Patent Description:
Historically, the production of bimodal ethylene-based polymers occurs through processes with a single reactor with a single catalyst or dual reactor with a dual catalyst. In most methods for the production of bimodal ethylene-based polymers, this results in limitations in the properties of the bimodal ethylene-based polymers being produced. In particular, when using dual catalysts it can be difficult to produce bimodal polymers with tailored splits of low density and high density fractions, as it can be difficult to control the reactions of components in the presence of catalyst.

Therefore, as competition increases in the polymer industry, producers of ethylene-based polymers strive to make their products with broader ranges of properties. As such, ongoing needs exist for processes that are capable of producing ethylene-based polymers having a wider array of properties, such as, for example, high molecular weight high density fractions. It has been found that by controlling the location of the catalyst inlet, such that it is upstream from a first reactor and downstream from a second reactor, reactions of components in the presence of the catalyst can better be controlled. Further, because the catalyst is being combined with the components in a flow restricted area, compared to a bulk of a reactor, the catalyst and the components sufficiently mix before they reach the second reactor, and the second reactor can be non-agitated reactor, which reduces costs and energy consumption.

Accordingly, embodiments of the present disclosure are directed to dual reactor systems having various catalyst combinations, which are introduced at specific locations in the process and can produce a variety of bimodal products without substantially changing the current reactor set up.

Embodiments of the present disclosure are directed to a method of producing bimodal ethylene-based polymer comprising: reacting ethylene monomer and C<NUM>-C<NUM> α-olefin comonomer in solvent in the presence of a first catalyst in an agitated solution polymerization reactor to produce a first polymer fraction; outputting effluent from the agitated solution polymerization reactor, wherein effluent comprises the first polymer fraction, unreacted ethylene monomer, and unreacted C<NUM>-C<NUM> α-olefin comonomer; adding a second catalyst to the effluent downstream of the agitated solution polymerization reactor and upstream from a non-agitated solution polymerization reactor, wherein the second catalyst facilitates further reaction of the unreacted ethylene monomer and unreacted C<NUM>-C<NUM> α-olefin comonomer to produce a second polymer fraction having a density and melt index (I<NUM>) different from the first polymer fraction and the second catalyst and effluent mix in at least one mixer downstream from the agitated solution polymerization reactor and upstream of the non-agitated solution polymerization reactor; passing the second catalyst, second polymer fraction, and the first polymer fraction to the non-agitated solution polymerization reactor; and passing additional ethylene monomer, additional C<NUM>-C<NUM> α-olefin comonomer, and solvent to the non-agitated solution polymerization reactor, wherein the additional ethylene monomer, additional C<NUM>-C<NUM> α-olefin comonomer react in the presence of the second catalyst to produce more second polymer fraction and thereby the bimodal ethylene-based polymer, the bimodal ethylene-based polymer comprising the first polymer fraction and the second polymer fraction.

Additional features and advantages will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments described herein, including the detailed description which follows, the claims, as well as the appended drawings.

Specific embodiments of the present application will now be described. The disclosure may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth in this disclosure. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

According to one embodiment, a method of producing bimodal ethylene-based polymer comprising: reacting ethylene monomer and C<NUM>-C<NUM> α-olefin comonomer in solvent in the presence of a first catalyst in an agitated solution polymerization reactor to produce a first polymer fraction; outputting effluent from the agitated solution polymerization reactor, wherein effluent comprises the first polymer fraction, unreacted ethylene monomer, and unreacted C<NUM>-C<NUM> α-olefin comonomer; adding a second catalyst to the effluent downstream of the agitated solution polymerization reactor and upstream from a non-agitated solution polymerization reactor, wherein the second catalyst facilitates further reaction of the unreacted ethylene monomer and unreacted C<NUM>-C<NUM> α-olefin comonomer to produce a second polymer fraction having a density and melt index (I<NUM>) different from the first polymer fraction and the second catalyst and effluent mix in at least one mixer downstream from the agitated solution polymerization reactor and upstream of the non-agitated solution polymerization reactor; passing the second catalyst, second polymer fraction, and the first polymer fraction to the non-agitated solution polymerization reactor; and passing additional ethylene monomer, additional C<NUM>-C<NUM> α-olefin comonomer, and solvent to the non-agitated solution polymerization reactor, wherein the additional ethylene monomer, additional C<NUM>-C<NUM> α-olefin comonomer react in the presence of the second catalyst to produce more second polymer fraction and thereby the bimodal ethylene-based polymer, the bimodal ethylene-based polymer comprising the first polymer fraction and the second polymer fraction.

The term "polymer" refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term "homopolymer," usually employed to refer to polymers prepared from only one type of monomer as well as "copolymer" which refers to polymers prepared from two or more different monomers. The term "interpolymer," as used herein, refers to a polymer prepared by the polymerization of at least two different types of monomers. The generic term interpolymer thus includes copolymers, and polymers prepared from more than two different types of monomers, such as terpolymers.

As used herein, "bimodal" means compositions that can be characterized by having at least two (<NUM>) polymer subcomponents or "fractions" with varying densities and weight averaged molecular weights, and optionally, may also have different melt index values. In one embodiment, bimodal may be defined by having at least two distinct peaks in a Gel Permeation Chromatography (GPC) chromatogram showing the molecular weight distribution. In another embodiment, bimodal may be defined by having at least two distinct peaks in a Crystallization Elution Fractionation (CEF) chromatogram showing the short chain branching distribution. Bimodal includes resins having two peaks as well as resins having more than two peaks.

As used herein, the "solution polymerization reactor" is a vessel, which performs solution polymerization, wherein ethylene monomer and at least C<NUM>-C<NUM> α-olefin comonomer copolymerize after being dissolved in a non-reactive solvent that contains a catalyst. In the solution polymerization process, hydrogen may be utilized; however, it is not required in all solution polymerization processes.

"Polyethylene" or "ethylene-based polymer" shall mean polymers comprising greater than <NUM>% by mole of units derived from ethylene monomer. This includes ethylene-based homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of polyethylene known in the art include, but are not limited to, Low Density Polyethylene (LDPE); Linear Low Density Polyethylene (LLDPE); Ultra Low Density Polyethylene (ULDPE); Very Low Density Polyethylene (VLDPE); single-site catalyzed Linear Low Density Polyethylene, including both linear and substantially linear low density resins (m-LLDPE); Medium Density Polyethylene (MDPE); and High Density Polyethylene (HDPE).

The term "LDPE" may also be referred to as "high pressure ethylene polymer" or "highly branched polyethylene" and is defined to mean that the polymer is partly or entirely homopolymerized or copolymerized in autoclave or tubular reactors at pressures above <NUM>,<NUM> psi (<NUM> MPa) with the use of free-radical initiators, such as peroxides (see, for example, <CIT>, which is hereby incorporated by reference). LDPE resins typically have a density in the range of <NUM> to <NUM>/cm.

The term "LLDPE", includes resin made using Ziegler-Natta catalyst systems as well as resin made using single-site catalysts, including, but not limited to, bis-metallocene catalysts (sometimes referred to as "m-LLDPE"), phosphinimine, and constrained geometry catalysts; and resin made using post-metallocene, molecular catalysts, including, but not limited to, bis(biphenylphenoxy) catalysts (also referred to as polyvalent aryloxyether catalysts). LLDPE includes linear, substantially linear, or heterogeneous ethylene-based copolymers or homopolymers. LLDPEs contain less long chain branching than LDPEs and include the substantially linear ethylene polymers, which are further defined in <CIT>; <CIT>; <CIT>; and <CIT>; the homogeneously branched ethylene polymers such as those in <CIT>; the heterogeneously branched ethylene polymers such as those prepared according to the process disclosed in <CIT>; and blends thereof (such as those disclosed in <CIT> or <CIT>). The LLDPE resins can be made via gas-phase, solution-phase or slurry polymerization or any combination thereof, using any type of reactor or reactor configuration known in the art. The LLDPE resins can be made via gas-phase, solution-phase, or slurry polymerization or any combination thereof, using any type of reactor or reactor configuration known in the art.

The term "procatalyst" refers to a compound that has catalytic activity when combined with an activator. The term "activator" refers to a compound that chemically reacts with a procatalyst in a manner that converts the procatalyst to a catalytically active catalyst. As used herein, the terms "cocatalyst" and "activator" are interchangeable terms.

The term "non-agitated reactor" refers to a reactor that does not include mechanical agitation, such as agitation by a stirrer, a mixer, a kneader, or the like. Examples of non-agitated reactors include plug flow reactors, tank reactors, and loop reactors, all without stirrers, mixers, or the like.

The term "mixer" refers to an apparatus that mechanically mixes the components present in the apparatus. Examples of mixers include static mixers, flow shapers, and vessels comprising a stirrer, mixer, kneader, or the like. In embodiments, components present in the mixer-such as monomers, comonomer, etc.-will react in the mixer.

Reference will now be made in detail to systems for producing bimodal ethylene-based polymers having high molecular weight high density fraction according to embodiments disclosed and described herein.

With reference now to the FIG. , a system <NUM> for producing bimodal ethylene-based polymer having a high molecular weight high density fraction according to embodiments comprises a first reactor <NUM> and a second reactor <NUM> fluidly connected to the first reactor <NUM>. The type of reactors used for the first reactor <NUM> and the second reactor <NUM> are not limited and, in embodiments, are reactors suitable for use as solution polymerization reactors. In embodiments, the first reactor <NUM> is an agitated solution polymerization reactor, such as, for example a loop reactor, an isothermal reactor, an adiabatic reactor, and a continuous stirred tank reactor in parallel, series, and any combinations thereof. The second reactor <NUM>, according to embodiments, is a non-agitated solution polymerization reactor, such as, for example, a non-agitated tank reactor or a tubular reactor (e.g., a plug flow reactor, a piston flow reactor, etc.).

According to embodiments, one or more mixers <NUM> are positioned downstream from a first reactor <NUM> and upstream from a second reactor <NUM>. Although the FIG. only depicts one mixer, it should be understood that additional mixers may be positioned in series or parallel downstream from the first reactor <NUM> and upstream from the second reactor <NUM>. The mixer <NUM> may be a flow shaper or static mixer. For example, in some embodiments, mixer <NUM> may comprise a flow shaper and a static mixer. A "flow shaper" as used herein may be any type of apparatus that alters the flow of a component stream, such as, for example, a tapered pipe, a diffuser, or a nozzle. In embodiments, such as the embodiment depicted in the FIG. , the mixer <NUM> and the non-agitated rector <NUM> may be separate physical apparatuses. However, in some embodiments, the mixer <NUM> and the non-agitated reactor <NUM> may be a single physical apparatus with two distinct zones. As an example, in embodiments, the mixer <NUM> and non-agitated reactor <NUM> may both be housed in an elongated tube. In static mixer may be positioned in a first portion of the elongated tube, while a second portion of the elongated tube does not include the static mixer-or any other type of agitator. In such an embodiment, the first zone of the elongated tube where the static mixer is present is the mixer <NUM> and the second zone of the elongated tube where no agitator is present is the non-agitated reactor <NUM>. In such an embodiment, the mixer <NUM> and the non-agitated reactor are housed in a single physical apparatus.

As shown in the embodiment depicted in the FIG. , the first reactor <NUM> is configured to receive: feed stream <NUM> that comprises ethylene monomer and C<NUM>-C<NUM> α-olefin comonomer in solvent; first catalyst stream <NUM>; and, optionally, hydrogen (H<NUM>) stream <NUM>. The components of feed stream <NUM>, first catalyst stream <NUM>, and optional hydrogen stream <NUM> are reacted in the first reactor <NUM> to produce a first polymer fraction. This first polymer fraction is outputted from the first reactor <NUM> as effluent 111a. In embodiments, effluent 111a comprises unreacted ethylene monomer and unreacted C<NUM>-C<NUM> α-olefin comonomer in addition to the first polymer fraction. It should be understood that, in some embodiments, the components of the feed stream <NUM> may be added to the first reactor <NUM> together or as separate streams. For example, ethylene monomer and solvent may be added to the first reactor as a separate stream from the C<NUM>-C<NUM> α-olefin comonomer. The order at which the ethylene monomer, C<NUM>-C<NUM> α-olefin comonomer, and solvent into the first reactor <NUM> is not limited.

With reference still to the FIG. , second catalyst stream <NUM> is added to the effluent 111a downstream of the first reactor <NUM> (i.e., agitated solution polymerization reactor) and upstream from the second reactor <NUM> (i.e., non-agitated solution polymerization reactor). The second catalyst stream <NUM> may, in embodiments be added into the mixer <NUM>. In other embodiments, the second catalyst stream <NUM> may be added immediately before the mixer <NUM>. Second catalyst stream <NUM> comprises a different catalyst than the first catalyst stream <NUM> and facilitates reaction of unreacted ethylene monomer and unreacted C<NUM>-C<NUM> α-olefin comonomer present in the effluent 111a to produce a second polymer fraction. In embodiments, the second polymer fraction has a density and melt index (I<NUM>) that differ from the density and melt index (I<NUM>) of the first polymer fraction. The modified effluent 111b, which comprises the first polymer fraction, the second polymer fraction, and second catalyst, is passed from the mixer <NUM> to the second reactor <NUM>.

A second feed stream <NUM> comprising additional ethylene monomer, additional C<NUM>-C<NUM> α-olefin comonomer, and solvent is passed to second reactor <NUM>. The additional ethylene monomer and additional C<NUM>-C<NUM> α-olefin comonomer from the second feed stream <NUM> react in the presence of the second catalyst introduced into the second reactor <NUM> via the modified effluent 111b to form additional second polymer fraction. Accordingly, a bimodal ethylene-based polymer, which comprises first polymer fraction and second polymer fraction is outputted from the second reactor <NUM> in product stream <NUM>.

By introducing the second catalyst stream <NUM> downstream from the first reactor <NUM> and upstream from the second reactor <NUM>, the second catalyst stream <NUM> mixes with unreacted ethylene monomer and unreacted C<NUM>-C<NUM> α-olefin comonomer present in effluent 111a prior introduction of second catalyst into the second reactor <NUM>. This circumvents a common issue that occurs when second catalyst is introduced directly into the second reactor <NUM>; gumming of the second catalyst inlet that undesirably restricts the amount of second catalyst that is added to the second reactor <NUM>. Accordingly, by provided the second catalyst stream <NUM> downstream from the first reactor <NUM> and upstream from the second reactor <NUM>, agitation is not required in the second reactor <NUM>, which can reduce equipment and operating costs. A mixer <NUM> mixes the second catalyst stream <NUM> with unreacted ethylene monomer and unreacted C<NUM>-C<NUM> α-olefin comonomer present in effluent 111a prior to passing effluent 111a and the second catalyst stream <NUM> to the second reactor <NUM>. The mixing of unreacted ethylene monomer and unreacted C<NUM>-C<NUM> α-olefin comonomer in the mixer <NUM> in the presence of second catalyst allows for reactions of the unreacted ethylene monomer and unreacted C<NUM>-C<NUM> α-olefin comonomer at low temperatures and high ethylene monomer concentrations, which results in a second polymer fraction with high density, high molecular weight portions to be formed in the mixer <NUM>.

Additionally, in some embodiments, additional ethylene monomer may be added downstream from the first reactor <NUM> and upstream from the second reactor <NUM>, such as, for example, into the mixer <NUM>, to facilitate formation of the second polymer fraction before modified effluent 111b enters the second reactor <NUM>. In some embodiments, the additional ethylene monomer may be added to effluent 111a (i.e., before the second catalyst stream <NUM> is introduced into the mixer <NUM>), and in other embodiments, the additional ethylene monomer may be added to the mixer <NUM>.

Reference will now be made in detail to methods and components used in systems of embodiments disclosed above for producing bimodal ethylene-based polymers having high molecular weight high density fraction according to embodiments disclosed and described herein.

As disclosed previously herein, and with reference to the FIG. , the first reactor <NUM>, which is an agitated solution polymerization reactor, receives feed stream <NUM>, first catalyst stream <NUM>, and, optionally, hydrogen stream <NUM>. The components of the feed stream <NUM>-optionally with hydrogen from hydrogen stream <NUM>-react in the presence of a first catalyst, which is introduced into the first reactor <NUM> via first catalyst stream <NUM>, to form a first polymer fraction. The first polymer fraction and non-reacted components exit the first reactor <NUM> via effluent 111a. Each of these streams and the reaction conditions within the first reactor <NUM> are described in more detail below.

Feed stream <NUM> comprises ethylene monomer and C<NUM>-C<NUM> α-olefin comonomer in solvent. In some embodiments, the comonomer is C<NUM>-C<NUM> α-olefin. Exemplary α-olefin comonomers include, but are not limited to, propylene, <NUM>-butene, <NUM>-pentene, <NUM>-hexene, <NUM>-heptene, <NUM>-octene, <NUM>-nonene, <NUM>-decene, and <NUM>-methyl-<NUM>-pentene. The one or more α-olefin comonomers may, in embodiments, be selected from the group consisting of propylene, <NUM>-butene, <NUM>-hexene, and <NUM>-octene. The solvent present in the feed stream may, in embodiments, be aromatic and paraffin solvents. In some embodiments, the solvent may be isoparaffins, such as, for example, ISOPAR E manufactured by ExxonMobil Chemical.

The hydrogen stream <NUM> is essentially pure hydrogen and, in embodiments, comprises greater than <NUM> volume percent (vol. %) hydrogen, such as greater than <NUM> vol. % hydrogen, or greater than <NUM> vol. % hydrogen.

The first catalyst is added to the first reactor <NUM> via first catalyst stream <NUM> and facilitates reactions between ethylene monomer, C<NUM>-C<NUM> α-olefin comonomer, and, optionally, hydrogen. Catalysts that may be used in embodiments include, but are not limited to, a post-metallocene catalyst, a constrained geometry complex (CGC) catalyst, a phosphinimine catalyst, or a bis(biphenylphenoxy) catalyst. Details and examples of CGC catalysts are provided in <CIT>; <CIT>; <CIT>; and <CIT>, which are all incorporated herein by reference in their entirety. Details and examples of bis(biphenylphenoxy) catalysts are provided in <CIT>; <CIT>; <CIT>; <CIT>; <CIT>, which are all incorporated herein by reference in their entirety. In embodiments, the first catalyst may be a molecular catalyst including, but not limited to, bis(biphenylphenoxy) catalysts (also referred to as polyvalent aryloxyether catalysts).

Bis(biphenylphenoxy) catalysts are multi-component catalyst systems comprising a bis(biphenylphenoxy) procatalyst, a cocatalyst that activates the procatalyst, as well as other optional ingredients. In embodiments, the bis(biphenylphenoxy) procatalyst may include a metal-ligand complex according to Formula (I):
<CHM>.

In Formula (I), M is a metal chosen from titanium, zirconium, or hafnium, the metal being in a formal oxidation state of +<NUM>, +<NUM>, or +<NUM>; n is <NUM>, <NUM>, or <NUM>; when n is <NUM>, X is a monodentate ligand or a bidentate ligand; when n is <NUM>, each X is a monodentate ligand and is the same or different; the metal-ligand complex is overall charge-neutral; O is O (an oxygen atom); each Z is independently chosen from -O-, -S-, -N(RN)-, or -P(RP)-; L is (C<NUM>-C<NUM>)hydrocarbylene or (C<NUM>--C<NUM>)heterohydrocarbylene, wherein the (C<NUM>-C<NUM>)hydrocarbylene has a portion that comprises a <NUM>-carbon atom to <NUM>-carbon atom linker backbone linking the two Z groups in Formula (I) (to which L is bonded) or the (C<NUM>-C<NUM>)heterohydrocarbylene has a portion that comprises a <NUM>-atom to <NUM>-atom linker backbone linking the two Z groups in Formula (I), wherein each of the <NUM> to <NUM> atoms of the <NUM>-atom to <NUM>-atom linker backbone of the (C<NUM>-C<NUM>)heterohydrocarbylerie independently is a carbon atom or heteroatom, wherein each heteroatom independently is O, S, S(O), S(O)<NUM>, Si(RC)<NUM>, Ge(RC)<NUM>, P(RC), or N(RC), wherein independently each RC is (C<NUM>-C<NUM>)hydrocarbyl or (C<NUM>-C<NUM>)heterohydrocarbyl; R<NUM> and R<NUM> are independently selected from the group consisting of (C<NUM>-C<NUM>)hydrocarbyl, (C<NUM>-C<NUM>)heterohydrocarby, -Si(RC)<NUM>, -Ge(RC)<NUM>, -P(RP)<NUM>, -N(RN)<NUM>, -ORC, -SRC, -NO<NUM>, -CN, -CF<NUM>, RCS(O)-, RCS(O)<NUM>-, (RC)<NUM>C=N-, RCC(O)O-, RCOC(O)-, RCC(O)N(RN)-, (RN )<NUM>NC(O)-, halogen, and radicals having Formula (<NUM>), Formula (III), or Formula (IV):
<CHM>.

In Formulas (II), (III), and (IV), each of R<NUM>-<NUM>, R<NUM>-<NUM>, or R<NUM>-<NUM> is independently chosen from (C<NUM>-C<NUM>)hydrocarbyl, (C<NUM>-C<NUM>)heterohydrocarbyl, -Si(RC)<NUM>, -Ge(RC)<NUM>, -P(RP)<NUM>, -N(RN)<NUM>, -ORC -SRC, -NO<NUM>, -CN, -CF<NUM>, RCS(O)-, RCS(O)<NUM>-, (RC)<NUM>C=N-, RCC(O)O-, RCOC(O)-, RCC(O)N(RN)-, (RN)<NUM>NC(O)-, halogen, or -H, provided at least one of R<NUM> or R<NUM> is a radical having Formula (II), Formula (III), or Formula (IV).

In Formula (I), each of R<NUM>-<NUM>, R<NUM>-<NUM>, and R<NUM>-<NUM> is independently selected from (C<NUM>-C<NUM>)hydrocarbyl, (C<NUM>-C<NUM>)heterohydrocarbyl, -Si(RC)<NUM>, -Ge(RC)<NUM>, -P(RP)<NUM>, -N(RN)<NUM>-ORC, -SRC, -NO<NUM>, -CN, -CF<NUM>, RCS(O)-, RCS(O)<NUM>-, (RC)<NUM>C=N-, RCC(O)O-, RCOC(O)-, RCC(O)N(RN)-, (RC)<NUM>NC(O)-, halogen, and -H.

Detailed embodiments of various functional groups that can be present in the compositions depicted in Formulae (I) - (IV) will now be described in detail. It should be understood that the following functional groups are exemplary and are disclosed to provide non-limiting examples of the bis(biphenylphenoxy) procatalyst that can be used according to embodiments.

"Independently selected" as used herein indicates that the R groups, such as, R<NUM>, R<NUM>, R<NUM>, R<NUM>, and R<NUM> can be identical or different (e.g., R<NUM>, R<NUM>, R<NUM>, R<NUM>, and R<NUM> may all be substituted alkyls or R<NUM> and R<NUM> may be a substituted alkyl and R<NUM> may be an aryl, etc.). Use of the singular includes use of the plural and vice versa (e.g., a hexane solvent, includes hexanes). A named R group will generally have the structure that is recognized in the art as corresponding to R groups having that name. These definitions are intended to supplement and illustrate, not preclude, the definitions known to those of skill in the art.

When used to describe certain carbon atom-containing chemical groups, a parenthetical expression having the form "(Cx-Cy)" or a non-parenthetical expression having the form "Cx-Cy" means that the unsubstituted form of the chemical group has from x carbon atoms to y carbon atoms, inclusive of x and y. For example, a (C<NUM>-C<NUM>)alkyl is an alkyl group having from <NUM> to <NUM> carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups may be substituted by one or more substituents such as RS. An RS substituted version of a chemical group defined using the "(Cx-Cy)"' parenthetical or "Cx-Cy" non-parenthetical may contain more than y carbon atoms depending on the identity of any groups RS. For example, a "(C<NUM>-C<NUM>)alkyl substituted with exactly one group RS, where RS is phenyl (mC<NUM>H<NUM>)" may contain from <NUM> to <NUM> carbon atoms. Thus, in general when a chemical group defined using the "(Cx-Cy)" parenthetical Cx-Cy" non-parenthetical is substituted by one or more carbon atom-containing substituents RS, the minimum and maximum total number of carbon atoms of the chemical group is determined by adding to both x and y the combined sum of the number of carbon atoms from all of the carbon atom-containing substituents RS.

In some embodiments, each of the chemical groups (e.g., X, R, etc.) of the metal-ligand complex of Formula (I) may be unsubstituted having no RS substituents. In other embodiments, at least one of the chemical groups of the metal-ligand complex of Formula (I) may independently contain one or more than one RS. In some embodiments, the sum total of RS in the chemical groups of the metal-ligand complex of Formula (I) does not exceed <NUM>. In other embodiments, the sum total of RS in the chemical groups does not exceed <NUM>. For example, if each R<NUM>-<NUM> was substituted with two RS, then X and Z cannot be substituted with an RS. In another embodiment, the sum total of RS in the chemical groups of the metal-ligand complex of Formula (I) may not exceed <NUM> RS. When two or more than two RS are bonded to a same chemical group of the metal-ligand complex of Formula (I), each RS is independently bonded to the same or different carbon atom or heteroatom and may include persubstitution of the chemical group.

"Substitution" as used herein means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., RS). The term "persubstitution" as used herein means that every hydrogen atom (H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., RS). The term "polysubstitution" as used herein means that at least two, but fewer than all, hydrogen atoms bonded to carbon atoms or heteroatoms of a corresponding unsubstituted compound or functional group are replaced by a substituent.

As used herein, "-H" means a hydrogen or hydrogen radical that is covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable, and unless clearly specified mean the same thing.

"(C<NUM>-C<NUM>)hydrocarbyl" as used herein means a hydrocarbon radical of from <NUM> to <NUM> carbon atoms and the term "(C<NUM>-C<NUM>)hydrocarbylene" means a hydrocarbon diradical of from <NUM> to <NUM> carbon atoms, in which each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (including mono- and poly-cyclic, fused and non-fused polycyclic, including bicyclic; <NUM> carbon atoms or more) or acyclic and is unsubstituted or substituted by one or more RS.

As used in this disclosure, a (C<NUM>-C<NUM>)hydrocarbyl can be an unsubstituted or substituted (C<NUM>-C<NUM>)alkyl, (C<NUM>-C<NUM>)cycloalkyl, (C<NUM>-C<NUM>)cycloalkyl-(C<NUM>-C<NUM>)alkylene, (C<NUM>-C<NUM>)aryl, or (C<NUM>-C<NUM>)aryl-(C<NUM>-C<NUM>)alkylene. In some embodiments, each of the aforementioned (C<NUM>-C<NUM>)hydrocarbyl groups has a maximum of <NUM> carbon atoms (i.e., (C<NUM>-C<NUM>)hydrocarbyl) and other embodiments, a maximum of <NUM> carbon atoms.

"(C<NUM>--C<NUM>)alkyl" and "(C<NUM>-C<NUM>)alkyl" as used herein mean a saturated straight or branched hydrocarbon radical of from <NUM> to <NUM> carbon atoms or from <NUM> to <NUM> carbon atoms, respectively, which is unsubstituted or substituted by one or more RS. Examples of unsubstituted (C<NUM>-C<NUM>)alkyl are unsubstituted (C<NUM>-C<NUM>)alkyl; unsubstituted (C<NUM>-C<NUM>)alkyl; unsubstituted (C<NUM>-C<NUM>)alkyl; methyl; ethyl; <NUM>-propyl; <NUM>-propyl; <NUM>-butyl; <NUM>-butyl; <NUM>-methylpropyl; <NUM>,<NUM>-dimethylethyl; <NUM>-pentyl; <NUM>-hexyl; <NUM>-heptyl; <NUM>-nonyl; and <NUM>-decyl. Examples of substituted (C<NUM>-C<NUM>)alkyl are substituted (C<NUM>-C<NUM>)alkyl, substituted (C<NUM>-C<NUM>)alkyl, trifluoromethyl, and [C<NUM>]alkyl. The term "[C<NUM>]alkyl" (with square brackets) as used herein means there is a maximum of <NUM> carbon atoms in the radical, including substituents, and is, for example, a (C<NUM>-C<NUM>)alkyl substituted by one RS, which is a (C<NUM>-C<NUM>)alkyl, respectively. Each (C<NUM>-C<NUM>)alkyl may be methyl, trifluoromethyl, ethyl, <NUM>-propyl, <NUM>-methylethyl, or <NUM>,<NUM>-dimethylethyl.

"(C<NUM>-C<NUM>)aryl" as used herein means an unsubstituted or substituted (by one or more RS) mono-, bi- or tricyclic aromatic hydrocarbon radical of from <NUM> to <NUM> carbon atoms, of which at least from <NUM> to <NUM> of the carbon atoms are aromatic ring carbon atoms, and the mono-, bi- or tricyclic radical comprises <NUM>, <NUM>, or <NUM> rings, respectively; wherein the <NUM> ring is aromatic and the <NUM> or <NUM> rings independently are fused or non-fused and at least one of the <NUM> or <NUM> rings is aromatic. Examples of unsubstituted (C<NUM>-C<NUM>)aryl are unsubstituted (C<NUM>-C<NUM>)aryl unsubstituted (C<NUM>-C<NUM>)aryl; <NUM>-(C<NUM>-C<NUM>)alkyl-phenyl; <NUM>,<NUM>-bis(C<NUM>-C<NUM>)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Examples of substituted (C<NUM>-C<NUM>)aryl are substituted (C<NUM>-C<NUM>)aryl; substituted (C<NUM>-C<NUM>)aryl; <NUM>,<NUM>-bis[(C<NUM>)alkyl]-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-<NUM>-one-<NUM>-yl.

"(C<NUM>-C<NUM>)cycloalkyl" as used herein means a saturated cyclic hydrocarbon radical of from <NUM> to <NUM> carbon atoms that is unsubstituted or substituted by one or more RS. Other cycloalkyl groups (e.g., (Cx-Cy)cycloalkyl) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more RS. Examples of unsubstituted (C<NUM>-C<NUM>)cycloalkyl are unsubstituted (C<NUM>-C<NUM>)cycloalkyl, unsubstituted (C<NUM>-C<NUM>)cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted (C<NUM>-C<NUM>)cycloalkyl are substituted (C<NUM>-C<NUM>)cycloalkyl, substituted (C<NUM>-C<NUM>)cycloalkyl, cyclopentanon-<NUM>-yl, and <NUM>-fluorocyclohexyl.

Examples of (C<NUM>-C<NUM>)hydrocarbylene include unsubstituted or substituted (C<NUM>-C<NUM>)arylene, (C<NUM>-C<NUM>)cycloalkylene, and (C<NUM>-C<NUM>)alkylene (e.g., (C<NUM>-C<NUM>)alkylene). In some embodiments, the diradicals are on the same carbon atom (e.g., -CH<NUM>-) or on adjacent carbon atoms (i.e., <NUM>,<NUM>- diradicals), or are spaced apart by one, two, or more than two intervening carbon atoms (e.g., respective <NUM>,<NUM>-diradicals, <NUM>,<NUM>-diradicals, etc.). Some diradicals include α,ω-diradical. The α,ω-diradical is a diradical that has maximum carbon backbone spacing between the radical carbons. Some examples of (C<NUM>-C<NUM>)alkylene α,ω-diradicals include ethan-<NUM>,<NUM>-diyl (i.e., -CH<NUM>CH<NUM>), propan-<NUM>,<NUM>-diyl (i.e., -CH<NUM>CH<NUM>CH<NUM>-), <NUM>-methylpropan-<NUM>,<NUM>-diyl (i.e., -CH<NUM>CH(CH<NUM>)CH<NUM>-). Some examples of (C<NUM>-C<NUM>)arylene α,ω-diradicals include phenyl-<NUM>,<NUM>-diyl, napthalen-<NUM>,<NUM>-diyl, or napthalen-<NUM>,<NUM>-diyl.

"(C<NUM>-C<NUM>)alkylene" as used herein means a saturated straight chain or branched chain diradical (i.e., the radicals are not on ring atoms) of from <NUM> to <NUM> carbon atoms that is unsubstituted or substituted by one or more RS. Examples of unsubstituted (C<NUM>-C<NUM>)alkylene are unsubstituted (C<NUM>-C<NUM>)alkylene, including unsubstituted-CH<NUM>CH<NUM>-, -(CH<NUM>)<NUM>-, -(CH<NUM>)<NUM>-, -(CH<NUM>)<NUM>-, -(CH<NUM>)<NUM>-, -(CH<NUM>)<NUM>-, -(CH<NUM>)<NUM>-, -CH<NUM>C*HCH<NUM>, and -(CH<NUM>)<NUM>C*(H)(CH<NUM>), in which "C*" denotes a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Examples of substituted (C<NUM>-C<NUM>)alkylene are substituted (C<NUM>-C<NUM>)alkylene, -CF<NUM>-, -C(O)-, and -(CH<NUM>)<NUM>C(CH<NUM>)<NUM>(CH<NUM>)<NUM>- (i.e., a <NUM>,<NUM>-dimethyl substituted normal-<NUM>,<NUM>-eicosylene). Since as mentioned previously two RS may be taken together to form a (C<NUM>-C<NUM>)alkylene, examples of substituted (C<NUM>-C<NUM>)alkylene also include l,<NUM>-bis(methylene)cyclopentane, <NUM>,<NUM>- bis(methylene)cyclohexane, <NUM>,<NUM>-bis(methylene)-<NUM>,<NUM>-dimethyl-bicyclo[<NUM>. <NUM>]heptane, and <NUM>,<NUM>- bis (methylene)bicyclo [<NUM>. <NUM>] octene.

"(C<NUM>-C<NUM>)cycloalkylene" as used herein means a cyclic diradical (i.e., the radicals are on ring atoms) of from <NUM> to <NUM> carbon atoms that is unsubstituted or substituted by one or more RS.

"Heteroatom" as used herein refers to an atom other than hydrogen or carbon. Examples of groups containing one or more than one heteroatom include O, S, S(O), S(O)<NUM>, Si(RC)<NUM>, P(RP), N(RN), -N=C(RC)<NUM>, -Ge(RC)<NUM>-, or -Si(RC)-, where each RC and each RP is unsubstituted (C<NUM>-C<NUM>)hydrocarbyl or -H, and where each RN is unsubstituted (C<NUM>-C<NUM>)hydrocarbyl. The term "heterohydrocarbon" refers to a molecule or molecular framework in which one or more carbon atoms are replaced with a heteroatom. The term "(C<NUM>-C<NUM>)heterohydrocarbyl" means a heterohydrocarbon radical of from <NUM> to <NUM> carbon atoms, and the term "(C<NUM>-C<NUM>)heterohydrocarbylene" means a heterohydrocarbon diradical of from <NUM> to <NUM> carbon atoms, and each heterohydrocarbon has one or more heteroatoms. The radical of the heterohydrocarbyl is on a carbon atom or a heteroatom, and diradicals of the heterohydrocarbyl may be on: (<NUM>) one or two carbon atom, (<NUM>) one or two heteroatoms, or (<NUM>) a carbon atom and a heteroatom. Each (C<NUM>-C<NUM>)heterohydrocarbyl and (C<NUM>-C<NUM>)heterohydrocarbylene may be unsubstituted or substituted (by one or more RS), aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (including mono- and poly-cyclic, fused and non-fused polycyclic), or acyclic.

The (C<NUM>-C<NUM>)heterohydrocarbyl may be unsubstituted or substituted. Non-limiting examples of the (C<NUM>-C<NUM>)heterohydrocarbyl include (C<NUM>-C<NUM>)heteroalkyl, (C<NUM>-C<NUM>)hydrocarbyl-O-, (C<NUM>-C<NUM>)hydrocarbyl-S-, (C<NUM>-C<NUM>)hydrocarbyl-S(O)-, (C<NUM>-C<NUM>)hydrocarbyl-S(O)<NUM>-, (C<NUM>-C<NUM>)hydrocarbyl-Si(RC)<NUM>-, (C<NUM>-C<NUM>)hydrocarbyl-N(RN)-, (C<NUM>-C<NUM>)hydrocarbyl-P(RP), (C<NUM>-C<NUM>)heterocycloalkyl, (C<NUM>-C<NUM>)heterocycloalky-<NUM>-(C<NUM>-C<NUM>)alkylene, (C<NUM>-C<NUM>)cycloalkyl-(C<NUM>-C<NUM>)heteroalkylene, (C<NUM>-C<NUM>)heterocycloalkyl-(C<NUM>-C<NUM>)heteroalkylene, (C<NUM>-C<NUM>)heteroaryl, (C<NUM>-C<NUM>)heteroaryl-(C<NUM>-C<NUM>)alkylene, (C<NUM>-C<NUM>)aryl-(C<NUM>-C<NUM>)heteroalkylene, or (C<NUM>-C<NUM>)heteroaryl-(C<NUM>-C<NUM>)heteroalkylene.

"(C<NUM>-C<NUM>)heteroaryl" as used herein means an unsubstituted or substituted (by one or more RS) mono-, bi- or tricyclic heteroaromatic hydrocarbon radical of from <NUM> to <NUM> total carbon atoms and from <NUM> to <NUM> heteroatoms, and the mono-, bi- or tricyclic radical comprises <NUM>, <NUM> or <NUM> rings, respectively, wherein the <NUM> or <NUM> rings independently are fused or non-fused and at least one of the <NUM> or <NUM> rings is heteroaromatic. Other heteroaryl groups (e.g., (Cx-Cy)heteroaryl generally, such as (C<NUM>-C<NUM>)heteroaryl) are defined in an analogous manner as having from x to y carbon atoms (such as <NUM> to <NUM> carbon atoms) and being unsubstituted or substituted by one or more than one RS. The monocyclic heteroaromatic hydrocarbon radical is a <NUM>-membered or <NUM>-membered ring. The <NUM>-membered ring has <NUM> minus h carbon atoms, wherein h is the number of heteroatoms and may be <NUM>, <NUM>, or <NUM>; and each heteroatom may be O, S, N, or P. Examples of <NUM>-membered ring heteroaromatic hydrocarbon radical are pyrrol-<NUM>-yl; pyrrol-<NUM>-yl; furan-<NUM>-yl; thiophen-<NUM>-yl; pyrazol-<NUM>-yl; isoxazol-<NUM>-yl; isothiazol-<NUM>-yl; imidazol-<NUM>-yl; oxazol-<NUM>-yl; thiazol-<NUM>-yl; <NUM>,<NUM>,<NUM>-triazol-<NUM>-yl; <NUM>,<NUM>,<NUM>-oxadiazol-<NUM>-yl; <NUM>,<NUM>,<NUM>-thiadiazol-<NUM>-yl; tetrazol-<NUM>-yl; tetrazol-<NUM>-yl; and tetrazcsl-<NUM>-yl. The <NUM>-membered ring has <NUM> minus h carbon atoms, wherein h is the number of heteroatoms and may be <NUM> or <NUM> and the heteroatoms may be N or P. Examples of <NUM>-membered ring heteroaromatic hydrocarbon radical are pyridine-<NUM>-yl; pyrimidin-<NUM>-yl; and pyrazin-<NUM>-yl. The bicyclic heteroaromatic hydrocarbon radical can be a fused <NUM>,<NUM>- or <NUM>,<NUM>-ring system. Examples of the fused <NUM>,<NUM>-ring system bicyclic heteroaromatic hydrocarbon radical are indol-<NUM>-yl; and benzimidazole-<NUM>-yl. Examples of the fused <NUM>,<NUM>-ring system bicyclic heteroaromatic hydrocarbon radical are quinolin-<NUM>-yl; and isoquinolin-<NUM>-yl. The tricyclic heteroaromatic hydrocarbon radical can be a fused <NUM>,<NUM>,<NUM>-; <NUM>,<NUM>,<NUM>-; <NUM>,<NUM>,<NUM>-; or <NUM>,<NUM>,<NUM>-ring system. An example of the fused <NUM>,<NUM>,<NUM>-ring system is <NUM>,<NUM>-dihydropyrrolo[<NUM>,<NUM>-f]indol-<NUM>-yl. An example of the fused <NUM>,<NUM>,<NUM>-ring system is <NUM>-benzo[f] indol-<NUM>-yl. An example of the fused <NUM>,<NUM>,<NUM>- ring system is <NUM>-carbazol-<NUM>-yl. An example of the fused <NUM>,<NUM>,<NUM>-ring system is acrydin-<NUM>-yl.

The aforementioned heteroalkyl may be saturated straight or branched chain radicals containing (C<NUM>-C<NUM>) carbon atoms, or fewer carbon atoms and one or more of the heteroatoms. Likewise, the heteroalkylene may be saturated straight or branched chain diradicals containing from <NUM> to <NUM> carbon atoms and one or more than one heteroatoms. The heteroatoms, as defined above, may include Si(RC)<NUM>, Ge(RC)<NUM>, Si(RC)<NUM>, Ge(RC)<NUM>, P(RP)<NUM>, P(RP), N(RN)<NUM>, N(RN), N, O, ORC, S, SRC, S(O), and S(O)<NUM>, wherein each of the heteroalkyl and heteroalkylene groups are unsubstituted or substituted by one or more RS.

Examples of unsubstituted (C<NUM>-C<NUM>)heterocycloalkyl are unsubstituted (C<NUM>-C<NUM>)heterocycloalkyl, unsubstituted (C<NUM>-C<NUM>)heterocycloalkyl, aziridin-<NUM>-yl, oxetan-<NUM>-yl, tetrahydrofuran-<NUM>-yl, pyrrolidin-<NUM>-yl, tetrahydrothiophen-S,S-dioxide-<NUM>-yl, morpholin-<NUM>-yl, <NUM>,<NUM>-dioxan-<NUM>-yl, hexahydroazepin-<NUM>-yl, <NUM>-oxa-cyclooctyl, <NUM>-thio-cyclononyl, and <NUM>-aza-cyclodecyl.

"Halogen atom" or "halogen" as used herein mean the radical of a fluorine atom (F), chlorine atom (Cl), bromine atom (Br), or iodine atom (I). The term "halide" means anionic form of the halogen atom: fluoride (F-), chloride (Cl-), bromide (Br-), or iodide (I-).

"Saturated" as used herein means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon phosphorous, and carbon-silicon double bonds. Where a saturated chemical group is substituted by one or more substituents RS, one or more double and/or triple bonds optionally may or may not be present in substituents RS. The term "unsaturated" means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorous, and carbon-silicon double bonds, not including any such double bonds that may be present in substituents RS, if any, or in (hetero) aromatic rings, if any.

Various process control methodologies are contemplated. In one embodiment, Fourier Transform Near-Infrared (FTnIR) Spectrometer may be utilized in a process control feedback loop. For example, in the first solution polymerization reactor, the first and second ethylene-based components will be produced with sufficiently different densities using two catalysts with sufficiently different reactivity ratios. The weight percent of each component can then be precisely monitored in real time through the comonomer concentration measured by the FTnIR Spectrometer at the first reactor exit. Catalyst feed ratio can be adjusted accordingly to reach the target comonomer concentration which is responsible for reaching the target weight percent of each component inside the first reactor. Alternatively, Raman Spectrometer may be utilized in the process control feedback loop, as it provides better comonomer concentration measurement resolution and precision than the Fourier Transform Near-Infrared (FTnIR) Spectrometer.

As noted above, the first catalyst may, in embodiments, comprise a procatalyst-such as, for example, the bis(biphenylphenoxy) procatalyst described above-and one or more cocatalysts that activate the procatalyst. Suitable activating cocatalysts for use according to embodiments include alkyl aluminums; polymeric or oligomeric alumoxanes (also known as aluminoxanes); neutral or strong Lewis acids; and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). Exemplary suitable cocatalysts include, but are not limited to: modified methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl tetrakis(pentafluorophenyl)borate(<NUM>-) amine, triethylaluminum (TEA), and combinations thereof. A suitable activating technique is bulk electrolysis. Combinations of one or more of the foregoing activating cocatalysts and techniques are also contemplated. The term "alkyl aluminum" as used herein means a monoalkyl aluminum dihydride or monoalkylaluminum dihalide, a dialkyl aluminum hydride or dialkyl aluminum halide, or a trialkylaluminum. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.

Lewis acid activators (cocatalysts) according to embodiments include Group <NUM> metal compounds containing from <NUM> to <NUM> (C<NUM>-C<NUM>)hydrocarbyl substituents as described herein. In embodiments, Group <NUM> metal compounds are tri((C<NUM>-C<NUM>)hydrocarbyl)-substituted-aluminum or tri((C<NUM>-C<NUM>)hydrocarbyl)-boron compounds. In other embodiments, Group <NUM> metal compounds are tri(hydrocarbyl)-substituted-aluminum, tri(hydrocarbyl)-boron compounds, tri((C<NUM>-C<NUM>)alkyl)aluminum, tri((C<NUM>-C<NUM>)aryl)boron compounds, and halogenated (including perhalogenated) derivatives thereof. In further embodiments, Group <NUM> metal compounds are tris(fluoro-substituted phenyl)boranes, tris(pentafluorophenyl)borane. In some embodiments, the activating cocatalyst is a tetrakis((C<NUM>-C<NUM>)hydrocarbyl borate (e.g. trityl tetrafluoroborate) or a tri((C<NUM>-C<NUM>)hydrocarbyl)ammoniun tetra((C<NUM>-C<NUM>)hydrocarbyl)borane (e.g. bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane). As used herein, the term "ammonium" means a nitrogen cation that is a ((C<NUM>-C<NUM>)hydrocarbyl)<NUM>N+ a ((C<NUM>-C<NUM>)hydrocarbyl)<NUM>N(H)+, a ((C<NUM>-C<NUM>)hydrocarbyl)<NUM>N(H)<NUM>+, (C<NUM>-C<NUM>)hydrocarbylN(H)<NUM>+, or N(H)<NUM>+, wherein each (C<NUM>-C<NUM>)hydrocarbyl, when two or more are present, may be the same or different.

Combinations of neutral Lewis acid activators (cocatalysts) as described herein include mixtures comprising a combination of a tri((C<NUM>-C<NUM>)alkyl)aluminum and a halogenated tri((C<NUM>-C<NUM>)aryl)boron compound, especially a tris(pentafluorophenyl)borane. Other embodiments are combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane. Ratios of numbers of moles of (metal-ligand complex): (tris(pentafluoro-phenylborane): (alumoxane) [e.g., (Group <NUM> metal-ligand complex) :(tris(pentafluoro-phenylborane):(alumoxane)] are from <NUM>:<NUM>:<NUM> to <NUM>:<NUM>:<NUM>, in other embodiments, from <NUM>:<NUM>:<NUM> to <NUM>:<NUM>:<NUM>.

In embodiments, a ratio of total number of moles of one or more metal-ligand complexes of Formula (I) to total number of moles of one or more of the activating cocatalysts is from <NUM>:<NUM>,<NUM> to <NUM>:<NUM>. In some embodiments, the ratio is at least <NUM>:<NUM>, in some other embodiments, at least <NUM>:<NUM>; and <NUM>:<NUM> or less, and in some other embodiments, <NUM>:<NUM> or less. When an alumoxane alone is used as the activating cocatalyst, in some embodiments the number of moles of the alumoxane that are employed is at least <NUM> times the number of moles of the metal-ligand complex of Formula (I). When tris(pentafluorophenyl)borane alone is used as the activating cocatalyst, in some other embodiments, the number of moles of the tris(pentafluorophenyl)borane that are employed to the total number of moles of one or more metal-ligand complexes of Formula (I) from <NUM>: <NUM> to <NUM>:<NUM>, from <NUM>:<NUM> to <NUM>:<NUM>, or from <NUM>:<NUM> to <NUM>:<NUM>. The remaining activating cocatalysts are generally employed in approximately mole quantities equal to the total mole quantities of one or more metal-ligand complexes of Formula (I).

The reaction conditions in the first reactor <NUM> for reacting ethylene monomer, C<NUM>-C<NUM> α-olefin comonomer, and, optionally, hydrogen in the presence of the first embodiments of which are provided above-will now be described.

To facilitate the reaction of ethylene monomer with C<NUM>-C<NUM> α-olefin comonomer in the presence of the first catalyst, in embodiments the first reactor <NUM> is heated to a temperature from <NUM> to <NUM>, such as from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, or from <NUM> to <NUM>. In embodiments, the first reactor is heated to a temperature from <NUM> to <NUM>, such as from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, or from <NUM> to <NUM>. It should be understood that the above temperature ranges include the endpoints recited therein (e.g., "from <NUM> to <NUM>" includes both <NUM> and <NUM>) and the temperature of the first reactor <NUM> may be measured with any conventional reactor temperature monitoring systems and software.

The feed stream <NUM> that is introduced in to the first reactor <NUM>, in embodiments, comprises a high concentration of ethylene monomer. In some embodiments, the feed stream <NUM> comprises from <NUM> grams per liter (g/L) to <NUM>/L ethylene monomer. In some embodiments, the feed stream <NUM> comprises from <NUM>/L to <NUM>/L ethylene monomer, such as from <NUM>/L. to <NUM>/L. ethylene monomer, from <NUM>/L to <NUM>/L. ethylene monomer, from <NUM>/L to <NUM>/L ethylene monomer, from <NUM>/L to <NUM>/L ethylene monomer, from <NUM>/L to <NUM>/L ethylene monomer, from <NUM>/L to <NUM>/L ethylene monomer, from <NUM>/L to <NUM>/L ethylene monomer, from <NUM>/L. to <NUM>/L ethylene monomer, from <NUM>/L. to <NUM>/L ethylene monomer, from <NUM>/L to <NUM>/L ethylene monomer, or from <NUM>/L to <NUM>/L ethylene monomer. In other embodiments, the feed stream <NUM> comprises from <NUM>/L to <NUM>/L ethylene monomer, such as from <NUM>/L to <NUM>/L ethylene monomer, from <NUM>/L to <NUM>/L ethylene monomer, from <NUM>/L to <NUM>/L ethylene monomer, from <NUM>/L to <NUM>/L ethylene monomer, from <NUM>/L to <NUM>/L ethylene monomer, from <NUM>/L to <NUM>/L ethylene monomer, from <NUM>/L. to <NUM>/L ethylene monomer, from <NUM>/L to <NUM>/L ethylene monomer, from <NUM>/L to <NUM>/L ethylene monomer, from <NUM>/L to <NUM>/L ethylene monomer, or from <NUM>/L to <NUM>/L ethylene monomer.

The concentration of comonomer in the feed stream <NUM> is not limited and can be present in a concentration from <NUM>/L to <NUM>/L, such as from <NUM>/L to <NUM>/L, from <NUM>/L to <NUM>/L, from <NUM>/L to <NUM>/L, from <NUM>/L to <NUM>/L, from <NUM>/L to <NUM>/L, from <NUM>/L to <NUM>/L, from <NUM>/L to <NUM>/L, from <NUM>/L. to <NUM>/L, or from <NUM>/L to <NUM>/L. In some embodiments, the concentration of comonomer in the feed stream <NUM> is from <NUM>/L to <NUM>/L, from <NUM>/L to <NUM>/L, from <NUM>/L to <NUM>/L, from <NUM>/L to <NUM>/L, from <NUM>/L to <NUM>/L, from <NUM>/L to <NUM>/L, from <NUM>/L to <NUM>/L, from <NUM>/L to <NUM>/L, or from <NUM>/L to <NUM>/ L.

In embodiments, the first catalyst is present in the first reactor <NUM> at a concentration from <NUM> micromole per liter (µmol/L) to <NUM>µmol/L, such as from <NUM>µmol/L to <NUM>µmol/L, from <NUM>µmol/L to <NUM>µmol/L, from <NUM>µmol/L to <NUM>µmol/L, from <NUM>µmol/L to <NUM>µmol/L, or from <NUM>µmol/L to <NUM>µmol/L. In embodiments, the first catalyst is present in the first reactor <NUM> at a concentration from <NUM>µmol/L to <NUM>µmol/L, such as from <NUM>µmol/L to <NUM>µmol/L, from <NUM>µmol/L to <NUM>µmol/L, from <NUM>µmol/L to <NUM>µmol/L, from <NUM>µmol/L to <NUM>µmol/L, from <NUM>µmol/L to <NUM>µmol/L, or from <NUM>µmol/L to <NUM>µmol/L.

Under these reaction conditions, ethylene monomer, C<NUM>-C<NUM> α-olefin comonomer, and, optionally, hydrogen react in the presence of the first catalyst, such as, for example, the catalysts described above, to form the first polymer fraction. In embodiments, this first polymer fraction is lower in density and lower in melt index (I<NUM>) than the second polymer fraction formed in the mixer <NUM>.

As described previously in this disclosure, at least the first polymer fraction, unreacted ethylene monomer, and unreacted C<NUM>-C<NUM> α-olefin comonomer exit the first reactor <NUM> in effluent 111a. A second catalyst is introduced to the effluent 111a via second catalyst stream <NUM> causing the unreacted ethylene monomer and unreacted C<NUM>-C<NUM> α-olefin comonomer to react in the presence of the second catalyst and form a second polymer fraction. The high concentration of ethylene monomer present in both the feed stream <NUM> and the effluent 111a ensures there is sufficient ethylene present when the second catalyst stream <NUM> is introduced to the effluent 111a at mixer <NUM> to allow for formation of the second polymer fraction.

In embodiments, the effluent 111a comprises from <NUM> grams per liter (g/L) to <NUM>/L ethylene monomer. In some embodiments, the effluent 111a comprises from <NUM>/L to <NUM>/L ethylene monomer, such as from <NUM>/L to <NUM>/L ethylene monomer, from <NUM>/L to <NUM>/L ethylene monomer, or from <NUM>/L to <NUM>/L ethylene monomer. In other embodiments, effluent 111a comprises from <NUM>/L to <NUM>/L ethylene monomer, such as from <NUM>/L to <NUM>/L ethylene monomer, from <NUM>/L to <NUM>/L ethylene monomer, or from <NUM>/L to <NUM>/L ethylene monomer.

As the modified effluent 111b-comprising ethylene monomer, C<NUM>-C<NUM> α-olefin comonomer, second catalyst, and second polymer fraction-travels through the mixer <NUM> toward the second reactor <NUM>, the ethylene monomer and C<NUM>-C<NUM> α-olefin comonomer present in the modified effluent 111b continue to react in the presence of the second catalyst to form second polymer fraction. It should be understood that the temperature where the second catalyst stream <NUM> is introduced to the effluent 111a is approximately equal to the temperature within the first reactor <NUM> (i.e., from <NUM> to <NUM>), which is lower than the temperature in the second reactor. Further, although ethylene monomer is reacted in the first reactor <NUM> to form the first polymer fraction, the amount of ethylene introduced into the first reactor <NUM> is such that the concentration of unreacted ethylene monomer in the effluent 111a is sufficient to form second polymer fraction. In some embodiments, additional, fresh ethylene monomer may be added to either the effluent 111a (i.e., before the second catalyst stream <NUM> is introduced to the effluent) or to the modified effluent 111b (i.e., after the second catalyst stream <NUM> is introduced to the effluent). In embodiments, reactions of ethylene monomer and C<NUM>-C<NUM> α-olefin comonomer in the presence of the second catalyst occur in the mixer <NUM>. Reacting ethylene monomer and C<NUM>-C<NUM> α-olefin comonomer in the presence of the second catalyst before the modified effluent 111b is introduced into the second reactor <NUM> produces a second polymer fraction that has a high molecular weight high density fraction, which in turn results in a bimodal ethylene-based polymer with better balance of density and melt index. Without being bound by any particular theory, it is believed that the relatively low temperature of the modified effluent 111b and the high concentration of ethylene monomer in the modified effluent 111b results in increased propagation rates, such as, for example, propagation rates <NUM> to <NUM> times higher than propagation rates achieved in conventional processes where a second catalyst is added at the second reactor and at higher temperatures. It is believed that the increased propagation rate provides a high molecular weight high density fraction in the bimodal ethylene-based polymer.

The second catalyst that is introduced to the effluent 111a via the second catalyst stream <NUM> is, in embodiments, a Ziegler-Natta catalyst or a second molecular catalyst-which were described in detail above. In embodiments, exemplary Ziegler-Natta catalysts are those derived from (<NUM>) organomagnesium compounds, (<NUM>) alkyl halides or aluminum halides or hydrogen chloride, and (<NUM>) a transition metal compound. Examples of such catalysts are described in <CIT>), <CIT>), and <CIT>), the teachings of which are incorporated herein by reference in their entirety. The Ziegler-Natta procatalyst may be formed by (a) reacting a hydrocarbon-soluble organomagnesium compound or complex thereof and an active non-metallic or metallic halide to form a halogenated magnesium support; b) contacting the magnesium halide support with a conditioning compound containing an element selected from the group consisting of boron, aluminum, gallium, indium and tellurium under conditions sufficient to form a conditioned magnesium halide support; (c) contacting the magnesium halide support and a compound containing, as a first metal, titanium, to form a supported titanium compound; and (d) optionally, contacting the supported titanium compound and a second metal and optionally a third metal independently selected from the transition metal series, provided that the second metal and the third metal are not the same; and further provided that the molar ratio of the magnesium to a combination of the titanium and the second and third metals ranges from <NUM>:<NUM> to <NUM>:<NUM>; all under conditions sufficient to form a procatalyst.

Particularly suitable organomagnesium compounds for use in Ziegler-Natta catalysts include, for example, hydrocarbon soluble dihydrocarbylmagnesium such as the magnesium dialkyls and the magnesium diaryls. Exemplary suitable magnesium dialkyls include particularly n-butyl-secbutylmagnesium, diisopropylmagnesium, di-n-hexylmagnesium, isopropyl-n-butyl-magnesium, ethyl-n-hexylmagnesium, ethyl-n-butylmagnesium, di-n-octylmagnesium and others wherein the alkyl has from <NUM> to <NUM> carbon atoms. Exemplary suitable magnesium diaryls include diphenylmagnesium, dibenzylmagnesium and ditolylmagnesium. Suitable organomagnesium compounds include alkyl and aryl magnesium alkoxides and aryloxides and aryl and alkyl magnesium halides. In some embodiments, the organomagnesium compound is a halogen-free organomagnesium.

The modified effluent 111b-which comprises unreacted methylene, unreacted C<NUM>-C<NUM> α-olefin comonomer, second catalyst, first polymer fraction, and second polymer fraction-is present in the mixer <NUM> for a duration from <NUM> minutes to <NUM> minutes, such as from <NUM> minutes to <NUM> minutes, or from <NUM> minutes to <NUM> minutes before it is introduced into the second reactor <NUM>.

After the modified effluent 111b is introduced into the second reactor <NUM>, which is a non-agitated solution polymerization reactor, the modified effluent 111b is heated to a temperature that is greater than the temperature in the first reactor <NUM> and greater than the temperature of the modified effluent 111b in the mixer <NUM>. In embodiments, the temperature within the second reactor <NUM> is from <NUM> to <NUM>. The temperature within the second reactor <NUM> is, in some embodiments, from <NUM> to <NUM>, such as from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, or from <NUM> to <NUM>. In other embodiments, the temperature within the second reactor is from <NUM> to <NUM>, such as from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, or from <NUM> to <NUM>. It should be understood that the above temperature ranges include the endpoints recited therein (e.g., "from <NUM> to <NUM>" includes both <NUM> and <NUM>) and the temperature of the second reactor <NUM> may be measured with any conventional reactor temperature monitoring systems and software.

The unreacted ethylene monomer and unreacted C<NUM>-C<NUM> α-olefin comonomer in the modified effluent 111b that enters the second reactor <NUM> will react in the presence of the second catalyst to form additional second polymer fraction. In addition, a second feed stream <NUM> that comprises ethylene monomer and C<NUM>-C<NUM> α-olefin comonomer in solvent is introduced into the second reactor <NUM>. The ethylene monomer and C<NUM>-C<NUM> α-olefin comonomer from the second feed stream <NUM> will also react in the presence of the second catalyst to form additional second polymer fraction. It should be understood that although <FIG> depicts second feed stream <NUM> as a single feed stream, the components may be individually introduced into the second reactor <NUM>.

After a sufficient amount of time in the second reactor <NUM>, product stream <NUM> that comprises a bimodal ethylene-based polymer exits the second reactor <NUM>. Properties of the bimodal ethylene-based polymer present in product stream <NUM> will be described in more detail below. Although not shown in <FIG> and <FIG>, it should be understood that any unreacted ethylene monomer, unreacted C<NUM>-C<NUM> α-olefin comonomer, and solvent present in product stream <NUM> may be separated from the bimodal ethylene-based polymer and recycled back to the system <NUM> or <NUM> in feed stream <NUM> to the first reactor <NUM> or in second feed stream <NUM> to the second reactor <NUM>.

The over conversion rate of ethylene monomer in the system <NUM> is from <NUM>% to <NUM>%, such as from <NUM>% to <NUM>%, from <NUM>% to <NUM>%, or from <NUM>% to <NUM>%.

Exemplary properties of bimodal ethylene-based polymers produced according to embodiments disclosed and described herein will now be provided. As noted above, and without being bound to any particular theory, it is believed that the combination of the exemplary properties listed below is made possible by the processes and systems disclosed and described hereinabove.

According to embodiments, the bimodal ethylene-based polymer may have a density from <NUM> to <NUM>/cc measured according to ASTM D792. In some embodiments, the bimodal ethylene-based polymer has a density from <NUM>/cc to <NUM>/cc, such as from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, or from <NUM>/cc to <NUM>/cc. In other embodiments the bimodal ethylene-based polymer has a density from <NUM>/cc to <NUM>/cc, such as from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, or from <NUM>/cc to <NUM>/cc. In yet other embodiments, the bimodal ethylene-based polymer has a density from <NUM>/cc to <NUM>/cc, such as from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc, from <NUM>/cc to <NUM>/cc from <NUM>/cc to <NUM>/cc, or from <NUM>/cc to <NUM>/cc. In still other embodiments, the bimodal ethylene-based polymer has a density from <NUM>/cc to <NUM>/cc, or from <NUM>/cc to <NUM>/cc. It should be understood that the above density ranges include the endpoints recited therein.

The bimodal ethylene-based polymers of embodiments have a high density fraction (HDF)-measured by crystallization elution fractionation (CEF) integration at temperatures from <NUM> to <NUM>-from <NUM>% to <NUM>%, such as from <NUM>% to <NUM>%, from <NUM>% to <NUM>%, from <NUM>% to <NUM>%, from <NUM>% to <NUM>%. from <NUM>% to <NUM>%. from <NUM>% to <NUM>%, from <NUM>% to <NUM>%, or from <NUM>% to <NUM>%. In other embodiments, the bimodal ethylene-based polymers of embodiments have an HDF from <NUM>% to <NUM>%, such as from <NUM>°% to <NUM>%, from <NUM>% to <NUM>%, from <NUM>% to <NUM>%, from <NUM>% to <NUM>%, from <NUM>% to <NUM>%, from <NUM>% to <NUM>%, or from <NUM>% to <NUM>%. In still other embodiments the bimodal ethylene-based polymers of embodiments have an HDF from <NUM>% to <NUM>%, such as from <NUM>% to <NUM>%, from <NUM>% to <NUM>%, or from <NUM>% to <NUM>%. It should be understood that the above HDF ranges include the endpoints recited therein.

In embodiments, the bimodal ethylene-based polymer has a melt index (I<NUM>)-measured according to ASTM D <NUM> at a load of <NUM> kgm-from <NUM> grams per <NUM> minutes (g/<NUM> mins) to <NUM>/<NUM> mins, such as from <NUM>/<NUM> mins to <NUM>/<NUM> mins, from <NUM>/<NUM> mins to <NUM>/<NUM> mins, from <NUM>/<NUM> mins to <NUM>/ <NUM> mins, from <NUM>/<NUM> mins to <NUM>/<NUM> mins, from <NUM>/<NUM> mins to <NUM>/<NUM> mins, from <NUM>/<NUM> mins to <NUM>/<NUM> mins, from <NUM>/<NUM> mins to <NUM>/<NUM> mins, or from <NUM>/<NUM> mins to <NUM>/<NUM> mins. In other embodiments, the bimodal ethylene-based polymer has an I<NUM> from <NUM>/<NUM> mins to <NUM>/<NUM> mins, such as from <NUM>/<NUM> mins to <NUM>/<NUM> mins, from <NUM>/<NUM> mins to <NUM>/<NUM> mins, from <NUM>/<NUM> mins to <NUM>/<NUM> mins, from <NUM>/<NUM> mins to <NUM>/<NUM> mins, from <NUM>/<NUM> mins to <NUM>/<NUM> mins, from <NUM>/<NUM> mins to <NUM>/<NUM> mins, or from <NUM>/<NUM> mins to <NUM>/<NUM> mins. In yet other embodiments, the bimodal ethylene-based polymer has an I<NUM> from <NUM>/<NUM> mins to <NUM>/<NUM> mins, such as from <NUM>/<NUM> mins to <NUM>/<NUM> mins, from <NUM>/<NUM> mins to <NUM>/<NUM> mins, from <NUM>/<NUM> mins to <NUM>/<NUM> mins, or from <NUM>/<NUM> mins to <NUM>/<NUM> mins. It should be understood that the above I<NUM> ranges include the endpoints recited therein.

The bimodal ethylene-based polymer may have an I<NUM>/I<NUM> ratio-where I<NUM> is the melt index when measured according to ASTM D <NUM> at a load of <NUM> and temperature of <NUM> and I<NUM> is the melt index when measured according to ASTM D <NUM> at a load of <NUM> and temperature of <NUM>-from <NUM> to <NUM>, such as from <NUM> to <NUM>, from <NUM> to <NUM>, or from <NUM> to <NUM>, from <NUM> to <NUM>. In some embodiments, the bimodal ethylene-based polymer may have an I<NUM>/I<NUM> ratio from <NUM> to <NUM>, such as from <NUM> to <NUM>, or from <NUM> to <NUM>. In yet other embodiments, the bimodal ethylene-based polymer has an I<NUM>/I<NUM> ratio from <NUM> to <NUM>. It should be understood that the above I<NUM>/I<NUM> ratio ranges include the endpoints recited therein.

The short chain branching distribution (SCBD) of bimodal ethylene-based polymers is, according to embodiments, less than <NUM>-measured by CEF full width at half height. In some embodiments, the SCBD of bimodal ethylene-based polymers is less than <NUM>, less than <NUM>, less than <NUM>, less than <NUM>, less than <NUM>, less than <NUM>, or less than <NUM>. It should be understood that the above SCBD ranges include the endpoints recited therein.

The bimodal ethylene-based polymer has, according to embodiments, a zero shear viscosity ratio from <NUM> to <NUM>, such as from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, or from <NUM> to <NUM>. In some embodiments, the bimodal ethylene-based polymer has a zero shear viscosity ration from <NUM> to <NUM>, such as from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, or from <NUM> to <NUM>. In still other embodiments, the bimodal ethylene-based polymer has a zero shear viscosity ratio from <NUM> to <NUM>, such as from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, from <NUM> to <NUM>, or from <NUM> to <NUM>. It should be understood that the above zero shear viscosity ratio ranges include the endpoints recited therein.

In bimodal ethylene-based polymer, according to embodiments, comprises from <NUM> weight percent (wt. %) to <NUM> wt. % of the first polymer fraction and from <NUM> wt. % to <NUM> wt. % of the second polymer fraction. In some embodiments, the bimodal ethylene-based polymer comprises from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, such as from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, or from <NUM> wt. % to <NUM> wt. % of the first polymer fraction. In other embodiments, the bimodal ethylene-based polymer comprises from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, such as from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, or from <NUM> wt. % to <NUM> wt. % of the first polymer fraction. In still other embodiments, the bimodal ethylene-based polymer comprises from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, such as from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, from <NUM> wt. % to <NUM> wt. % of the first polymer fraction, or from <NUM> wt. % to <NUM> wt. % of the first polymer fraction. It should be understood that the above weight percent ranges include the endpoints recited therein.

In some embodiments, the bimodal ethylene-based polymer comprises from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, such as from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, or from <NUM> wt. % to <NUM> wt. % of the second polymer fraction. In other embodiments, the bimodal ethylene-based polymer comprises from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, such as from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, or from <NUM> wt. % to <NUM> wt. % of the second polymer fraction. In still other embodiments, the bimodal ethylene-based polymer comprises from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, from <NUM> wt. % to <NUM> wt. % of the second polymer fraction, or from <NUM> wt. % to <NUM> wt. % of the second polymer fraction. It should be understood that the above weight percent ranges include the endpoints recited therein.

The amount of each polymer fraction in the bimodal ethylene-based polymer may be adjusted based on the application or use. For example, a different balance of properties may be desirable in low temperature applications (e.g., below <NUM>) versus applications where the bimodal ethylene-based polymer is subjected to higher temperatures (e.g., temperatures greater than <NUM>).

In embodiments, the melt index and density of the second polymer fraction consists of the polymer fraction formed in the mixer <NUM> and the reaction environment of the second reactor <NUM>. The polymer fraction made in the mixer <NUM> has a lower melt index (MI), and the polymer fraction formed in the second reactor <NUM> has higher MI (e.g., about <NUM> times higher than polymer fraction formed in the mixer <NUM>). The combined second polymer fraction formed in the mixer <NUM> and the second reactor <NUM> has a high density fraction that is greater than the density of the first ethylene-based polymer fraction by at least <NUM>/cc, such as greater than the density by at least <NUM>/cc as shown by the CEF peak temperatures. In addition, using processes for forming a bimodal ethylene-based polymer according to embodiments disclosed and described herein, the final bimodal ethylene-based polymer (i.e., including the first polymer fraction and the second polymer fraction) has a higher density and higher melt index (I<NUM>) than the first polymer fraction. Also, the portion of the second polymer fraction formed in the mixer has a higher molecular weight than the portion of the second polymer fraction formed in the second, non-agitated reactor.

The testing methods include the following:
Melt index (I<NUM>) and (I<NUM>).

Melt index (I<NUM>) values for the bimodal ethylene-based polymers measured in accordance to ASTM D1238 at <NUM> at <NUM>. Similarly, melt index (I<NUM>) values for the bimodal ethylene-based polymers were measured in accordance to ASTM D1238 at <NUM> at <NUM>. The values are reported in g/<NUM>, which corresponds to grams eluted per <NUM> minutes. The melt index (I<NUM>) values for the first ethylene-based component, the second ethylene-based component, and the third ethylene-based component were calculated according to Equation <NUM> and the methodology described below.

Density measurements for the bimodal ethylene-based polymers were made in accordance with ASTM D792, Method B. For the first and second ethylene-based components, the density values were obtained using Equation <NUM> and the methodology described below. For the third ethylene-based component, the density value was calculated using Equation <NUM>.

The chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infra-red detector (IR5). The autosampler oven compartment was set at <NUM> and the column compartment was set at <NUM>. The columns used were <NUM> Agilent "Mixed A" <NUM> <NUM>-micron linear mixed-bed columns. The chromatographic solvent used was <NUM>,<NUM>,<NUM> trichlorobenzene and contained <NUM> ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was <NUM> microliters and the flow rate was <NUM> milliliters/minute.

Calibration of the GPC column set was performed with at least <NUM> narrow molecular weight distribution polystyrene standards with molecular weights ranging from <NUM> to <NUM>,<NUM>,<NUM>/mol and were arranged in <NUM> "cocktail" mixtures with at least a decade of separation between individual molecular weights. The standards were purchased from Agilent Technologies. The polystyrene standards were prepared at <NUM> grams in <NUM> milliliters of solvent for molecular weights equal to or greater than <NUM>,<NUM>,<NUM>/mol, and <NUM> grams in <NUM> milliliters of solvent for molecular weights less than <NUM>,<NUM>,<NUM>/mol. The polystyrene standards were dissolved at <NUM> with gentle agitation for <NUM> minutes. The polystyrene standard peak molecular weights were converted to ethylene-based polymer molecular weights using Equation <NUM> (as described in <NPL>)). : <MAT> where M is the molecular weight, A has a value of <NUM> and B is equal to <NUM>.

A fifth order polynomial was used to fit the respective ethylene-based polymer - equivalent calibration points. A small adjustment to A (from approximately <NUM> to <NUM>) was made to correct for column resolution and band-broadening effects such that NIST standard NBS <NUM> is obtained at a molecular weight of <NUM>,<NUM>/mol.

The total plate count of the GPC column set was performed with Eicosane (prepared at <NUM> in <NUM> milliliters of TCB and dissolved for <NUM> minutes with gentle agitation). The plate count (Equation <NUM>) and symmetry (Equation <NUM>) were measured on a <NUM> microliter injection according to the following equations: <MAT> where RV is the retention volume in milliliters, the peak width is in milliliters, the peak max is the maximum height of the peak, and half height is one half of the height of the peak maximum. <MAT> where RV is the retention volume in milliliters and the peak width is in milliliters, Peak max is the maximum position of the peak, one tenth height is one tenth of the height of the peak maximum, and where rear peak refers to the peak tail at later retention volumes than the peak max and where front peak refers to the peak front at earlier retention volumes than the peak max. The plate count for the chromatographic system should be greater than <NUM>,<NUM> and symmetry should be between <NUM> and <NUM>.

Samples were prepared in a semi-automatic manner with the PolymerChar "Instrument Control" Software, wherein the samples were weight-targeted at <NUM>/ml, and the solvent (contained <NUM> ppm BHT) was added to a pre nitrogen-sparged septa-capped vial, via the PolymerChar high temperature autosampler. The samples were dissolved for <NUM> hours at <NUM> under "low speed" shaking.

The calculations of Mn(GPC), Mw(GPC), and Mz(GPC) were based on GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations <NUM>-<NUM>, using PolymerChar GPCOne™ software, the baseline-subtracted IR chromatogram at each equally-spaced data collection point i (IRi) and the ethylene-based polymer equivalent molecular weight obtained from the narrow standard calibration curve for the point i (Mpolyethylene,i in g/mol) from Equation <NUM>. Subsequently, a GPC molecular weight distribution (GPC-MWD) plot (wtGPC(lgMW) vs. IgMW plot, where wtGPC(lgMW) is the weight fraction of ethylene-based polymer molecules with a molecular weight of IgMW) for the ethylene-based polymer sample can be obtained. Molecular weight is in g/mol and wtGPC(lgMW) follows the Equation <NUM>.

Number-average molecular weight Mn(GPC), weight-average molecular weight Mw(GPC) and z-average molecular weight Mz(GPC) can be calculated as the following equations. <MAT> <MAT> <MAT>.

In order to monitor the deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled with the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (Flowrate(nominal)) for each sample by RV alignment of the respective decane peak within the sample (RV(FM Sample)) to that of the decane peak within the narrow standards calibration (RV(FM Calibrated)). Any changes in the time of the decane marker peak are then assumed to be related to a linear-shift in flow rate (Flowrate(effective)) for the entire run. To facilitate the highest accuracy of a RV measurement of the flow marker peak, a least-squares fitting routine is used to fit the peak of the flow marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation is then used to solve for the true peak position. After calibrating the system based on a flow marker peak, the effective flow rate (with respect to the narrow standards calibration) is calculated as Equation <NUM>. Processing of the flow marker peak was done via the PolymerChar GPCOne™ Software. Acceptable flow rate correction is such that the effective flowrate should be within <NUM>% of the nominal flowrate.

A calibration for the IR5 detector rationing was performed using at least ten ethylene-based polymer standards (ethylene-based polymer homopolymer and ethylene/octene copolymers) of known short chain branching (SCB) frequency (The comonomer content of the reference materials is determined using 13C NMR analysis in accordance with techniques described, for example, in <CIT>) and by <NPL>, which are incorporated herein by reference), ranging from homopolymer (<NUM> SCB/<NUM> total C) to approximately <NUM> SCB/<NUM> total C, where total C is equal to the carbons in backbone plus the carbons in branches. Each standard had a weight-average molecular weight from <NUM>,<NUM>/mole to <NUM>,<NUM>/mole and had a molecular weight distribution from <NUM> to <NUM>, as determined by GPC. Typical Copolymer Standards properties and measurements are shown in Table A.

The "IR5 Area Ratio (or "IR5 Methyl Channel Area / IR5 Measurement Channel Area")" of "the baseline-subtracted area response of the IR5 methyl channel sensor" to "the baseline-subtracted area response of IR5 measurement channel sensor" (standard filters and filter wheel as supplied by PolymerChar: Part Number IR5_FWM01 included as part of the GPC-IR instrument) was calculated for each of the "Copolymer" standards. A linear fit of the Wt. % Comonomer versus the "IR5 Area Ratio" was constructed in the form of the following Equation <NUM>: <MAT>.

Therefore, a GPC-CC (GPC-Comonomer Content) plot (wt. % comonomer vs. 1gMW) can be obtained. End-Group Correction of the wt. % Comonomer data can be made via knowledge of the termination mechanism if there is significant spectral overlap with the comonomer termination (methyls) via the molecular weight determined at each chromatographic slice.

Comonomer distribution analysis, also commonly called short chain branching distribution (SCBD), is measured with Crystallization Elution Fractionation (CEF) (PolymerChar, Spain) (<NPL>), which is incorporated herein by reference in its entirety) equipped with an IR (IR-<NUM> or IR-<NUM>) detector (PolymerChar, Spain) and <NUM>-angle light scattering detector Model <NUM> (Precision Detectors, currently Agilent Technologies). Distilled anhydrous ortho-dichlorobenzene (ODCB) with <NUM> ppm antioxidant butylated hydroxytoluene (BHT) was used as solvent. For the autosampler with the capability of N<NUM> purge, no BHT was added. A GPC guard column (<NUM> microns, or <NUM> microns, 50X7. <NUM>) (Agilent Technologies) is installed just before the IR detector in the detector oven. Sample preparation is done with an autosampler at <NUM> for <NUM> hours under shaking at <NUM>/ml (unless otherwise specified). The injection volume is <NUM>µl. The temperature profile of CEF is: crystallization at <NUM> /min from <NUM> to <NUM>, the thermal equilibrium at <NUM> for <NUM> minutes, elution at <NUM>/min from <NUM> to <NUM>. The flow rate during crystallization was at <NUM>/min. The flow rate during elution is at <NUM>/min. The data was collected at one data point/second.

The CEF column is packed by The Dow Chemical Company with glass beads at <NUM> ± <NUM>% (MO-SCI Specialty Products) with <NUM>/<NUM>-inch stainless tubing. Glass beads are acid washed by MO-SCI Specialty by request from The Dow Chemical Company. Column volume is <NUM>. Column temperature calibration was performed by using a mixture of NIST Standard Reference Material Linear ethylene-based polymer 1475a (<NUM>/ml) and Eicosane (<NUM>/ml) in ODCB. Temperature was calibrated by adjusting elution heating rate so that NIST linear ethylene-based polymer 1475a has a peak temperature at <NUM>, and Eicosane has a peak temperature of <NUM>. The CEF column resolution was calculated with a mixture of NIST linear ethylene-based polymer 1475a (<NUM>/ml) and hexacontane (Fluka, purum ≥ <NUM>%, <NUM>/ml). A baseline separation of hexacontane and NIST ethylene-based polymer 1475a was achieved. The area of hexacontane (from <NUM> to <NUM>) to the area of NIST 1475a from <NUM> to <NUM> is <NUM> to <NUM>, the amount of soluble fraction below <NUM> is less than <NUM> wt. The CEF column resolution is defined in Equation <NUM>: <MAT> where the half height width is measured in temperature and resolution is at least <NUM>.

An additional parameter to describe the short chain branching distribution is the CEF full width at half height. This is done by the procedure outlined below:.

The high density fraction (HDF) can be calculated as an integral from the CEF curve from <NUM> to <NUM>. This is defined as the integral of the IR-<NUM> chromatogram (baseline subtracted measurement channel) in the elution temperature ranging from <NUM> to <NUM> divided by the total integral from <NUM> to <NUM> according to the following equation: <MAT>
where T is the elution temperature (from the calibration discussed above).

Zero-shear viscosity ratio is defined as the ratio of the zero-shear viscosity (ZSV) of the branched polyethylene material to the ZSV of a linear polyethylene material (see ANTEC proceeding below) at the equivalent weight average molecular weight (Mw(conv gpc)), according to the following Equation <NUM>:
<MAT>.

The ZSV value was obtained from creep test, at <NUM>, via the method described above. The Mw(conv gpc) value was determined by the conventional GPC method (Equation <NUM>), as discussed above. The correlation between ZSV of linear polyethylene and its Mw(conv gpc) was established based on a series of linear polyethylene reference materials. A description for the ZSV-Mw relationship can be found in the ANTEC proceeding: <NPL>.

The following examples illustrate features of the present disclosure but are not intended to limit the scope of the disclosure.

A bimodal ethylene-based polymer was formed using a loop reactor as the first reactor and a plug flow reactor as the second reactor. The feed stream into the first reactor included <NUM> pounds per hour (lb/hr) ISOPAR-E solvent, <NUM> lb/hr ethylene monomer, <NUM> lb/hr hexene. Hydrogen was also introduced into the first reactor at <NUM> sccm. The first reactor exit ethylene concentration was <NUM>/L. The first catalyst introduced into the first reactor included a procatalyst and a cocatalyst. The procatalyst was C<NUM>H<NUM>O<NUM>Zr; Zirconium,dimethyl[[<NUM>,<NUM>‴-[<NUM>,<NUM>-propanediylbis(oxy-κO)]bis[<NUM>",<NUM>,<NUM>"-tris(<NUM>,<NUM>-dimethylethyl)-<NUM>'-methyl[<NUM>,<NUM>':<NUM>',<NUM>"-terphenyl]-<NUM>'-olato-κO]](<NUM>-)] having the following structure:
<CHM>
The procatalyst was added as needed to control <NUM>/L reactor exit ethylene concentration and procatalyst loading was typically <NUM>µmol/L in the reactor exit. The cocatalyst was bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(<NUM>-) amine.

The first reactor was heated to a temperature of <NUM> and the ethylene monomer and hexene reacted in the presence of the first catalyst to form a first polymer fraction.

A second catalyst was added to the effluent downstream from the first reactor and upstream from the second reactor to form a modified effluent. The second catalyst was a Ziegler-Natta catalyst at a concentration of about <NUM>µmol/L. The modified effluent was introduced into the second, plug flow reactor where the unreacted ethylene and the unreacted hexene and unreacted hydrogen reacted in the presence of the second catalyst to form a second polymer fraction.

The bimodal ethylene-based polymer produced in the foregoing example comprised <NUM> wt. % first polymer fraction, <NUM> wt. % second polymer fraction measured using traditional modeling of ethylene consumption in the first and second reactors. The bimodal ethylene-based polymer had a melt index (I<NUM>) of <NUM>/<NUM>) min, a density of <NUM>/cc, and an I<NUM>/I<NUM> ratio of <NUM>, each measured in accordance with the techniques disclosed previously.

A bimodal ethylene-based polymer was formed using a loop reactor as the first reactor and a plug flow reactor as the second reactor. The feed stream into the first reactor included <NUM> lb/hr ISOPAR-E solvent, <NUM> lb/hr ethylene monomer, <NUM> lb/hr hexene. Hydrogen was also introduced into the first reactor at <NUM> sccm. The first reactor exit ethylene concentration was <NUM>/L. The first catalyst introduced into the first reactor included a procatalyst and a cocatalyst. The procatalyst was C<NUM>H<NUM>O<NUM>Zr; Zirconium,dimethyl[[<NUM>,<NUM>‴-[<NUM>,<NUM>-propanediylbis(oxy-κO)]bis[<NUM>",<NUM>,<NUM>"-tris(<NUM>,<NUM>-dimethylethyl)-<NUM>'-methyl[<NUM>,<NUM>':<NUM>',<NUM>"-terphenyl]-<NUM>'-olato-κO]](<NUM>-)] having the following structure:
<CHM>
The procatalyst was added as needed to maintain <NUM>/L ethylene concentration. The catalyst loading was about <NUM>µmol/L in the reactor exit. The cocatalyst was bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(<NUM>-) amine.

The first reactor was heated to a temperature of <NUM> and the ethylene monomer and hexene and hydrogen reacted in the presence of the first catalyst to form a first polymer fraction.

The bimodal ethylene-based polymer produced in the foregoing example comprised <NUM> wt. % first polymer fraction, <NUM> wt. % second polymer fraction using traditional modeling of ethylene consumption in the first and second reactors. The bimodal ethylene-based polymer had a melt index (I<NUM>) of <NUM>/<NUM>, a density of <NUM>/cc, and an I<NUM>/I<NUM> ratio of <NUM>, each measured in accordance with the techniques disclosed previously.

A bimodal ethylene-based polymer was formed using a loop reactor as the first reactor and a plug flow reactor as the second reactor. The feed stream into the first reactor included <NUM> pounds per hour (lb/hr) ISOPAR-E solvent, <NUM> lb/hr ethylene monomer, and <NUM> lb/hr octene. Hydrogen was also introduced into the first reactor at <NUM>,<NUM> sccm. The ethylene concentration in the effluent was <NUM>/L. The first catalyst introduced into the first reactor included a procatalyst and a cocatalyst. The procatalyst was Hafnium, [[<NUM>',<NUM>‴-[<NUM>,<NUM>- butanediylbis(oxy-. O)]bis[<NUM>-(<NUM>-carbazol-<NUM>-yl)-<NUM>-methyl[<NUM>,<NUM>'-biphenyl]-<NUM>-olato-. O]](<NUM>-)]dimethyl-
<CHM>
The procatalyst was added as needed to control <NUM>/L ethylene concentration in the effluent, and procatalyst loading was typically <NUM>µmol/L in the effluent. The cocatalyst was bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(<NUM>-) amine.

The first reactor was heated to a temperature of <NUM> and the ethylene monomer and octene reacted in the presence of the first catalyst to form a first polymer fraction.

A second catalyst was added to the effluent downstream from the first reactor and upstream from the second reactor to form a modified effluent. The second procatalyst was of chemical formula C<NUM>H<NUM>F<NUM>HfN<NUM>O<NUM>; Hafnium, [[<NUM>,<NUM>‴-[[<NUM>,<NUM>-propanediylbis(oxy-kO)]bis[<NUM>-[<NUM>,<NUM>-bis(<NUM>,<NUM>-dimethylethyl)-<NUM>-carbazol-<NUM>-yl]-<NUM>'-fluoro-<NUM>'-methyl-<NUM>-(<NUM>,<NUM>,<NUM>,<NUM>-tetramethylbutyl)[<NUM>,<NUM>'-biphenyl]-<NUM>-olato-kO]](<NUM>-)]dimethyl- and was added at concentration typically of <NUM> umol/L. The structure of the second catalyst was as follows:
<CHM>.

The modified effluent was introduced into the second, plug flow reactor where the unreacted ethylene and the unreacted octene and unreacted hydrogen reacted in the presence of the second catalyst to form a second polymer fraction.

Claim 1:
A method of producing bimodal ethylene-based polymer comprising:
reacting ethylene monomer and C<NUM>-C<NUM> α-olefin comonomer in solvent in the presence of a first catalyst in an agitated solution polymerization reactor to produce a first polymer fraction;
outputting effluent from the agitated solution polymerization reactor, wherein effluent comprises the first polymer fraction, unreacted ethylene monomer, and unreacted C<NUM>-C<NUM> α-olefin comonomer;
adding a second catalyst to the effluent downstream of the agitated solution polymerization reactor and upstream from a non-agitated solution polymerization reactor, wherein the second catalyst facilitates further reaction of the unreacted ethylene monomer and unreacted C<NUM>-C<NUM> α-olefin comonomer to produce a second polymer fraction having a density and melt index (I<NUM>) different from the first polymer fraction and the second catalyst and effluent mix in at least one mixer downstream from the agitated solution polymerization reactor and upstream of the non-agitated solution polymerization reactor;
passing the second catalyst, second polymer fraction, and the first polymer fraction to the non-agitated solution polymerization reactor; and
passing additional ethylene monomer, additional C<NUM>-C<NUM> α-olefin comonomer, and solvent to the non-agitated solution polymerization reactor, wherein the additional ethylene monomer, additional C<NUM>-C<NUM> α-olefin comonomer react in the presence of the second catalyst to produce more second polymer fraction and thereby the bimodal ethylene-based polymer, the bimodal ethylene-based polymer comprising the first polymer fraction and the second polymer fraction.