively, the catalyst or multiple catalysts can be fed to both reactors separately. Typically, monomerr feeds are fed into both reactors. Alternatively, one monomer is fed into one reactor and another monomer is fed into the other reactor. The polypropylene copolymers produced from each reactor can have the same or different molecular weight. In some embodiments, one reactor is used to produce polypropylene copolymer with lower molecular weight than that produced from the second reactor. The mixture of the two reactor products can have a bimodal molecular weight distribution. Downstream of the reactor or reactors, the polymerization can be terminated by addition of a quenching agent. This quenching agent can be any heteroatomic compound that readily neutralizes the polymerization reaction. Alternatively, the quenching agent can be withheld to allow continued polymerization and yield polymers with broader molecular weight and composition distribution.

[0084] Polypropylene copolymers of the second reactor can be produced at polymer concentration is 8 wt% or more, or 10 wt% or more, or 15 wt% or more, or 20 wt% or more,

[0085] A final polypropylene copolymer product (e.g., dried effluent from a parallel or series reactor configuration) can have about 2 wt% to about 40 wt% (such as 5 wt% to about 35 wt%, or such as 10 wt% to about 30 wt%) polymer formed from the second reactor and about 60 wt% to about 98 wt% (such as 65 wt% to about 95 wt%, or such as 70 wt% to about 90 wt%)polymer formed from the first reactor. In some embodiments, a polypropylene copolymer has about 2 wt% to about 20 wt% polymer formed from the second reactor, such as about 5 wt% to about 15 wt%, such as about 10 wt% to about 15 wt%, alternatively about 2 wt% to about 10 wt%, such as about 2 wt% to about 5 wt%, alternatively about 20 wt% to about 40 wt%, such as about 25 wt% to about 35 wt%.

[0086] In some embodiments, the weight average molecular weight (Mw(LS)) of the first polymer component (of the first reactor) is greater than that of the second polymer component (of the second reactor), which is indicated by the lower MFR of the first polymer component than that of the second polymer component and that of the polypropylene copolymer. In some embodiments, the weight average molecular weight of the final polypropylene copolymer product is about 100,000 g / mol to about 500,000 g / mol, or about 100,000 g / mol to about 400,000 g / mol, or about 150,000 g / mol to about 400,000 g / mol, or about 200,000 g / mol to about 300,000 g / mol. In some embodiments, the number average molecular weight (Mn(LS)) of the final polypropylene copolymer product is about 10,000 g / mol to about 350,000 g / mol, or about 20,000 g / mol to about 250,000 g / mol, or about 30,000 g / mol to about 200,000 g / mol, or about 30,000 g / mol to about 175,000 g / mol. In some embodiments, the z-average molecular weight (Mz(LS)) of the final polypropylene copolymer product is about 200,000 g / mol to about 800,000 g / mol, or about 300,000 g / mol to about 700,000 g / mol, or about 380,000 g / mol to about 650,000 g / mol.

[0087] In some embodiments, the MFR(g / 10 min, 230 ⁰C / 2.16kg) of the second copolymer is higher such as at least about 25% higher, such as at least about 50% higher, such as at least about 75% higher, such as at least about 100% higher than than the MFR(g / 10 min, 230 ⁰C / 2.16kg) of the first copolymer.

[0088] In some embodiments, the polypropylene copolymer produced has a Mw(LS) / Mn(LS) value of about 1.5 to about 15, alternatively about 1.7 to about 12, alternatively about 1.8 to about 10.

[0089] In some embodiments, the polypropylene copolymer produced has a melt flow rate (MFR) of 20 g / 10 minutes or less, 10 g / 10 minutes or less, or 5 g / 10 minutes or less, or 3 g / 10 minutes or less, or 1 g / 10 minutes or less, such as about 0.1 g / 10 minutes to about 2 g / 10 minutes, such as about 0.2 g / 10 minutes to about 1 g / 10 minutes, such as about 0.3 g / 10 minutes to about 0.9 g / 10 minutes, such as about 0.4 g / 10 minutes to about 0.9 g / 10 minutes, such as about 0.6 g / 10minutes to about 1 g / 10 minutes, alternatively about 1 g / 10 minutes to about 5 g / 10 minutes, such as about 1.5 g / 10 minutes to about 3.5 g / 10 minutes.

[0090] In some embodiments, the polypropylene copolymer produced has the first copolymer component comprising about 5 to about 30 wt%, or about 10 to about 26 wt%, or about 15 to about 25 wt%, or about 16 to about 24 wt%, or about 17 to about 23 wt%, or about 18 to about 22 wt% ethylene units and about 70 to about 95 wt%, or about 74 to about 90 wt%, or about 75 to about 85 wt%, or about 76 to about 84 wt%, or about 77 to about 83 wt%, or about 72 to about 82 wt% propylene units and a second copolymer comprising an ethylene content at least about 3 wt% less, or about 5 wt% less, or about 7 wt% less, or about 9 wt% less, or about 10 wt% less than the ethylene conent of the first copolymer.

[0091] In some embodiments, the polypropylene copolymer produced has a glass transition temperature (Tg) of 0°C or less, -5°C or less, -10°C or less, -20°C or less, such about -20oC to about -45oC, such as about -30oC to about -36oC, such as about -30oC to about -35oC, according to ASTM D3418-03.

[0092] In some embodiments, the polypropylene copolymer produced has a heat of fusion (Hf) of about 50 J / g or less, about 30 J / g or less, about 25 J / g or less, or about 21 J / g or less. In another embodiment, the polypropylene copolymer produced can have a heat of fusion of at least 1 J / g, or at least 5 J / g, or at least 10 J / g, or at least 15 J / g, or at least 20 J / g. For example, the polypropylene copolymer produced can have a heat of fusion of about 1 J / g to about 25 J / g, such as about 3 J / g to about 8 J / g, alternatively about 18 J / g to about 25 J / g.

[0093] In some embodiments, the second polymer (second polypropylene copolymer) has a heat of fusion of 100 J / g or less, 80 J / g or less, 70 J / g or less. In another embodiment, the second polymer (second polypropylene copolymer) can have a heat of fusion of at least 1 J / g, or at least 5 J / g, or at least 10 J / g, or at least 15 J / g, or at least 20 J / g. For example, the second polymer (second polypropylene copolymer) can have a heat of fusion of about 1 J / g to about 25 J / g, such as about 10 J / g to about 50 J / g, alternatively about 20 J / g to about 70 J / g.

[0094] In some embodiments, the first polymer (first polypropylene copolymer) has a heat of fusion of 20 J / g or less, 10 J / g or less, 5 J / g or less, 2 J / g or less, 1 J / g or less. In at least one embodiment, the second polymer (second polypropylene copolymer) of the present disclosure can has a melt temperature (Tm) of about 50 °C to about 140°C, such as about 60°C to about 135°C, such as about 70°C to about 130°C, such as about 80°C to about 128°C, alternatively about 87oC to about 125oC.

[0095] In some embodiments, the polypropylene copolymer produced has an mm triad tacticity of about 75% or greater, or about 85% or greater, or about 90% or greater, or about 93%or greater, or about 95% or greater, or about 96% or greater, or about 97% or greater.

[0096] In some embodiments, the polypropylene copolymer produced has an r1r2 in a range of 1 to 3.0, alternatively from 1.2 to 3.0, alternatively from 1.4 to 3.0, alternatively from 1.4 to 3.0, alternatively from 1.4 to 3.0, alternatively from 1.2 to 2.0, alternatively from 1.4 to 1.8. In some embodiments, the r1r2 is greater than 1.0, such as greater than 1.1 and with an upper limit of 3.0, alternatively 2.8, alternatively 2.5, alternatively 2.2, alternatively 2.0. In some embodiments, the r1r2 of the polypropylene copolymer is greater than 1.12-(0.0157x), where x is the wt% of ethylene, as measured by 13C NMR.

[0097] In some embodiments, the polypropylene copolymer produced has has total regio defects (also called regio errors) from 0.01 to 1.2 mol%, such as from 0.1 to 1.2 mol%, alternatively from 0.1 to 1.15 mol%, alternatively from about 0.3 to about 1.15 mol%, alternatively about 0.4 to about 1.15 mol%.

[0098] In some embodiments, the polypropylene copolymer produced has an [PPP] triad content of about 40 mol% to about 60 mol%, such as about 43 mol% to about 58 mol%, such as about 45 mol% to about 55 mol%, such as about 45 mol% to about 50 mol%, as determined by13C nuclear magnetic resonance (13C NMR). (“P” is propylene). In some embodiments, the polypropylene copolymer produced has an [EEE] triad content of about 0.5 mol% to about 4 mol%, about 1 mol% to about 4 mol%, such as about 1.1 mol% to about 4.0 mol%, such as about 1.1 mol% to about 3.8 mol%, such as about 1.5 mol% to about 3.8 mol%, such as about 2 mol% to about 3.8 mol%, as determined by13C NMR). (“E” is ethylene). In some embodiments, the polypropylene polymer produced has an [EEP] triad content of about 5 mol% to about 12 mol%, such as about 6 mol% to about 11 mol%, such as about 6 mol% to about 10 mol%, as determined by 13C NMR). In some embodiments, the polypropylene polymer produced has an [PEP] triad content of about 8 mol% to about 15 mol%, such as about 10 mol% to about 14 mol%, such as about 11 mol% to about 14 mol%, as determined by 13C NMR). In some embodiments, the polypropylene polymer produced has an [EPE] triad content of about 3 mol% to about 8 mol%, such as about 4 mol% to about 7 mol%, such as about 4 mol% to about 6 mol%, as determined by 13C NMR). In some embodiments, the polypropylene polymer produced has an [EPP] triad content of about 18 mol% to about 26 mol%, such as about 20 mol% to about 25 mol%, such as about 22 mol% to about 24 mol%, as determined by 13C NMR).

[0099] In some embodiments, the polypropylene copolymer produced has an [EEE] triad content of greater than (3*10-5)x2+ 0.0005x – 0.0039, where x is the wt% of ethylene, as determined by13C NMR.

[0100] In some embodiments, the polypropylene copolymer produced has an agglomerationnumber at 55 ºC of 500 second or less, or 200 second or less, or 100 second or less, or 50 second or less, or 30 second or less, or 20 second or less, or 10 second or less.

[0101] In some embodiments, the polypropylene copolymer produced has a flowability number at 55 ºC of 500 second or less, or 300 second or less, or 200 second or less, or 100 second or less, or 80 second or less, or 70 second or less.

[0102] Other additives may also be used in the polymerization, as desired, such as one or more scavengers, hydrogen, aluminum alkyls, silanes, or chain transfer agents (such as alkylalumoxanes, a compound represented by the formula AlR3 or ZnR2 (where each R is, independently, a C1-C8aliphatic radical, such as methyl, ethyl, propyl, butyl, pentyl, hexyl octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof). Catalyst Compounds

[0103] The terms “catalyst”, “compound”, “catalyst compound”, and “complex” may be used interchangeably to describe a transition metal complex that forms an olefin polymerization catalyst when combined with a suitable activator.

[0104] The catalyst complexes of the present disclosure are referred to as bis(phenolate) Lewis base catalyst compounds and comprise a metal selected from the group 4 transition metals of the Periodic Table of the Elements, a tridentate dianionic ligand containing two anionic donor groups and a neutral heterocyclic Lewis base donor, wherein the heterocyclic donor is covalently bonded between the two anionic donors. For example, the dianionic, tridentate ligand features a central heterocyclic donor group and two phenolate donors and the tridentate ligand coordinates to the metal center to form two eight-membered rings.

[0105] The metal can be selected from group 4 elements. In some embodiments, the metal, M, is zirconium or hafnium.

[0106] In some embodiments, the heterocyclic Lewis base donor features a nitrogen or oxygen donor atom. In some embodiments, heterocyclic groups include derivatives of pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, and substituted variants of thereof. In some embodiments, the heterocyclic Lewis base lacks hydrogen(s) in the position alpha to the donor atom. In some embodiments, heterocyclic Lewis base donors include pyridine, 3-substituted pyridines, and 4-substituted pyridines.

[0107] The anionic donors of the tridentate dianionic ligand may be arylthiolates, phenolates, or anilides. In some embodiments, anionic donors are phenolates. In some embodiments, the tridentate dianionic ligand coordinates to the metal center to form a complex that lacks a mirror plane of symmetry. In some embodiments, the tridentate dianionic ligand coordinates to the metalcenter to form a complex that has a two-fold rotation axis of symmetry; when determining the symmetry of the bis(phenolate) complexes only the metal and dianionic tridentate ligand are considered (i.e. ignore remaining ligands).

[0108] The bis(phenolate) ligands of the present disclosure can be tridentate dianionic ligands that coordinate to the metal M in such a fashion that a pair of 8-membered metallocycle rings are formed. The bis(phenolate) ligands wrap around the metal to form a complex with a 2-fold rotation axis, thus giving the complexes C2symmetry. The C2geometry and the 8-membered metallocycle rings are features of these complexes that make them effective catalyst components for the production of polyolefins, particularly isotactic poly(alpha olefins). If the ligands were coordinated to the metal in such a manner that the complex had mirror-plane (Cs) symmetry, then the catalyst would be expected to produce only atactic poly(alpha olefins); these symmetry- reactivity rules are summarized by Bercaw, J. E. (2009) in Macromolecules, v.42, pp.8751-8762. The pair of 8-membered metallocycle rings of the inventive complexes is also a notable feature that is advantageous for catalyst activity, temperature stability, and isoselectivity of monomer enchainment. Related group 4 complexes featuring smaller 6-membered metallocycle rings are known (Bercaw, J. E. (2009) in Macromolecules, v.42, pp.8751-8762) to form mixtures of C2 and Cssymmetric complexes when used in olefin polymerizations and are thus not well suited to the production of highly isotactic poly(alpha olefins).

[0109] Bis(phenolate) ligands that contain oxygen donor groups (i.e. E = E’ = oxygen in Formula (I)) of the present disclosure can be substituted with alkyl, substituted alkyl, aryl, or other groups. It is advantageous that each phenolate group be substituted in the ring position that is adjacent to the oxygen donor atom. In some embodiments, substitution at the position adjacent to the oxygen donor atom be an alkyl group containing 1-20 carbon atoms. In some embodiments, substitution at the position next to the oxygen donor atom be a non-aromatic cyclic alkyl group with one or more five- or six-membered rings. In some embodiments, substitution at the position next to the oxygen donor atom be a cyclic tertiary alkyl group. In some embodiments, substitution at the position next to the oxygen donor atom be adamantan-1-yl or substituted adamantan-1-yl.

[0110] The neutral heterocyclic Lewis base donor is covalently bonded between the two anionic donors via “linker groups” that join the heterocyclic Lewis base to the phenolate groups. The “linker groups” are indicated by (A3A2) and (A2’A3’) in Formula (I). The choice of each linker group may affect the catalyst performance, such as the tacticity of the poly(alpha olefin) produced. Each linker group is typically a C2-C40divalent group that is two-atoms in length. One or both linker groups may independently be phenylene, substituted phenylene, heteroaryl, vinylene, or a non-cyclic two-carbon long linker group. When one or both linker groups are phenylene, the alkylsubstituents on the phenylene group may be chosen to optimize catalyst performance. Typically, one or both phenylenes may be unsubstituted or may be independently substituted with C1 to C20 alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, or an isomer thereof, such as isopropyl, etc.

[0111] The present disclosure further relates to catalyst compounds, and catalyst systems comprising such compounds, represented by the Formula (I):wherein: M is a group 4 (i.e. Hf, Zr or Ti); E and E' are each independently O, S, or NR9, where R9is independently hydrogen, C1-C40 hydrocarbyl, C1-C40 substituted hydrocarbyl, or a heteroatom-containing group, such as O, such as both E and E' are O; Q is group 14, 15, or 16 atom that forms a dative bond to metal M, such as Q is C, O, S or N, such as Q is C, N or O, such as Q is N; A1QA1’are part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms that links A2to A2’via a 3-atom bridge with Q being the central atom of the 3-atom bridge (A1QA1’combined with the curved line joining A1and A1’represents the heterocyclic Lewis base), A1and A1'are independently C, N, or C(R22), where R22is selected from hydrogen, C1-C20 hydrocarbyl, and C1-C20 substituted hydrocarbyl. For example, A1and A1'are C; is a divalent group containing 2 to 40 non-hydrogen atoms that links A1to the E-bonded aryl group via a 2-atom bridge, such as ortho-phenylene, substituted ortho- phenylene, ortho-arene, indolene, substituted indolene, benzothiophene, substituted benzothiophene, pyrrolene, substituted pyrrolene, thiophene, substituted thiophene, 1,2-ethylene (-CH2CH2-), substituted 1,2-ethylene, 1,2-vinylene (-HC=CH-), or substituted 1,2- vinylene, such as is a divalent hydrocarbyl group;is a divalent group containing 2 to 40 non-hydrogen atoms that links A1'to the E'-bonded aryl group via a 2-atom bridge such as ortho-phenylene, substituted ortho- phenylene, ortho-arene, indolene, substituted indolene, benzothiophene, substituted benzothiophene, pyrrolene, substituted pyrrolene, thiophene, substituted thiophene, 1,2-ethylene (-CH2CH2-), substituted 1,2-ethylene, 1,2-vinylene (-HC=CH-), or substituted 1,2- vinylene, such as is a divalent hydrocarbyl group; each L is independently a Lewis base; each X is independently an anionic ligand; n is 1, 2 or 3; m is 0, 1, or 2; n+m is not greater than 4; each of R1, R2, R3, R4, R1', R2', R3', and R4'is independently hydrogen, C1-C40hydrocarbyl, C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group (such as R1'and R1are independently a cyclic group, such as a cyclic tertiary alkyl group), or one or more of R1and R2, R2and R3, R3and R4, R1'and R2', R2’and R3', R3'and R4'may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and where substitutions on the ring can join to form additional rings; any two L groups may be joined together to form a bidentate Lewis base; an X group may be joined to an L group to form a monoanionic bidentate group; any two X groups may be joined together to form a dianionic ligand group.

[0112] The present disclosure is further related to catalyst compounds, and catalyst systems comprising such compounds, represented by the Formula (II):wherein: M is a group 4 (i.e. Hf, Zr or Ti);E and E' are each independently O, S, or NR9, where R9is independently hydrogen, C1-C40 hydrocarbyl, C1-C40 substituted hydrocarbyl, or a heteroatom-containing group, such as O, such as both E and E' are O; each L is independently a Lewis base; each X is independently an anionic ligand; n is 1, 2 or 3; m is 0, 1, or 2; n+m is not greater than 4; each of R1, R2, R3, R4, R1', R2', R3', and R4'is independently hydrogen, C1-C40hydrocarbyl, C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R1and R2, R2and R3, R3and R4, R1'and R2', R2’and R3', R3'and R4'may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and where substitutions on the ring can join to form additional rings; any two L groups may be joined together to form a bidentate Lewis base; an X group may be joined to an L group to form a monoanionic bidentate group; any two X groups may be joined together to form a dianionic ligand group; each of R5, R6, R7, R8, R5’, R6’, R7’; R8’, R10, R11, and R12is independently hydrogen, C1- C40hydrocarbyl, C1-C40substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R5and R6, R6and R7, R7and R8, R5’and R6’, R6’and R7’, R7’and R8’, R10and R11, or R11and R12may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and where substitutions on the ring can join to form additional rings.

[0113] The metal, M, can be selected from group 4 elements. For example, the metal, M, is zirconium or hafnium.

[0114] The donor atom Q of the neutral heterocyclic Lewis base (in Formula (I)) can be nitrogen, carbon, or oxygen. For example, Q is nitrogen.

[0115] Non-limiting examples of neutral heterocyclic Lewis base groups include derivatives of pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, and substituted variants of thereof. Example heterocyclic Lewis base groups can include derivatives of pyridine, pyrazine, thiazole, and imidazole.

[0116] Each A1and A1’of the heterocyclic Lewis base (in formula I) are independently C, N, or C(R22), where R22is selected from hydrogen, C1-C20 hydrocarbyl, and C1-C20 substituted hydrocarbyl. In some embodiments, A1and A1'are carbon. When Q is carbon, it is preferred thatA1and A1’be selected from nitrogen and C(R22). When Q is nitrogen, it is preferred that A1and A1’be carbon. In some embodiments, Q = nitrogen, and A1= A1’= carbon. When Q is nitrogen or oxygen, the heterocyclic Lewis base in Formula (I) might not have any hydrogen atoms bound to the A1or A1’atoms. This is preferred because it is thought that hydrogens in those positions may undergo unwanted decomposition reactions that reduce the stability of the catalytically active species.

[0117] The heterocyclic Lewis base (of Formula (I)) represented by A1QA1’combined with the curved line joining A1and A1’can be selected from the following, with each R23group selected from hydrogen, heteroatoms, C1-C20alkyls, C1-C20alkoxides, C1-C20amides, and C1-C20substituted alkyls.

[0118] In Formula (I) or (II), E and E’ are each selected from oxygen or NR9, where R9is independently hydrogen, C1-C40hydrocarbyl, C1-C40substituted hydrocarbyl, or a heteroatom- containing group. In some embodiments, E and E’ are oxygen. When E and / or E’ are NR9it is preferred that R9be selected from C1to C20hydrocarbyls, alkyls, or aryls. In at least one embodiment, E and E’ are each selected from O, S, or N(alkyl) or N(aryl), where the alkyl is preferably a C1to C20alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodeceyl and the like, and aryl is a C6 to C40 aryl group, such as phenyl, naphthalenyl, benzyl, methylphenyl, and the like.

[0119] In embodiments,are independently a divalent hydrocarbyl group, such as C1to C12hydrocarbyl group.

[0120] In complexes of Formula (I) or (II), when E and E’ are oxygen it is advantageous that each phenolate group be substituted in the position that is next to the oxygen atom (i.e. R1and R1’in Formula (I) and (II)). Thus, when E and E’ are oxygen it is preferred that each of R1and R1'is independently a C1-C40 hydrocarbyl, a C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, such as each of R1and R1'is independently a non-aromatic cyclic alkyl group with one or more five- or six-membered rings (such as cyclohexyl, cyclooctyl, adamantanyl, or 1-methylcyclohexyl, or substituted adamantanyl), such as a non-aromatic cyclic tertiary alkyl group (such as 1-methylcyclohexyl, adamantanyl, or substituted adamantanyl).

[0121] In some embodiments of Formula (I) or (II), each of R1and R1'is independently a tertiary hydrocarbyl group. In other embodiments of Formula (I) or (II), each of R1and R1'is independently a cyclic tertiary hydrocarbyl group. In other embodiments of Formula (I) or (II), each of R1and R1'is independently a polycyclic tertiary hydrocarbyl group.

[0122] The linker groups (i.e. and in Formula (I)) can be an ortho- phenylene group, such as a substituted ortho-phenylene group. In some embodiments, the R7and R7’positions of Formula (II) to be hydrogen, or C1to C20alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, or an isomer thereof, such as iospropyl, etc. For applications targeting polymers with high tacticity it may be preferred for the R7and R7’positions of Formula (II)to be a C1to C20alkyl, such as both R7and R7’are a C1to C3alkyl.

[0123] In some embodiments of Formula (I), Q is C, N or O, such as Q is N.

[0124] In some embodiments of Formula (I), A1and A1'are independently carbon, nitrogen, or C(R22), with R22selected from hydrogen, C1-C20 hydrocarbyl, C1-C20 substituted hydrocarbyl. In some embodiments, A1and A1’are carbon.

[0125] In some embodiments of Formula (I), A1QA1’is part of a heterocyclic Lewis base, such as a pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, or a substituted variant of thereof.

[0126] In embodiments of Formula (I) herein, A1QA1’are part of a heterocyclic Lewis base containing 2 to 20 non-hydrogen atoms that links A2to A2’via a 3-atom bridge with Q being the central atom of the 3-atom bridge. In some embodiments, each A1and A1'is a carbon atom and the A1QA1’fragment forms part of a pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, or a substituted variant of thereof group, or a substituted variant thereof.

[0127] In at least one embodiment, of Formula (I) herein, Q is carbon, and each A1and A1'is N or C(R22), where R22is selected from hydrogen, C1-C20 hydrocarbyl, C1-C20 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group. In this embodiment, the A1QA1’fragment forms part of a cyclic carbene, N-heterocyclic carbene, cyclic amino alkyl carbene, or asubstituted variant of thereof group, or a substituted variant thereof.

[0128] In embodiments of Formula (I) herein, is a divalent group containing 2 to 20 non-hydrogen atoms that links A1to the E-bonded aryl group via a 2-atom bridge, where the is a linear alkyl or forms part of a cyclic group (such as an optionally substituted ortho-phenylene group, or ortho-arylene group) or a substituted variant thereof.

[0129] is a divalent group containing 2 to 20 non-hydrogen atoms that links A1'to the E'-bonded aryl group via a 2-atom bridge, where the is a linear alkyl or forms part of a cyclic group (such as an optionally substituted ortho-phenylene group, or ortho-arylene group or, or a substituted variant thereof.

[0130] In some embodiments of Formula (I) and (II), M is a group 4 metal, such as Hf or Zr.

[0131] In some embodiments of Formula (I) and (II), E and E' are O.

[0132] In some embodiments of Formula (I) and (II), R1, R2, R3, R4, R1', R2', R3', and R4'is independently hydrogen, C1-C40hydrocarbyl, C1-C40substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R1and R2, R2and R3, R3and R4, R1'and R2', R2’and R3', R3'and R4'may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and where substitutions on the ring can join to form additional rings, such as hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof.

[0133] In some embodiments of Formula (I) and (II), R1, R2, R3, R4, R1', R2', R3', R4',and R9are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (such as methylphenyl and dimethylphenyl), benzyl, substituted benzyl (such as methylbenzyl), naphthalenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and isomers thereof.

[0134] In some embodiments of Formula (I) and (II), R3and R3'is independently hydrogen or a C1 to C3 hydrocarbyl, such as methyl, ethyl, n-propyl or isopropyl.

[0135] In some embodiments of Formula (I) and (II), each R2, R4, R2', and R4'is hydrogen.

[0136] In some embodiments of Formula (I) and (II), R9is hydrogen, C1-C40 hydrocarbyl, C1-C40 substituted hydrocarbyl, or a heteroatom-containing group, such as hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof. In some embodiments, R9is methyl, ethyl, propyl, butyl, C1to C6alkyl, phenyl, 2-methylphenyl,2,6-dimethylphenyl, or 2,4,6-trimethylphenyl.

[0137] In some embodiments of Formula (I) and (II), each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms (such as alkyls or aryls), hydrides, amides, alkoxides, sulfides, phosphides, halides, alkyl sulfonates, and a combination thereof, (two or more X’s may form a part of a fused ring or a ring system), such as each X is independently selected from halides, aryls, and C1to C5alkyl groups, such as each X is independently a hydrido, dimethylamido, diethylamido, methyltrimethylsilyl, neopentyl, phenyl, benzyl, methyl, ethyl, propyl, butyl, pentyl, fluoro, iodo, bromo, or chloro group.

[0138] Alternatively, each X may be, independently, a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group.

[0139] In some embodiments of Formula (I) and (II), each L is a Lewis base, independently, selected from the group consisting of ethers, thioethers, amines, nitriles, imines, pyridines, halocarbons, and phosphines, such as ethers and thioethers, and a combination thereof, optionally two or more L’s may form a part of a fused ring or a ring system, such as each L is independently selected from ether and thioether groups, such as each L is a ethyl ether, tetrahydrofuran, dibutyl ether, or dimethylsulfide group.

[0140] In some embodiments of Formula (I) and (II), R1and R1’are independently cyclic tertiary alkyl groups.

[0141] In some embodiments of Formula (I) and (II), n is 1, 2 or 3, typically 2.

[0142] In some embodiments of Formula (I) and (II), m is 0, 1 or 2, typically 0.

[0143] In some embodiments of Formula (I) and (II), R1and R1'are not hydrogen.

[0144] In some embodiments of Formula (I) and (II), M is Hf or Zr, E and E' are O; each of R1and R1’is independently a C1-C40 hydrocarbyl, a C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, each R2, R3, R4, R2', R3', and R4'is independently hydrogen, C1- C20 hydrocarbyl, C1-C20 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R1and R2, R2and R3, R3and R4, R1'and R2', R2’and R3', R3'and R4'may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and where substitutions on the ring can join to form additional rings; each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms (such as alkyls or aryls), hydrides, amides, alkoxides, sulfides, phosphides, halides, and a combination thereof, (two or more X’s may form a part of a fused ring or a ring system); each L is, independently, selected from the group consisting of ethers, thioethers, and halo carbons (two or more L’s may form a part of a fused ring or a ring system).

[0145] In some embodiments of Formula (II), each of R5, R6, R7, R8, R5', R6', R7', R8',R10, R11and R12is independently hydrogen, C1-C40 hydrocarbyl, C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more adjacent R groups may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and where substitutions on the ring can join to form additional rings.

[0146] In some embodiments of Formula (II), each of R5, R6, R7, R8, R5', R6', R7', R8',R10, R11and R12is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof.

[0147] In some embodiments of Formula (II), each of R5, R6, R7, R8, R5', R6', R7', R8', R10, R11and R12is are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (such as methylphenyl and dimethylphenyl), benzyl, substituted benzyl (such as methylbenzyl), naphthalenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and isomers thereof.

[0148] In some embodiments of Formula (II), M is Hf or Zr, E and E' are O; each of R1and R1'is independently a C1-C40 hydrocarbyl, a C1-C40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, each R1, R2, R3, R4, R1', R2', R3', and R4'is independently hydrogen, C1-C20hydrocarbyl, C1-C20substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R1and R2, R2and R3, R3and R4, R1'and R2', R2’and R3', R3'and R4'may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and where substitutions on the ring can join to form additional rings; R9is hydrogen, C1-C20hydrocarbyl, C1-C20substituted hydrocarbyl, or a heteroatom-containing group, such as hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof; each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms (such as alkyls or aryls), hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, (two or more X’s may form a part of a fused ring or a ring system); n is 2; m is 0; and each of R5, R6, R7, R8, R5', R6', R7', R8',R10, R11and R12is independently hydrogen, C1-C20hydrocarbyl, C1-C20substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more adjacent R groups may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings,substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and where substitutions on the ring can join to form additional rings, such as each of R5, R6, R7, R8, R5', R6', R7', R8',R10, R11and R12is are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (such as methylphenyl and dimethylphenyl), benzyl, substituted benzyl (such as methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and isomers thereof.

[0149] In some embodiments of Formula (I), M is Zr or Hf, Q is nitrogen, both A1and A1’are carbon, both E and E’are oxygen, and both R1and R1’are C4-C20 cyclic tertiary alkyls.

[0150] In some embodiments of Formula (I), M is Zr or Hf, Q is nitrogen, both A1and A1’are carbon, both E and E’are oxygen, and both R1and R1’are adamantan-1-yl or substituted adamantan-1-yl.

[0151] In some embodiments of Formula (I), M is Zr or Hf, Q is nitrogen, both A1and A1’are carbon, both E and E’are oxygen, and both R1and R1’are C6-C20aryls.

[0152] In some embodiments of Formula (II), M is Zr or Hf, both E and E’are oxygen, and both R1and R1’are C4-C20cyclic tertiary alkyls.

[0153] In some embodiments of Formula (II), M is Zr or Hf, both E and E’are oxygen, and both R1and R1’are adamantan-1-yl or substituted adamantan-1-yl.

[0154] In some embodiments of Formula (II), M is Zr or Hf, both E and E’are oxygen, and each of R1, R1’, R3and R3’are adamantan-1-yl or substituted adamantan-1-yl.

[0155] In some embodiments of Formula (II), M is Zr or Hf, both E and E’are oxygen, both R1and R1’are C4-C20cyclic tertiary alkyls, and both R7and R7’are C1-C20alkyls.

[0156] In some embodiments of Formula (I), M is Zr or Hf, Q is nitrogen, both A1and A1’are carbon, and form aryl groups, each of E and E’is oxygen, both R1and R1’are independently a C4-C20 tertiary hydrocarbyl group (such as tert-butyl, unsubstituted adamantan-1-yl or substituted adamantan-1-yl, preferably substituted or unsubstituted adamantan- 1-yl), each R2, R4, R2', and R4'are hydrogen, each R3and R3'is independently hydrogen or a C1 to C4hydrocarbyl (such as methyl, ethyl, propyl or butyl and isomers thereof).

[0157] In some embodiments of Formula (II), M is Zr or Hf, both E and E’are oxygen, and both R1and R1’are independently a tertiary hydrocarbyl group such as tert-butyl, unsubstituted adamantan-1-yl or substituted adamantan-1-yl, preferably substituted or unsubstituted adamantan- 1-yl.

[0158] In some embodiments of Formula (II), M is Zr or Hf, both E and E’are oxygen, andboth R1and R1’are independently a C4-C20tertiary hydrocarbyl group (such as tert-butyl, unsubstituted adamantan-1-yl or substituted adamantan-1-yl, preferably substituted or unsubstituted adamantan-1-yl), each R2, R4, R2', and R4'are hydrogen, each R3and R3'is independently hydrogen or a C1 to C4 hydrocarbyl (such as methyl, ethyl, propyl or butyl and isomers thereof), each R5, R6, R8, R5', R6', R8',R10, and R12are hydrogen, each R7and R7'are hydrogen or C1 to C3 hydrocarbyl (such as methyl, ethyl, n-propyl, or isopropyl), and R11is hydrogen or a C1to C10hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl and isomers thereof).

[0159] In some embodiments of the invention, M is zirconium.

[0160] Catalyst compounds that are particularly useful include one or more of: dimethylzirconium[2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]- 2-olate)], dimethylhafnium[2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'- biphenyl]-2-olate)], dimethylzirconium[6,6'-(pyridine-2,6-diylbis(benzo[b]thiophene-3,2- diyl))bis(2-adamantan-1-yl)-4-methylphenolate)], dimethylhafnium[6,6'-(pyridine-2,6- diylbis(benzo[b]thiophene-3,2-diyl))bis(2-adamantan-1-yl)-4-methylphenolate)], dimethylzirconium[2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-methyl-[1,1'- biphenyl]-2-olate)], dimethylhafnium[2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)- 5-methyl-[1,1'-biphenyl]-2-olate)], dimethylzirconium[2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)- adamantan-1-yl)-4',5-dimethyl-[1,1'-biphenyl]-2-olate)], dimethylhafnium[2',2'''-(pyridine-2,6- diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-4',5-dimethyl-[1,1'-biphenyl]-2-olate)].

[0161] Catalyst compounds can include those represented by one or more of the formulas:

[0162] 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 can be chosen such that the two are compatible. A simple screening method such as by1H or13C NMR, known to those of ordinary skill in the art, can be used to determine which transition metal compounds are compatible. It can be preferable to use the same activator for the transition metal compounds, however, two different activators, such as a non- coordinating anion activator and an alumoxane, can be used in combination. If one or more transition metal compounds contain an X group which is not a hydride, hydrocarbyl, or substituted hydrocarbyl, then the alumoxane can be contacted with the transition metal compounds prior to addition of the non-coordinating anion activator.

[0163] The two transition metal compounds (pre-catalysts) may be used in any ratio. Example 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

[0164] The terms “cocatalyst” and “activator” are used herein interchangeably.

[0165] The catalyst systems described herein typically comprises a catalyst complex, such as the transition metal bis(phenolate) complexes described above, and an activator such as alumoxane or a non-coordinating anion. These catalyst systems may be formed by combining the catalyst components described herein with activators in any manner known from the literature. The catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in the monomer). Catalyst systems of the present disclosure may have one or more activators and one, two or more catalyst components. Activators are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral metal compound to a catalytically active metal compound cation. Non-limiting activators, for example, include alumoxanes, ionizing activators, which may be neutral or ionic, and conventional-type cocatalysts. Example activators typically include alumoxane compounds,modified alumoxane compounds, and ionizing anion precursor compounds that abstract a reactive metal ligand making the metal compound cationic and providing a charge-balancing non- coordinating or weakly coordinating anion, e.g. a non-coordinating anion. Alumoxane Activators

[0166] Alumoxane activators are utilized as activators in the catalyst systems described herein. Alumoxanes are generally oligomeric compounds containing -Al(R1)-O- sub-units, where R1is 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. It may be preferable to use a visually clear methylalumoxane. A cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution. A useful alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, covered under patent number U.S. Patent No. 5,041,584). Another useful alumoxane is solid polymethylaluminoxane as described in US 9,340,630; US 8,404,880; and US 8,975,209.

[0167] When the activator is an alumoxane (modified or unmodified), typically the maximum amount of activator is at up to a 5,000-fold molar excess Al / M over the catalyst compound (per metal catalytic site). The minimum activator-to-catalyst-compound is a 1:1 molar ratio. Alternate ranges include from 1:1 to 500:1, alternately from 1:1 to 200:1, alternately from 1:1 to 100:1, or alternately from 1:1 to 50:1.

[0168] In an alternate embodiment, little or no alumoxane is used in the polymerization processes described herein. In some embodiments, alumoxane is present at zero mole %, alternately the alumoxane is present at a molar ratio of aluminum to catalyst compound transition metal less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1. Ionizing / Non Coordinating Anion Activators

[0169] The term "non-coordinating anion" (NCA) means an anion which either does not coordinate to a cation or which is only weakly coordinated to a cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral transition metal compound and a neutral by-product from the anion. Non-coordinating anions useful in accordance with the present disclosure are those that are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge at +1, and yet retain sufficient lability to permitdisplacement during polymerization. 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. Any metal or metalloid that can form a compatible, weakly coordinating complex may be used or contained in the non- coordinating anion. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus, and silicon.

[0170] It is within the scope of the present disclosure to use an ionizing activator, neutral or ionic. It is also within the scope of the present disclosure to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators.

[0171] In embodiments of the present disclosure, the activator is represented by the Formula (III):wherein Z is (L-H) or a reducible Lewis Acid, L is an neutral Lewis base; H is hydrogen; (L-H)+is a Bronsted acid; Ad-is a non-coordinating anion having the charge d-; and d is an integer from 1 to 3 (such as 1, 2 or 3), such as Z is (Ar3C+), where Ar is aryl or aryl substituted with a heteroatom, a C1to C40hydrocarbyl, or a substituted C1to C40hydrocarbyl. The anion component Ad-includes those having the formulawherein 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 40 carbon atoms (optionally with the proviso that in not more than 1 occurrence is Q a halide). For example, each Q is a fluorinated hydrocarbyl group having 1 to 40 (such as 1 to 20) carbon atoms, such as each Q is a fluorinated aryl group, such as a perfluorinated aryl group, such as each Q is a pentafluoryl aryl group or perfluoronaphthalenyl group. Examples of suitable Ad-also include diboron compounds as disclosed in U.S. Patent No.5,447,895, which is fully incorporated herein by reference.

[0172] When Z is the activating cation (L-H), it can be a Bronsted acid, capable of donating a proton to the transition metal catalytic precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, sulfoniums, and mixtures thereof, such as ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline,N-methyl-4-nonadecyl-N-octadecylaniline, N-methyl-4-octadecyl-N-octadecylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, dioctadecylmethylamine, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxoniums from ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane, sulfoniums from thioethers, such as diethyl thioethers, tetrahydrothiophene, and mixtures thereof.

[0173] In particularly useful embodiments of the present disclosure, the activator is soluble in non-aromatic-hydrocarbon solvents, such as aliphatic solvents.

[0174] In one or more embodiments, a 20 wt% mixture of the activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof, forms a clear homogeneous solution at 25°C, such as a 30 wt% mixture of the activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof, forms a clear homogeneous solution at 25°C.

[0175] In some embodiments of the present disclosure, the activators described herein have a solubility of more than 10 mM (or more than 20 mM, or more than 50 mM) at 25°C (stirred 2 hours) in methylcyclohexane.

[0176] In some embodiments of the present disclosure, the activators described herein have a solubility of more than 1 mM (or more than 10 mM, or more than 20 mM) at 25°C (stirred 2 hours) in isohexane.

[0177] In some embodiments of the present disclosure, the activators described herein have a solubility of more than 10 mM (or more than 20 mM, or more than 50 mM) at 25°C (stirred 2 hours) in methylcyclohexane and a solubility of more than 1 mM (or more than 10 mM, or more than 20 mM) at 25°C (stirred 2 hours) in isohexane.

[0178] In some embodiments, the activator is a non-aromatic-hydrocarbon soluble activator compound.

[0179] Non-aromatic-hydrocarbon soluble activator compounds useful herein include those represented by the Formula (V):wherein: is nitrogen or phosphorous;is 3; ^ is 4, 5, or 6);and are independently a C1to C50hydrocarbyl group optionally substituted with one or more alkoxy groups, silyl groups, a halogen atoms, or halogen containing groups,whereinand ^ together comprise 15 or more carbon atoms;^^ is an element selected from group 13 of the Periodic Table of the Elements, such as B or Al; and each ^ is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical.

[0180] Non-aromatic-hydrocarbon soluble activator compounds useful herein include those represented by the Formula (VI): wherein: ^ is nitrogen or phosphorous; is a methyl group; ^ are independently ishydrocarbyl group optionally substituted with one or more alkoxy groups, silyl groups, a halogen atoms, or halogen containing groups wherein and together comprise 14 or morecarbon atoms; ^ is boron; and, and ^are independently hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical.

[0181] Non-aromatic-hydrocarbon soluble activator compounds useful herein include those represented by the Formula (VII) or Formula (VIII): andwherein: is nitrogen; andare independently is hydrocarbyl group optionally substituted with oneor more alkoxy groups, silyl groups, a halogen atoms, or halogen containing groups wherein and ^ (if present) together comprise 14 or more carbon atoms;andare independently ahydrocarbyl or substituted Chydrocarbyl group;B is boron; andandare independently hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical.

[0182] Optionally, in any of Formulas (V), (VI), (VII), or (VIII) herein,and are pentafluorophenyl.

[0183] Optionally, in any of Formulas (V), (VI), (VII), or (VIII) herein, ^ , andare pentafluoronaphthalenyl.

[0184] Optionally, in any embodiment of Formula (VIII) herein, and ^ are hydrogenatoms and ^ is a Chydrocarbyl group which is optionally substituted with one or more alkoxy groups, silyl groups, a halogen atoms, or halogen containing groups.

[0185] Optionally, in any embodiment of Formula (VIII) herein, ^is a Chydrocarbyl group which is optionally substituted with one or more alkoxy groups, silyl groups, a halogen atoms, or halogen containing groups.

[0186] Optionally, in any embodiment of Formula (VII) or (VIII) herein, and ^ areindependently a C12-C22 hydrocarbyl group.and ^together comprise 15 or more carbon atoms (such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 38 or more carbon atoms, such as 40 or more carbon atoms, such as 15 to 100 carbon atoms, such as 25 to 75 carbon atoms).

[0188] Optionally, ^and ^ together comprise 15 or more carbon atoms (such as 18 ormore carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 38 or more carbon atoms, such as 40 or more carbon atoms, such as 15 to 100 carbon atoms, such as 25 to 75 carbon atoms).

[0189] Optionally, and ^^#together comprise 15 or more carbon atoms (such as 18or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 38 or more carbon atoms, such as 40 or more carbon atoms, such as 15 to 100 carbon atoms, such as 25 to 75 carbon atoms).

[0190] Optionally, when^ is a fluorophenyl group, thenis not a Clinear alkyl group (alternately ^ is not an optionally substituted C linear alkyl group).^^ [ 9 p^^ 0 ] i^^ 0 1 t^^ 1 O onally, each of ^ , ^ , ^ , and ^ is an aryl group (such as phenyl or ^ ^ ^ ^ naphthalenyl), wherein at least one of ^^, ^^, ^^, and ^^is substituted with at least one ^ ^ ^ ^ fluorine atom, such as each of ^^, ^^, ^^, and ^^is a perfluoroaryl group (such as perfluorophenyl or perfluoronaphthalenyl).

[0192] Optionally, each ^ is an aryl group (such as phenyl or naphthalenyl), wherein at least one ^ is substituted with at least one fluorine atom, such as each ^ is a perfluoroaryl group (such as perfluorophenyl or perfluoronaphthalenyl). ^ ^ ^

[0193] Optionally, ^^is a methyl group; ^^is C6-C50 aryl group; and ^^is independently C1-C40linear alkyl or C5-C50-aryl group. ^ ^

[0194] Optionally, each of ^^and ^^is independently unsubstituted or substituted with at least one of halide, C1-C35 alkyl, C5-C15 aryl, C6-C35 arylalkyl, C6-C35 alkylaryl, wherein ^^, and ^^together comprise 20 or more carbon atoms.

[0195] Optionally, each ^ is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical, provided that when Q is a fluorophenyl group, ^ ^ then ^^is not a C1-C40 linear alkyl group, such as ^^is not an optionally substituted C1-C40 lin ar a kyl^^ e l group (alternately when ^ is a substituted phenyl group, then ^ is not a C1-C40linear ^ alkyl group, such as ^^is not an optionally substituted C1-C40linear alkyl group). Optionally, ^ when ^ is a fluorophenyl group (alternately when ^ is a substituted phenyl group), then ^^is a meta- and / or para-substituted phenyl group, where the meta and para substituents are, independently, an optionally substituted C1to C40hydrocarbyl group (such as a C6to C40aryl group or linear alkyl group, a C12 to C30 aryl group or linear alkyl group, or a C10 to C20 aryl group or linear alkyl group), an optionally substituted alkoxy group, or an optionally substituted silyl group. Optionally, each ^ is a fluorinated hydrocarbyl group having 1 to 30 carbon atoms, suchas each ^ is a fluorinated aryl (such as phenyl or naphthalenyl) group, such as each ^ is aperflourinated aryl (such as phenyl or naphthalenyl) group. Examples of suitable ^^^^^^^^^^also include diboron compounds as disclosed in US Patent No. 5,447,895, which is fully incorporated herein by reference. Optionally, at least one ^ is not substituted phenyl. Optionally all ^ are not substituted phenyl. Optionally at least one ^ is not perfluorophenyl. Optionally all ^ are not perfluorophenyl. ^ ^ ^

[0196] In some embodiments, ^^is not methyl, ^^is not C18 alkyl and ^^is not C18 alkyl, a^^ t r e^^ a e t^^ l n ly ^ is not methyl, ^ is not C18 alkyl and ^ is not C18 alkyl and at least one ^ is not substituted phenyl, optionally all ^ are not substituted phenyl.

[0197] Useful cation components in Formulas (III) and (V) to (VIII) include those represented by the formula:

[0198] Useful cation components in Formulas (III) and (V) to (VIII) include those represented by the formulas:

[0199] The anion component of the activators described herein includes those represented by the formulawherein ^ is 1, 2, or 3; ^ is 1, 2, 3, 4, 5, or 6 (such as 1, 2, 3, or 4), (such as ^ s 3; n is 4, 5, or 6, such as when ^ is ^, n is 4); ^^ is an element selected from Group 13 of the Periodic Table of the Elements, such as boron or aluminum, and ^ is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said ^ having up to 20 carbon atoms with the proviso that in not more than 1 occurrence is ^ a halide. For example, each ^ is a fluorinated hydrocarbyl group, optionally having 1 to 20 carbon atoms, such as each ^ is a fluorinated aryl group, and such as each ^ is a perfluorinated aryl group. For example, at least one ^ is not substituted phenyl, such as perfluorophenyl, such as all ^ are not substituted phenyl, such as perfluorophenyl.

[0200] In at least one embodiment, the borate activator comprises tetrakis(heptafluoronaphth- 2-yl)borate.

[0201] In at least one embodiment, the borate activator comprises tetrakis(pentafluorophenyl)borate.

[0202] Anions for use in the non-coordinating anion activators described herein also include those represented by Formula 7, below:wherein: M* is a group 13 atom, such as B or Al, such as B; each R11is, independently, a halide, such as a fluoride; each R12is, independently, a halide, a C6 to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula –O-Si-Ra, where Rais a C1to C20hydrocarbyl or hydrocarbylsilyl group, such as R12is a fluoride or a perfluorinated phenyl group; each R13is a halide, a C6to C20substituted aromatic hydrocarbyl group or a siloxy group of the formula –O-Si-Ra, where Rais a C1 to C20 hydrocarbyl or hydrocarbylsilyl group, such as R13is a fluoride or a C6perfluorinated aromatic hydrocarbyl group; wherein R12and R13can form one or more saturated or unsaturated, substituted or unsubstituted rings, such as R12and R13form a perfluorinated phenyl ring. In some embodiments, the anion has a molecular weight of greater than 700 g / mol, and, in some embodiments, at least three of the substituents on the M* atom each have a molecular volume of greater than 180 cubic Å.

[0203] "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.

[0204] 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 ofChemical Education, v.71(11), November 1994, pp.962-964. Molecular volume (MV), in units of cubic Å, is calculated using the formula: MV = 8.3Vs, where Vsis the scaled volume. Vsis the sum of the relative volumes of the constituent atoms, and is calculated from the molecular formula of the substituent using Table A below of relative volumes. For fused rings, the Vsis decreased by 7.5% per fused ring. The Calculated Total MV of the anion is the sum of the MV per substituent, for example, the MV of perfluorophenyl is 183 Å3, and the Calculated Total MV for tetrakis(perfluorophenyl)borate is four times 183 Å3, or 732 Å3. Table A

[0205] Exemplary anions useful herein and their respective scaled volumes and molecular volumes are shown in Table B below. The dashed bonds indicate bonding to boron.Table B te tri (p (p (p te ra te [(

[0206] The activators may be added to a polymerization in the form of an ion pair using, for example, [M2HTH]+ [NCA]- in which the di(hydrogenated tallow)methylamine (“M2HTH”) cation reacts with a basic leaving group on the transition metal complex to form a transition metal complex cation and [NCA]-. Alternatively, the transition metal complex may be reacted with a neutral NCA precursor, such as B(C6F5)3, which abstracts an anionic group from the complex to form an activated species. Useful activators include di(hydrogenated tallow)methylammonium[tetrakis(pentafluorophenyl)borate] (i.e., [M2HTH]B(C6F5)4) and di(octadecyl)tolylammonium [tetrakis(pentafluorophenyl)borate] (i.e., [DOdTH]B(C6F5)4).

[0207] Activator compounds can include one or more of: ,N-octadecyl-N-hexadecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-hexadecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-tetradecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-hexadecyl-N-tetradecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-hexadecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-hexadecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-tetradecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-tetradecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-dodecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-hexadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-tetradecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-dodecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-decylanilinium [tetrakis(perfluorophenyl)borate], and N-methyl-N-octylanilinium [tetrakis(perfluorophenyl)borate].

[0208] Additional useful activators and the synthesis non-aromatic-hydrocarbon soluble activators are described in USSN 16 / 394,166 filed April 25, 2019, USSN 16 / 394,186, filed April 25, 2019, and USSN 16 / 394,197, filed April 25, 2019, which are incorporated by reference herein.

[0209] Likewise, particularly useful activators also include dimethylaniliniumtetrakis (pentafluorophenyl) borate and dimethylanilinium tetrakis(heptafluoro-2-naphthalenyl) borate. For a more detailed description of useful activators please see WO 2004 / 026921 page 72, paragraph

[0119] to page 81 paragraph

[0151] . A list of additionally particularly useful activators that can be used herein may be found at page 72, paragraph

[0177] to page 74, paragraph

[0178] of WO 2004 / 046214.

[0210] For descriptions of useful activators please see US 8,658,556 and US 6,211,105.

[0211] Example activators for use herein also include N-methyl-4-nonadecyl-N- octadecylbenzenaminium tetrakis(pentafluorophenyl)borate, N-methyl-4-nonadecyl-N- octadecylbenzenaminium tetrakis(perfluoronaphthalenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthalenyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthalenyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Me3NH+][B(C6F5)4-]; 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6- tetrafluorophenyl)pyrrolidinium; and tetrakis(pentafluorophenyl)borate, 4- (tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

[0212] In some embodiments, the activator comprises a triaryl carbenium (such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthalenyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

[0213] In another embodiment, the activator comprises one or more of trialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(perfluoronaphthalenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-dialkylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthalenyl)borate, N,N-dialkylanilinium tetrakis(perfluoronaphthalenyl)borate, trialkylammonium tetrakis(perfluorobiphenyl)borate, N,N-dialkylanilinium tetrakis(perfluorobiphenyl)borate, trialkylammonium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, N,N-dialkylanilinium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, N,N-dialkyl-(2,4,6-trimethylanilinium) tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, (where alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl, or t-butyl).

[0214] The typical activator-to-catalyst ratio, e.g., all NCA activators-to-catalyst ratio is about a 1:1 molar ratio. Alternate ranges include from 0.1:1 to 100:1, alternately from 0.5:1 to 200:1, alternately from 1:1 to 500:1 alternately from 1:1 to 1000:1. A particularly useful range is from 0.5:1 to 10:1, such as 1:1 to 5:1.

[0215] 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 0573120 B1; WO 1994 / 007928; and WO 1995 / 014044 (the disclosures of which are incorporated herein by reference in their entirety) which discuss the use of an alumoxane in combination with an ionizing activator). Optional Scavengers, Co-Activators, Chain Transfer Agents

[0216] In addition to activator compounds, scavengers or co-activators may be used. A scavenger is a compound that is typically added to facilitate polymerization by scavengingimpurities. Some scavengers may also act as activators and may be referred to as co-activators. A co-activator, that is not a scavenger, may also be used in conjunction with an activator in order to form an active catalyst. In some embodiments a co-activator can be pre-mixed with the transition metal compound to form an alkylated transition metal compound.

[0217] Co-activators can include alumoxanes such as methylalumoxane, modified alumoxanes such as modified methylalumoxane, and aluminum alkyls such trimethylaluminum, tri-isobutylaluminum, triethylaluminum, and tri-isopropylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum or tri-n-dodecylaluminum. Co- activators are typically used in combination with Lewis acid activators and ionic activators when the pre-catalyst is not a dihydrocarbyl or dihydride complex. Sometimes co-activators are also used as scavengers to deactivate impurities in feed or reactors.

[0218] 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 dialkyl zinc, such as diethyl zinc.

[0219] Chain transfer agents may be used in the compositions and or processes described herein. Useful chain transfer agents are typically hydrogen, alkylalumoxanes, a compound represented by the formula AlR3, ZnR2 (where each R is, independently, a C1-C8 aliphatic radical, such as methyl, ethyl, propyl, butyl, pentyl, hexyl octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof. Polyolefin Products

[0220] The present disclosure also relates to compositions of matter produced by the methods described herein. The processes described herein may be used to produce polymers of olefins or mixtures of olefins. Polymers that may be prepared include copolymers of propylene with ethylene, copolymers of propylene with C4-C20olefins, and terpolymers of propylene and ethylene with C4-C20olefin, such as having an ethylene content of less than 35 mol%. In some embodiments, diene is absent from the copolymers produced herein.

[0221] In some embodiments, the process described herein produces polypropylene copolymers, such as propylene-ethylene and / or propylene- C4to C20alphaolefin copolymers (such as propylene-hexene copolymers or propylene-octene copolymers) having a Mw / Mn of between 1 to 15 (such as 2-8, such as 2-6, such as 2-5).

[0222] In some embodiments, the final polypropylene copolymer product (e.g., dried effluent from a parallel or series reactor configuration) can have about 2 wt% to about 40 wt% (such as 5wt% to about 35 wt%, or such as 10 wt% to about 30 wt%) polymer formed from the second reactor and about 60 wt% to about 98 wt% (such as 65 wt% to about 95 wt%, or such as 70 wt% to about 90 wt%)polymer formed from the first reactor. In some embodiments, a polypropylene copolymer has about 2 wt% to about 20 wt% polymer formed from the second reactor, such as about 5 wt% to about 15 wt%, such as about 10 wt% to about 15 wt%, alternatively about 2 wt% to about 10 wt%, such as about 2 wt% to about 5 wt%, alternatively about 20 wt% to about 40 wt%, such as about 25 wt% to about 35 wt%.

[0223] In some embodiments, the polypropylene copolymer produced has the first copolymer component comprising about 5 to about 30 wt%, or about 10 to about 26 wt%, or about 15 to about 25 wt%, or about 16 to about 24 wt%, or about 17 to about 23 wt%, or about 18 to about 22 wt% ethylene units and about about 70 to about 95 wt%, or about 74 to about 90 wt%, or about 75 to about 85 wt%, or about 76 to about 84 wt%, or about 77 to about 83 wt%, or about 72 to about 82 wt% propylene units and a second copolymer comprising an ethylene content at least about 3 wt% less, or about 5 wt% less, or about 7 wt% less, or about 9 wt% less, or about 10 wt% less than the ethylene conent of the first copolymer.

[0224] In at least one embodiment, the polymers produced herein are copolymers of propylene, such as those having from 0.1 to 30 wt% (alternately about 10 to about 25 wt%, alternately about 15 to about 25 wt%, such as about 18 to about 23 wt%, such as about 19 wt% to about 21 wt%, alternatively about 14 wt% to about 16 wt%, alternatively about 2 wt% to about 80 wt%, such as about 4 wt%, alternatively about 6 wt% to about 16 wt%, such as about 7 wt% to about 10 wt%, such as about 8 wt%) of one or more of ethylene and / or C4 to C20 olefin comonomer (such as ethylene and / or C4 to C12 alpha-olefin, such as ethylene, butene, hexene, octene, decene, dodecene, such as ethylene, butene, hexene, octene).

[0225] In at least one embodiment, the polymers produced herein are copolymers of propylene, such as those having from 99.9 to 70 wt% (alternately about 75 to about 90 wt%, alternately about 75 to about 85 wt%, such as about 77 to about 82 wt%, such as about 79 wt% to about 81 wt%, alternatively about 92 wt% to about 98 wt%, such as about 96 wt%, alternatively about 84 wt% to about 94 wt%, such as about 90 wt% to about 93 wt%, such as about 92 wt%) of propylene.

[0226] In some embodiments, the polypropylene copolymer (formed from a single reactor, series of reactors,or parallel reactors) has a weight average molecular weight (Mw)(LS) of 100,000 g / mol or more, such as 150,000 g / mol or more, such as about 200,000 g / mol to about 500,000 g / mol, such as about 250,000 g / mol to about 400,000 g / mol, such as 275,000 g / mol to about 350,000 g / mol, alternatively about 225,000 g / mol to about 275,000 g / mol; a number average molecular weight (Mn)(LS) of 10,000 g / mol or more, such as about 100,000 g / mol to about250,000 g / mol, such as about 100,000 g / mol to about 175,000 g / mol, such as about 120,000 g / mol to about 165,000 g / mol, alternatively about 20,000 g / mol to about 50,000 g / mol, such as about 30,000 g / mol to about 40,000 g / mol, a z-average molecular weight (Mz) of about 200,000 g / mol or more, such as about 400,000 g / mol to about 800,000 g / mol, such as about 400,000 g / mol 650,000 g / mol, such as about 450,000 g / mol to about 525,000 g / mol; and / or a g’ (vis) value of about 0.7 to about 1, such as about 0.8 to about 1, such as about 0.9 to about 1, alternatively about 0.95 to about 01. In some embodiments, the weight average molecular weight (Mw(LS)) of the first polymer component (of the first reactor) is greater than that of the second polymer component (of the second reactor), which is indicated by the lower MFR of the first polymer component than that of the second polymer component and that of the polypropylene copolymer. Molecular weight and its moments are determined using GPC-4D.

[0227] In some embodiments, the MFR(g / 10 min, 230 ⁰C / 2.16kg) of the second copolymer is higher, such as at least about 25% higher, such as at least about 50% higher, such as at least about 75% higher, such as at least about 100% higher than the MFR(g / 10 min, 230 ⁰C / 2.16kg) of the first copolymer.

[0228] In at least one embodiment, a polypropylene copolymer of the present disclosure has an Mw(LS) / Mn(LS) (PDI) value about 1.5 to about 15, such as about 1.8 to about 10, such as about 1.8 to about 3, such as about 1.8 to about 2.5, alternatively a polypropylene copolymer is bimodal having a PDI of about 6 to about 10, such as about about 7 to about 9.

[0229] In embodiments, the polypropylene copolymer has a melt flow rate (MFR) of 20 g / 10 minutes or less, or 10 g / 10 minutes or less, or 5 g / 10 minutes or less, or 3 g / 10 minutes or less, or 1 g / 10 minutes or less, such as about 0.1 g / 10 minutes to about 2 g / 10 minutes, such as about 0.2 g / 10 minutes to about 1 g / 10 minutes, such as about 0.3 g / 10 minutes to about 0.9 g / 10 minutes, such as about 0.4 g / 10 minutes to about 0.9 g / 10 minutes, such as about 0.6 g / 10 minutes to about 1 g / 10 minutes, alternatively about 1 g / 10 minutes to about 5 g / 10 minutes, such as about 1.5 g / 10 minutes to about 3.5 g / 10 minutes.

[0230] In some embodiments, the polypropylene copolymer has a melting temperature of 140 °C or less, 130°C or less, 120°C or less, 110°C or less, 100°C or less, 90°C or less. In another embodiment, the polymer produced herein can have a melting point of at least 10°C, or at least 20°C, or at least 30°C, or at least 50°C, or at least 60°C. For example, the polymer can have a melting point of at least 10°C to about 130°C. Alternatively, the polymer produced herein has a melting temperature of 10°C or less, such as 5°C or less. Alternatively, the polymer produced herein has a melting temperature of about 50 °C to about 140°C, such as about 60°C to about 135°C, such as about 70°C to about 130°C, such as about 80°C to about 128°C, alternatively about87oC to about 125oC. In at least one embodiment, the second polymer (second polypropylene copolymer) of the present disclosure can has a melt temperature (Tm) of about 50 °C to about 140°C, such as about 60°C to about 135°C, such as about 70°C to about 130°C, such as about 80°C to about 128°C, alternatively about 87oC to about 125oC.

[0231] In some embodiments, the polypropylene copolymer has a crystallization temperature of 130°C or less, 120°C or less, 110°C or less, 100°C or less, 80°C or less. In another embodiment, the polymer produced herein can have a crystallization point of at least 0°C, or at least 10°C, or at least 15°C, or at least 20°C, or at least 30°C. For example, the polymer can have a crystallization point from at least 0°C to about 130°C.

[0232] In some embodiments, the polypropylene copolymer has a glass transition temperature of 0°C or less, -5°C or less, -10°C or less, -20°C or less, such about -20oC to about -45oC, such as about -30oC to about -36oC, such as about -30oC to about -35oC, according to ASTM D3418-03.

[0233] In some embodiments, the polypropylene copolymer has a heat of fusion of 100 J / g or less, 80 J / g or less, 70 J / g or less. In another embodiment, the polymer produced herein can have a heat of fusion of at least 1 J / g, at least 5 J / g, or at least 10 J / g, or at least 15 J / g, or at least 20 J / g. For example, the polymer can have a heat of fusion from at least 0.5 J / g to about 180 J / g. Alternatively, the polypropylene copolymer produced has a heat of fusion (Hf) of about 50 J / g or less, about 30 J / g or less, about 25 J / g or less, or about 21 J / g or less. In another embodiment, the polypropylene copolymer produced can have a heat of fusion of at least 1 J / g, or at least 5 J / g, or at least 10 J / g, or at least 15 J / g, or at least 20 J / g. For example, the polypropylene copolymer produced can have a heat of fusion of about 1 J / g to about 25 J / g, such as about 3 J / g to about 8 J / g, alternatively about 18 J / g to about 25 J / g.

[0234] In some embodiments, the first polymer (first polypropylene copolymer) has a heat of fusion of 20 J / g or less, 10 J / g or less, 5 J / g or less, 2 J / g or less, 1 J / g or less.

[0235] In at least one embodiment, a propylene copolymer of the present disclosure can have a melt temperature (Tm) (°C) of about 30°C to about 130°C and such as about 40°C to about 120°C.

[0236] In some embodiments, the polypropylene copolymer has a Vicat softening temperature of about 30oC to about 90oC, such as about 40oC to about 75oC, such as about 40oC to about 55oC, alternatively about 65oC to about 75oC, such as about 60oC, as determined by ASTM D1525.

[0237] In some embodiments, the polypropylene copolymer has a Shore A hardness that is about 10 to about 90, such as about 40 to about 80, such as about 50 to about 78, as determined by ASTM D2240.

[0238] In some embodiments, the polypropylene copolymer has a Shore D hardness that is about 10 to about 25, such as about 11 to about 24, such as about 12 to about 23, as determined by ASTM D2240.

[0239] In some embodiments, the polypropylene copolymer has a tear strength (die C) that is greater than about 10 N / mm, such as from about 15 N / mm to about 50 N / mm, such as from about 20 N / mm to about 45 N / mm, such as from about 22 N / mm to about 43 N / mm. The tear strength (die C) is determined according to ASTM D624.

[0240] In some embodiments, the polypropylene copolymer has an elongation at break of about 500% to about 1,100%, such as about 600% to about 1,000%, such as about 750% to about 900% according to ASTM D638.

[0241] By definition, a blocky copolymer is one in which the product of the reactivity ratios (r1r2) is greater than 1. A copolymerization between monomers “E” and “P” in the presence of catalyst “M” can be represented by the following reaction schemes and rate equations where R11is the rate of “E” insertion after “E”, R12 is the rate of “P” insertion after “E”, R21 is the rate of “E” insertion after “P”, R22is the rate of “P” insertion after “P”, and k11, k12, k21, and k22are the corresponding rate constants for each. The reactions scheme and rate equations are illustrated below.

[0242] The reactivity ratios r1 and r2 are:

[0243] The product of r1 x r2 provides information on how the different monomers distribute themselves along the polymer chain. Below, are illustrations of alternating, random and blocky copolymers and how the product of r1 x r2 relates to each:r1and r2also represent the reactivity of ethylene and propylene in the copolymer, respectively, which are used to describe the characteristic of the catalyst system. r1r2, the product of r1 and r2, represents the distribution of monomers in the main chain of the copolymer. In at least one embodiment, the polypropylene copolymer produced has an r1r2 in a range of 1 to 3.0, alternatively from 1.2 to 3.0, alternatively from 1.4 to 3.0, alternatively from 1.4 to 3.0, alternatively from 1.4 to 3.0, alternatively from 1.2 to 2.0, alternatively from 1.4 to 1.8. In some embodiments, the r1r2is greater than 1.0, such as greater than 1.1 and with an upper limit of 3.0, alternatively 2.8, alternatively 2.5, alternatively 2.2, alternatively 2.0. In some embodiments, the r1r2of the polypropylene copolymer is greater than 1.12-(0.0157x), where x is the wt% of ethylene, as measured by13C NMR.

[0244] In some embodiments, the polypropylene copolymer can have a complex shear viscosity (η*) @ 0.1 rad / sec and 190ºC of about 1,000 to about 100,000 Pa·s, such as from a low of any one of about 1,000, 5,000, 10,000, 15,000, 20,000, 30,000, 35,000, 40,000, 45,000, 50,000, or 55,000 Pa·s to a high of any one of about 20,000, 30,000, 35,000, 40,000, 45,000, 50,000, 55,000, 60,000, 65,000, or 70,000 Pa·s, with ranges from any low end to any high end contemplated (for example, about 15,000 to about 35,000 Pa·s or about 50,000 to about 70,000 Pa·s).

[0245] Complex shear viscosity (η*) @ 100 rad / sec and 190ºC may be about 300 to about 10,000 Pa·s, such as from a low of any one of about 300, 500, 1,000, 1,500, 2,000, 3,000, 3,500, 4,000, 4,500, 5,000, or 5,500 Pa·s to a high of any one of about 10,000, 8,800, 7,600, 7,000, 6,500, 6,000, or 5,800 Pa·s, with ranges from any foregoing low to any foregoing high also contemplated (for example, about 1,000 to 3,000 Pa·s or about 3,000 to about 7,000 Pa·s).

[0246] In some embodiments, a polypropylene copolymer has a G’ / G”@0.1s-1value (which is a ratio of shear storage modulus (Pa) to shear loss modulus (Pa) at 0.1s-1) of about 0.2 to about 2, such as about 0.5 to about 2, such as about 0.5 to about 1, alternatively about 1 to about 2, such as about 1 to about 1.5.

[0247] In some embodiments, a polypropylene copolymer has a density of about 0.8 to about 0.9 g / cm3, such as from a low of any one of about 0.815, 0.82, 0.83, 0.84, 0.85, or 0.86 g / cm3to a high of any one of 0.9, 0.89, 0.88, 0.87, 0.86, or 0.85 g / cm3, with combinations from any low to any high contemplated (provided the high end is greater than the low end), e.g., about 0.84 to about 0.89 g / cm3, such as about 0.85 to about 0.88 g / cm3, such as about 0.85 to about 0.87 g / cm3, such as about 0.855 to about 0.865 g / cm3. Density testing can follow ASTM D1505, column density. Samples can be molded under ASTM D4703-10a, Procedure C, then conditioned under ASTM D618-08 (23° ± 2°C and 50±10% Relative Humidity) for 40 hours before testing.

[0248] Rheological data such as “Complex shear viscosity (η*),” reported in Pascal seconds, can be measured at 0.01 rad / sec and 100 rad / sec. Complex shear viscosity and other rheological measurements can be obtained from small angle oscillatory shear (SAOS) experiments.

[0249] For instance, complex shear viscosity can be measured with a rotational rheometer such as an Advanced Rheometrics Expansion System (ARES-G2 model) or Discovery Hybrid Rheometer (DHR-3 Model) using parallel plates (diameter=25 mm) in a dynamic mode under nitrogen atmosphere. The rheometer can be thermally stable at 190°C for at least 20 minutes before inserting compression-molded specimen onto the parallel plates. To determine the specimen’s viscoelastic behavior, a frequency sweep in the range from 0.01 to 628 rad / s can be carried out at a temperature of 190°C under constant strain that does not affect the measured viscoelastic properties. The sweep frequencies are equally spaced on a logarithmic scale, so that 5 frequencies are probed per decade. Depending on the molecular weight and temperature, strains of 3% can be used and linearity of the response is verified. A nitrogen stream is circulated through the oven to minimize chain extension or cross-linking during the experiments. The specimens can be compression molded at 190°C, without stabilizers. A sinusoidal shear strain can be applied. The complex shear viscosity (η*) versus frequency (ω) curves can be fitted using the Carreau- Yasuda model: η*- η∞ = (η0 - η∞)*(1 + (λω)a)(n–1) / a.

[0250] The five parameters in this model are: η0, the zero-shear viscosity; λ, the relaxation time; and n, the power-law index; η∞,the infinite rate viscosity; and a, the transition index. The zero-shear viscosity is the value at a plateau in the Newtonian region of the flow curve at a low frequency, where the dynamic viscosity is independent of frequency. The relaxation time corresponds to the inverse of the frequency at which shear-thinning starts. The power-law exponent describes the extent of shear-thinning, in that the magnitude of the slope of the flow curve at high frequencies approaches n-1 on a log(η*)-log(ω) plot. For Newtonian fluids, n=1 and the dynamic complex viscosity is independent of frequency.

[0251] In addition to dynamic and complex viscosity (each in Pascal seconds), at each frequency sweep in the SAOS experiment, various other parameters are collected, including storage modulus (Pa), Loss modulus (Pa), Complex Modulus (Pa), and tan(delta).13MR Spectroscopy on Polyolefins

[0252] Polypropylene microstructure is determined by13C-NMR spectroscopy, including the concentration of isotactic and syndiotactic diads ([m] and [r]), triads ([mm] and [rr]), and pentads ([mmmm] and [rrrr]). The designation “m” or “r” describes the stereochemistry of pairs of contiguous propylene groups, “m” referring to meso and “r” to racemic. Samples are dissolvedin d2-1,1,2,2-tetrachloroethane, and spectra recorded at 120°C using a 125 MHz (or higher) NMR spectrometer. Polymer resonance peaks are referenced to mmmm = 21.83 ppm. Calculations involved in the characterization of polymers by NMR are described by F. A. Bovey in Polymer Conformation and Configuration (Academic Press, New York 1969) and J. Randall in Polymer Sequence Determination, 13C-NMR Method (Academic Press, New York, 1977).

[0253] In at least one embodiment, the propylene polymers have isotactic stereo-regular propylene crystallinity. The term "stereo-regular" as used herein means that the predominant number, i.e. greater than 80% of the propylene residues in the polypropylene exclusive of any other monomer such as ethylene, has the same 1,2 insertion and the stereo-chemical orientation of the pendant methyl groups is the same, either meso or racemic.

[0254] The “mm triad tacticity index” of a polymer is a measure of the relative isotacticity of a sequence of three adjacent propylene units connected in a head-to-tail configuration. More specifically, the mm triad tacticity index (also referred to as the “mm Fraction”) of a polypropylene homopolymer or copolymer is expressed as the ratio of the number of units of meso tacticity to all of the propylene triads in the copolymer:where PPP(mm), PPP(mr) and PPP(rr) denote peak areas derived from the methyl groups of the second units in the possible triad configurations for three head-to-tail propylene units, shown below in Fischer projection diagrams:

[0255] The calculation of the mm Fraction of a propylene polymer is described in U.S. Patent 5,504,172 (homopolymer: column 25, line 49 to column 27, line 26; copolymer: column 28, line 38 to column 29, line 67). For further information on how the mm triad tacticity can be determined from a13C-NMR spectrum, see 1) J. A. Ewen, Catalytic Polymerization of Olefins: Proceedings of the International Symposium on Future Aspects of Olefin Polymerization, T. Keii and K. Soga, Eds. (Elsevier, 1986), pp. 271-292; and 2) U.S. Patent Application Publication No. US2004 / 054086 (paragraphs

[0043] to

[0054] ).

[0256] In some embodiments, the polypropylene copolymer produced has an mm triad tacticity of about 75% or greater, or about 85% or greater, or about 90% or greater, or about 93% or greater, or about 95% or greater, or about 96% or greater, or about 97% or greater.

[0257] 13C NMR can be used to determine monomer content and sequence distribution for the ethylene-propylene copolymers using the procedure from J.C. Randall’s paper: Polymer Reviews, 1989, v.29(2), pp. 201-317. Included in the paper are measurement and calculations for 1,2 propylene addition triad sequence distributions termed EEE, EEP, PEP, EPE, EPP and PPP, and reported as mole fractions. Mole fraction values reported can be converted to mol% by multiplying by 100. The propylene content in mol%, run number, average sequence length, and diad / triad distributions were all calculated per the method established in the above paper. Calculations for r1r2can be based on the equation r1r2= 4*[EE]*[PP] / [EP]2; where [EE], [EP], [PP] are the diad molar concentrations; E is ethylene, P is propylene. For other copolymers of ethylene, a similar methodology is used.

[0258] In some embodiments, a polypropylene copolymer has an [PPP] triad content of about 40 mol% to about 60 mol%, such as about 43 mol% to about 58 mol%, such as about 45 mol% to about 55 mol%, such as about 45 mol% to about 56 mol%, as determined by13C nuclear magnetic resonance (13C NMR). (“P” is propylene). In some embodiments, a polypropylene copolymer has an [EEE] triad content of about 0.5 mol% to about 4 mol%, such as about 1 mol% to about 4 mol%, such as about 1.1 mol% to about 4.0 mol%, such as about 1.1 mol% to about 3.8 mol%, such as about 1.5 mol% to about 3.8 mol%, such as about 2 mol% to about 3.8 mol%, as determined by13C NMR). (“E” is ethylene). In some embodiments, a polypropylene copolymer has an [EEP] triad content of about 5 mol% to about 12 mol%, such as about 6 mol% to about 11 mol%, such as about 6 mol% to about 10 mol%, as determined by13C NMR). In some embodiments, a polypropylene copolymer has an [PEP] triad content of about 8 mol% to about 15 mol%, such as about 10 mol% to about 14 mol%, such as about 11 mol% to about 14 mol%, as determined by13C NMR). In some embodiments, a polypropylene copolymer has an [EPE] triad content of about 3 mol% to about 8 mol%, such as about 4 mol% to about 7 mol%, such as about 4 mol% to about 6 mol%, as determined by13C NMR). In some embodiments, a polypropylene copolymer has an [EPP] triad content of about 18 mol% to about 26 mol%, such as about 20 mol% to about 25 mol%, such as about 22 mol% to about 24 mol%, as determined by13C NMR).

[0259] In some embodiments, the polypropylene copolymer has an [EEE] triad content of greater than (3*10-5)x2+ 0.0005x – 0.0039, where x is the wt% of ethylene, as determined by13C NMR.

[0260] In another embodiment, the polymers produced herein have regio defects (as determined by13C NMR), based upon the total propylene monomer. Three types of defects are defined to be the regio defects: 2,1-erythro, 2,1-threo, and 3,1-isomerization as well as a defect followed by ethylene insertion. The structures and peak assignments for these are given in [L. Resconi, et al. (2000), Chem. Rev., v.100, pp. 1253-1345]. The regio defects (also called regio errors) each give rise to multiple peaks in the carbon NMR spectrum, and these are all integrated and averaged (to the extent that they are resolved from other peaks in the spectrum), to improve the measurement accuracy. The chemical shift offsets of the resolvable resonances used in the analysis are tabulated below. The precise peak positions may shift as a function of NMR solvent choice.

[0261] The average integral for each defect is divided by the integral for total area (CH3, CH, CH2), and multiplied by 100 to determine the total defect concentration, reported as mol% regio defects (also called regio errors). Definition of species (αβ and βγ) are as defined in Randall in “A Review Of High Resolution Liquid Carbon Nuclear Magnetic Resonance Characterization of Ethylene-Based Polymers”, Polymer Reviews, v.29:2,201-5 pg. 317 (1989). The sum of the different types of measured regio defects (i.e. 2,1-E + 2,1-P + 2,1-EE) may be presented as the “total regio defects” in units of mol%.

[0262] In some embodiments, the polypropylene copolymer produced has total regio defects (also called regio errors) from 0.01 to 1.2 mol%, such as from 0.1 to 1.2 mol%, alternatively from 0.1 to 1.15 mol%, alternatively from about 0.3 to about 1.15 mol%, alternatively about 0.4 to about 1.15 mol%.

[0263] In some embodiments, the polypropylene copolymer produced has an agglomeration number at 55 ºC of 500 second or less, or 200 second or less, or 100 second or less, or 50 second or less, or 30 second or less, or 20 second or less, or 10 second or less.

[0264] In some embodiments, the polypropylene copolymer produced has a flowability number at 55 ºC of 500 second or less, or 300 second or less, or 200 second or less, or 100 second or less, or 80 second or less, or 70 second or less.Pellet Formation

[0265] Pellets of the present disclosure can be formed using any suitable pellet forming apparatus. In some embodiments, a pellet forming apparatus is a horizontal ring pellet mill.

[0266] FIGS. 2A-2B is a pellet mill, according to an embodiment. The polymer solids are converted to pellets using a pelletizing machine (260), known as a die press machine.

[0267] As shown in FIGS. 2A-2B, the pellet press (260) has a horizontal fixed die (221), which can achieve high throughput. Four horizontal rollers (262) are arranged in a radial direction around a vertical shaft, like spokes of a wheel, and are attached to the shaft. A motor (223), coupled to a gear box at the base of the machine, provides the rotational force to the shaft, through the gear box, to rotate the shaft at about 70 to 80 rpm. In some embodiments, the gear box includes a worm- gear that provides driving force. The roller assembly is attached to a computer controlled hydraulic jack (264), which maintains downward pressure on the rollers. The downward pressure is controlled based on data input into a control computer (not shown). A cutting tool (e.g., a series of knives or cutters) (225) are attached to the vertical shaft underneath the die (221). Cutters (225) cut the material off at a fixed length as the material is extruded through die (221).

[0268] In operation, polymer solids are gravity fed into the pellet press (260) via a polymer solids inlet (266) above the die. In some embodiments, the raw material is fed into the hopper using a vibratory feeder. As the vertical shaft of the press (260) is turned, the rollers (262) pass over fixed die (221) and press the polymer solids through the die. When the mixture is pressed into die (221), heat is generated by the friction of squeezing the material at extreme compaction ratios. Steam is also admitted into the press to further heat die (221). As the polymer solids come in contact with the heated die, the polymer solids form a layer. As each layer pushes out of the die, a pellet is created.

[0269] As the polymer solids are pressed through the die, the knives or cutters (225) pass underneath the die (221), cutting off a length of extruded polymer solids, thereby forming pellets. The knives or cutters (225) are attached to the same shaft as the rollers (262) which extrude the material through the die (221). The cutting tool (225) are at a fixed operating angle, or dwell angle, behind the rollers (262), and shear off the pellet at a precise length. The length of the pellet coincides with finished granular polymer product. Discharge wiper blades move the material out of the machine and on to the cooler.

[0270] FIGS. 2A-2B is a detailed depiction of the pelleting and cutting portion of the press (260). As shown, the polymer solids (as a layer) rests on die (221). Die (221) rotates such that the polymer solids are presented to grinder roller (262). Roller (262) forces the polymer solids through the die. The heat generated during the pelleting process and steam introduced to the die(221) can laminate the pieces of polymer solids together. The polymer solids are extruded through the die and cut off into substantially equal size pellets by cutting tool (225). Due to the known rate of extrusion, the cutting tool can be placed such that a desired length pellet is achieved. In at least embodiment, in place of the straight roller (262), a conical roller may be used.

[0271] A pellet discharge chute (268) can be arranged beneath the cutting tool (225) to catch the extruded pellets. A cooler can be used to reduce the temperature of the pellets.

[0272] In contrast to prior art ring-die configured machines, a horizontal die press machine has less wear, produces less heat, and consumes less energy. This die press, which typically has a relatively large mass, does not move. Thus, the rotational speed of the rollers can be relatively slow. For example, for a given die size, an approximately 40% increase in throughput has been achieved with an approximately 50% reduction in energy usage. This die press machine can also produce a more uniform and consistent pellet. An additional advantage of pellet press (260) is that it does not utilize mechanical shear pins to limit the pressure of the rollers on the die. Instead, hydraulic pressure applied to the rollers can be monitored with sensing devices and can be controlled in one embodiment by a programmable logic controller (PLC).

[0273] Pellet press (260) provides an ability to influence the density of the pellets, and therefore the density of the finished product, by increasing or decreasing the hydraulic pressure applied to the rollers. Tolerances can be achieved using this configuration improving the uniformity of the resultant pellets. Additionally, depending on the dimensions of the die used, the so-called die specifications, the density of the finished product can also be changed. Forcing the material through the die promotes a chemical change in the materials by the application of heat and friction. Different die specifications change the compression of the polymer solids and the amount of time that the polymer solids are compressed, known as the dwell time. Pellet press (260) provides an added advantage in that the die can be changed in a relatively short duration of time compared to changing the die of a vertical die pellet mill.

[0274] Pellets of the present disclosure may be formed at temperatures of less than about 250oC, such as less than about 230oC, such as about 120oC to about 230oC, such as about 150oC to about 230oC, such as about 170oC to about 220oC, such as about 190oC to about 220oC. Pressures used for forming pellets may be up to about 5,000 pounds per square inch (psi). In some embodiments, pellets can be formed about 1,300 psi to 4,500 psi, such as about 1,500 psi to about 3,000 psi, such as about 1,700 psi to about 2,500 psi, such as about 1,800 psi to about 2,200 psi.

[0275] The pellets can then be sintered to further dry and / or otherwise solidify the pellets.Blends

[0276] In another embodiment, the polymer (the polypropylene copolymer) produced herein is combined with one or more additional polymers prior to being formed into a film, molded part or other article. Other useful polymers include polyethylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene, and / or butene, and / or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene-1, isotactic polybutene, ABS resins, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic block copolymers, polyamides, polycarbonates, PET resins, cross linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidine fluoride, polyethylene glycols, and / or polyisobutylene.

[0277] In some embodiments, the polymer (polypropylene copolymer of the present disclosure) is present in the above blends, at from 10 wt% to 99 wt%, based upon the weight of the polymers in the blend, such as 20 wt% to 95 wt%, such as at least 30 wt% to 90 wt%, such as at least 40 wt% to 90 wt%, such as at least 50 wt% to 90 wt%, such as at least 60 wt% to 90 wt%, such as at least 70 wt% to 90 wt%.

[0278] The blends described above may be produced by mixing the polymers of the present disclosure with one or more polymers (as described above), by connecting reactors together in either series or parelle to make reactor blends or by using more than one catalyst in the same reactor to produce multiple species of polymer. The polymers can be mixed together prior to being put into the extruder or may be mixed in an extruder.

[0279] The blends may be formed using conventional equipment and methods, such as by dry blending the individual components and subsequently melt mixing in a mixer, or by mixing the components together directly in a mixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin-screw extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization process, which may include blending powders or pellets of the resins at the hopper of the film extruder. Additionally, additives may be included in the blend, in one or more components of the blend, and / or in a product formed from the blend, such as a film, as desired. Such additives are well known in the art, and can include, for example: fillers; antioxidants (e.g., hindered phenolics such as IRGANOXTM1010 or IRGANOXTM1076 available from BASF); phosphites (e.g., IRGAFOSTM168 available from BASF); anti-cling additives; tackifiers, such as polybutenes,terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosins; UV stabilizers; heat stabilizers; anti-blocking agents; release agents; anti- static agents; pigments; colorants; dyes; waxes; silica; fillers; talc; and the like. Films

[0280] Specifically, any of the foregoing polymers, such as the foregoing polypropylenes or blends thereof, may be used in a variety of end-use applications. Such applications include, for example, mono- or multi-layer blown, extruded, and / or shrink films. These films may be formed by any number of well-known extrusion or coextrusion techniques, such as a blown bubble film processing technique, wherein the composition can be extruded in a molten state through an annular die and then expanded to form a uni-axial or biaxial orientation melt prior to being cooled to form a tubular, blown film, which can then be axially slit and unfolded to form a flat film. Films may be subsequently unoriented, uniaxially oriented, or biaxially oriented to the same or different extents. One or more of the layers of the film may be oriented in the transverse and / or longitudinal directions to the same or different extents. The uniaxially orientation can be accomplished using typical cold drawing or hot drawing methods. Biaxial orientation can be accomplished using tenter frame equipment or a double bubble processes and may occur before or after the individual layers are brought together. For example, a polyethylene layer can be extrusion coated or laminated onto an oriented polypropylene layer or the polyethylene and polypropylene can be coextruded together into a film then oriented. Likewise, oriented polypropylene could be laminated to oriented polyethylene or oriented polyethylene could be coated onto polypropylene then optionally the combination could be oriented even further. Typically the films are oriented in the Machine Direction (MD) at a ratio of up to 15, such as between 5 and 7, and in the Transverse Direction (TD) at a ratio of up to 15, such as 7 to 9. However, in another embodiment the film is oriented to the same extent in both the MD and TD directions.

[0281] In some embodiments, a film including a polypropylene copolymer of the present disclosure has a tensile strength at break of about 4 MPa to about 20 MPa, such as about 5 MPa to about 17 MPa, such as about 6 MPa to about 15 MPa. Tensile strength at break can be measured according to ASTM D638.

[0282] In some embodiments, a film including a polypropylene copolymer of the present disclosure has an averaged 1% Secant Modulus (M), at 23oC according to a ASTM D790 (Pro B) of about 5 MPa to about 50 MPa, such as about 6 MPa to about 40 MPa, such as about 8 MPa to about 35 MPa, such as about 9 MPa to about 33 MPa, alternatively about 9 MPa to about 15 MPa, alternatively about 30 MPa to about 35 MPa.

[0283] The films may vary in thickness depending on the intended application; however, filmsof a thickness from 1 to 50 µm are usually suitable. Films intended for packaging are usually from 10 to 50 µm thick. The thickness of the sealing layer is typically 0.2 to 50 µm. There may be a sealing layer on both the inner and outer surfaces of the film or the sealing layer may be present on only the inner or the outer surface.

[0284] In another embodiment, one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwave. In some embodiments, one or both of the surface layers is modified by corona treatment. End Uses

[0285] Any of the foregoing polymers and compositions in combination with optional additives (see, for example, U.S. Patent Application Publication No. 2016 / 0060430, paragraphs

[0082] -

[0093] ) may be used in a variety of end-use applications. Such end uses may be produced by methods known in the art. End uses include polymer products and products having specific end-uses. Exemplary end uses are films, film-based products, diaper backsheets, housewrap, wire and cable coating compositions, articles formed by molding techniques, e.g., injection or blow molding, extrusion coating, foaming, casting, and combinations thereof. End uses also include products made from films, e.g., bags, packaging, and personal care films, pouches, medical products, such as for example, medical films and intravenous (IV) bags. Preferred end uses also include thermoplastic polyolefin (TPO) roof sheeting, foam, nonwovens, 3D printing, and recycling solutions. TEST METHODS

[0286] Dynamic shear melt rheology test: Dynamic shear melt rheological data was measured using with the Advanced Rheometrics Expansion System (ARES-G2) from TA Instruments. A sample of approximately 1.0 gm weight is compression molded in a disk (diameter = 25 mm, thickness = 2 mm) at 190°C and no stabilizers were added. Then the sample is mounted between the parallel plates (diameter = 25 mm) of the ARES-G2. The test temperature is 190°C, the applied strain is 10%, and the angular frequency was varied from 0.1 rad / s to 200 rad / s. A nitrogen stream was purged through a force convection oven to minimize cross-linking or degradation during the experiments. A sinusoidal shear strain is applied to the material. A small strain amplitude is applied within the linear visco-elastic regime. The complex modulus (G*) and complex viscosity (η*) are measured at each frequency. Complex viscosity, loss modulus (G”) and storage modulus (G’) as function of frequency are provided by the small amplitude oscillatory shear test. Dynamic viscosity is also referred to as complex viscosity or dynamic shear viscosity. The phase or the loss angle (δ), is the inverse tangent of the ratio of G'' (shear loss modulus) to G' (shear storage modulus).

[0287] Solvent Gradient Interactive Chromatography (SGIC) analysis was done using an SGIC-2D instrument from Polymer Char, S.A., Valencia, Spain. The principles of SGIC-2D analysis are explained in the article Bhati, S. et al. Polyolefins J. 2016, 3, 119. In particular, the schematic configuration shown in Fig.1(a) of this article is an appropriate depiction of the schematic for the apparatus used in the present case. Pertinent features of the apparatus and relevant details of the analysis method, as they apply to the present case, are as follows.

[0288] The IR5 infrared detector (Polymer Char) was used to generate an absorbance signal that is proportional to the concentration of polymer in the eluting flow. The composition signal, in terms of methyl content, was measured as described in the article Ortin, A. et al. Chromatogr. A 2012, 1257, 66. A Hypercarb™ (Thermo Fisher™) column of dimensions 4.6 x 100 mm (I.D. x L.) and a stationary phase of porous graphitic carbon (PGC) particles (5 µm, particle size; 138.2 m2 / gm, surface area) was used in the first dimension. A PL Rapide H (Agilent Technologies) SEC column of dimensions 7.5 x 150 mm (I.D. x L.) packed with 10-µm particles was used in the second dimension.

[0289] The solvents used for preparing the sample solution and for elution were 98+% 1-decanol (decanol) and ≥99% 1,2,4-trichlorobenzene (TCB) as the adsorption- and desorption- promoting mobile phases, respectively; the decanol was used as received whereas the TCB was filtered using a membrane filter (0.1 μm JV, Omnipore™). At the beginning of the analysis, the PGC column was flushed and filled with 100-vol% decanol. Temperatures of the PGC and SEC columns were kept at 160 and 170 °C, respectively, throughout the analysis. The sample to be analyzed (1–13 mg) was dissolved in 8 ml of decanol (metered at ambient temperature) by shaking (Medium setting) at 160 °C for 90 min. The solution was then used to completely fill a 100-μl injection-valve loop. Then the injection valve was switched to let the flow from the gradient pump carry the volume in the loop towards the PGC column, and the switching of the valve coincided with the start of a solvent-gradient profile, shown here as a sequence of time (min), TCB (vol%): 0, 0; 150, 30; 170, 30; 190, 50; 200, 100; 312, 100. Flow rates used for the PGC and SEC columns were set to 0.025 ml / min of mixed solvent (gradient pump) and 1.5 ml / min of TCB (isocratic pump), respectively, from start to finish of the gradient profile. The transfer-valve loop volume was 100 μl and the valve-switching time was 3 min, thereby filling the loop to 75 μl for each SEC injection and generating 104 SEC chromatograms per sample analyzed.

[0290] The data generated was processed using an in-house MATLAB application for setting baselines (for subtraction) and integration limits, calibrating the IR5 detector and SEC column, and calculating all relevant metrics from the processed data. For calibrating the CH3 / CH2 band ratio of the IR5 detector to obtain the CH3 / 1000TC signal, up to 39 polyolefin samples withCH3 / 1000TC in the range of 0–333.3 were used. For calibrating the elution volume from the SEC column to obtain the molecular weight of the eluting polymer, nine narrow polystyrene standards (Agilent Technologies) having a peak molecular weight in the range of 1–6035 kg / mol were used. RCP composition of bimodal grades was measured by SGIC.

[0291] GPC-4D: Unless otherwise indicated, for purposes of the Claims, the distribution and the moments of molecular weight (Mw, Mn, Mz, Mw / Mn, etc.), the comonomer content 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 about 2700 cm-1to about 3000 cm-1(representing saturated C-H stretching vibration) , an 18-angle light scattering detector and a viscometer. Three Agilent PLgel 10-µm Mixed-B LS columns are used to provide polymer separation. Reagent grade 1,2,4-trichlorobenzene (TCB) (from Sigma- Aldrich) comprising ~300 ppm antioxidant BHT can be used as the mobile phase at a nominal flow rate of ~1.0 mL / min and a nominal injection volume of ~200 μL. The whole system including transfer lines, columns, and detectors can be contained in an oven maintained at ~145°C. A given amount of sample can be weighed and sealed in a standard vial with ~10 μL flow marker (heptane) added thereto. After loading the vial in the auto-sampler, the oligomer or polymer may automatically be dissolved in the instrument with ~8 mL added TCB solvent at ~160°C with continuous shaking. The sample solution concentration can be from ~0.2 to ~2.0 mg / ml, with lower concentrations used for higher molecular weight samples. The concentration, c, at each point in the chromatogram can be calculated from the baseline-subtracted IR5 broadband signal, I, using the equation: c=αI, where α is the mass constant determined with polyethylene or polypropylene standards. The mass recovery can be calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume. The conventional molecular weight (IR MW) is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to 10M gm / mole. The MW at each elution volume is calculated with following equation: log ^ =log'()* / (,-)* + 1- + 1+- + 1 log ^)*where the variables with subscript “PS” stand for polystyrene while those without a subscript are for the test samples. In this method, αPS= 0.67 and KPS= 0.000175, α and K for other materials are as calculated by GPC ONE™ software (Polymer Characterization, S.A., Valencia, Spain). Concentrations are expressed in g / cm3, molecular weight is expressed in g / mole, andintrinsic viscosity (hence K in the Mark–Houwink equation) is expressed in dL / g unless otherwise noted.

[0292] 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 1000 total carbons (CH3 / 1000TC) as a function of molecular weight. The short- chain branch (SCB) content per 1000TC (SCB / 1000TC) is then computed as a function of molecular weight by applying a chain-end correction to the CH3 / 1000TC function, assuming each chain to be linear and terminated by a methyl group at each end. The weight % comonomer is then obtained from the following expression in which 0 is 0.3, 0.4, 0.6, 0.8, and so on for C3, C4, C6, C8, and so on co-monomers, respectively:The bulk composition of the polymer from the GPC-IR and GPC-4D analyses is obtained by considering the entire signals of the CH3and CH2channels between the integration limits of the concentration chromatogram. First, the following ratio is obtainedThen the same calibration of the CH3 and CH2 signal ratio, as mentioned previously in obtaining the CH3 / 1000TC as a function of molecular weight, is applied to obtain the bulk CH3 / 1000TC. A bulk methyl chain ends per 1000TC (bulk CH3end / 1000TC) is obtained by weight-averaging the chain-end correction over the molecular-weight range. Thenbulk SCB / 1000TC = bulk CH3 / 1000TC − bulk CH3end / 1000TCand bulk SCB / 1000TC is converted to bulk 12 in the same manner as described above.

[0293] The LS detector is the 18-angle Wyatt Technology High Temperature DAWN HELEOSII. The LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (Light Scattering from Polymer Solutions; Huglin, M. B., Ed.; Academic Press, 1972.):Here, ΔR(θ) is the measured excess Rayleigh scattering intensity at scattering angle θ, c is the polymer concentration determined from the IR5 analysis, A2 is the second virial coefficient, P(θ) is the form factor for a monodisperse random coil, and Ko is the optical constant for the system:=4π2n2 K (dn / dc ) 2 o λ 4 N A where NA is Avogadro’s number, and (dn / dc) is the refractive index increment for the system, n = 1.500 for TCB at 145 °C and λ = 665 nm. For analyzing polyethylene homopolymers, ethylene- hexene copolymers, and ethylene-octene copolymers, dn / dc = 0.1048 ml / mg and A2 = 0.0015; for analyzing ethylene-butene copolymers, dn / dc = 0.1048*(1-0.00126*w2) ml / mg and A2 = 0.0015 where w2 is weight percent butene comonomer.

[0294] A high temperature Agilent (or Viscotek Corporation) viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity, ηs, for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [η], at each point in the chromatogram is calculated from the equation [η]= ηs / c, where c is concentration and is determined from the IR5 broadband +1cosity MW at each point is calculated asM = K Mα PSchannel output. The visPS [ η ], where αpsis 0.67 and Kpsis 0.000175.

[0295] The branching index (g'vis) is calculated using the output of the GPC-IR5-LS-VIS method as follows. The average intrinsic viscosity, [η]avg, of the sample is calculated by: [ηwhere the summations are over the chromatographic slices, i, between the integration limits.

[0296] The branching index g'visis defined as gwhere Mvis the viscosity-average molecular weight based on molecular weights determined by LS analysis and the K and α are for the reference linear polymer, which are, for purposes of the present disclosure, α = 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.

[0297] Experimental and analysis details not described above, including how the detectors are calibrated and how to calculate the composition dependence of Mark-Houwink parameters and the second-virial coefficient, are described by T. Sun, et al. (2001) Macromolecules, v.34(19), pp.6812-6820.

[0298] Ethylene content is determined using FTIR according to ASTM D3900. The content of other comonomers can be obtained using13C NMR by methods well known to those in the art. The FTIR method is preferred for the ethylene content determination.

[0299] The comonomer content and sequence distribution of the polymers can be measured using13C nuclear magnetic resonance (NMR) by methods well known to those skilled in the art. Reference is made to U.S. Patent No.6,525,157 which contains more details of the determination of ethylene content by NMR. Calculations involved in the characterization of polymers by NMR follow the work of J. Randall in Polymer Sequence Determination, 13C-NMR Method, Academic Press, New York, 1977 and Frank Bovey et.al. (1976) Macromolecules, v.9, pp.76-80.

[0300] Comonomer content of discrete molecular weight ranges can be measured using methods well known to those skilled in the art, including Fourier Transform Infrared Spectroscopy (FTIR) in conjunction with samples by GPC, as described in Wheeler and Willis (1993) Applied Spectroscopy, v.47, pp.1128-1130.

[0301] Peak melting point, Tm, (also referred to as melting point), peak crystallization temperature, Tc, (also referred to as crystallization temperature), glass transition temperature (Tg), heat of fusion (∆Hf or Hf), and percent crystallinity were determined using the following DSC procedure according to ASTM D3418-03. Differential scanning calorimetric (DSC) data were obtained using a TA Instruments model Q200 machine. Samples weighing approximately 5-10 mg were sealed in an aluminum hermetic sample pan. The DSC data were recorded by first gradually heating the sample to 200°C at a rate of 10°C / minute. The sample was kept at 200°C for 2 minutes, then cooled to -90°C at a rate of 10°C / minute, followed by an isothermal for 2 minutes and heating to 200°C at 10°C / minute. Both the first and second cycle thermal events were recorded. Areas under the endothermic peaks were measured and used to determine the heat of fusion and the percent of crystallinity. The percent crystallinity is calculated using the formula, [area under the melting peak (Joules / gram) / B (Joules / gram)] * 100, where B is the heat of fusion for the 100% crystalline homopolymer of the major monomer component. These values for B are to be obtained from the Polymer Handbook, Fourth Edition, published by John Wiley and Sons, New York 1999, provided; however, that a value of 189 J / g (B) is used as the heat of fusion for 100% crystalline polypropylene, a value of 290 J / g is used for the heat of fusion for 100% crystalline polyethylene. The melting and crystallization temperatures reported here were obtained during the second heating / cooling cycle unless otherwise noted.

[0302] For polymers displaying multiple endothermic and exothermic peaks, all the peak crystallization temperatures and peak melting temperatures were reported. The heat of fusion foreach endothermic peak was calculated individually. The percent crystallinity is calculated using the sum of heat of fusions from all endothermic peaks. Some of the polymer blends produced show a secondary melting / cooling peak overlapping with the principal peak, which peaks are considered together as a single melting / cooling peak. The highest of these peaks is considered the peak melting temperature / crystallization point. For the amorphous polymers, having comparatively low levels of crystallinity, the melting temperature is typically measured and reported during the first heating cycle. Prior to the DSC measurement, the sample was aged (typically by holding it at ambient temperature for a period of 2 days) or annealed to maximize the level of crystallinity. Vicat Softening

[0303] Vicat softening temperature is measured using Ceast HDT 3 Vicat instrument. The specimens between 3 mm and 6.5 mm thick with at least 10 mm square or 10 mm in diameter are used. Three samples were conditioned in controlled temperature and humidity lab per ASTM D618 requirement (23°±2°C and 50±10%) relative humidity. The Vicat temperature reported is the temperature at which aflat-ended needle of 1-mm2 circular cross section penetrate a thermoplastic specimen to a depth of 1 mm under a 200 gm load perpendicular to the test specimen using a selected uniform rate of 50 C / hr. Silo-Flowability Test

[0304] 1) Place 500 g of pellets in "Silo test tube" (see drawing in the figure below). Pellets were pre-heated at 55°C for 2 hours in the oven. Use fresh sample after each temperature. 2) Place weight (9.5 kg) on top of the pellets. 3) Wait 5 min. before testing. 4) Remove weight. 5) Record flowability number, time (in second), to empty the silo. 6) If silo is not empty within 1500 sec (25 min.), stop test.Agglomeration Test

[0305] 1) Place 500 g of pellets in "Agglomeration test tube" (pellets pre-heated at 55°C during 2 hours in the oven). The agglomeration test tube is a similar setup as the silo test tube except that the tube is a cylinder instead of a tube with a corn at the bottom. Use fresh sample after each temperature. 2) Place weight (9.5 kg) on top of the pellets. 3) Wait 24 hrs before testing. 4) Remove weight. 5) Record agglomeration number, time (in second), to empty the silo. 6) If silo is not empty within 1500 sec (25 min.), stop test. Experimental

[0306] N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (DMAH-BF20, Activator A-1) can be purchased from WR Grace and Co. or Boulder Scientific Co.

[0307] [2',2'''-(pyridine-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2- olate)]zirconium dimethyl (Catalyst A) can be prepared as described in US11,254,763.Polymerization

[0308] The VMX6102 polymer is a commercial dual reactor grade produced using a metallocene based catalyst system by ExxonMobil Product Solutions Company, Houston, TX. All other polymer examples were produced using a bis(phenolate) Lewis base catalyst system, specifically, [2',2'''-(pyridine-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2- olate)]zirconium dimethyl with [N,N-dimethylanilinium] [tetrakis(perfluorophenyl)borate] as the activator. Additional experimental detail for the examples is provided further below. The polymer characteristics are summarized in Tables 1 and 4. Table 1: Summary of final polymer characteristicsTable 1: Summary of final polymer characteristics (continued) (Table 1: Summary of final polymer characteristics (continued)*Samples for SGIC were from individual lots that were mixed to prepare the example blends. The composition reported is the wt.% of the RCP component realative to the total polymer conent.

[0309] Ethylene (C2) content of polymers was determined by13C NMR, or FTIR according the ASTM D3900; the FTIR method is preferred for the ethylene content determination. MFR is melt flow rate in g / 10 minutes measured at a temperature of 230°C and a weight of 2.16 kg according to ASTM D1238. Brookfield viscosity was determined by Brookfield Viscometer at 190 ⁰C according to ASTM D2983. Shore Hardness A and D data was measured using ASTM D2240. Tensile property data was measured using ASTM D638 (Type IV, t=0.075" specimen, at 20 in / min). Die C tear data was measured using ASTM D624. Flexural modulus data was measured using ASTM D790 (Proc A and B). Density data was measured using ASTM D1505.

[0310] Polymerizations of ethylene (C2) and propylene (C3) were carried out using a solution process in one or two 28 liter continuous stirred-tank reactor(s) (autoclave reactors) run in parallel when both were used. These reactors are referred to as R1 and R2. When only one reactor was used, it was R2. Each autoclave reactor was equipped with an agitator, a pressure controller, and insulation to prevent heat loss. The reactor temperature for each reactor was controlled by controlling the catalyst feed rates and heat removal was provided by feed chilling. All solvents and monomers were purified over beds of alumina and molecular sieves. The reactor(s) was operated liquid full and at a pressure of 1600 psi. Isohexane (iC6) was used as a solvent. It was fed into the reactor(s) using a centrifugal pump and its flow rate was controlled by a mass flow controller downstream. The compressed, liquefied propylene feed was controlled by a mass flow controller. Hydrogen, when used, was fed to the reactor(s) by a thermal mass flow controller. Ethylene feed was also controlled by a mass flow controller. The ethylene, propylene and hydrogen (if used) were mixed into the isohexane at separate addition points via manifolds to each reactor being used. A 3 wt.% mixture of tri-n-octylaluminum in isohexane was also added to the manifold(s) through a separate line (used as a scavenger) and the combined mixture of monomers, scavenger, and solvent was fed into the reactor(s) through a single tube.

[0311] An activated Catalyst A ([2',2'''-(pyridine-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert- butyl)-[1,1'-biphenyl]-2-olate)]zirconium dimethyl) solution was prepared in a 4 L Erlenmeyer flask in a nitrogen-filled glove box. The flask was charged with 4 L of air-free anhydrous toluene, 0.5 g (~0.00005 mole) of Catalyst A and 0.4 g Activator A-1 (N,N-dimethylanilinium tetrakis(perfluorophenyl)borate), in a ~1:1 molar ratio to make the solution. After the solids dissolved, with stirring, the solution was charged into an ISCO pump and metered into the reactor(s).

[0312] The catalyst feed rate was controlled along with the monomer feed rates and reaction temperature, as shown in Tables 2A and 2B, to produce the polymers also described in Table 2A. The reactor product stream was treated with trace amounts of methanol to halt the polymerization.The mixture was then freed from solvent via a low-pressure flash separation, treated with Irganox™ 1076, then subjected to a devolatilizing extruder process. The dried polymer was then pelletized.

[0313] Some of the comparative and inventive examples are blends of individual materials with similar process conditions and polymer properties.

[0314] In general, the process conditions targeted for the main reactor (the first reactor, R2) making the first copolymer with about 14 to about 21% ethylene are as follows: Reactor temperature was about 70 to about 84.5oC; C2 conversion of about 58 to about 90%; C3 conversion of about 30 to about 75%; C3 concentration of about 0.7 to about 2.8 mol / L; C2 concentration of about 0.09 to about 0.5 mol / L; Hydrogen amount of zero.

[0315] For dual reactor processes, the process conditions targeted for the second reactor (R1) making the second copolymer product with about 3 to about 10% ethylene are as follows: Reactor temperature was about 75 to about 135oC; C2 conversion of about 54 to about 90%; C3 conversion of about 41 to about 75%; C3 concentration of about 0.3 to about 2.4 mol / L; C2 concentration of about 0.02 to about 0.13 mol / L; Various amounts of hydrogen.

[0316] For dual reactor products, reactor samples of the first copolymer from the first reactor and the second copolymer from the second reactor were collected and characterized by FTIR and MFR to determine composition and viscosity. The reactor samples were collected in a solution state followed by solvent removal. The composition of the first polymer and the second polymer can be characterized by SGIC or calculated by the balance of ethylene content using the measured ethylene conent of the first polymer, the second polymer and the finished pellets, the later of which is preferred.Table 4A: GPC-4D properties

[0317] Table 4B shows DSC results of the R2 and R1 (RCP) components as measured of the dual reactor grade pellets. The RCP component of the inventive dual reactor grade pellets 5 (examples E-1 to E-4) have higher crystallinity (Tm and Hf) as compared to that of the commercial dual reactor grade, VMX 6102 provided by ExxonMobil (example C5), and the comparative single reactor grades (comparative examples C1 to C4). Overall, higher Tm and Hfis expected to enhance pellet stability. Like VMX6102, no apparent Tm and Hfof the R2 component of the inventive dual reactor grades were observed. 10 Table 4B: Tm and Hf of the first reactor, R2, and the second reactor, R1, (RCP) component of polymer pellets and Tg of polymer pellets as characterized by DSC.

[0318] As shown in Table 5, the inventive dual reactor grades have generally lower Vicat temperature than both the VMX6102 dual reactor grade and the comparative single reactor grades, even though their Tm and Hfare higher. The Vicat temperature of the inventive dual reactor grades can be increased by increasing the R1 RCP content; for example, E3 has a Vicat 5 temperature of 70.5.

[0319] As shown in Table 5, the inventive dual reactor grades have lower agglomeration number and lower flowability number at 55 ºC than the comparative single reactor grades even with lower Vicat temperature. The inventive dual reactor grades have lower agglomeration number but higher flowability number at 55 ºC than the comparative single reactor grades.10Agglomeration number mimics pellet stability during longer-time pellet storage, and flowability number mimics pellet stability during shorter-time pellet production; a lower agglomeration number and flowability number suggests higher pellet stability.

[0320] As shown in Table 5, the inventive dual reactor grades have lower Tg than the VMX6102 dual reactor grade and the comparative single reactor grades, which is consistent 15 with the higher C2 of the R2 component of the dual reactor grades than the single reactor grades.

[0321] As shown in Table 5, the inventive dual reactor grades have lower hardness than the VMX6102 dual reactor grade and all of the comparative single reactor grades except for example C3 that has a higher C2% than the other single reactor grade.20

[0322] As shown in Table 5, the inventive dual reactor grades have lower tensile strength than the VMX6102 dual reactor grade and the comparative single reactor grades, while still having comparable strain at max stress.

[0323] As shown in Table 5, the inventive dual reactor grades have lower Die C tear strength than the VMX6102 dual reactor grade and all of the comparative single reactor grades 25 except for example C3 that has a higher C2% than the other single reactor grade.

[0324] As shown in Table 5, the inventive dual reactor grades have lower flexural modulus than the comparative single reactor grades. Their flexural modulus can be comparable to that of VMX6102 even though their C2% is ~3.5% higher.

[0325] As shown in Table 5, the inventive dual reactor grades have higher density than that30of VMX6102 dual reactor grade. The density of the inventive dual reactor grades is comparable with that of comparative single reactor grades even with higher C2 content.

[0326] Overall, solution processes of the present disclosure can utilize catalyst structure, concentration of ethylene and propylene, molar ratio of ethylene and propylene, and reactor temperature to provide propylene copolymers having unique and advantageous properties, suchas bimodality, improved pellet stability, good high and low temperature properties, and softness as compared to conventional monomodal polypropylene polymers made by the bis(phenolate) Lewis base catalysts (such as Catalyst A) and bimodal polymers (such as VMX6102) made by metallocene catalysts. For example, polypropylene polymers of the present disclosure can have 5 low glass transition temperature (e.g., provided by higher ethylene content) for good low temperature performance. The higher ethylene content provides softness, which would need to be balanced with pellet stablity. However, catalysts of the present disclosure can provide softness and good pellet stability. The thermal and physical properties of polypropylene copolymers of the present disclosure can be comparable to those of the comparative polymers.10

[0327] The phrases, unless otherwise specified, "consists essentially of" and "consisting essentially of" do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of the present disclosure, additionally, they do not exclude impurities and variances normally associated with the elements and materials used. 15

[0328] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.20Additionally, within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

[0329] All documents described herein are incorporated by reference herein, including any 25 priority documents and or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended that the present disclosure be limited thereby. Likewise, the term30“comprising” is considered synonymous with the term “including” for purposes of United States law. Likewise, whenever a composition, an element or a group of elements is preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation ofthe composition, element, or elements and vice versa.

[0330] While the present disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit 5 of the present disclosure.

Claims

CLAIMS What is claimed is 1. A polymerization process comprising: a) introducing into a first reactor, in a homogeneous phase, a solvent feed, a monomer feed comprising a propylene feed and ethylene feed wherein the ratio of propylene feed (kg / hr) to ethylene feed (kg / hr) is from about 3 to about 30 (kg / kg), and a catalyst system comprising an activator and a bis(phenolate) Lewis base catalyst compound, and obtaining a first copolymer effluent from the first reactor (“the first reactor effluent”); b) providing to the second reactor in a homogeneous phase, a solvent feed, a second monomer feed comprising propylene feed and ethylene feed wherein the ratio of propylene feed (kg / hr) to ethylene feed (kg / hr) is from about 5 to about 65 (kg / kg), and a catalyst system comprising an activator and a bis(phenolate) Lewis base catalyst compound, and obtaining a second copolymer effluent from the second reactor (“the second reactor effluent”); c) introducing the first reactor effluent into the second reactor, or combining the first reactor effluent with a second reactor effluent post reactor; and d) obtaining a polymer comprising a first copolymer having from about 5 to about 30 wt% ethylene and about 70 to about 95 wt% propylene, and a second copolymer having an ethylene content at least about 3 wt% less than the ethylene content of the first copolymer, and wherein the second copolymer is from about 2 to about 40 wt% of the total polymer composition.

2. The process of claim 1, wherein the propylene concentration in the first reactor is from about 4 to 0.1 mole / liter and the ethylene concentration in the first reactor is from about 2 to 0.01 mole / liter.

3. The process of claim 1, wherein the propylene concentration in the second reactor is from about 3 to 0.1 mole / liter and the ethylene concentration in the second reactor is from about 1 to 0.005 mole / liter.

4. The process of claim 1, wherein a molar ratio of propylene to ethylene in the first reactor is from about 20 to about 2.

5. The process of claim 1, wherein a molar ratio of propylene to ethylene in the second reactor is from about 70 to about about 4.

6. The process of claim 1, wherein a total monomer conversion in the first reactor is from about 30 to about 90 wt%, and the total monomer conversion in the second reactor is from about 25 wt% or greater.

7. The process of claim 1, wherein within the first reactor, an ethylene conversion is from about 50 wt% to about 90 wt%, a propylene conversion is from about 25 wt% to about 65 wt%.

8. The process of claim 1, wherein within the second reactor, an ethylene conversion is from about 45 wt% to about 95 wt%, a propylene conversion is from about about 25 wt% to about 75 wt%.

9. The process of claim 1, wherein the first and second reactors are independently operated at a pressure of between 500 and 2000 psig.

10. The process of claim 1, wherein a reactor temperature of the first reactor during the polymerization process is from about 60oC to about 140oC.

11. The process of claim 1, wherein a reactor temperature of the second reactor during the polymerization process is from about 60oC to about 140oC.

12. The process of claim 1, wherein a monomer feed temperature to each reactor is independently from about -20°C to 50°C.

13. The process of claim 1, wherein a hydrogen to propylene feed ratio is from about 0 to about 3 (g / kg) to the first reactor.

14. The process of claim 1, wherein a hydrogen to propylene feed ratio is from about 0 to about 5 (g / kg) to the second reactor.

15. The process of claim 1, wherein a hydrogen concentration in the first reactor is fromabout 0 to 0.05 mole / liter, and the hydrogen concentration in the second reactor is from about 0 to 0.4 mole / liter.

16. The process of claim 1, wherein the bis(phenolate) Lewis base catalyst compound comprises a group 4 transition metal, a tridentate dianionic ligand containing two anionic donor groups and a neutral heterocyclic Lewis base donor, wherein the heterocyclic donor is covalently bonded between the two anionic donors.

17. The process of claim 16, wherein the tridentate dianionic ligand coordinates to the metal with two anionic oxygen donors and one neutral heterocyclic nitrogen donor to form a pair of eight-membered metallocycle rings.

18. The process of claims 16, wherein the bis(phenolate) Lewis base catalyst compound is represented by Formula (I): wherein: M is a group 4 transition metal; each of E and E' is independently O, S, or NR9where R9is independently hydrogen, unsubstituted C1-C40 hydrocarbyl, substituted C1-C40 hydrocarbyl or a heteroatom- containing group; Q is a group 14, 15, or 16 atom that forms a dative bond to metal M; A1QA1’is part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms and links A2to A2’via a 3-atom bridge with Q being the central atom of the 3-atom bridge, each of A1and A1'is independently C, N, or C(R22), wherein R22is selected from hydrogen, unsubstituted C1-C20 hydrocarbyl, or substituted C1-C20 hydrocarbyl;divalent group containing 2 to 40 non-hydrogen atoms that links A1to the E-bonded aryl group via a 2-atom bridge;s a divalent group containing 2 to 40 non-hydrogen atoms that links A1'to theE'-bonded aryl group via a 2-atom bridge; L is a Lewis base; X is an anionic ligand; n is 1, 2 or 3; m is 0, 1, or 2; n+m is 4 or less; each of R1, R2, R3, R4, R1', R2', R3', and R4'is independently hydrogen, substituted C1-C40hydrocarbyl, unsubstituted C1-C40 hydrocarbyl, a heteroatom or a heteroatom-containing group; one or more of R1and R2, R2and R3, R3and R4, R1'and R2', R2’and R3', or R3'and R4'may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and where substitutions on the ring may join to form additional rings; any two L groups may be joined together to form a bidentate Lewis base; an X group may be joined to an L group to form a monoanionic bidentate group; and any two X groups may be joined together to form a dianionic ligand group.

19. The process of claim 16, wherein the bis(phenolate) Lewis base catalyst compound is represented by the Formula (II):wherein: M is a group 4 transition metal; each of E and E' is independently O, S, or NR9, wherein R9is independently hydrogen, unsubstituted C1-C40 hydrocarbyl, substituted C1-C40 hydrocarbyl, or heteroatom- containing group; each L is independently a Lewis base; each X is independently an anionic ligand; n is 1, 2 or 3;m is 0, 1, or 2; n+m is 4 or less; each of R1, R2, R3, R4, R1', R2', R3', and R4'is independently hydrogen, unsubstituted C1-C40hydrocarbyl, substituted C1-C40 hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R1and R2, R2and R3, R3and R4, R1'and R2', R2’and R3', R3'and R4'may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and wherein substitutions on the ring can join to form additional rings; any two L groups may be joined together to form a bidentate Lewis base; an X group may be joined to an L group to form a monoanionic bidentate group; any two X groups may be joined together to form a dianionic ligand group; and each of R5, R6, R7, R8, R5’, R6’, R7’, R8’, R10, R11, and R12is independently hydrogen, unsubstituted C1-C40 hydrocarbyl, substituted C1-C40 hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R5and R6, R6and R7, R7and R8, R5’and R6’, R6’and R7’, R7’and R8’, R10and R11, or R11and R12may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and wherein substitutions on the ring can join to form additional rings.

20. The process of any of claims 18 and 19, wherein the M of Formulas (I) or (II) comprises Hf or Zr.

21. The process of any of claims 18 and 19, wherein each E and E' of Formulas (I) or (II) is O.

22. The process of any of claims 18 and 19, wherein each of R1and R1’of Formulas (I) or (II) is independently a C4-C40 tertiary hydrocarbyl group.

23. The process of any of claims 18 and 19, wherein R1and R1’of Formulas (I) or (II) is independently a C4-C40 cyclic tertiary hydrocarbyl group.

24. The process of claim 18, wherein for Formula (I), M is Zr or Hf, Q is nitrogen, both A1and A1’are carbon form aryl groups, each of E and E’isoxygen, and both R1and R1’are independently tert-butyl, unsubstituted adamantan-1-yl orsubstituted adamantan-1-yl, each R2, R4, R2', and R4'are hydrogen, and R3and R3'is independently hydrogen or a C1 to C4 hydrocarbyl.

25. The process of any of claim 19, wherein for Formula (II), M is Zr or Hf, both E and E’are oxygen, and both R1and R1’are independently tert-butyl, unsubstituted adamantan- 1-yl or substituted adamantan-1-yl, each R2, R4, R2', and R4'are hydrogen, R3and R3'are independently hydrogen or a C1 to C4 hydrocarbyl, each R5, R6, R8, R5', R6', R8', R10, and R12are hydrogen, each R7and R7'are hydrogen or C1to C3hydrocarbyl, and R11is hydrogen or a C1 to C10 hydrocarbyl.

26. The process of any of claims 16 to 25, wherein the catalyst compound is:

27. The process of any of claims 16 to 25, wherein the activator is selected from one or more of:

28. The process of claim 1, wherein the polymer produced has a Mw(LS) / Mn(LS) value of about 1.8 to about 10.

29. The process of claim 1, wherein the second copolymer has a MFR (g / 10 min, 230oC / 2.16kg) that is higher than the MFR (g / 10 min, 230oC / 2.16kg) of the first copolymer.

30. The process of claim 1, wherein the polymer produced has a MFR (g / 10 min, 230oC / 2.16kg) of 20 or less.

31. The process of claim 1, wherein the polymer produced has a mm triad tacticity of about 75% or greater.

32. The process of claim 1, wherein the polymer produced has a r1r2of about 1 to about 3.

33. The process of claim 1, wherein the polymer produced has total regio defects from about 0.01 mol% to about 1.2 mol%.

34. The process of claim 1, wherein the polymer produced has an [EEE] triad content of about 0.5 mol% to about 4 mol%.

35. The process of claim 1, wherein the polymer produced has a weight average molecular weight (Mw(LS)) of about 100,000 g / mol to about 500,000 g / mol, a number average molecular weight (Mn(LS)) of about 10,000 g / mol to about 350,000 g / mol, and a z-average molecular weight (Mz(LS)) of about 200,000 g / mol 800,000 g / mol.

36. The process of claim 1, wherein the polymer produced has: a [PPP] triad content of about 45 mol% to about 56 mol%, an [EEE] triad content of about 1 mol% to about 4 mol%, an [EEP] triad content of about 6 mol% to about 11 mol%, a [PEP] triad content of about 10 mol% to about 13 mol%, an [EPE] triad content of about 4 mol% to about 7 mol%, and an [EPP] triad content of about 20 mol% to about 25 mol%.

37. The process of claim 1, wherein the polymer produced has an agglomeration number at 55 ºC of 500 seconds or less.

38. The process of claim 1, wherein the polymer produced has a flowability number at 55 ºC of 500 seconds or less.

39. The process of claim 1, wherein the polymer produced has a glass transition temperature (Tg) of about -20oC or lower.

40. The process of claim 1, wherein the first copolymer has a heat of fusion (Hf) of 5 J / g or less, the second copolymer has a Hfof 100 J / g or less, and the total polymer produced has a Hfof about 50 J / g or less.

41. The process of claim 1, wherein the polymer produced has a melt temperature (Tm) of about 50 °C to about 140°C, and the second copolymer has a Tm of about 50 °C to about 140°C.

42. A polypropylene polymer composition comprising: a first copolymer comprising about 5 to about 30 wt% ethylene units and about 70 to about 95 wt% propylene units, the first copolymer comprising: a mm triad tacticity of about 95% or greater, a r1r2 of about 1 to about 3, a second copolymer comprising an ethylene content at least about 3 wt% less than the ethylene content of the first copolymer, wherein the second copolymer has a weight average molecular weight (Mw(LS)) that is less than the weight average molecular weight of the first copolymer, and wherein the composition of the second copolymer is 2 - 40 wt% of the total polymer composition.

43. The composition of claim 42, wherein the polymer comprises a total regio defects from about from 0.01 mol% to about 1.2 mol%.

44. The composition of claim 42, wherein the polymer comprises an agglomeration number at 55 ºC of 500 seconds or less.

45. The composition of claim 42, wherein the polymer comprises a flowability number at 55ºC of 500 seconds or less.

46. The composition of claim 42, wherein the polymer comprises an [EEE] triad content of about 0.5 mol% to about 4 mol%.

47. The composition of claim 42, wherein the polymer comprises a Vicat softening temperature of about 40oC to about 75oC.

48. The composition of claim 42, wherein the first copolymer comprises about 16 wt% to about 23 wt% ethylene units and about 77 wt% to about 84 wt% propylene units.

49. The composition of claim 42, wherein the polymer comprises a Mw(LS) / Mn(LS) from about 1.5 to about 15 or from about 1.8 to about 10.

50. The composition of claim 42, wherein the first copolymer comprises an MFR (g / 10 min, 230oC / 2.16kg) of about 20 or less.

51. The composition of claim 42, wherein the second copolymer comprises an MFR (g / 10 min, 230oC / 2.16kg) that is higher than the MFR (g / 10 min, 230oC / 2.16kg) of the first copolymer.

52. The composition of claim 42, wherein the polymer comprises a glass transition temperature (Tg) of about -20oC or lower.

53. The composition of claim 42, wherein the first copolymer has a heat of fusion (Hf) of 5 J / g or less, the second copolymer has a Hf of 100 J / g or less, and the total polymer composition has a Hf of about 50 J / g or less.

54. The composition of claim 42, wherein the polymer composition has a melt temperature (Tm) of about 50 °C to about 140°C, and the second copolymer has a Tm of about 50 °C to about 140°C.

55. The composition of claim 42, wherein the polymer comprises a density of about 0.85 g / cm3to about 0.88 g / cm3.

56. The composition of claim 42, wherein the polymer comprises: a weight average molecular weight (Mw(LS)) of about 100,000 g / mol to about 500,000 g / mol, a number average molecular weight (Mn(LS)) of about 10,000 g / mol to about 350,000 g / mol, and a z-average molecular weight (Mz(LS)) of about 200,000 g / mol 800,000 g / mol.

57. The composition of claim 42, wherein the polymer comprises an mm triad tacticity of about 96% or greater.

58. The composition of claim 42, wherein the polymer comprises regio defects from about 0.1 mol% to about 1.15 mol%.

59. The composition of claim 42, having: a [PPP] triad content of about 45 mol% to about 55 mol%, an [EEE] triad content of about 1 mol% to about 3.8 mol%, an [EEP] triad content of about 6 mol% to about 10 mol%, a [PEP] triad content of about 10 mol% to about 12 mol%, an [EPE] triad content of about 4 mol% to about 7 mol%, and an [EPP] triad content of about 20 mol% to about 25 mol%.

60. The composition of claim 42, wherein the second copolymer comprises about 2 wt% to about 15 wt% ethylene content.

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